Surface-Initiated Controlled Radical Polymerization: State-of-the-Art

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Surface-Initiated Controlled Radical Polymerization: State-of-the-Art, Opportunities, and Challenges in Surface and Interface Engineering with Polymer Brushes Justin O. Zoppe, Nariye Cavusoglu Ataman, Piotr Mocny, Jian Wang, John Moraes, and Harm-Anton Klok* Institut des Matériaux and Institut des Sciences et Ingénierie Chimiques, Laboratoire des Polymères Bâtiment MXD, Ecole Polytechnique Fédérale de Lausanne (EPFL), Station 12 CH-1015 Lausanne, Switzerland ABSTRACT: The generation of polymer brushes by surface-initiated controlled radical polymerization (SI-CRP) techniques has become a powerful approach to tailor the chemical and physical properties of interfaces and has given rise to great advances in surface and interface engineering. Polymer brushes are defined as thin polymer films in which the individual polymer chains are tethered by one chain end to a solid interface. Significant advances have been made over the past years in the field of polymer brushes. This includes novel developments in SI-CRP, as well as the emergence of novel applications such as catalysis, electronics, nanomaterial synthesis and biosensing. Additionally, polymer brushes prepared via SI-CRP have been utilized to modify the surface of novel substrates such as natural fibers, polymer nanofibers, mesoporous materials, graphene, viruses and protein nanoparticles. The last years have also seen exciting advances in the chemical and physical characterization of polymer brushes, as well as an ever increasing set of computational and simulation tools that allow understanding and predictions of these surfacegrafted polymer architectures. The aim of this contribution is to provide a comprehensive review that critically assesses recent advances in the field and highlights the opportunities and challenges for future work.

CONTENTS 1. Introduction 2. Synthetic Methods 2.1. Surface-Initiated Controlled Radical Polymerization (SI-CRP) in the Presence of Cu0 2.2. Electrochemically Mediated SI-ATRP 2.3. Light-Mediated SI-CRP 2.4. Surface Reversible Addition−Fragmentation Chain Transfer Polymerization (S-RAFT) 2.4.1. S-RAFT from Fe2O3 Nanoparticles 2.4.2. S-RAFT from Indium Tin Oxide (ITO) 2.4.3. S-RAFT from Polymer Substrates 2.4.4. S-RAFT from SiOx 2.4.5. Determination of the Surface Concentration of Anchored RAFT CTAs 2.5. Cleaving Polymer Brushes from Substrates 2.6. Novel Monomers 2.7. Mechanistic Considerations 2.7.1. Kinetics of SI-CRP 2.7.2. Effect of Surface Curvature on Molecular Weight and Dispersity 2.7.3. Effect of Chain Confinement on Polymer Brush Growth Kinetics 2.7.4. Molecular Weight and Dispersity of Free Polymers vs Cleaved Polymers 3. Architectures 3.1. Two-Layer, Bimodal Polymer Brushes

© 2017 American Chemical Society

3.2. Loop-Type Polymer Brushes 3.3. Binary and Y-Shaped Mixed Brushes 3.4. “Polymer Carpets” 4. Substrates 4.1. Novel Substrates 4.1.1. Biobased Substrates 4.1.2. Electrospun Nanofibers 4.1.3. Mesoporous Materials 4.1.4. Graphene and Graphene-Related Materials 4.2. Initiator/Chain Transfer Agent Immobilization on Surfaces 4.2.1. Development of Water Tolerant Initiator Immobilization Methods 4.2.2. Substrate-Independent “Universal” Methods 4.3. Stability and “Mechanochemical” Effects 5. Patterning Strategies 5.1. Photolithography, Including Interference Lithography 5.2. E-Beam Lithography 5.3. Scanning Probe Based Techniques 5.4. Microcontact Printing 5.5. Other Patterning Techniques

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Received: May 16, 2016 Published: January 30, 2017 1105

DOI: 10.1021/acs.chemrev.6b00314 Chem. Rev. 2017, 117, 1105−1318

Chemical Reviews 6. Postpolymerization Modification of Polymer Brushes 6.1. Postpolymerization Modification of Ester Side-Chain Functionalized Polymer Brushes 6.2. Postpolymerization Modification to Yield Acid Side Chain Functionalized Brushes 6.3. Postpolymerization Modification of Carboxylic Acid Side-Chain Functionalized Polymer Brushes 6.4. Postpolymerization Modification to Yield Quaternized Polymer Brushes 6.5. Postpolymerization Modification of Hydroxyl Side-Chain Functionalized Polymer Brushes 6.6. Postpolymerization Modification of Poly(glycidyl methacrylate) Brushes 6.7. Postpolymerization Modification of Other Side-Chain Functional Brushes 6.8. (Selective) Chain End Postpolymerization Modification of Polymer Brushes 7. Characterization of Polymer Brushes 7.1. Characterization of Polymer Brush Thickness and Grafting Density 7.2. Chemical Characterization 7.2.1. X-ray Photoelectron Spectroscopy (XPS) 7.2.2. Matrix-Assisted Laser Desorption Ionization Time-of-Flight (MALDI-ToF) and Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) 7.3. Physical Characterization 7.3.1. Nanomechanical Cantilever Sensor Arrays (NCS) 7.3.2. Silicon Photonic Microring Resonators 7.3.3. Tilted Fiber Bragg Gratings (TFBG) 7.3.4. Neutron Reflectometry (NR) and SmallAngle Neutron Scattering (SANS) 7.3.5. Colloidal Probe Microscopy (CPM) 7.3.6. In Situ Ellipsometry 7.3.7. Quartz Crystal Microbalance with Dissipation Monitoring (QCM-D) 8. Polymer Brush Theory 8.1. Alexander−de Gennes (AdG) Theory 8.2. Self-Consistent Field Theory (SCFT) 8.3. Density Functional Theory (DFT) 8.4. Monte Carlo and Molecular Dynamics Simulations 8.4.1. Monte Carlo Simulations of Polymer Brush Structure 8.4.2. Monte Carlo Simulations of SI-CRP Reactions 8.4.3. Molecular Dynamics Simulations of Polymer Brush Structure 8.4.4. Molecular Dynamics Simulations of SICRP Reactions 9. Properties and Novel Applications 9.1. Stimuli-Responsive Surfaces and Colloids 9.2. Brush-Modulated Gating through Nanopores and Nanochannels 9.3. Janus Particles 9.4. Pickering Emulsion Systems 9.5. Polymer Nanocomposites 9.6. Catalysis

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9.7. Brush-Assisted Synthesis of Metallic and Inorganic Nanoparticles and Thin Films 9.8. Chiral Polymer Brushes 9.9. High Binding Capacity Layers for Biomolecular Mass Spectrometry 9.10. Liquid Crystalline Brushes 9.11. Polymer Brushes for Photonic Applications 9.12. Proton Conducting Membranes 9.13. Polymer Brushes for Field Effect Transistors and Photovoltaic Devices 9.14. Energy Storage 10. Conclusions, Opportunities, and Challenges Author Information Corresponding Author Notes Biographies Acknowledgments Abbreviations References

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1. INTRODUCTION Surface modification by means of polymer brushes has become a powerful approach to tailor the chemical and physical properties of interfaces and has given rise to great advances in surface and interface engineering.1−29 In the most general sense, polymer brushes are defined as thin polymer films in which the individual polymer chains are tethered by one chain end to a solid interface.30−32 Depending on the density at which polymer chains are anchored to the surface and their molecular weight, surface-anchored polymer chains can adopt various conformations, from the so-called “mushroom” or “pancake” regime at low grafting densities to the high density “brush” regime (Figure 1). Often, these different regimes are

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Figure 1. Schematic illustration of three different types of conformations of surface-attached polymers: (A) pancake, (B) mushroom, and (C) brush-type surface-anchored polymers.

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colloquially referred to as “polymer brushes,” even though, strictly speaking, this term only applies to the high grafting density regime. Polymer brushes can be prepared by grafting to as well as grafting from methods (Figure 2).5,33,34 While the grafting onto method is experimentally straightforward, grafting from approaches are often preferred as they generally allow access to higher grafting densities and film thicknesses. Grafting

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Figure 2. Schematic illustration of the preparation of polymer brushes via (A) the grafting onto and (B) the grafting from strategy. 1106


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Scheme 1. Overview of the Four Most Prominent SI-CRP Strategies Illustrated by SI-ATRP of MMA,465 SI-NMP of Styrene,2554 SI-PIMP of Acrylic Acid,931 and Surface-RAFT (R-Group Approach) of VBC226

advances have been made over the past recent years, especially for emerging applications such as catalysis, electronics, nanomaterial synthesis and biosensing. In addition, polymer brushes prepared via SI-CRP have found use for the modification of novel substrates such as natural fibers, polymer nanofibers, mesoporous materials, graphene, viruses and protein nanoparticles. Recent years have also seen exciting advances in the synthesis of polymer brushes and their chemical and physical characterization, as well as an ever increasing set of computational and simulation tools that allow understanding and predictions of these surface-grafted polymer architectures. In accordance with our previous efforts,5 our primary aim is to provide a new comprehensive tutorial review that critically assesses the advances in the field and the opportunities and challenges that have emerged. Herein, we assess the most significant scientific achievements over the past years in the field of polymer brushes produced via SI-CRP, covering the literature starting from where we left off at the end of 20095 until mid-2016.

densities of polymer brushes prepared via grafting onto methods are limited due to steric hindrance between polymer chains, which makes it difficult to tether chain ends at short intermolecular distances. The film thicknesses of brush films obtained by grafting onto approaches are defined and limited by the molecular weight of the precursor polymers. Grafting from strategies, in contrast, are bottom up approaches in which polymer chains are grown via surface-initiated polymerization from a substrate modified with functional groups that can initiate a polymerization reaction. In this way, surface-anchored polymer assemblies with high grafting densities are accessible. Surface-initiated controlled radical polymerization (SI-CRP), also referred to as surface-initiated reversible-deactivation radical polymerization (SI-RDRP), allows for precise control over polymer architecture, composition, molecular weight, and ultimately brush thickness, providing a means to functionalize a wide variety of substrates with thin polymer films. Its versatility and tolerance toward a variety of functional groups has seen it widely employed as a synthetic technique to prepare polymer brushes. Polymer brushes have flourished over the past 20 years, especially for such applications as stimuli-responsive surfaces,9,10,12,22,24,27 nonbiofouling surfaces,5,16,23,25,35,36 colloidal stabilization, wetting and adhesion. However, significant

2. SYNTHETIC METHODS The concept of living radical polymerization was described first in 1982 by Otsu et al.,37 who reported the polymerization of MMA in the presence of phenylazotriphenylmethane and 1107


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Table 1. Overview of Polymer Brushes Prepared via Surface-Initiated Controlled Radical Polymerizationb

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H, B, and R refer to homopolymer, block copolymer, and random copolymer brushes. SET/SARA refers to single electron transfer living radical polymerization (SET-LRP)/supplemental activator and reducing agent atom transfer radical polymerization (SARA ATRP). A(R)GET refers to activators (re)generated by electron transfer. ATRPase refers to SI-ATRP catalyzed by enzymes. The superscripts are references to the relevant publications. bNew monomers utilized after 2009 are in red.

benzyl dithiocarbamate. It was not until the early/mid-1990s, however, that controlled/“living” radical polymerization started to attract the broad interest of the polymer science community. The dawn of modern living radical polymerization was marked by seminal contributions of Georges et al.38 (stable free radical

polymerization), who reported the controlled polymerization of styrene using TEMPO, Rizzardo, Moad and Thang39 who developed RAFT polymerization, and Matyjaszewski et al.,40 Percec et al.,41 and Sawamoto et al.42 (transition metalcatalyzed living radical polymerization). Since then, the field of 1134


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Table 2. Overview of Common ATRP Initiators that Have Been Used to Grow Polymer Brushes from Various Substrates

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brushes by SI-ARGET ATRP from silica nanoparticles with adsorbed cationic macroinitiators. Use of halide exchange (HE) during ATRP generally improves control, due to the improved stability of C−Cl bonds over C−Br bonds.61 Similar to ATRP, nitroxide-mediated polymerization (NMP) also depends on the reversible activation−deactivation of propagating polymer chains by a nitroxide radical.62−67 Various alkoxyamines are used as initiators, such as 2,2,6,6-tetramethylpiperidinyloxy (TEMPO)68 and N-tert-butyl-N-[1-diethylphosphono-(2,2-dimethylpropyl)] nitroxide (DEPN).69,70 Reversible addition−fragmentation chain transfer polymerization (RAFT) is based on reversible chain transfer and utilizes a combination of a conventional free radical initiator and a chain transfer agent (CTA), such as a dithiocarbamate, dithioester and dithiocarbonate.39,71,72 Surface RAFT (SRAFT) can be carried out either via surface-immobilized conventional free radical initiators or surface-immobilized RAFT chain transfer agents. The fourth major CRP technique uses a unique class of unconventional initiators called “iniferters,” which can simultaneously act as initiators, chain transfer agents and terminators.37,73,74 In photoiniferter-mediated polymerization (PIMP), the rate of polymerization is controlled by the intensity of irradiated UV light and, therefore, can be spatially and temporally controlled when initiated from surfaces. In what follows below, we will present several selected recent developments in the field of SI-CRP. First, novel synthetic techniques based on the principles of ATRP and recent developments in S-RAFT will be presented. After that, the detachment of surface-grafted brushes and the rational design of cleavable anchoring groups will be discussed. Then, we will highlight new monomers that have been used over the past years to generate polymer brushes via SI-CRP. Finally, this section will discuss several mechanistic aspects related to SICRP, which include effects of substrate curvature, chain confinement, and molecular weight and dispersity of cleaved polymer brushes versus free polymers synthesized via sacrificial initiators.

polymer chemistry has been revolutionized by rapid advances in controlled radical polymerization (CRP) techniques.7,43−48 Such radical-based controlled/“living” polymerization techniques are still, by far, the most frequently applied in engineering surfaces and interfaces with polymer brushes, as a result of their simple experimental setup, mild reaction conditions, tolerance toward a variety of functional groups and compatibility with aqueous and organic media. As in our previous review, the focus of this contribution will be on the four major surface-initiated controlled radical polymerization (SI-CRP) techniques, namely, surface-initiated atom transfer radical polymerization (SI-ATRP), surface reversible addition−fragmentation chain transfer polymerization (S-RAFT), surface-initiated nitroxide-mediated polymerization (SI-NMP), and surface-initiated photoinifertermediated polymerization (SI-PIMP). Scheme 1 shows typical examples of each of the four major SI-CRP techniques. Other noteworthy SI-CRP techniques that have been recently developed include surface-initiated reverse iodine transfer polymerization (SI-RITP),49,50 surface-initiated organotellurium-mediated living radical polymerization (SI-TERP),51 and surface-initiated metalloenzymatic radical polymerization.52 Table 1 is an updated version of the same table in our previous review5 and provides an overview of the various polymer brushes that have been prepared by the four major SICRP techniques. The polymer brushes in Table 1 are organized according to the nature of the polymer backbone, CRP technique, and brush architecture, while new entries after 2009 are highlighted. The mechanisms of the four major SI-CRP techniques have been discussed in great detail elsewhere;4,5,7,8,10,17,21 therefore, only the essential points of each will be briefly discussed here. Over the past two decades, atom transfer radical polymerization (ATRP) has evolved to become the most extensively utilized CRP technique to modify surfaces with polymer brushes.14,17,25,29 ATRP depends on the reversible activation− deactivation equilibrium between a transition metal complex and a dormant alkyl halide-terminated polymer chain-end to generate a radical that can propagate in the presence of monomers.53,54 Table 2 provides an overview of the most common initiators that have been used to grow polymer brushes via SI-ATRP. The most commonly applied initiators are those containing α-bromoisobutyrate groups, which can be easily immobilized on various substrates. Radical termination reactions cause accumulation of the deactivator transition metal complex, which decreases the rate of polymerization but also decreases the rate of termination, known as the persistent radical effect (PRE).55,56 When initiated from planar substrates, addition of deactivator57 or sacrificial initiator58 is required due to the low concentration of immobilized initiators, which do not themselves generate a sufficient concentration of deactivators. Several variations of the original ATRP process have been developed, including “reverse” and A(R)GET (activators (re)generated by electron transfer) ATRP.43 “Reverse” ATRP involves the addition of transition metal complexes in the higher oxidation state and the generation of the lower oxidation state activator via reaction with a conventional free radical initiator. Similarly, A(R)GET ATRP relies on a reducing agent, such as ascorbic acid,59 to (re)generate the active transition metal complex by reduction of the higher oxidation state transition metal complex. For example, Cheesman et al.60 recently demonstrated the synthesis of poly(2-(diethylamino)ethyl methacrylate) (PDEAEMA)

2.1. Surface-Initiated Controlled Radical Polymerization (SI-CRP) in the Presence of Cu0

CRP in the presence of Cu0 has been heralded as an ultrafast method for the synthesis of linear polymethacrylates and polyacrylates with ultrahigh molecular weight, low dispersity, and high chain-end fidelity under ambient conditions.45,75,76 There are two current models in the literature, which describe the mechanism of CRP in the presence of Cu0, which are referred to as single-electron transfer living radical polymerization (SET-LRP)45,48,75,77,78 and supplemental activator and reducing agent atom transfer radical polymerization (SARA ATRP), respectively.79−82 While SET-LRP is primarily an outer-sphere electron transfer process (OSET), SARA ATRP primarily involves an inner-sphere electron transfer (ISET) process. Scheme 2 summarizes the dominant reactions in SARA ATRP and SET-LRP. As it is not our objective to defend any interpretations of the experimental evidence supporting one model or the other, we shall use the term “SET-LRP/SARA ATRP” to describe CRP in the presence of Cu0 for the purpose of this review. SET-LRP/SARA ATRP is a highly attractive technique due to its high tolerance to air and impurities, mild conditions and overall simplicity in experimental setup. Its robustness has been demonstrated in a number of complex media, such as PBS83 1137


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polymer brushes synthesized by a typical SI-ATRP reaction may have also been affected by disproportionation and/or comproportionation among Cu0, CuI, and CuII species, leading to unusually high thicknesses, especially during the polymerization of hydrophilic monomers, such as N-isopropylacrylamide (NIPAM),92 DMAM,93−95 and HEMA.96 One of the earliest reports by Ding et al.91 provided a comparison of SI-ATRP and SI-(SET-LRP/SARA ATRP) of amino (meth)acrylates initiated from silicon wafers. Among other varied parameters, Cu0 powder was used as replacement for the typical CuX/CuX2 catalyst system. The authors determined that comparable film thicknesses were achieved with shorter reactions times and lower temperatures under SI(SET-LRP/SARA ATRP) conditions, but only reaching up to 54 nm overall. SI-(SET-LRP/SARA ATRP) in the presence of Cu0 powder has also been used to graft PDMAM95,97 and polystyrene (PS)98 from PS particles, PVC sheets and (mesoporous) silica particles, respectively. In the former case, PDMAM brushes of up to 2170 kDa in Mn (Mw/Mn = 1.66) and grafting densities up to 1.13 chains/nm2, one of the highest ever reported, were described.95 It is interesting to note that GPC analysis was performed on PDMAM brushes cleaved from PVC sheets and not on free polymers formed by sacrificial initiator, thus affording “true” molecular weights and dispersity (Mw/Mn) of the surface-grafted polymers. The high molecular weights and grafting densities observed for the PDMAM brushes may have been (partly) due to the presence of negative surface charges, which have been proposed to enrich copper catalytic species near the surface.92−94,99 Chirra et al.100 grafted cross-linked PNIPAM-co-PEGDMA brush films from micropatterned gold surfaces in the presence of Cu0 powder and obtained dry film thicknesses up to nearly 600 nm. Cu0 wire has been utilized to graft polymer brushes from latex particles101 and graphene oxide dispersions.102,103 On the one hand, Cu0 wire can be introduced into deoxygenated mixtures containing solvent, monomer and ligand with101 or without CuX2103 to initiate polymerization. Alternatively, Cu0 wire and all other components can be introduced in the polymerization reactor, followed by freeze− pump−thaw cycles,102 or by performing the polymerization in a closed vial.103 It should be noted that Cu0 wire has been primarily applied for SI-(SET-LRP/SARA ATRP) from dispersed systems of (nano)particles, while Cu0 powder has been applied as the catalytic species to graft polymer brushes from planar surfaces. Thus, one interesting question is how does the accessible surface area of Cu0 species (powder or wire)104 affect the kinetics of SI-(SET-LRP/SARA ATRP) from planar surfaces? Also, since disproportionation and/or comproportionation among Cu0, CuI and CuII species are affected by alkyl halides,45,48,79−81,89 how and to what extent does the addition of sacrificial initiator influence polymer brush growth kinetics, especially from a planar substrate? Recent work by Zhang et al.85,86 utilized a copper plate adjacent to initiatormodified substrates to rapidly grow a wide range of polymer brushes on a wafer scale under ambient conditions, demonstrating that fast and well-controlled polymerizations can be conducted from planar substrates even using low surface area Cu0 species. Instead of introducing Cu0 powder or wire directly into the polymerization medium, SI-(SET-LRP/SARA ATRP) can also be carried out by forming Cu0 in situ via disproportionation of CuX to Cu0 and CuX2.105−114 To date, this has been the most common approach to produce polymer brushes via SI-(SET-

Scheme 2. Dominant Reactions in SARA-ATRP (Blue Italic)/SET-LRP (Red Underlined)a

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Adapted from ref 90. Reactions common to both mechanisms are shown in black. Note: RBr and R• represent dormant and active species, respectively. No distinction is made between initiator and polymer species in this simplified reaction scheme. CuBr and CuBr2 represent all dissolved CuI and CuII species, respectively, and the corresponding rate constants represent weighted averages of the individual rate constants for each species. Cu* represents highly reactive nanosized copper (ka0* ≫ ka0).

and a variety of alcoholic beverages.84 SET-LRP/SARA ATRP is conducted either in the presence of Cu0 powder (or wire), a copper plate,85,86 or by forming Cu0 in situ via disproportionation of CuX species to Cu0 and CuX2. Disproportionation of CuX is typically mediated by nitrogen-containing ligands in polar media, such as dimethyl sulfoxide (DMSO) or water, and also hydrophilic monomers, such as 2-hydroxyethyl methacrylate (HEMA) and N,N-dimethylacrylamide (DMAM). Nitrogen-containing ligands commonly used include Me6TREN, TREN and PMDETA.45 Exceptional nitrogen-containing ligands that do not mediate disproportionation of CuX in polar media include HMTETA and TPMA.87 In that case, the mechanism follows normal ATRP. Contrariwise, Cu0 and CuX2 species can also comproportionate under the same conditions to generate CuX.79 When Cu0 is formed in situ via disproportionation of CuX species, the experimental procedure mirrors that of typical ATRP. Due to the linear evolution of polymer molecular weight as a function of monomer conversion, low molecular weight distribution and high chainend fidelity, SET-LRP/SARA ATRP has been considered “immortal”;88,89 however, the rate of termination is affected by experimental parameters, such as the addition of CuX2 deactivator, suggesting that “in the long run we are all dead.”90 Since our last review,5 polymer brushes synthesized via SETLRP/SARA ATRP have emerged in the literature.91 It is, however, interesting to note that many previous reports of 1138


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LRP/SARA ATRP). Thomson et al.110,111 reported SI-(SETLRP/SARA ATRP) copolymerization of PEGMA and polyethylene glycol methacrylate azide (PEGMAN) from silicacoated superparamagnetic nanoparticles. The authors allowed CuCl−Me6TREN to disproportionate in methanol/water solutions assisted by sonication, prior to addition to the nanoparticle suspension containing sacrificial initiator, CuBr2Me6TREN and monomers. With this method, the authors obtained a 500 nm increase in hydrodynamic particle diameter measured by DLS after 40 min under ambient conditions.111 Shi et al.109 also allowed full disproportionation of CuCl/ Me 6 TREN in the presence of NIPAM and ADA in isopropanol/water solution prior to addition to another vessel containing the initiator-functionalized silicon wafers. In this way, P(NIPAM-co-ADA) copolymer brushes with dry film thicknesses between 10 and 35 nm were obtained after 2 h. Similar thicknesses were obtained for PNIPAM grafted from silicon wafers; however, polymerizations were conducted at 90 °C in DMF without prior disproportionation.112 When SI(SET-LRP/SARA ATRP) of NIPAM was conducted under the same conditions, but in the presence of cysteamine chain transfer agent, an increased apparent rate of propagation of free polymers was observed and also provided amine end-group functional PNIPAM brushes.113 As a concluding note, SI-(SET-LRP/SARA ATRP) does not appear to be limited to Cu species, as PAN brushes have been grafted from sweet potato starch residue in the presence of ascorbic acid and a novel La0 powder/hexamethylenetetramine (HMTA) catalytic system.115 Overall, investigations of SI(SET-LRP/SARA ATRP) systems are still in their infancy, hence offering exciting opportunities and new challenges for surface and interface engineering with polymer brushes.

Scheme 3. Mechanism of Electrochemically Induced SurfaceInitiated ATRP at a Cathodic Current to Generate the CuICl/bipy Complex that Triggers the Polymerization (Kt = Rate Constant of Chain Termination, Kp = Rate Constants of Chain Propagation)a

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Adapted from ref 118.

eATRP could also be conducted in the presence of air and the polymerization solution could be recycled several times. Shortly thereafter, the authors reported SI-eATRP from nonconducting substrates.119 Initially, CuI/L activator was generated at a working electrode, followed by diffusion to an initiatormodified nonconducting substrate which, in turn, triggered polymer brush growth. By taking advantage of ion diffusion, a stable concentration gradient of [CuII/L]/[CuI/L] was generated in the gap between the working electrode and initiator-modified substrate. By controlling the distance between the working electrode and initiator-modified substrate, kinetics of polymer brush growth could be adjusted. In addition, by simply tilting the initiator-modified substrate, gradient polymer brushes were synthesized, providing a straightforward approach to generate surface gradients. This was a result of differences in the CuI/CuII ratio along the substrate interface, leading to different rates of polymerization. Driven by the need for an electrochemical setup as well as the relatively large reaction solution volume that are necessary for SI-eATRP, Yan et al.120 proposed an alternative electrochemical approach to grow polymer brushes, namely sacrificial anode ATRP (sa-ATRP). The method is inspired by the use of Zn as a sacrificial anode in corrosion engineering and involves the use of sacrificial metal surfaces, such as Al, Fe, Co, and Zn, which have a larger oxidation potential than CuI/CuII. All of the aforementioned metal surfaces were able to reduce CuII to CuI species, which diffused to the initiator-modified substrate to initiate polymerization of conventional brushes and gradients. This system allowed controlled growth of 200 nm thick PSPMA brushes using very small volumes (down to 5 μL) in the presence of air. As an alternative to the use of a nonconducting initiatormodified substrate to which the CuI activator needs to diffuse from a sacrificial anode in order to initiate polymerization, Hosseiny and van Rijn121 reported the direct growth of PHEMA and PPEGMEMA brushes from initiator-modified gold electrodes in pure aqueous solution without supporting electrolytes. In this way, the authors achieved controlled brush growth up to 47 nm within 2 h.

2.2. Electrochemically Mediated SI-ATRP

A main challenge in implementing SI-ATRP is the oxidation of CuI species to deactivating CuII by the presence of trace oxygen in the polymerization media and the persistent radical effect (PRE).55,56 Consequently, polymerizations are performed in an inert atmosphere and with relatively large quantities of CuI activating species. Matyjaszewski et al.116 have introduced variations of ATRP, such as ARGET ATRP, that allow to work with reduced active catalyst quantities and reduce the effects of limited amounts of oxygen. Motivated by the desire to further enhance control over the ATRP process while maintaining the O2 tolerance and low catalyst levels that characterize the ARGET process, Magenau et al.117 developed electrochemically mediated ATRP (eATRP), which is based on the electrochemical generation of active CuI from an air-insensitive CuII salt at an electrode surface. Such a system would be ideal for surface-initiated polymerizations, since initiators can be immobilized at an electrode interface and initially generate a high local concentration of activating species near the surface. Li et al.118 first reported the controlled growth of PSPMA and PHEMA brushes via SI-eATRP from an initiator-decorated gold electrode. As a result of initiator monolayer impedance to charge transfer, mixed monolayers of 2-thionaphthiol and ω− mercaptoundecyl bromoisobutyrate produced more homogeneous films with improved brush growth. Scheme 3 illustrates the mechanism of electrochemically induced SI-ATRP. By adjusting the fraction of initiator and applied potentials, good control over polymer brush film thickness was attained. Not only were the authors able to produce substantially thick polymer brush layers (e.g., 260 nm) in a controlled fashion, SI1139


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Utilizing an in situ AFM apparatus, Li et al.122 were able to follow PSPMA and PMETAC brush growth during SI-eATRP in real time. Starting with a micropatterned initiator-modified gold substrate, polyelectrolyte brush growth kinetics and morphology were monitored simultaneously. The authors highlighted the effects of counterion screening of monomer charge, especially for PMETAC brushes, in which enhanced growth was observed upon the addition of counteranions of ionic liquid electrolytes.

while other monomers led to lower thicknesses. It was noted that polymer brush growth occurred in a more linear fashion than conventional SI-ATRP, but at a slower rate, likely due to the time required to generate sufficient amounts of catalytic CuI species upon UV exposure. In addition, the rate of termination was likely reduced as a result of low free radical concentration. Not only did the authors grow brushes from gold substrates, but also from nanostructured TiO2 via a self-catalytic UV−SIATRP process. Utilizing a dopamine-inspired initiator that selfassembled on TiO2 nanowires, PSPMA brushes were grown directly from the electron-donating TiO2 interface under UV irradiation. The same group later reported the use of dyesensitized TiO2 as a catalyst to generate brush patterns with conventional photomasks and anodic aluminum oxide (AAO) membranes as templates.128 As in the case of SI-eATRP, monomer solutions can be recycled multiple times in UV−SIATRP, providing another simple and cost-effective method for surface engineering with polymer brushes. A range of very thick (up to 1 μm) polyacrylate129 and PHPMAM130 brushes were rapidly produced via UV-induced SI-SET-LRP/SARA ATRP using only ppb concentrations of copper catalyst. Hawker and co-workers developed another light-mediated CRP method using an iridium-based photoredox catalyst to activate alkyl halides (i.e., conventional ATRP initiators), in which dormant polymer chains are propagated upon activation of iridium complexes by exposure to a visible light source, without the addition of deactivating species.131−133 This CRP technique has also been successfully utilized for the lightmediated growth of surface-grafted polymer brushes.134 With a conventional photomask, brush growth was spatially confined to visible light-exposed domains, leaving the unexposed areas with active initiators for subsequent patterned binary polymer brush films, without the need for initiator backfilling. This method also afforded polymer brush gradients simply by utilizing a neutral density filter to moderate visible light intensity which, in turn, spatially moderated the rate of polymer brush propagation. As a proof-of-concept, the authors grew PMMA brushes from initiator-modified silicon wafers and achieved ca. 120 nm thicknesses within 1 h with continuous irradiation supplied by a commercial 26 W fluorescent lamp. In addition, “on−off” experiments demonstrated the “living” character of polymer brush growth and the use of a negative photomask showed that PMMA brushes could be patterned with submicron features. Patterned PMMA-b-PtBMA brushes were produced from a uniform PMMA layer and photomask to give complex bimodal or “two-layer” architectures. Subsequent hydrolysis of PtBMA blocks with trifluoroacetic acid (TFA) yielded bimodal PMMA-b-PMAA brushes. This iridium-based photoredox catalyst-mediated strategy has also been applied to grow PMMA, PHEMA, PGMA, and PPEGMA brushes from microporous polypropylene membranes (MPPM).135 Zhang et al.136 have recently shown that no photoredox catalyst is required to perform visible light-mediated SI-CRP, as CuX2 deactivators can be reduced to active CuX with a household fluorescent lamp to grow homo-, block copolymer, and patterned brushes. By irradiating silicon oxide substrates modified with ATRP initiators immersed in a solution containing monomer and CuII complexes with a fluorescent lamp, these authors were able to generate patterned as well as homogeneous PMMA brushes and also PMMA-b-PtBMA block copolymer brush films. While on the one hand this method stands out due to its simplicity, it also illustrates the photosensitivity of the copper catalyst complexes and the

2.3. Light-Mediated SI-CRP

Although the notion of inducing “controlled” radical polymerizations with an external UV light source (i.e., PIMP) was first reported over 30 years ago by Otsu et al.,37,73,74 the use of UV light to induce ATRP was only more recently described by Kwak and Matyjaszewski123 and Tasdelen et al.124,125 In the former case, a well-controlled polymerization was achieved using copper catalyst complexes and a dithiocarbamate initiator, such as those used in the PIMP technique.123 Alternatively, direct UV-photochemical generation of the active copper species from the higher oxidization state can be used to perform ATRP without the use of reducing agents.124,125 Even earlier, already in 2000, Guan and Smart126 reported that visible light significantly enhanced the control and rate of ATRP of MMA. Yan et al.127 applied a UV light-based approach to initiate ATRP from surfaces. Similar to SI-eATRP, UV-induced SIATRP (UV−SI-ATRP) relies on the reduction of CuII complexes to CuI complexes by an electron-donating interface. In this case, reduction of CuII is achieved via electrons provided by TiO2 nanoparticles under UV irradiation. The UV−SIATRP process is schematically illustrated in Scheme 4. This Scheme 4. Mechanism of UV Light-Induced SurfaceInitiated Atom Transfer Radical Polymerization. Adapted from ref 127

strategy offers two ways to manipulate polymer brush growth; by varying the TiO2 nanoparticle concentration or the UV irradiation intensity. During UV illumination, TiO2 readily absorbs photons and excites valence electrons that can spontaneously reduce CuII complexes to the active CuI species. Consequently, polymerization can be reversibly turned “on” and “off” by UV irradiation and exposure to air, respectively, to provide a “living” polymerization system. With this method, PDMAEMA, PSPMA, PDMAEMA-b-PSPMA, PNIPAM and PPEGMA brushes were grown from gold substrates.127 The authors were able to grow 200 nm thick PSPMA brushes in 2 h, 1140


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Scheme 5. Three Main Approaches to Surface RAFT Polymerization: (A) Using a Surface Immobilized Initiator,186,1471,1771 (B) Using a Z-Group Anchored CTA,2260 and (C) Using a R-Group Anchored CTA203

RAFT polymerization. Scheme 5 schematically depicts the different RAFT approaches that can be used to generate surface-tethered polymer brushes. Throughout the remainder of this article we will use the term surface-RAFT to universally refer to either of these strategies. As mentioned above, one approach toward surface-RAFT polymerization is to attach an azo initiator to the surface and conduct the polymerization in the presence of a free CTA in solution. This approach has been used to polymerize a range of monomers including VBTAC,138 glucose-based monomers,139 and more conventional monomers such as MA,140 BzMA,141 DMAEMA,140 NIPAM,141−144 NAM,143 and styrene.145 Bain et al. note that, when a surface-tethered initiator is used to initiate the polymerization of styrene, the film thickness of the brush as well as the molecular weights of the polymers generated in solution decrease with increasing concentration of CTA.145 This is understandable since increasing the CTA concentration decreases the ratio of monomer/CTA thus leading to a lower degree of polymerization, a finding that was mirrored by

possible effects of external light sources (fume hood lights on or off) on SI-ATRP experiments. Recently, Discekici et al.137 reported the use of a N-phenyl phenothiazine-based metal-free SI-ATRP process to fabricate large area homo- and block copolymer brush patterns and nanoparticle hybrids. 2.4. Surface Reversible Addition−Fragmentation Chain Transfer Polymerization (S-RAFT)

In contrast to ATRP, NMP, and PIMP, RAFT can be thought of as a conventional radical polymerization with the addition of a chain transfer agent (CTA), which mediates the polymerization. Thus, the radical source in a RAFT polymerization is a radical initiator, which can either add to a monomer or react reversibly with the RAFT CTA. Since RAFT polymerization requires both a radical source as well as a CTA, one has the choice of anchoring either the radical source or the CTA on the surface in order to conduct a surface-RAFT polymerization. Surface-mediated RAFT polymerization can be performed by tethering the RAFT agent either via its Z- or R- group. R group tethering of the RAFT agent is most abundantly used in S1141


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Table 3. Overview of the Utilization of the Two Most Commonly Used R-Group Anchored RAFT Agents to Prepare Surface Grafted Polymer Brushes

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Table 3. continued

group of the RAFT agent or the stabilizing “Z” group. Given this choice, in the literature, there is an almost exclusive preference for anchoring the CTA via the R-group. This may be because the synthesis of RAFT agents often results in a carboxylic acid residue on the R-group which serves a convenient handle for functionalization. Table 3 illustrates the versatility and scope of use of the most widely used R-group anchored RAFT agents. The remaining agents are variations on xanthates, dithiobenzoates or trithiocarbonates with small variations in the R-group between the CS bond and the anchoring point. The two RAFT agents shown in Table 3 are most commonly used as, between them they can mediate controlled polymerization of the majority of acrylate, methacrylate, acrylamide, methacrylamide, and styrene based monomers. To establish fine control over the RAFT polymerization, the criteria to select the appropriate RAFT agent for a wide variety of monomers have been described by Moad et al.71 Surfaces that present covalently bound RAFT CTAs can be prepared via two main approaches. In the first approach, the CTA is synthesized with a reactive anchoring group that allows it to be covalently bound to an unmodified substrate. The

Takahashi et al. for the polymerization of NIPAM.144 The work of Takahashi et al. is also interesting since they also varied the density of initiator on the (glass) surface and noted that, with decreasing initiator concentrations, decreasing grafting densities are noted. Thus, both the chain length and grafting densities are elegantly controlled via the CTA concentration and initiator concentration, respectively. Wei and co-workers have used a similar approach and anchored benzophenone instead of an azo initiator onto polypropylene surfaces. The benzophenone was used to initiate RAFT-mediated polymerization of acrylic acid,146,147 acrylamide,147 and NIPAM.146 A more common approach to surface-RAFT polymerization is to anchor the RAFT agent to the surface and to have a free initiator in solution. This approach has been used to graft polymer brushes from carbon nanotubes,148,149 quantum dots, 150−152 gold surfaces, 153−156 iron oxide nanoparticles,157−165 montmorillonite,166,167 halloysite nanotubes,168,169 graphene,170 ITO,153,154,171−176 polymer substrates,146,177−182 silica,183−212 BaTiO3,213 ZnO/ZnS,214 carbon fibers,215 TiO2 nanoparticles,216 and stainless steel.217 In these solutioninitiated, surface-RAFT polymerizations, the researcher has the choice to anchor the CTA either via the reinitiating “R” 1143


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second approach relies on grafting a functional RAFT agent to a substrate previously modified to present a reactive group, which is complementary to the one on the RAFT CTA. The former approach can be synthetically more challenging but has been used for a range of substrates including CNTs,149 carbon fibers,215 silica,185−187,189,203−207 and Fe2O3 nanoparticles.159,204 The second approach has the advantage that it facilitates purification of the CTA and helps to avoid common side reactions such as the condensation of CTA-bound alkoxysilane groups. This appears to be the more popular approach and has been used to anchor CTAs onto, for example, Fe2O3165,218 and silica nanoparticles,190−192,201,211,212 quantum dots,150,151 cellulose,219 halloysite nanotubes,168 silicon,106,220 and polysulfone180 substrates. Akin to this approach is the introduction of a NHS-ester of the CTA to an aminated or hydroxylated silica184,193,194,208,209 or Fe2O3161 surface. In the same vein, click chemistry has also been used to anchor CTAs to silica,221 graphene170 or reduced graphene oxide surfaces.222 Alternatively, halide modified surfaces can be used to attach appropriate reactive CTA derivatives. This approach, among others, has been used to introduce RAFT agents onto silica nanoparticles,196−198 TiO2 nanoparticles,216 cellulosic substrates,223 carbon nanotubes,148 electrospun fibers,177 halloysite nanotubes,169 hydroxyapatite nanocrystals169,224 and ZnO/ZnS substrates.214 Finally, presynthesized RAFT CTAs may be electro-polymerized onto electrically conductive substrates such as ITO153,154,171,172,175,176 and gold.153−155 The following sections will briefly discuss S-RAFT polymerization from a few of the more widely explored substrates. 2.4.1. S-RAFT from Fe2O3 Nanoparticles. Whereas there were no reported examples of S-RAFT from Fe2O3 nanoparticles at the time of writing our previous overview, numerous reports have appeared since then, which describe the polymerization of NIPAM,162,163,165 DMAM,164 acrolein,163 styrene,159,161 acrylonitrile,160 MA,158 BA,204 and MAA157 from these substrates. In this case, the CTAs were anchored either by reacting an amino-functionalized Fe2O3 nanoparticle with a RAFT CTA157,158,160,161,165 or via direct functionalization of the surface with a presynthesized CTA.159,162−164,204 In terms of the former approach, APTES is the most common way to introduce an amino group onto the nanoparticles; however, dopamine has also been used for this purpose.165 For the latter approach, presynthesized silane-containing CTAs are most commonly used;159,204 however, an alternate has also been demonstrated wherein the commercially available 4-cyano-4[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid (CDTP) CTA can directly be used to functionalize the Fe 2 O 3 nanoparticles via the carboxylic acid end group.162,163 2.4.2. S-RAFT from Indium Tin Oxide (ITO). Advincula and co-workers have extensively explored RAFT mediated polymerization to graft polymer brushes from ITO substrates. To this end, a CTA functionalized monomer (such as 2(thiophen-3-yl)ethyl 4-cyano-4-(phenylcarbonothioylthio)pentanoate 2-(2,5-di(thiophen-2-yl)thiophen-3-yl)ethanol)154 (Chart 1) was electropolymerized onto the ITO surfaces and subsequently used to mediate RAFT polymerization of PMMA,154,171 PPEGMA,171 styrene,153,154,172,176 tBA,153 and VK.175 Another innovation in this area of research has been made by Liu et al., who used a dopamine functionalized-CTA to functionalize ITO surfaces via a titanium-diol bond.173 The RAFT-mediated PS brushes grown via this method could then be detached by incubating in a pH 9.0 phosphate buffer solution.

Chart 1. Chemical Structure of 2-(Thiophen-3-yl)ethyl 4cyano-4-(phenylcarbonothioylthio)pentanoate 2-(2,5di(thiophen-2-yl)thiophen-3-yl)ethanol154

2.4.3. S-RAFT from Polymer Substrates. A range of polymer substrates has been used as surfaces from which RAFT-mediated polymerization was conducted. These include polypropylene,146 P4VP,181,182 polysulfone180 and styrenedivinylbenzene copolymer177−179 from which PPEGMA,177 PAM,177 PNIPAM,178,182 PVPBA,179 PMPC,180 PHEMA,181 and PAA177 brushes have been grafted. The grafting densities of brushes grown from polymer substrates vary from 1.00 to 1.03181 and 1.1−1.2182 chains/nm2 for PHEMA and PNIPAM brushes, respectively grown from P4VP substrates to 0.63 chains/nm2 for PMPC brushes grown from polysulfone substrates.180 2.4.4. S-RAFT from SiOx. SiOx surfaces are by far the most common substrates from which surface-RAFT polymerizations have been conducted. A range of monomers including NIPAM,196,201,204 styrene,188,204,208,210,225 MMA,204,208 DMAEMA,194,211 AA,191 HEMA,212 PDSM,194 BA,187,204 MA,206,207 tBMA, 184,193,209 HPMAM, 193 4VP, 198 PEGMEMA, 155 VBC,203,226 PFPA,185 PFMA,189 DMAM, 164,186 NAS,186 VBTAC,221 and DMAPMAM190 have been used to grow brushes via surface-RAFT polymerization. There are several instances of silane-containing RAFT agents being anchored to the SiOx surfaces;185−187,189,203−207,210 however, a far more common method is to react a surface previously functionalized with APTES with a carboxylic acid-functionalized RAFT agent using a NHS active ester intermediate.184,190,192,193,195,201,208,209,211,212 As an alternative to APTES, SiOx substrates can also be modified with 5,6epoxyhexyltriethoxysilane191 or 4-(chloromethylphenyl) trimethoxysilane196−198 to generate epoxide or benzyl chloride functionalized surfaces, which can be successively used to anchor a RAFT agent. 2.4.5. Determination of the Surface Concentration of Anchored RAFT CTAs. The surface concentration of substrate anchored CTAs is an important parameter as it places an upper limit on the grafting density of the final brushes. The surface concentration of CTAs on nanoparticles is typically assessed using one of three methods: thermogravimetric analysis (TGA), elemental analysis and UV−vis spectroscopy (UV). Often silica particles are modified with CTAs to mediate the growth of polymer brushes. Table 4 provides a summary of surface concentrations that have been reported for various RAFT CTA modified silica nanoparticles using one or several of these techniques. TGA can be used to determine CTA surface concentrations but is prone to errors since it measures mass loss of not only 1144


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Table 4. Overview of Surface Concentrations Determined for Various RAFT Agents on Silica Particles

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Table 5. Overview of Initiators/Chain Transfer Agents that Allow Facile Cleavage of Polymer Brushes from Substrates

the CTA but also from other impurities on the silica such as CTA precursors or partially condensed silane precursors. As pointed out by Duan et al., a mere 0.5 wt % error in the TGA corresponds to a ca. 25 μmol/g uncertainty in the determination of CTA surface concentration (for a CTA with a molecular weight of 200 g/mol). This is rather high when the typical surface concentrations of the CTAs on the silica are in the order of 10−100 μmol/g, corresponding to 0.05−0.80 CTAs/nm2.187 Elemental analysis is a robust alternative to TGA as the technique measures the sulfur content, which is unique to the RAFT CTA. CTA surface concentrations detected using this

technique are reported in variety of ranges and are as low as 0.06 CTAs/nm2 and as high as 3.9 CTAs/ nm2.193,198,203,204,206,207 A third technique that allows CTA surface concentrations to be measured is UV−vis spectroscopy. This method was already used in 2001 by Fukuda et al.227 However, while this method works well for small particles, as particle size increases past 100 nm, the absorption of the silica causes significant errors in the quantification. Duan et al. have recently reported an elegant approach to negate the effect of silica absorption from these measurements thereby rendering the technique eminently useable to quantify CTA surface concentration. The authors 1146


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Table 6. Overview of Polymer Brushes that Have Been Cleaved from Silicon Oxide Substrates Using Hydrofluoric Acid (HF) and Their Molecular Characteristics

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Table 6. continued

a

Results refer to values corresponding to the highest number-average molecular weight (Mn) obtained by the cited authors for cleaved polymer brushes. bBulk or solution polymers produced simultaneously or under the same reaction conditions. The superscripts are references to the relevant publications.

done to obtain “true” molecular weights and dispersity via cleaving tethered polymers from substrates. To this end, various cleavable initiators/CTAs have been designed for ease of polymer brush analysis. Table 5 provides a summary of several initiators/CTAs, which are easily cleaved from substrates via mild acid−base chemistry,173,239,240 reducing agents241−243 or UV light.244,245 The remainder of this section will discuss the most commonly applied methods to cleave polymer brushes from the substrates from which they were grown. Polymer brushes grown from silica substrates are usually cleaved via high concentrations of hydrofluoric acid (HF). In addition to the dissolution of silica, susceptible functional groups of tethered initiators/CTAs will also be hydrolyzed, leaving a solution primarily of cleaved polymers and hexafluorosilicic acid. When cleaving hydrophobic polymers, the reaction is typically performed in the presence of quaternary ammonium phase-transfer catalysts, such as tetraoctylammonium bromide,204,246 and has negligible effects on the polymer backbone. Table 6 provides an overview of polymer brushes cleaved with HF from silica substrates. The Table also lists the molecular weight (Mn) and dispersity (Mw/ Mn) of the cleaved polymers as obtained by GPC as well as the grafting density, if provided by the authors. Additionally, if a corresponding free polymer was synthesized simultaneously or under similar reaction conditions, molecular weight and dispersity from GPC analysis are also provided. Section 2.7.4 will address the disparities sometimes observed between the molecular weight and dispersity of free “sacrificial” polymers and polymer brushes cleaved from substrates. As can be seen from Table 6, a variety of (meth)acrylate, acrylamide and

did this by subtracting the silica contribution to the absorbance of the silica-grafted CTA thereby deriving a more accurate value for the surface concentration. The silica contribution to the CTA maxima (at 308 nm) was estimated by fitting a curve to the silica-CTA absorption curve at wavelengths on either side of 308 nm. As an added benefit, the limit of detection for this technique is significantly lower than TGA or elemental analysis (0.05 CTA/nm2 to 0.8 CTA/nm2, depending on the size of the particle).187 In addition to silica nanoparticles, the techniques discussed above have also been used to assess RAFT CTA surface concentration on a variety of other particle based substrates. TGA for example has been used to measure CTA concentrations grafted on Fe3O4 nanoparticles,157,159,196 TiO2216 and halloysite nanotubes.168 Also, elemental analysis has been used to measure the sulfur content of CTA molecules, which were grafted on Fe3O4 nanoparticles.161 2.5. Cleaving Polymer Brushes from Substrates

One important challenge in the polymer brush field is the characterization of the “true” molecular weight and dispersity of the surface-tethered polymer chains. There is a debate in the literature regarding the assumption that free polymers produced by sacrificial initiators/CTAs exhibit similar molecular weights and dispersities compared to the corresponding surface-tethered polymer.228−238 These anomalies are particularly challenging to address for planar substrates due to their low surface area, thus producing limited amounts of sample for subsequent GPC and/or NMR analysis of the cleaved polymers. Among the many interesting developments over the past years, is the substantial amount of work that has been 1148


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Table 7. Overview of Polymer Brushes that Have Been Cleaved from Silicon Oxide Substrates Using Reagents Other than Hydrofluoric Acid (HF) and Their Molecular Characteristics

a


ester-containing ATRP initiator could be cleaved with ammonium bifluoride (NH 4 HF 2 ). While most of the aforementioned brushes were synthesized via SI-ATRP, in the case of brushes produced by S-RAFT, excess AIBN can be used to cleave polymer chains when the CTA is anchored to the substrate surface via its “Z-group”, i.e., its dithio moiety.205 In addition to silicon oxide substrates, there is a great deal of literature that describes methods of cleaving polymer brushes from other types of substrates, such as metals and their oxides, carbon materials, clay minerals, biopolymers, synthetic polymer particles and thin films. Table 8 provides a summary of polymer brushes cleaved from substrates other than silicon oxide. Results are organized by polymer brush and substrate, including the cleavable group(s) and cleaving agent. While acid/base hydrolysis is frequently used, some groups have introduced novel methods of cleaving brushes depending on substrate surface chemistry. Ma et al.,254,255 for example, tethered ATRP initiators to cationic imogolite nanotubes with phosphonate anchoring groups, which have also been recently applied to titania,256 silica and mica surfaces.257 Polymer brushes, such as PMMA,258 PHEMA,259 PNIPAM,260 and block copoly-

styrene based (co)polymer brushes have been cleaved from silica substrates via HF solutions. While HF is most often used to cleave polymer brushes from silicon oxide substrates, a variety of other methods have been used as well. These are listed in Table 7, which includes a number of methacrylate and styrene based homo- and block copolymer brushes grown from substrates modified with initiators/CTAs that can be cleaved using other strong acids, such as p-toluenesulfonic240,247−250 or sulfuric acid.251 In cases where the tethered initiators/CTAs contain ester groups, alkaline hydrolysis presents an alternative to acid hydrolysis. Borozenko et al.252 for example utilized tris(hydroxymethyl)aminomethane (Tris) buffer to cleave fluorescently labeled PAA brushes from glass substrates and monitored degrafting in real-time by total internal reflection fluorescence microscopy (TIRF). The authors determined that cleavage of PAA only occurred at pH ≥ 9.5 in the presence of salt, likely causing conformational changes in the polymer layer. These results will be discussed in more detail in section 4.3. Haque et al.253 demonstrated that liquid crystalline PMMA-b-PMDPAB brushes grown from a quartz substrate modified with an 1149


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Table 8. Overview of Polymer Brushes that Have Been Cleaved from Various Substrates and Their Molecular Characteristics

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Table 8. continued

a


mers259,260 grafted from gold substrates can be cleaved by iodine. In addition to gold, iodine has also been used to cleave PHEMA brushes from silicone rubber.261 Tetra-n-butylammonium fluoride (TBAF) was used to cleave PBA brushes grown from Al2O3 nanoparticles.262 The use of disulfide-containing initiators/CTAs has allowed the use of reducing agents such as 1,4-dithiothreitol (DTT) to cleave PMMA and PPEGMEMA brushes from various substrates, such as cellulose fibers241,242 or PLA nanofibers.243

PEGMA.266 Monomers with pendant carbohydrate residues such as 2-(2,3,4,6-tetra-O-acetyl-β-D-glucosyloxy)ethyl methacrylate (AcGEMA), 267 glucosylureaethyl methacrylate (GUMA),139 4-vinylbenzenesulfonamidoethyl 1-thio-β-D-saccharides (VBSAEZ),268 N-2−4-(vinylbenzenesulfonamido)ethyl lactobionamide (VBSAELA),269,270 2′-acrylamidoethyl D-pyranosides (AAEP), 271−274 glucosamine-derivatized GMA275 and cellulose derivatives276,277 offer novel platforms for biosensors and chiral stationary phases due to specific interactions with biomolecules, such as proteins. The introduction of chirality into polymer brushes is interesting for chiral separations, bioengineering scaffolds and enantioselective sensing. In addition, incorporation of amino acids, such as cysteine and aspartic acid, in random thermoresponsive copolymer brushes has led to unexpected superhydrophobicity.278 Wang et al.279 synthesized chiral polymer brush films based on N-acryloyl-L-valine and Nacryloyl-D-valine, which showed distinct interactions with cells. L-valine based brushes induced markedly improved cell adhesion and proliferation. Later, the same group also synthesized polymer brush films with N-acryloyl-L(D)-alanine and N-acryloyl-L(D)-leucine and showed that the larger side groups of valine and leucine lead to more distinct differences in cell behavior between isomers.280 Novel zwitterionic monomers, such as hydroxyethyl-derivatized carboxybetaine methacrylate (HECBMA)281 and N,Ndimethyl-N-(p-vinylbenzyl)-N-(3-sulfopropyl)ammonium) (DMVSA)282−284 were polymerized via SI-ATRP to generate nonfouling surfaces. A serine-based zwitterionic monomer, serine methacrylate (SerMA), was polymerized by SI-PIMP and also strongly resisted cell adhesion.285 Nucleotide detection

2.6. Novel Monomers

In addition to the synthetic advances and refinements in SICRP, some of which have been discussed in the previous sections, approximately 150 new monomers have been used to grow polymer brushes since 2009. These monomers are highlighted in Table 1. The use of these monomers to produce polymer brushes was mostly application-driven and includes the generation of polymer brushes for sensing, separation and nonfouling applications, as well as stimuli-responsive interfaces. Table 9 provides an overview of the properties and/or applications targeted by the use of polymer brushes based on these novel monomers. In some cases, monomers that have been historically problematic to polymerize in a controlled fashion due to functional group reactivity and radical instabilities, such as acrolein163 and vinyl acetate,223,263 have now been incorporated into polymer brush films via SI-CRP. Hydrophilic monomers with potential use in biomedical applications include N-acryloylmorpholine (NAM),101,143 4hydroxyphenylethyl methacrylate (HPEMA),264,265 N-(p-vinylbenzyl)-phthalimide (VBP)264 and a dendronized form of 1153


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Table 9. Overview of Structural Properties and Applications of Polymer Brushes Based on Novel Functional Monomers that Have Been Polymerized via SI-CRP

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Table 9. continued

a

For monomer chemical structures, refer to Table 1.

systems based on Acrydite-modified oligonucleotides286,287 and 3-(acrylamido)phenylboronic acid and trifluoromethyl phenylthiourea acrylamide288 were developed. Prasad et al.289 used pnitrophenyl acrylate monomers to make MIPS for highly sensitive dopamine detection. Monomers with adamantane groups to immobilize β-cyclodextrin have been polymerized by SI-NMP290 and SI-SET LRP/SARA ATRP.109 A potassiumselective QCM sensor based on crown-ether functionalized methacrylate291 and cadmium-selective SERS sensor based on 2-(4-(2-hydroxyethylamino)-4-oxobutanamido)ethyl methacrylate further demonstrated the versatility of polymer brush platforms for sensing applications.292 Due to the finite availability of petroleum resources, biobased plastics have attracted great interest over the last decades, but natural compounds derived from biomass that can be polymerized by radical methods are limited. Recently, Higaki et al.293 showed that a biomass compound derived from tulips, α-methylene-γ-butyrolactone (MBL), can be used to grow polymer brushes via SI-ATRP. The authors also demonstrated that 70 nm thick PMBL brushes exhibited a higher elastic modulus and improved friction resistance as compared to PMMA brushes of similar thickness and grafting density.

parameter that must be defined in order to unambiguously determine whether surface-tethered polymers exist within the brush regime. From a survey of the literature published in the field over the past years, over 150 articles report the “true” molecular weight and dispersity of brushes cleaved from substrates (see Tables 6−8). The remaining literature usually relies on characterization of free polymers produced via sacrificial initiators during polymer brush growth or do not report molecular weights of surface grafted polymers. Some investigations have shown a pronounced effect of substrate curvature294−299 and confinement19,233,300−302 on the kinetics of SI-CRP. Furthermore, computer simulations have suggested significant differences in the molecular weight and dispersity of bulk versus surface-initiated polymers231,234,235 and also indicate that the rate of termination of tethered chains is dependent on the grafting density.303−306 Tchoul et al.307 found that thermal self-initiation of styrene produces unattached polymer during SI-ATRP from silica nanoparticles without the presence of sacrificial initiator. This fraction of unattached polystyrene chains remained after multiple precipitations, which could thus complicate analysis of cleaved polystyrene brushes. This fraction of unattached polystyrene could be reduced, albeit not to zero, by decreasing the polymerization temperature and using more reactive CuI catalyst complexes. The aim of this Section is to present several of these fundamental questions. In what follows below we will highlight some of the kinetic anomalies of SI-CRP, discuss effects of substrate curvature and chain confinement and address the controversy regarding the molecular weight of polymers grafted from substrates versus

2.7. Mechanistic Considerations

Although SI-CRP is widely employed to produce polymer brushes for a variety of applications, there are still a number of fundamental synthetic questions and challenges. Direct experimental characterization of polymer brush molecular weight and dispersity, for example, is not a trivial task. Molecular weight determination of polymer brushes has critical implications for calculating grafting density, which is a 1156


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those of polymers produced using sacrificial initiators in homogeneous solution or in bulk. 2.7.1. Kinetics of SI-CRP. Tables 6-8 indicate that in some instances, SI-CRP can lead to polymers with extremely high molecular weights. Pietrasik et al.308 reported number-average molecular weights (Mn) up to 27 million Da for polymethacrylate that was obtained via high-pressure SI-AGET ATRP from silica nanoparticles, while maintaining good control (Mw/ Mn = 1.17). Therein, molecular weight was determined by GPC after cleaving of the tethered polymers from the silica substrate. In this case, polymerizations were conducted under pressures up to 6 kbar at room temperature, which increased the rate of propagation and reduced the rate of termination. An interesting comparison of hexyl-, dodecyl-, and octadecyl methacrylate brushes prepared by SI-ATRP showed that dodecyl methacrylate growth was much faster than the hexyl- or octadecyl methacrylates, producing nearly 350 nm thick brushes.309 Kang et al.244 reported a number-average molecular weight (Mn) of 900 kDa for PLMA cleaved from silicon wafers. The corresponding dry thickness of the brushes was 220 nm. PMMA brushes of ∼1 μm thickness were grown from glassy carbon electrodes via SI-ATRP by the use of a multilayered initiator structure electrografted by diazonium chemistry.310 Liu et al.311 found enhanced propagation rates of polystyrene brush growth with the addition of 1% wt. polystyrene in the bulk monomer, which may have reduced irreversible termination of surface-tethered chains. Simple experimental parameters can also affect the outcome of SI-CRP. Kim et al.229 demonstrated the negative effects of stirring on growth of PMMA brushes from gold surfaces. They proposed this phenomenon to be a result of higher chain motion, causing increased rates of termination. In SI-ARGET ATRP of DEAEMA, the use of the sodium salt form of ascorbic acid as a reducing agent, instead of the acid form, lead to higher rates of polymer brush growth.294 Supplying monomers through the grafting surface, as in the case of initiator-modified dialysis membranes, reverses the monomer concentration gradient of a typical SI-CRP from an impenetrable substrate, thus promoting the well-controlled growth of shorter chains with low dispersity.312 Behling et al.238 investigated the influence of grafting density on the kinetics of SI-ATRP of styrene from clay particles in bulk. A grafting density of 1 chain/nm2 was reported to result in a 7-fold increase in the rate of propagation in comparison to polymers synthesized in bulk. As the grafting density was gradually reduced, bulk-like kinetics were observed. The authors proposed a model based on a “growing viscous front” caused by a high local viscosity at the particle interface and low separation of active sites (Figure 3). This means that local heterogeneities of the activating and deactivating species exist, which leads to a higher probability that any given chain end will be in its active state. In other words, CuI catalytic complexes are enriched near the “viscous front” at the expense of CuII species because of mass transport limitations, therefore providing higher rates of polymerization with higher initiator grafting density. The concept of localized increases in viscosity causing higher polymerization rates has also been described for conventional free radical polymerization (FRP) conducted in bulk313 and from surfaces,314 termed the “Trommsdorff (gel) effect”, or in the case of surface-tethered polymer brushes, the “2-D Trommsdorff (gel) effect”.315 In this case, the rate of chain termination is limited by diffusion through growing polymer chains, therefore resulting in an increased rate of

Figure 3. Schematic of surface-initiated ATRP from MMT with the dark-gray box portraying the “growing viscous front” of small but finite thickness. Legend: Halide terminated chains (▲), nonfunctional initiators (×), and an active chain (*). In this region, there is a locally elevated concentration of chain ends, which observe local concentration heterogeneities resulting from the conversion of (a) CuII (◊) to CuI (○) or (b) CuI to CuII. The bulk catalyst concentrations then work to re-establish equilibrium, where the more abundant CuI has a much stronger driving force and lower steric resistance to mass transfer. Reprinted with permission from ref 238. Copyright 2009 American Chemical Society.

polymerization. Boven et al.314 first observed the Trommsdorff effect when grafting PMMA from silica particles via SI-FRP, in which surface-tethered polymers resulted in higher molecular weight (Mn) than free polymers at reaction times between 30 min and 2 h. Behling et al.238 argued that their observations were not due to the Trommsdorff effect, since termination reactions are already strongly suppressed in SI-ATRP. As described in section 2.1, the presence of negative surface charges at the substrate interface may also accelerate polymer brush growth leading to high thicknesses and grafting densities, as a result of surface enrichment of catalytic species, especially for transition metal-mediated SI-CRP conducted in aqueous media.92−95,99 Jayachandran et al.93 first proposed a qualitative model to explain enhanced initiator efficiency (up to 65%) and PDMAM brush growth kinetics compared to those in solution, in which both CuX/L and CuX2/L species were enriched at negatively charged polystyrene latex particle interfaces due to electrostatic forces, i.e., formation of double layers. The authors found that both CuCl and CuBr complexes with PMDETA and Me6TREN were strongly associated with fixed negative surface charges. Although enhanced polymer brush growth was observed, brush grafting density increased at lower charge densities, suggesting that catalyst complexes became partially immobilized and unavailable to initiate polymerization.94 The same group later grew PDMAM brushes with number-average molecular weight of up to 2170 kDa in Mn (Mw/Mn = 1.66) from charged PVC sheets with grafting densities up to 1.13 chains/nm2, one of the highest ever reported.95 However, addition of NaCl inhibited SI-CRP, likely due to screening of surface charges, which in turn reduced surface concentrations of catalytic species. PDMAM brushes grown from neutral PVC sheets displayed both lower molecular weight and grafting density under identical conditions. When PDMAM was grafted from cellulose nanocrystals (CNCs) via SI-ATRP, higher initiator efficiency was observed for substrates with higher surface charge density, but at the expense of higher dispersity as a result of inefficient deactivation.99 Thus, initiation from charged interfaces appears to be complex since initiation of polymer chains could either be facilitated95,99 or inhibited94 depending on the concentration of catalytic species and surface charge density. 1157


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photonic microring resonators, Limpoco and Bailey 325 observed that PMDETA afforded significantly higher polymer brush growth compared to bpy. The above results corresponded to a large extent with the activation rate constants determined for ATRP in solution.326 In contrast, bpy gave higher rates of polymerization than PMDETA during SI-ATRP of MMA from fumed silica nanoparticles in xylene, but limited solubility of bpy complexes may have caused adsorption to silica nanoparticle surfaces leading to higher activation rates.327 Qian et al.328 grew thicker PHEMA brushes (16 nm) by using TPMA ligand instead of bpy or Me4Cyclam by SI-AGET ATRP. Terayama et al.329 found that high molecular weights, but lower initiation efficiencies were obtained by using PMDETA or Me6TREN compared to bpy when grafting PSBMA from silicon wafers by SI-ATRP in mixtures of an ionic liquid and 2,2,2-trifluoroethanol. Unprotected glycomonomers polymerized via SI-ATRP displayed higher thicknesses with Me6TREN ligands compared to HMTETA.272 Overall, it is clear that the effect of ligand structure on SI-CRP may not necessarily correspond to trends observed in solution or bulk.326 As will be shown in the following sections, the kinetics of SI-CRP not only depend on the traditional parameters of solution-based CRP, but also on the initiator/CTA grafting density as well as the nature of the substrate, i.e., surface area, surface curvature, and porosity. 2.7.2. Effect of Surface Curvature on Molecular Weight and Dispersity. The pioneering work of Alexander330 and de Gennes331 paved the way for polymer brush theory and is still widely used to describe polymer brush conformation on planar substrates (discussed later in section 8.1). For planar surfaces, the available volume for polymer chains increases linearly with distance from the interface, therefore providing a linear relationship between brush thickness and polymer chain length, assuming constant grafting density. On the other hand, polymer brushes at curved interfaces can be subject to conformational transitions from concentrated to semidilute brush regimes with increasing distance from the substrate (Figure 4).188 Furthermore, substrate curvature can have great implications on the miscibility of polymer brush-modified or “hairy” particles in polymer matrices296 and on their selfassembly behavior, leading to unique nanostructural features.295 Although many theoretical studies have addressed the conformation of solvated polymer brushes on flat versus curved surfaces,6,332−334 there are relatively few studies on how substrate curvature affects polymer brush growth kinetics. Nonetheless, molecular dynamics simulations have suggested a pronounced effect of substrate curvature on the initiation efficiency of SI-CRP, the molecular weight and the dispersity of the resulting surface-tethered polymers.298 It was predicted that higher initiation efficiencies and lower dispersity should be obtained with higher substrate curvature and chain growth should more closely resemble free solution-like behavior. Cheesman et al.294 investigated the effect of substrate curvature on polymer brush growth with the use of silica nanoparticles ranging from 120 to 840 nm and planar silicon wafers. The authors utilized a cationic macroinitiator, which strongly adsorbed onto negatively charged silica surfaces, followed by SI-ARGET ATRP of DEAEMA. Interestingly, increased polymer brush growth rates were observed for particles with a diameter less than 450 nm, while above this diameter, growth kinetics were similar to planar wafers. The authors attributed these observations to the increased separation of chain ends with increasing substrate curvature,

Negative surface charge has also been suspected to play a role in accelerated growth of PHEMA and PPEGMA brushes grown via SI-ATRP from initiator-DNA conjugates grafted to gold surfaces.316 Here, anionic sugar−phosphate backbones and bases of DNA were suspected to associate or form complexes with copper species, in comparison to a conventional SAM of alkyl thiols functionalized with ATRP initiators. Interestingly, DNA was also suggested to stabilize radicals and radical transfer in S-RAFT of PHEMA and PPEGMA, leading to accelerated brush growth.317 The structure of the initiator, or the initiating substrate, also has an influence on the outcome of the SI-CRP process. Chernyy et al.318 developed a multilayer initiator film on gold prepared by acylation of electrografted 2-phenylethanol with 2bromoisobutyryl bromide (BiBB), which resulted in nearly five times the amount of initiator groups compared to selfassembled monolayers of a BiBB initiator on gold. Subsequently, this resulted in higher PMMA brush thicknesses under the same conditions. The same group extended this methodology to silica substrates by anchoring a multilayered aminosilane prior to SI-ATRP of LAMA.319 The impact of carbon spacer length of immobilized alkoxysilane initiators on SI-ATRP of MMA from silica nanoparticles was investigated by Huang et al.236 The authors noted that the increased hydrophobicity of nanoparticle surfaces with longer alkyl carbon spacer lengths led to adsorption of MMA monomers, and ultimately higher grafting densities, initiation efficiencies and thicker polymer brushes. In contrast, Sunday et al.237 found that an optimum carbon spacer length of 11 led to higher molecular weight PS, as compared to carbon spacer lengths of 3 and 15, but at the same time, lower grafting density. They proposed that a conformational change in the 11 carbon spacer length initiator was the cause. In the case of Y-shaped initiators, some work has found that triethoxysilane-terminated initiators result in higher grafting densities compared to monochlorosilane-terminated initiators when tethered to silica particles.320 With the use of thin, cross-linked silane-based initiators immobilized on gold surfaces, Saha et al.321 grew PMMA brushes of 300 nm by SI-ATRP, whereas only 100 nm was achieved from commonly applied self-assembled initiator monolayers directly on gold. Sugnaux et al.322 examined PHEMA and PPEGMA brush growth from alumina surfaces with a small library of initiators. Benzoic acid- and phthalic acid−based initiators led to low grafting densities and minimal brush growth, if any, however catechol- and salicylate-based initiators led to rapid brush growth. The immobilization efficiency of CTAs with monomethoxy-, dimethoxy-, and trimethoxysilane anchoring groups for S-RAFT strongly depended on the solvent used in the immobilization step.323 It was found that 1,2-dimethoxyethane solvent resulted in lower grafting densities of CTAs compared to toluene, however with better defined surface structures, which ultimately yielded higher polymer grafting density. A number of reports has also addressed the influence of ligand structure on the SI-CRP process. Iruthayaraj et al.310 examined the effect of different ligands on the SI-ATRP of MMA from glassy carbon electrodes and found thicknesses that increased from bpy < Me6TREN < PMDETA, although the initial rate of polymerization (during the first ∼30 min.) was higher with Me6TREN. Xiao et al.324 showed a similar trend between PMDETA and bpy when grafting PBA brushes from cellulose microfibrils, but with an accompanying high dispersity, therefore less control. By growing PSBMA brushes from silicon 1158


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curvature and dispersity of polymer brushes is not as straightforward. Some previous work speculated that, in general, for SI-CRP from concave interfaces, higher dispersity are obtained with increased surface curvature.230,233,302 Liu et al.298 investigated surface-initiated polymerization both in spherical cavities as well as in cylindrical channels using large scale coarse-grained molecular dynamics simulations (Figure 5). They argued that, in some particular cases, the dispersity

Figure 5. Schematic illustrations of SIP in spherical cavity (a) and in cylindrical channel (b). Yellow beads are frozen to construct the concave grafting surfaces, and green sticks represent grafted polymer chains. The free monomers are omitted for clarity. Reprinted with permission from ref 298. Copyright 2012 American Chemical Society.

can decrease with increasing surface curvature in a particular range, i.e., R‑1 = 0.028−0.14. Here, R‑1 represents the inverse of the cavity or channel radius in terms of the Lennard-Jones potential length scale. At this optimum degree of curvature within a channel or cavity, the effective concentration of free monomers at the curved interface is expected to be lower than at a flat surface, which decreases the rate of brush propagation, which is, in turn, beneficial for decreasing the rate of termination and thus, can provide lower dispersity. Furthermore, a peak in the dispersity was obtained, independent of grafting density, at a critical pore diameter about 70 times larger than the diameter of the monomer. The authors provided the example of styrene (d = 0.593 nm), where this critical mesopore diameter would be about 41 nm, above and below which, lower dispersity may be obtained. In another interesting scenario, molecular dynamics simulations were carried out until 90% monomer conversion was reached. In this case, the authors found that increased surface curvature actually led to lower dispersity. The simulation results by Liu et al.298 were supported by experimental data from Pasetto et al.,302 which showed that PMMA brushes had higher dispersity in larger mesopores (Mw/ Mn = 6.9) than those obtained in smaller pores (Mw/Mn = 1.4) of ordered mesoporous silica (OMS) particles. It should be noted that Pasetto et al. compared the structural properties of both free polymer chains produced via sacrificial initiators and grafted chains through cleavage from OMS particle surfaces. Good control over ATRP of MMA and styrene in homogeneous medium was demonstrated in the presence of initiator-modified OMS particles. In contrast, a large proportion of dead low molecular weight polymer chains, produced from irreversible termination reactions inside mesopores, was confirmed by MALDI-TOF MS and GPC. The authors also suggested that control over SI-ATRP within nanoconfined environments was influenced by diffusion processes, since they observed decreased proportions of dead low molecular weight chains with shorter average lengths of cylindrical mesopores.

Figure 4. Schematic representation of different conformations of polymer brushes attached to curved substrates. Reprinted with permission from ref 188. Copyright 2010 American Chemical Society.

which decreases the chances of termination. The results of Cheesman et al.294 were in agreement with those reported by Morse et al.,335 who determined that the curvature of 13 μm diameter quartz fibers had negligible effects on the kinetics of SI-ATRP of MPC, in comparison to planar silicon wafers. 2.7.3. Effect of Chain Confinement on Polymer Brush Growth Kinetics. The previous section has focused on the effect of curvature of convex surfaces, as in the case of grafting polymer brushes from spherical particles, on the kinetics of surface-initiated brush growth. In this case, larger particles with lower degree of curvature resemble planar substrates, in that polymer brush growth can be hindered by low initiation efficiencies and undesired termination reactions due to the close proximity of active chain ends. In contrast to convex surfaces, concave surfaces represent a highly confined environment for the production of polymer brushes, as in the case of grafting from (meso)porous materials,19,302 spherical cavities298 and nanochannels.332,336 In these nanoconfined environments, the kinetics of polymer brush growth is expected to be limited by physical parameters, such as pore size and diffusion of reactants. Obviously, the kinetics of SI-CRP is highly dependent on surface curvature, as explained above. In molecular dynamics simulations, enhanced confinement in concave systems has been reported to lead to a decrease in molecular weight.298 However, the relationship between surface 1159


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2.7.4. Molecular Weight and Dispersity of Free Polymers vs Cleaved Polymers. The molecular weight and dispersity of polymer brushes are often assumed to be analogous to those of free polymers produced via sacrificial initiators in the same reaction medium. Analysis of Tables 6−8 reveals that there is quite a number of reports in which there is a good agreement between the molecular weight and dispersity of the cleaved, surface-tethered polymers and the corresponding free polymers.68,228,337 Tables 6−8, however, also include a number of entries, which show substantial differences in molecular weight and dispersity of bulk- or solution-based free polymers as compared to polymer brushes that were cleaved from substrates. Terayama et al.,329 for example, synthesized PSBMA brushes via SI-ATRP from silicon wafers in a water/ methanol mixture in the presence of sacrificial initiators. Cleaved PSBMA brushes were analyzed by GPC to give a number-average molecular weight (Mn) of 176 kDa, while the corresponding free polymer was more than double the Mn at 365 kDa. PMMA brushes grafted from silica nanoparticles via SI-AGET ATRP in DMF resulted in a Mn of 105 kDa in comparison to 65 kDa for the corresponding free polymer from sacrificial initiator.338 In contrast, S-RAFT of MMA from silica nanoparticles in dioxane showed the opposite trend.204 Analysis of cleaved PMMA chains led to a Mn of 48.7 kDa as compared to a Mn of 90.8 kDa for free polymers. Interestingly, in the same study, S-RAFT of styrene in DMF produced a Mn of 220 kDa for cleaved polystyrene chains in comparison 130 kDa for free polymers, which also had a larger fraction of low molecular weight chains. Although challenging to cleave from substrates due to labile ester bonds, under 3 M hydrochloric acid hydrolysis,339 PPEGMEMA was cleaved from iron oxide nanoparticles, yielding a Mn of 67.1 kDa in comparison to 11.4 kDa for the corresponding free polymer. In this case, SIATRP of PEGMEMA was carried out in the presence of DMSO. When PBA produced by bulk S-RAFT was cleaved from Laponite clay nanoparticles, a Mn more than three times that of the corresponding free polymer was determined, i.e., 12.7 kDa and 3.7 kDa, respectively.340 A similar trend was observed for S-RAFT of NIPAM from porous polymer thin films in water/acetone341 and PS grafted from iron oxide nanoparticles in toluene.159 In the latter case, cleaved polystyrene gave a Mn of 300 kDa, whereas free polymers yielded a Mn of 130 kDa. Finally, Behling et al.238 demonstrated the effect of grafting density on the kinetics of SI-ATRP of styrene from clay particles in bulk, in which cleaved polymer chains resulted in twice the Mn of free polymers with increased initiator grafting density, due to local catalyst complex concentration heterogeneities in the “viscous front.” However, in the case of styrene, thermal self-initiation may also contribute to lower molecular weight of free polymers.307,342 In contrast to Behling et al.,238 the recent work of Kang et al.343 found that the molecular weight (Mn) of surface-grafted poly(alkyl methacrylates) and PMA was lower than the corresponding free polymers at higher grafting densities on planar silicon wafers. An overall lower rate of polymerization at the surface was also demonstrated at higher grafting density, compared to that in solution, associated with molecular crowding at SIATRP reaction sites. Likewise, surface crowding also increased dispersity through increased probability of chain termination events. Similarly, PMMA grown from high surface area fibrous nylon membranes via SI-ATRP showed higher dispersity and lower molecular weight (Mn) for polymer brushes compared to free polymers, also associated with surface chain termination.344

Overall, the few conclusions of these experimental studies suggest a further dependence of substrate surface area, i.e., particles vs fibers vs planar surfaces, on SI-CRP reaction kinetics. Although clear differences in molecular weight have been observed for cleaved polymer brushes versus free polymers, overall experimental trends regarding dispersity are mostly inconclusive. On the other hand, computer simulations of SI-CRP suggested that surface-tethered polymers undergo earlier terminations,231,303,304,306 relative to free polymers, resulting in higher dispersity. Early terminations of polymer brushes can be circumvented by the addition of excess deactivator.305 This phenomenon was further highlighted especially for high grafting densities and poor solvent conditions.233 More recent simulations also suggested that polymer brushes should have lower molecular weight and higher dispersity than bulk polymers, but depended, again, on grafting density.234,235 Surprisingly, this is the opposite of most of the above-mentioned experimental observations of cleaved brushes versus free polymers, therefore suggesting that additional factors are at play. More detailed discussions on computer simulations and models of SI-CRP will follow in section 8. From the above examples, it is clear that the chain length and chain length distribution of polymer brushes do not always correspond to that of free polymers, however, it is difficult to make overall conclusions based solely on either the experimental data or computer simulations. First of all, local heterogeneities in the growing “viscous front”238 during SI-CRP may lead to higher polymerization rates at interfaces compared to bulk. Analysis of the references cited in Tables 6−8 suggests a possible effect of solvent polarity, since in most cases, higher molecular weights for cleaved polymer chains compared to free polymers were observed for SI-CRP conducted in the presence of polar solvents, such as water,341 DMSO,339 and DMF,204,338 although there were some exceptions.159,329 Indeed, the use of polar solvents for ATRP has resulted in higher rates of activation and lower rates of deactivation.59,345 Although, this, in turn, can lead to high radical concentrations and therefore increase rates of termination resulting in overall loss of control, especially in water.346 Additionally, hydrolysis of C-X bonds can decrease chain-end functionality and dissociation of halide ions from deactivator complexes can lead to inefficient deactivation.347 Furthermore, it has been argued that water accelerates SI-ATRP of hydrophilic monomers due to suppression of chain termination by water.96 However, one must also consider that, in the case of copper-mediated SI-CRP experiments with nitrogen-containing ligands in polar media, disproportionation and/or comproportionation among Cu0, CuI, and CuII species may also play a critical role in the kinetics of brush growth.45,48,75,77−81 To complicate SI-ATRP in polar media even further, some have suggested that an electrical double layer348,349 of ions or, in this case, CuI and CuII catalyst complexes is formed at charged polymer interfaces.92−95 This could also have implications in the case of silicon oxide substrates, in which unreacted silanol groups could be dissociated.350 As a result, local heterogeneities in catalyst complex concentrations at the substrate interface may give rise to higher rates of polymerization compared to free solution polymers. As a final note on substrate surface chemistry effects, Bruening and Baker have shown that PMMA brush growth occurs more rapidly from silica than from gold surfaces in polar solvents,321,351 but proposed this to be a result of thiol desorption that caused chain termination. Thiol desorption 1160


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from gold surfaces caused by copper halide catalyst complexes in the absence of monomer was recently shown by Tang et al.352

3. ARCHITECTURES The use of controlled radical polymerization techniques allows access to a wide variety of surface-tethered polymer architectures. SI-CRP has been applied to produce homo-, block, random (statistical), and branched (co)polymer brushes, binary (mixed) and gradient brushes, as well as several other surface-grafted polymer architectures (Figure 6). Interesting recent developments include t wo-layer, bimodal brushes,134,143,208,353−357 loop-type polymer brushes,206,207 binary and Y-shaped mixed brushes118,127,172,176,258,358,359 as well as free-standing brushes or “polymer carpets”.360−366 The next sections will provide a brief overview on the development of these advanced polymer brush architectures. 3.1. Two-Layer, Bimodal Polymer Brushes

Polymer coatings that interface synthetic materials with biological matter are often required to possess efficient nonfouling properties combined with the ability to present high surface concentrations of biofunctional groups or other ligands.16,354 This is challenging as often efficient nonfouling behavior and the presentation of high surface concentrations of accessible functional groups pose opposing requirements on the grafting density of the brushes. On the one hand, high grafting density polymer brush films can limit the incorporation of ligands. On the other hand, brushes with low grafting densities are more susceptible to nonspecific adsorption. Two-layer, bimodal polymer brush architectures provide one possible answer to address the dilemma between these two competing processes.143,353,354,357 An example of such a brush is shown in Figure 7. These polymer brushes have a two-layer or bimodal structure that results in a grafting density gradient orthogonal to the substrate interface. Such architectures can be produced by controlled termination or regeneration of polymer brush end groups208,353,354 and postpolymerization patterning methods.134,143,355−357 Huang et al.354 prepared two-layer, bimodal antigen binding platforms based on poly(carboxybetaine) type brushes, which were produced using SI-ATRP and SI-PIMP approaches, as illustrated in Figure 7. The substantial difference in retention of active chain-ends offers two pathways toward two-layer, bimodal polymer brush architectures; controlled termination or controlled regeneration. Controlled termination of bromide end groups was carried out via azide substitution after SI-ATRP of a carboxybetaine type monomer from gold surfaces (Figure 7A).353,354 Subsequently, ATRP was reinitiated to form poly(carboxybetaine) type brushes with a defined density gradient. This methodology was also applied by Rungta et al.208 to the S-RAFT of MMA from silica nanoparticles, in which the active chain-ends of the first brush layer were cleaved with AIBN. Consequently, CTAs were immobilized on exposed areas of nanoparticle surfaces, followed by S-RAFT to yield PMMA brushes in a two-layer architecture. Modifying silica nanoparticles with a bimodal-type brush architecture was found to improve dispersion in and interaction of these nanoparticles with the homopolymer matrix, as compared to particles that are modified with a simple, uniform brush layer. In similar work using SI-ATRP, controlled termination of bromide end groups was also accomplished with 4-butoxy-TEMPO to obtain twolayer, bimodal PS brushes grafted from silica particles.367

Figure 6. Overview of different surface grafted polymer architectures that can be prepared via SI-CRP: (A) Homopolymer brushes;92,538 (B) Block copolymer brushes;100,1231,1260 (C) Random copolymer brushes;1248,2120,2147 (D) Cross-linked brushes;537,1344,1345 (E) Freestanding brushes;394,395,1746 (F) Polymer carpets;360,393 (G) Surface grafted bottlebrush polymers;527,729,730 (H) Highly branched polymer brushes;1336,1745,1857 (I) Hyperbranched polymer brushes;517,1168,1169 (J) Molecular weight gradient polymer brushes;533,1482 (K) Grafting density gradient polymer brushes;835,836,2264 (L) Two-layer, bimodal polymer brushes;208,353,354 (M) Horizontal chemical gradient copolymer brushes;1183 (N) Vertical chemical gradient copolymer brushes;1574 (O) Binary mixed polymer brushes;361 (P) Y-shaped mixed copolymer brushes;320 (Q) Loop-type polymer brushes.206,207

To allow the formation of two-layer, bimodal brushes via SIPIMP, Huang et al.354 added tetraethylthiuram disulfide (TED) deactivator during poly(carboxybetaine) brush growth, which preserved photoiniferter groups at chain ends (Figure 7B). Afterward, a second layer was reinitiated resulting in higher film thicknesses in comparison to brushes without TED deactivator. EDC/NHS mediated postpolymerization modification of twolayer poly(carboxybetaine) brushes prepared either via SIATRP353,354 or SI-PIMP354 resulted in systems that showed enhanced antibody binding capacity as compared to the corresponding single layer brushes in combination with low 1161


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groups with a photoresist, followed by end group derivatization with ATRP initiators and grafting of the second layer. 3.2. Loop-Type Polymer Brushes

Polymer brush architectures such as homo-, block or random copolymers, in which the untethered polymer chain-ends are the first point of contact to the external environment, are relatively commonplace. On the other hand, loop-type206,207 architectures are less explored. A number of experimental369−373 as well as theoretical and simulation studies374−381 indicate that polymer loops possess superior surface and interfacial properties as compared to their single-tethered analogues. Dadmun et al.,382−384 for example, have shown that polymer loops effectively improve interfacial adhesion between multiple phases in polymer blends. Scaling theory has shown that loop conformations are less extended and occupy more lateral space than brush conformations, 373 leading to significantly different viscoelastic responses. Rotzoll et al.206 prepared PMA loops grafted from silica nanoparticles via immobilization of bifunctional RAFT CTAs. The authors used two different doubly anchored CTAs, namely 1,4-bis(3′-trimethoxysilylpropyltrithiocarbonylmethyl)benzene (Z-group approach, Figure 8A) and 1,6-bis(o,p-2′trimethoxysilylethylbenzyltrithiocarbonyl)hexane (R-group approach, Figure 8B). After immobilization of bifunctional CTAs on the silica nanoparticles, S-RAFT of MA was conducted either in the presence of free CTAs or without free CTAs. It was found that with free CTA in solution, control over S-RAFT was improved (Mw/Mn = 1.5), while the grafting density was higher with the R-group approach. PMA loops with numberaverage molecular weight (Mn) up to 53 kDa were obtained via GPC analysis of cleaved polymers. In a related study, Rotzoll et al.207 later reported a bifunctional azo-initiator grafted to silica nanoparticle surfaces for subsequent S-RAFT of MA. Here, the authors investigated immobilized bifunctional azo-initiator alone or in combination with bifunctional CTAs reported in their previous work.206 When MA was polymerized by S-RAFT from nanoparticles that only presented the azo-initiator, high molecular weight PMA was obtained, possibly a result of the “2D Trommsdorff effect.”314,315 In contrast, the combination of immobilized CTAs and azo-initiators led to controlled growth of PMA loops and showed distinct benefits for the Z-group approach due to radical generation on the surface.

Figure 7. Illustration of two-layer, bimodal polymer brushes that combine an ultra low fouling first layer and high loading second layer achieved using (A) “termination” or (B) “regeneration” approaches. Reprinted with permission from ref 354. Copyright 2012 Wiley-VCH.

fouling properties. An alternative approach to utilize SI-PIMP for the preparation of two-layer, bimodal brushes was reported by Ma et al.357 Here, the authors first grafted a layer of PPEGMA via SI-PIMP from cycloolefin polymer sheets, followed by a second layer of PAA from the few remaining active chain-ends. Immunoglobulin was then immobilized in the two-layer brush film to produce a nonfouling, yet highly selective platform for immunoassays. Not only can two-layer, bimodal polymer brush architectures be produced by chemical methods as discussed above, but also with the assistance of patterning strategies. As discussed in section 2.3, light-mediated SI-CRP provides a straightforward approach to fabricate complex polymer brush architectures, simply with visible light exposure and a conventional photomask.134 In this way, Poelma et al. produced PMMA-bPtBMA and PMMA-b-PMAA brushes with two-layer architectures.134 After initiating a single polymer brush layer with visible light, a photomask was applied before reinitiation, leading to a patterned second layer. Two-layer, bimodal (“stratified”) PHEMA-b-PSPMA brushes have been prepared by microcontact printing patterned, ATRP-initiator-integrated polydopamine onto a PHEMA brush layer, followed by subsequent SI-ATRP of 3-sulfopropyl methacrylate potassium salt.355 Yom et al.356 utilized a patterned photoresist to fabricate multicomponent block copolymer brush films via SI-ATRP of HEMA, NIPAM, and GMA. This sequential process was repeated three times to give complex 3-D patterns visualized colorimetrically by bright field microscopy. Similarly, Takahashi et al.143 coated a photoresist onto a PNIPAM brush layer produced via S-RAFT, to give patterned active chain-ends. PNIPAM-b-PNAM domains were then produced as the second layer. This hierarchical brush architecture gave rise to highly oriented human dermal fibroblasts by one-pot cell seeding. The oriented cells could be further harvested as a cell sheet by simply reducing the temperature below the LCST of PNIPAM. Chapman et al.368 fabricated PPEGMEMA-b-PMAA hierarchical brushes by patterning nitrophenyl protected amine end

3.3. Binary and Y-Shaped Mixed Brushes

Binary “mixed” homopolymer brushes are thin films, in which two distinct, immiscible polymers are immobilized on surfaces in random or alternating arrangements.27,385 While each component of a binary polymer brush is not necessarily sensitive to external stimuli, they can exhibit spontaneous chain reorganization in order to minimize free energy. This phenomenon can lead to unique interfacial properties and even predictable nanostructures.386 Toward a fundamental understanding of “hairy” nanoparticle self-assembly processes, phase morphology 3 8 7 , 3 8 8 and microphase separation295,320,389,390 of binary polymer brushes grafted from nanoparticles has been of great interest. Such “hairy” nanoparticles can self-assemble upon solvent casting and/or annealing leading to 3-D nanostructures.388 The synthesis of binary brushes from various substrates has been addressed in detail previously.5,27 Binary polymer brushes have been produced by SI-CRP using a variety of strategies involving the use of immobilized Y-shaped initiators/ CTAs,195,263,295,320,387−389 mixed monolayers of two different 1162


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The authors320 then went further to examine the effect of grafting density on microphase separation of the same binary brush system. It was observed that the feature sizes of the nanostructured films were smaller in the case of low grafting density (0.6−0.7 chains/nm2) brushes as compared to higher grafting density binary brushes of 0.9−1.2 chains/nm2. These results indicated that accurate control over the grafting density and molecular weight of binary polymer brushes provided a means to control nanostructured patterns in drop-casted and annealed films. Subsequently, the authors found that at or above a critical overall grafting density of 0.34 chains/nm2, the binary PtBA/PS brushes exhibited lateral microphase separation into “rippled” nanostructures.389 Below this value, the wavelength of ripples increased until no microphase separation was observed at 0.122 chains/nm2. Ripple wavelength also increased with increasing molecular weight of the binary brushes.390 When the same range of molecular weight and grafting density was produced from 67 nm silica nanoparticles, the authors observed truncated wedge-shaped nanostructures.295 To demonstrate the importance of surface curvature, when the same binary brush system was grafted from 160 nm silica nanoparticles, nanodomains of uniform width were obtained. These results suggest that, in addition to controlling the molecular weight and grafting density of binary polymer brushes, particle size plays a crucial role in microphase separation phenomena, offering an additional means to control nanoscale feature size and morphology. Finally, the same group was able to reconstruct the 3-D morphology of self-assembled films of 67 nm silica nanoparticles grafted with binary PtBA/PS brushes by electron tomography (3-D TEM).388 They observed that dense monolayers of binary brush grafted nanoparticles self-assembled into hierarchical nanostructures upon dropcasting, which were highly dependent on particle size dispersity and the interaction between the binary brushes grafted from adjacent particles. The microphase separation in dense monolayers of binary brush grafted nanoparticles were divided into four distinct regions orthogonal to the substrate surface, while isolated binary brush grafted nanoparticles only showed lateral microphase separation in the lower region closest to the substrate. This work evidently highlights the effect of the interactions between binary brushes grafted from adjacent nanoparticles during solvent casting that can lead to distinct phase separation behaviors into hierarchical 3-D nanostructures. While the above research endeavors on binary brushes grafted from nanoparticles focused on the fundamentals of their self-assembly and phase behavior on surfaces, other work has concentrated on exploiting potential functional properties of binary polymer brushes.195,258,292,391 Toward mesoporous silica nanoparticle (MSN)-based delivery systems,392 Huang et al.195 reported binary PHPMAM/PDEAEMA brushes via sequential S-RAFT and SI-ATRP, respectively. Amine-functionalized MSNs were first modified with a bifunctional Y-initiator/ CTA by an amino active ester moiety. Consequently, the binary brush grafted MSNs were loaded with doxorubicin as a model drug at pH 5.0 due to the pH-responsive behavior of PDEAEMA. These materials showed a pH-dependent release of doxorubicin and were determined to be noncytotoxic to MCF7 and 293T cells up to a concentration of 20 μg/mL. Song et al.258 developed a novel class of plasmonic vesicles based on amphiphilic gold nanocrystals grafted with polymer brushes via a combination of “grafting to” and “grafting from” approaches. Initially, gold nanocrystals were grafted with SAMs of PEG and

Figure 8. Proposed mechanism for the formation of polymer loops via doubly anchored bifunctional RAFT agents (w/chemical structures) through the (A) Z-group approach or (B) the R-group approach. Reprinted with permission from ref 206. Copyright 2008 Wiley Periodicals, Inc.

initiators/CTAs,263,359 or by a combination of layer-by-layer and surface-initiated polymerization techniques.361 Table 10 presents an overview of the different binary brush systems that have been reported over the past years. In this section, we will focus especially on binary brushes grafted from nanoparticles and their unique properties. Jiang et al.387 utilized Y-shaped initiators containing TEMPO and α-bromoisobutyrate moieties for sequential SI-NMP and SI-ATRP, respectively. First, SI-ATRP of tBA was carried out from Y-initiator functionalized silica nanoparticles (160 nm), followed by SI-NMP of styrene to obtain PtBA and PS grafts with number-average molecular weight (Mn) ranges of 14−30 kDa. Initially, microphase separation of binary brushes was suggested by results of differential scanning calorimetry analysis, which showed two glass transition temperatures after thermal annealing. Furthermore, TEM experiments on dropcasted and solvent annealed films showed that the phase morphology depended on the PS molecular weight. The observed morphology shifted from spherical PS microdomains within the PtBA matrix to nearly bicontinuous nanostructures. 1163


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Table 10. Overview of Binary and Y-Shaped Mixed Polymer Brushes Grafted from Various Substrates Using SI-CRP

tion of a Raman-active dye in combination with PEG and ATRP initiators. SI-ATRP of HEBAMA was then carried out to form binary PEG/PHEBAMA brushes, which could chelate toxic Cd2+ ions. In the presence of Cd2+, the previously welldispersed binary brush grafted nanoparticles formed aggregates that could be sensitively and selectively detected by the SERS fingerprint signal, even with other metal ions present. In addition to combining SI-CRP with “grafting to” methods, other techniques, such as surface-initiated ring-opening polymerization (SI-ROP) can also be used to produce binary polymer brushes. 3 9 1 Multiwalled carbon nanotubes (MWCNTs) were modified with this strategy to afford

2,2′-dithiobis[1-(2-bromo-2-methylpropionyloxy)] ethane (DTBE). After subsequent SI-ATRP of MMA, hydrophobic PMMA domains and hydrophilic PEG domains caused the gold nanocrystals to self-assemble into vesicles with tunable optical properties based on the surface plasmon resonance (SPR) of gold nanoparticles. To generate stimuli-responsive plasmonic vesicles, pH-responsive P4VP was incorporated (25% 4VP in the monomer feed) into hydrophobic PMMA grafts, which led to vesicles that broke upon decreasing the pH to 5. A new class of surface enhanced Raman scattering (SERS) sensors were also synthesized based on the SPR of gold nanoparticles.292 SERS-active gold nanoparticles were produced by immobiliza1164


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Table 11. Bio-Based Substrates, which Have Been Used to Graft Polymer Brushes via SI-CRP

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nanoparticles with “Janus-like” behavior in a mixture of selective and immiscible solvents. Diels−Alder cycloaddition was used to functionalize MWCNTs with ATRP initiators and hydroxyl groups for SI-ROP. Interestingly, SI-ROP and SIATRP were carried out simultaneously up to 45% conversion, in which different monomer combinations were respectively used, such as ε-caprolactone/styrene, ε-caprolactone/MMA, lactic acid/styrene and lactic acid/MMA.

for SI-ATRP of styrene. After patterning by photolithography, brush-modified wafers were placed in water at elevated temperature and brush nanofilms were transferred to new oxygen plasma-treated wafers by immersion in the suspension for a few hours. Upon drying, brush nanofilms folded into distinct 3-D nanostructures, likely caused by their Janus properties. Welch and Ober366 developed an HF-etch lift-off method that preserved the un-cross-linked initiator layer to detach PGMA and PS carpets produced by SI-ATRP from standard silicon wafers that were covered with a 2 μm silicon oxide layer. In this case, polymer brushes were coated with PMMA, annealed and coated with a positive photoresist for subsequent patterning into sections that could be detached by HF treatment.

3.4. “Polymer Carpets”

Polymer carpets are defined as free-standing polymer brushes grafted from a cross-linked monolayer or nanosheet.360,393 In contrast to free-standing polymer brushes,394,395 in a “carpet”, polymer brush chains are not cross-linked, therefore maintain their structural integrity in the native brush state. The process reported by Amin et al.393 starts with the preparation of a 1 nm thick nanosheet by electron irradiation cross-linking of a biphenyl SAM on gold. Nanosheets were detached396 and deposited onto a sacrificial silicon support. Subsequently, the supported nanosheet was utilized to grow PS, P4VP and PMMA brushes by self-initiated surface photopolymerization and photografting (SIPGP).393 Although not a SI-CRP technique, SIPGP has been utilized to prepare defined polymer brush films.397−399 This methodology could be easily transformed to a SI-CRP technique by immobilization of initiators/ CTAs on the silicon supported nanosheet prior to polymer brush growth. In addition to cross-linked SAMs, nanosheets have also been prepared by layer-by-layer (LbL) self-assembly.361,362 Estillore and Advincula first prepared ultrathin films of a macroinitiator by LbL on silica surfaces.361 Mixed brushes were produced by sequential SI-ATRP of NIPAM and SI-FRP of styrene. Finally, the substrate was exposed to an aqueous solution of poly(vinyl alcohol) (PVOH) and dried, resulting in a sacrificial layer that allowed easy detachment of the LbL/mixed polymer brush film. After dissolution of the PVOH layer by water, the free-standing polymer carpet could be transferred to another silicon wafer substrate. Similar approaches were used to produce freestanding polymer carpets of PS-b-PTFEMA synthesized by SIATRP,362 however cellulose acetate (CA) was utilized as a sacrificial layer on silicon wafers prior to LbL deposition of macroinitiators. Kohri et al.364 also used a cellulose acetate sacrificial layer, followed by deposition of a transparent polydopamine layer containing ATRP initiators. PHEMA brushes were grown via SI-ATRP and the polymer carpet was removed by dissolution of the sacrificial layer in DMF. The LbL brush films were exposed to acetone in order to dissolve the cellulose acetate underlayer, followed by detachment of the free-standing LbL brush film. Fujie et al.363 produced freestanding polymer carpets by spin-coating-assisted layer-by-layer assembly (SA-LbL) of polyelectrolytes on silica surfaces with a macroinitiator in the 11th layer, followed by thermal crosslinking. Then, PMPC brushes were grafted from supported LbL nanosheets via SI-ATRP and exfoliated with a sacrificial PVOH layer. The PMPC nanosheets were easily detached and transferred onto a cell culture dish and were determined nonfouling. Instead of using PVOH as a sacrificial layer to detach polymer carpets,361,363 Ohm and Ober365 introduced a novel strategy, which utilized PVOH thin films to grow PS brushes, which were etched into detachable sections by photolithography. The first step in this process involved spin-coating a PVOH film onto a silicon wafer, followed by grafting of BiBB

4. SUBSTRATES This section consists of three parts. First, a number of substrates will be discussed, which only recently attracted significant attention for the surface grafting of polymers via SICRP. After that, several new approaches for the immobilization of initiators and chain transfer agents will be presented. The final part of this section will elaborate on the stability of surfacetethered polymer films and the mechanochemical effects on their reactivity, in particular degrafting. 4.1. Novel Substrates

SI-CRP has been utilized to grow polymer brushes from a wide variety of substrates including silicon/silicon oxide, metals/ metal oxides, clay minerals, gold, carbon nanomaterials as well as polymer surfaces.3,5,13,16,17,21,25 Over the last years, a steadily increasing number of research groups are focusing on grafting polymer brushes from substrates new to SI-CRP. These include a variety of biobased substrates such as cellulose nanomaterials, chitin nanofibers, other natural fibers, proteins and microorganisms (Table 11), electrospun nanofibers (Table 12), mesoporous materials (Table 13), graphene (oxide) (Table 14), as well as boron nitride nanotubes.400 The following subsections will briefly highlight some interesting examples for each of these different classes of substrates. 4.1.1. Biobased Substrates. An increasing number of studies has reported the use of novel biobased materials as substrates to grow polymer brushes via SI-CRP (Table 11). Plant-derived and, in particular, cellulose-based materials are one example of such substrates. Cellulose is the world’s most abundant organic compound and is considered a practically inexhaustible source of stored carbon and solar energy.401 Historically, cellulose has been used primarily for energy, building materials, paper products and textile fibers. As a result of diminishing resources of fossil fuels, evolving environmental concerns and the decreasing need of paper, great efforts have been made over the last two decades to produce novel nanomaterials from cellulose.402−406 Cellulose nanomaterials (a.k.a. nanocellulose) can be divided into three main classes; cellulose nanocrystals (CNCs),407,408 cellulose nano- or microfibrils (CNF or CMF)409 and bacterial cellulose nanofibrils (BCNF).410 The primary differences between them are their method of production, aspect ratio and mechanical properties. Whereas cellulose nanofibrils contain both amorphous and crystalline regions with high aspect ratio, cellulose nanocrystals are primarily rigid crystals with lower aspect ratio. CNCs are typically produced by acid hydrolysis of native cellulose fibers by sulfuric or hydrochloric acid. Sulfuric acid hydrolysis results in highly stable aqueous dispersions of 1166


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Table 13. Mesoporous Substrates, which Have Been Modified with Polymer Brushes via SI-CRP

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Table 14. Graphene and Graphene Related Substrates, which Have Been Modified with Polymer Brushes via SI-CRP

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Table 14. continued

via SI-ATRP with a CuBr/HMTETA catalytic system at elevated temperatures. Shortly thereafter, Morandi et al.418 reported an extensive investigation on the reaction conditions of PS grafting from CNCs by SI-ATRP. In this case, BiBB modification of CNCs was carried out in the presence of triethylamine (TEA) in DMF, but without 4-DMAP catalyst. Initiator-modified CNCs were then grafted with PS via SIATRP in anisole with a CuBr/PMDETA catalytic system in the presence of sacrificial initiator. The same group later designed a photocleavable ATRP initiator, 3-(hydroxymethyl)-2-nitrobenzyl 2-bromo-2-methylpropanoate (see Table 5), that could be attached to CNC surface hydroxyl groups by 2,4-toluene diisocyanate coupling in THF.245 After SI-ATRP of styrene, PS grafts were cleaved after 5 h of exposure to 365 nm UV light, resulting in PS with similar molecular weight to free polymers produced by sacrificial initiators and low dispersity (Mw/Mn = 1.08). PNIPAM brushes were also grafted from CNCs by SI(SET-LRP/SARA ATRP) with a CuBr/PMDETA catalytic system in water/MeOH mixtures.105,419−421 BiBB was initially attached to CNCs following a protocol adapted from Zhang et al.414,415 in the presence of 4-DMAP. Due to the labile ester bonds, PNIPAM brushes were cleaved from CNCs by alkaline hydrolysis (2% NaOH, 48 h) for subsequent GPC analysis. High dispersity of PNIPAM grafts was observed, suggesting poor control over SI-(SET-LRP/SARA ATRP), likely caused by the absence of added deactivator, but also the heterogeneous nature of Cu0 activation. Alternatively, Chen et al.422 grafted PNIPAM brushes from CNCs via SI-AGET ATRP with CuBr2/ PMDETA and ascorbic acid reducing agent. Majoinen et al.423

rigid rod-shaped nanoparticles, capable of self-assembling into lyotropic chiral nematic liquid crystalline phases, because of anionic surface sulfate half-ester groups. CNF/CMFs are typically produced by high-pressure homogenization and/or grinding of pulps, but can also be prepared by TEMPOmediated oxidation or with the assistance of enzymatic pretreatments. BCNFs are produced by various genera of bacteria, which utilize low molecular weight saccharides to synthesize cellulose chains into a biofilm. Due to the unique optical and thermo-mechanical properties of cellulose nanomaterials, there is a growing interest to incorporate them into advanced materials, ranging from nanocomposites to medical devices, biosensors, Pickering emulsions and organic electronics.404,405,407,408 However, the hygroscopic nature of cellulose nanomaterials hinders their incorporation into hydrophobic matrices, thus surface modification by means of physisorption of surface active compounds or covalent functionalization with small molecules or polymers by “grafting to” or “grafting from” methods offers a means to tailor their interfacial properties.411−413 Zhang and co-workers414−416 first reported SI-ATRP from CNCs toward controlling their self-assembly into chiral nematic liquid crystalline phases. Utilizing the chemistry developed by Carlmark and Malmström417 for SI-ATRP from macroscopic cellulose fibers, ATRP initiators were immobilized on CNC surfaces by 4-dimethylaminopyridine (4-DMAP) catalyzed esterification of hydroxyl groups with α-bromoisobutyryl bromide (BiBB) in THF. Subsequently, PMMAZO,414 PS415 and PDMAEMA416 were grafted from initiator-modified CNCs 1171


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more, Gao et al.436 modified electrospun lignin nanofiber mats with PNIPAM by SI-ATRP, resulting in thermo- and ionresponsive nanofibers based on renewable starting materials, which were later also synthesized using ATRPases.437 Polymer brushes have also been grafted from a number of protein-based substrates as detailed in Table 11. In most instances, polymer brushes are grafted from proteins that have been modified with BiBB. BiBB has been used to modify the lysine groups in BSA,438 ferritin nanoparticles,439,440 chymotrypsin,441 cyclic peptides,442 denatured protein443 and yeast.444 Although in most cases one would expect that the amino groups will react preferentially with the acid bromide on BiBB, there must also be accounting for the analogous reaction of the hydroxyl residues443 (from Serine, Tyrosine and Threonine). Alternatively, the lysine residues can also be reacted with glutaraldehyde followed by 2,2′-(ethylenedioxy)-bis(ethylamine) and 2-bromo-2-methylpropanoyl bromide to yield the ATRP initiator-functionalized substrate.445 Other means of preparing protein-based substrates that allow SI-CRP include the use of trichlorosilane-based initiators446 and the coupling of acryloyloxyethyl 2-bromoisobutyrate to the thiols obtained from the reduction of disulfide bonds.447 Finally, Pokorski et al.448 functionalized viruses and virus-like particles with ATRP initiators via two-step “click” reactions for subsequent growth of PPEGMA brushes. 4.1.2. Electrospun Nanofibers. There has been an increasing interest in recent years in the utilization of SI-CRP to modify electrospun nano- and microfibers (Table 12), including both polymer fibers, as well as lignin-based fibers. In our earlier review, there was only a single example of SICRP from an electrospun fiber. The authors first used ATRP to polymerize styrene in solution and then subsequently electrospun the polystyrene into a fiber and used the pre-existing alkyl bromide groups to effect the surface grafting of PAM and PHMAM.449 Since that initial report, the trend has been to use a comonomer containing an ATRP initiator, which is then polymerized to yield a fiber that incorporates the ATRP initiator. This process has been used to graft PSBMA,450,451 PHDFDA,450,451 PHEMA, 450,452 PAM,177 PAA,177 PSS(Na),453,454 PFMA,452 PEGMASA,177 PTMSPMA,455 POEGMA,452,456 and PPEGMA brushes.177 The comonomers in these cases were usually based on either methacrylates (such as 2-(2-bromoisobutyryloxy)ethyl methacrylate)450,451 or styrene (such as 4-vinylbenzyl chloride177,453,455 or 4-vinylbenzyl 2bromopropionate),454 which are typically copolymerized with MMA or styrene respectively using FRP to yield the precursor copolymer for electrospinning. One exception was reported by Liu et al., who included an alkyl bromide-bearing vinyl monomer into a PDMS based copolymer.452 In addition to incorporating the ATRP initiators into the electrospun polymers via a direct copolymerization, an alternative approach involves the postpolymerization modification of prespun fibers with ATRP initiators for subsequent SICRP. This can be done by either chemically modifying the fiber,436,457−459 or by adsorbing a macroinitiator onto it.460 In terms of chemical modification, a number of techniques has been used such as the derivatization of surface hydroxyl groups with acid chlorides bearing ATRP-initiating groups.436 Alternatively, two-step protocols can be followed by first using hexamethylene diisocyanate457 or APTES458,459 to introduce amine or hydroxyl groups onto the fiber surface, which can subsequently be derivatized with BiBB to yield the ATRPinitiating sites. Using this postelectrospinning modification

introduced BiBB to CNC surfaces by chemical vapor deposition, followed by a solution-phase reaction in DMF in the presence of pyridine and 4-DMAP. Finally, Cu-mediated SICRP of tBA was performed with CuBr/PMDETA catalyst and sacrificial initiators, leading to a grafting density of 0.3 chains/ nm2. The same group later used similar chemistry to graft PDMAEMA-co-PNAPMA brushes from CNCs to reinforce nanocomposite hydrogels424 and quaternized PDMAEMA brushes for binding viruses.425 PDMAM brushes were recently grafted from CNCs with varying surface charge via SI-ATRP in aqueous media in order to elucidate the effects of sulfate halfester groups on initiator efficiency, brush molecular weight and dispersity.99 In addition to Cu-mediated polymerization, SRAFT has also been applied to graft PNIPAM and PNIPAMco-PAA from CNCs.426 In this case, the CTA was attached to CNC hydroxyl groups in chloroform via 4-DMAP catalyzed esterification of 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid (DDMAT) in the presence of N,N′-dicyclohexylcarbodiimide (DCC). As CNCs have relatively little amorphous domains and limited aspect ratio (L/d = 10−70),407 it is often desirable to modify CNF/CMFs by SI-CRP for applications requiring high ductility, such as nanocomposites324,427,428 and paper-based biosensors.429 In order to improve the compatibility and dispersion of CMFs in polypropylene (PP), Li et al.428 grafted PBA by SI-ATRP using a CuBr/PMDETA catalyst in toluene at 90 °C. PBA brushes were cleaved by HCl hydrolysis for GPC analysis, which revealed a dependence of dispersity on target molecular weight, most likely caused by recombination termination reactions. The same group later reported that the use of bpy as a ligand instead PMDETA improved control over SI-ATRP of BA from CMF in DMF.324 Toward a nanopaperbased human immunoglobulin G (hIgG) sensor, Zhang et al.429 reported SI-ARGET ATRP copolymerization of HEMA and AEMA, from CNF using ascorbic acid reducing agent, followed by immobilization of an hIgG peptide. To this end, BiBB was first attached to CNF either in suspension or from a spincoated layer by the 4-DMAP catalyzed esterification reaction discussed above.105,414,415 Interestingly, the authors found similar hIgG adsorption capacity with either PHEMA-cografting method, in suspension or as a spin-coated layer. Although SI-CRP is a promising method to graft polymer brushes from cellulose nanomaterials, so far there is only one report that utilizes bacterial cellulose nanofibrils (BCNF).427 In this unique case, BCNF membranes were produced by Gluconacetobacter sacchari and modified with BiBB by 4DMAP catalyzed esterification in DMF, but without TEA. Then, PMMA, PBA and PMMA-b-PBA brushes were grafted from initiator-modified BCNFs via SI-ATRP with a CuBr/ PMDETA catalytic system in DMF/water mixtures. Cleavage of polymer brushes with KOH in THF resulted in PMMA and PMMA-b-PBA with weight-average molecular weight (Mw) of 270 (Mw/Mn = 1.5) and 370 kDa (Mw/Mn = 1.6), respectively. While many reports in the area of SI-CRP from renewable substrates have focused on cellulose nanomaterials (see Table 11), SI-CRP has also been applied to macroscopic wood fibers to graft polymer brushes430,431 such as poly(vinyl acetate) (PVAc),223 PAM,432 PS,223 PEA,433 PBA,223 PSPMA,434 and PVBC-co-PS.223 The interesting case of PVAc brushes was attainable via macromolecular design via interchange of xanthate (MADIX) in combination with S-RAFT.223 Other natural polysaccharides of interest for surface modification by SI-CRP include crab exoskeleton-derived chitin.435 Further1172


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process researchers have grafted PPEGMA,457 PDMAEMA,459 PDEAEMA,460 PHEMA,459 PNIPAM,436,458 and polyglycerol monomethacrylate brushes.460 It is notable that most of the papers described above used ATRP to effect the SI-CRP of the corresponding monomers. There are only two instances in which RAFT is used due to the fact that the monomers polymerized do not lend themselves to well-controlled ATRP. In the first example the authors converted alkyl chlorides on the surface of the electrospun fibers into trithiocarbonates, which were used to mediate the polymerization of a PAM-co-PAA copolymer177 and in the second example PVBTAC was polymerized from electrospun cellulose acetate fibers.461 4.1.3. Mesoporous Materials. Table 13 presents an overview of the various mesoporous substrates that have been used to graft brushes via SI-CRP. There has been a significant increase in the utilization of mesoporous materials as substrates for SI-CRP. With three exceptions that report grafting from aluminum oxide,462 chloromethylated polystyrene463 and a zeolite,464 the majority of the papers in Table 13 focus on mesoporous silica. There are a few detailed investigations in this regard that allow a close examination of SI-CRP from these porous substrates compared to the more common form of silica, i.e., Stöber particles. Pasetto et al. noted that in SI-ATRP of MMA from mesoporous silica in the presence of a sacrificial initiator, the grafted chains, when cleaved from the substrates, showed a bimodal distribution.302 The high molecular weight fraction increased in molecular weight with increasing conversion indicating livingness while the low molecular weight fraction remained unchanged indicating dead chains. Furthermore, the high molecular weight chains showed a good correlation to the free chains derived from the sacrificial initiator (a result mirrored by several other studies246,465,466). The authors further showed that this bimodal distribution was not a consequence of remnant fluoride catalyst from the synthesis (of the mesoporous substrates) by obtaining identical results using particles from a catalyst-free synthesis. Additionally, the dead chains could not be attributed to chains grown within the mesopores and the living chains to chains grafted on the periphery as the weight proportion of the two populations was 1:1. Finally, the authors also investigated porous particles with varying lengths of mesopores from 9 to 14 nm and noted that with increasing length, the dispersity (Mw/Mn) of the grafted chains increased as a result of limited diffusion of monomers into the pores while restricting the livingness of SI-CRP from mesoporous structures.302 This finding was mirrored in the work by Blas et al., who performed SI-NMP of styrene from particles of varying porosity.467 Also in this study, longer pore channels were thought to lead to higher dispersity of the grafted chains. In terms of diffusion, the authors note that a pore diameter of 2 nm was too small to ensure a good diffusion of the reagents while diameters of 5 nm and above appeared to be sufficient. The papers discussed above confirm earlier work by Gorman et al., who calculated that the confinement of radicals and steric hindrance in the concave surfaces of mesopores leads to an increase in grafted chain dispersity.230 4.1.4. Graphene and Graphene-Related Materials. Graphene and graphene related materials have attracted enormous attention in recent years. A large number of studies have reported the grafting of polymers from these materials via SI-CRP. Table 14 summarizes these efforts and presents for six classes of graphene related substrates viz. graphene,170,468,469

functional graphene sheets, 102,470−473 reduced graphene oxide,222,434,473−475 exfoliated graphene oxide,107,108,476−479 graphite oxide,103,480−483 and graphene oxide,484−490 the anchoring chemistries and monomers used. Depending on the nature of the surface functional groups presented on graphene related materials, a variety of initiator immobilization strategies can be applied, depending on the desired electronic, optical and thermomechanical properties. Other frequently used carbon-based substrates for SI-CRP, such as carbon nanotubes (CNTs), have been reviewed elsewhere.5,491 A popular reactive group for the functionalization of graphene surfaces is the aryl diazonium group. This is either introduced directly to the graphene surfaces222,476 or generated in situ using aniline derivatives. The generation of the diazonium group in situ is accomplished by the use of isoamyl nitrite in a method first described by Dyke and Tour492 to modify SWCNTs and has since been used by polymer chemists to introduce alcohol groups onto carbonaceous surfaces for subsequent reaction with BiBB to generate an ATRP-initiating site102,469,471,472,474 or to introduce a propargyl group onto which a azido-RAFT agent could then be ‘clicked.’170 Alternatively, noncovalent π−π interactions between pyrenebearing initiators and the graphene surface can also be used to introduce ATRP-initiators to the graphene473,488 and graphene oxide.434,473 In recent years, dopamine-based initiators have also seen tremendous utility in the functionalization of graphene and graphene oxide surfaces. These can be used either by selfpolymerizing dopamine onto a graphene and graphene oxide surface475 (forming reduced graphene oxide)493 or by using the catechol groups bind to the oxide surfaces.434,473 In a similar vein to the polydopamine method, Ou et al. have demonstrated an elegant way to functionalize graphene with a 1,3-dipolar cycloaddition reaction using N-methylglycine and 3,4-dihydroxybenzaldehyde. In this case the authors noted no degradation of the electronic properties of the graphene and the hydroxyls on the catechol groups could be further derivatized with BiBB to yield surface-grafted ATRP initiators.468 The carboxylic acid groups on graphene oxide have also been used to introduce ATRP initiators to the surface by first reacting the acid groups with an excess of a diamine and then reacting the resultant surface-grafted amines with BiBB482,484,487 and BiBA.490 This is sometimes done with an intermediary step of converting the carboxylic acids to acid chlorides with thionyl chloride to increase their reactivity.478,483 The carboxylic acid groups can also be converted to acid chlorides and subsequently reacted with 2-hydroxylethyl-2′bromoisobutyrate to yield the surface-grafted initiator.481 It is interesting to note that the thus-prepared ATRP-initiating sites are sometimes converted to surface-bound RAFT CTAs for subsequent S-RAFT polymerizations.478,479,483 Instead of using the carboxylic acid groups as an electrophile, the hydroxyl groups on graphene oxide can also be used as electrophiles to react directly with BiBB with a TEA catalyst.103,107,108,479 Alternatively the hydroxyl groups can also be derivatized with TEMPO to yield an initiator for SI-NMP.489 The epoxide groups on graphene oxide have also been derivatized with tris(hydroxymethyl) aminomethane followed by BiBB to form a ternary ATRP-initiating site.107,108 While the above methods detail the most commonly used techniques to functionalize graphene, other methods such as photografting of aryl-azide based initiators,477 the use of ATRA to introduce 1173


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Scheme 6. Synthesis and Anchoring of a DOPA Modified ATRP Initiator and Subsequent Polymerization of OEGMEMAa

a

Reprinted with permission from ref 501. Copyright 2005 American Chemical Society.

thermoresponsive polymer brush films. By taking advantage of NHS ester chemistry, initiators/CTAs can be covalently attached to a variety of amine-functionalized substrates under well-controlled pH conditions. Another method to immobilize initiators/CTAs that is tolerant to water involves dopamine derivatives, inspired by mussel adhesive proteins.500−502 Likewise, Sugnaux et al. used catechol, phthalate and salicylate-based initiators to immobilize them onto alumina surface.322 The grafting process of catecholbased initiator was also found to be easily controlled by pH, which allowed tuning of the grafting density. Catechol mediated attachment of initiator/CTAs is not only attractive as it is water tolerant, but also as it can be applied to a very broad range of surfaces, as will be elaborated in the following section. 4.2.2. Substrate-Independent “Universal” Methods. Generally, the chemistry utilized to attach initiators/CTAs is highly substrate dependent. This is underlined by Tables 2−4, which list a diverse range of chemistries that are used to modify a wide variety of different substrates. Strategies that allow to attach initiators/CTAs independent of the substrate surface chemistry, obviously, are attractive. One very versatile approach relies on the use of catechol chemistry, which is inspired by mussel adhesive proteins, and was first reported by Fan et al.,501 as shown in Scheme 6. The basis of the chemistry relies on catechol adsorption from aqueous solution on the surface, forming a covalent metal oxide bond.503 Dopamine hydrochloride (DOPA) can be functionalized with an initiator/CTA under basic conditions using borate ester protection504 or by reaction with a 2-mercaptothiazoline ester.173 The DOPA functionalized initiators/CTAs are then typically immobilized on the substrate from aqueous solution under ambient conditions. Another variation is to first immobilize DOPA by self-polymerization, which generates a thin adherent film of polydopamine (PDOPA) that presents surface hydroxyl and/or amine groups, followed by initiator/ CTA attachment.505−507 Zhu et al.508 showed that initiator-

ATRP initiators,485 reaction with chlorosilane480,486 or alkyl halide485 based coupling agents, have also been studied and presented in Table 14. 4.2. Initiator/Chain Transfer Agent Immobilization on Surfaces

SI-CRP, in most instances, starts with the immobilization of the appropriate initiator or CTA on the substrate of interest. Typically, the synthetic steps taken to attach initiators/CTAs depend on the nature of the substrate and the existence of surface functional groups. Table 2−4 also present anchoring chemistries that have been used to attach ATRP initiators and RAFT agents to a broad variety of surfaces. Although alkoxyand chlorosilane chemistry has been extensively applied to immobilize initiators/CTAs to silica substrates, it has also been used to functionalize various other metal oxides,159,216,494−496 carbon nanomaterials,215,486 polymers,497 hydroxyapatite224 and rabbit fur.446 The details of the immobilization methods and variation of substrate have been reviewed extensively elsewhere.5,7,8,13,14,17,21 The remainder of this section will highlight two aspects that have received particular interest recently, viz. the development of water-tolerant initiator/CTA immobilization methods and strategies toward substrate-independent “universal” attachment protocols. 4.2.1. Development of Water Tolerant Initiator Immobilization Methods. Environmental concerns have led to an increased interest in synthetic methods that do not require the use of organic solvents. Moreover, conjugation of biomolecules to polymers or solid substrates usually relies on reactions that can be performed under biologically relevant, i.e. aqueous conditions. One of the most promising methods to modify surfaces with initiators/CTAs in water is by aminereactive N-hydroxysuccinimide (NHS) ester intermediates commonly used in peptide/protein coupling.498 Balamurugan et al.499 modified amine-functionalized PMMA surfaces via NHS-2-bromo-2-methylpropionate coupling in phosphate buffer at pH 7.3 overnight at room temperature. Then, PNIPAM was grafted from PMMA surfaces to give 1174


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Scheme 7. Plasma Deposition of Allylamine Provides a Substrate Independent Method to Generate Surface Coatings that Can Be Further Modified with ATRP Initiators and Used to Grow Brushes by SI-ATRPa

a

Reprinted with permission from ref 530. Copyright 2011 Wiley-VCH.

attachment independent of substrate, or which are at least applicable to a broader range of substrates. One interesting biomimetic strategy that has been reported involves the use of barnacle cement as anchoring layer to allow attachment of ATRP initiator groups.516 Sweat et al.529 reported a nonbiomimetic approach that is based on the use of copolymers of GMA and p-(2-bromoisobutyloylmethyl)-styrene (BiBMS), which can be thermally cross-linked to form stable films for polymer brush growth. Furthermore, polyallylamine layers prepared via pulsed plasma deposition have also been used as a substrate-independent surface modification platform (Scheme 7).530−533 An elegant, one step introduction of ATRP initiators onto substrates obtained by plasma polymerization of ethanol and EBiB was developed by Coad et al.534 Yameen et al.530 introduced this strategy to graft polymer brushes via SI-ATRP from polymer substrates, such as PEEK, PET, PI, PP, and PTFE. Allylamine and comonomers can be polymerized in a plasma reactor on surfaces, followed by initiator/CTA immobilization via coupling to exposed amine groups. Coad et al.532 reported plasma polymerization of allylamine on silicon wafers, gold, perfluorinated PE-co-PP and multiwell microtiter plates and demonstrated that silicon wafers modified in this manner could be modified with a terpolymer macroinitiator containing carboxylic acid groups for subsequent SI-ATRP of PEGMEMA.531 Furthermore, they extended this methodology to produce gradient-grafted polymer brushes by moving mask plasma copolymerization.534 In this case, plasma copolymerization of EBiB and EtOH on a polymer substrate resulted in an ATRP initiator surface gradient, which was subsequently used to graft PDMAM and PPEGMEMA brushes. The same methodology was also applied to plasma copolymerize 1,7octadiene and allylamine, followed by grafting of BiBB to

modified DOPA can also be polymerized leading to similar polymer brush growth kinetics. The DOPA motif has been used to graft initiators/CTAs on silica,509,510 gold,510 AAO membranes,322,511 carbon nanotubes,114,505,512 “diamond-like” carbon films,513 nylon membranes,506,514 PS-b-P4VP membranes, 515 stainless steel,501,507,516,517 iron oxide,165,518 PVDF,519 PVC,475 halloysite nanotube lumen,520 multielement compound fertilizer521,522 and titanium.501,523 Initiator-functionalized DOPA has also been patterned on substrates via microcontact printing.355,524 Macroinitiators containing DOPA segments have also been designed for modifying a wide range of surfaces.434,525 Kuang et al.526 designed a bifunctional tripeptide bromide containing DOPA, lysine and an alkyl bromide that could be used to deposit initiators on metal oxides, silica, gold, PC, PE, PU, and even PTFE in water. In situ copolymerization of DOPA and initiator-modified DOPA led to colorless thin layers on PS particles527 and planar silica surfaces.364 SI-ATRP of HEMA from these surfaces followed by removal of the particles or planar substrate afforded polymer brush modified capsules, respectively, free-standing polymer brush films. Macroinitiators carrying DOPA-side groups have also allowed various substrates to be functionalized with ATRP initiators.525 Furthermore, macroinitiators have been designed incorporating DOPA and pyrene moieties, in which the latter strongly adsorb onto carbon-based materials through π−π interactions.434 Aside from DOPA, Pranantyo et al.,528 inspired by tea stains, have recently introduced the use of plant polyphenolic tannic acid (TA) modified with ATRP initiators as a substrate-independent anchor for the growth of antifouling and antimicrobial polymer brushes. In addition to dopamine chemistry, a number of other strategies have been developed that allow initiator/CTA 1175


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synthesize PHEMA gradients by SI-ATRP.533 Adsorption of polyelectrolyte macroinitiators represents another attractive strategy to immobilize initiators/CTAs, although they depend on the existence of opposite surface charge to exploit electrostatic interactions.13

confirmed by XPS, FTIR and AFM measurements that showed removal of the (carboxylic acid-bearing) brush from the gold substrate.540 The group also demonstrated that the mechanochemical scission was pH and ionic strength dependent and that it was also observed for the scission of Pt−S and Pt−Ag bonds.542 Degrafting of PAA chains grown via SI-ATRP from a mica543 or glass substrate252 has also been demonstrated to take place at pH ≥ 9.5 in a 10 mM NaCl solution.252,543 Lower pH and salt concentrations were insufficient to induce degrafting which could be monitored with the incorporation of a fluorescent dye into the polymer brush.252 Enomoto et al. studied the degrafting of PSS polymer chains from a range of polymer membranes to demonstrate that the observed degrafting was not due to a degradation of polymer into subunits, but indeed due to a loss of the entire chain from the substrate.544 An interesting consideration to bear in mind when studying the degrafting of polymer chains is the effect noted when a thiol-based initiator is used to perform SI-CRP from gold surfaces. At temperatures greater that 60 °C which used to be commonplace for SI-ATRP, significant desorption of alkanethiol SAMs were noted.545,546 However, in recent years, it has become commonplace to perform SI-ATRP/SI-SET-LRP under milder conditions and thus the desorption at elevated temperatures can be avoided. However, it is interesting to note that significant loss of SAMs occur even under ambient conditions when a copper bromide is present in the reaction solution.352 Work from Tang et al. shows that this is not due to radicals generated as a result of the cleavage of the C−Br bond of the surface bound initiator as the same desorption is noted for 11-mercaptoundecanol SAMs. However, the authors go on to show that the desorption can be minimized by using a CuCl catalyst (as opposed to a CuBr species).352 This does have repercussions for SI-ATRP as CuBr is the more active species and thus a compromise between grafting density and reaction rate may have to be reached for SI-ATRP from gold surfaces. While a range of studies on the degrafting of polymer brushes have been conducted, this is still a relatively unexplored field with many open, fundamental questions. Additional systematic studies could help to shed light on e.g. the kinetics of the process and lead to strategies that could enable to prevent or control degrafting. On the other hand, from a more fundamental perspective, the results summarized above also highlight the potential of SI-CRP as an alternative method to induce chain extension and mechanochemically activate polymers. As SI-CRP, in comparison to, e.g., ultrasound or flow fields, does not require an external force, it represents an addition to the polymer mechanochemistry toolbox to investigate the fundamental effect of mechanical deformation and chain stretching on the reactivity of polymers.

4.3. Stability and “Mechanochemical” Effects

Surface-grafted polymer brushes are generally considered stable, robust surface coatings due to a covalent bond tethering one chain end to the substrate. However, there have been recent reports on the degrafting of polymer chains from the underlying substrate induced by a large swelling of the grafted brushes.535 Degrafting of surface-tethered polymer chains was first observed by Deng and Zhu who studied the growth of hyperbranched polyglycidol (HPG) brushes from a selfassembled initiator monolayer on a gold substrate. As the degree of polymerization increased, the authors noted that past a critical point (where the brush interactions with the solvent were more favorable than the single covalent bond to the substrate), the polymers desorbed from the surface.536 Shortly thereafter, this phenomenon was observed for PPEGMA brushes grown via SI-ATRP from silicon and glass substrates. Since SI-ATRP of PEGMA results in lightly interchain crosslinked brushes, degrafting was observed as delamination of the thin polymer films from the underlying substrate. The authors noted that thicker and more densely grafted brushes degrafted to a greater extent than their thinner and sparse counterparts. Furthermore, while the degrafting was observed in cell culture media, it was not observed in pure water leading the authors to hypothesize that it was the osmotic pressure on the brushes that facilitates the degrafting.537 These findings were confirmed in a subsequent study, this time with PMAA, PHEMA, PPEGMA and PPEGMEMA brushes.538 It was shown that increasing the hydrophobicity of the initiator lead to increased stability of grafted PHEMA brushes in cell culture medium. Also it was demonstrated that the growth of a first, hydrophobic brush of PMMA or PHEMA prior to the SIATRP of MAA was found to significantly retard or prevent degrafting. Based on these observations it was proposed that the degrafting of hydrophilic brushes from silicon substrates involves hydrolytic cleavage of the Si−O−Si bond that links the ATRP initiator to the surface and/or of the ester/amide links in the ATRP initiating moieties, which is facilitated by solventinduced stretching of the surface grafted polymer chains. These mechanochemical effects and the implications on the stability of surface-grafted polymer brushes have also been addressed in several more recent reports. In one example, the introduction of a hydrophobic block of PS or PMMA was also shown to enhance the stability of silicon-grafted PSBMAM brushes in marine environments.539 In another example, a study by Bain et al. investigated attachment of an esterless ATRP initiator to a surface. In this case, the SI-FRP grown PDMAEMA brushes using the esterless initiator were shown to be more stable than SI-ATRP grown PDMAEMA brushes using a conventional [11-(2-bromo-2-methyl)propionyloxy] undecyltrichlorosilane (BMPUS) initiator,145 which supports the hypothesis that hydrolytic cleavage of ester linkages in the surface-tethered ATRP initiator contributes to the degrafting. Ma et al. in a series of reports have investigated the degrafting of POEGMA-co-PHEMA brushes from gold surfaces. The group showed that a thicker brush delaminated almost instantly (as measured by QCM) while a thinner brush remained intact on exposure to PBS.540,541 The observation was

5. PATTERNING STRATEGIES Patterned polymer brushes are both of fundamental interest to probe basic aspects of brushes such as swelling and friction properties but are also of practical relevance for applications such as controlling bioadhesion.143,547−550 As an example of the versatility of patterning when used in conjunction with other techniques described in this review, it is notable that patterned brushes can be used to control the motion of silica spheres through repulsive interactions, which can be tuned with pH,551 while combining patterning and thermoresponsive brushes has been shown to yield detachable cell-sheets with unidirectional alignment.143 In general there are two types of patterning 1176


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irradiation to convert azide groups on oligomeric initiators to nitrenes, which are capable of reacting with the hydrocarbons on the underlying polymer. This has been demonstrated with PET, PLA, PP, PE, PU, and PS substrates highlighting its versatility.562,568 Photomasked light from a commercial household lamp has also been used to generate CuI species in situ (from a solution of CuII) and therefore to only graft brushes in the area of an initiator-functionalized wafer exposed to light.136 In terms of top-down patterning, recent years have seen the use of photolabile groups being incorporated into polymer brushes.569−573 These groups can then be cleaved by UV through a photomask to generate selectively patterned surfaces. While the trend is to integrate photocleavable groups in the side chain of the brushes,569,570,572,573 incorporating the photocleavable group into the initiator allows the synthesis of polymer brushes, which can be detached from the substrate only in the area exposed to UV.571,574 While this is primarily achieved with specially synthesized monomers, photodegradation has also been demonstrated with POEGMA brushes that have the advantage of being derived from a commercially available monomer.575,576 In this case the POEGMA brushes were photodegraded to yield aldehyde groups for further postpolymerization modification. The selective photocleavage is a powerful technique as it affords surfaces that can selectively be functionalized postpolymerization.570−572,575,576 In a unique twist to this approach, Brown et al. used triflic acid generated from the photocleavage of PAGMA to catalyze the aciddeprotection of tBMA in a PPAGMA-b-PtBMA block copolymer brush.573 In addition to conventional UV light sources, laser-based methods such as multiphoton lithography represent a powerful alternative to pattern brushes in a top-down manner. This has been used to tune peptide density on a brush-grafted surface and thereby control adhesion and migration of fibroblasts.577

strategies: (i) bottom-up approaches in which the SI-CRP initiator or CTA is patterned onto the surface prepolymerization and (ii) top-down strategies in which the polymer brush is grown unpatterned from a substrate and later patterned postpolymerization. Tables 15 and 16 provide an overview of a broad range of polymer brushes that have been prepared by combining SI-CRP techniques with either bottom-up (Table 15) or top-down (Table 16) patterning strategies. The examples listed in Tables 15 and 16 are organized according to the substrate the brushes were grown from and the specific patterning methodology that was used. The classification of the different patterning methods in Tables 15 and 16 is consistent with that used by Chen et al.11 and Ducker et al.552 The five categories used in this review are (1) photolithographic techniques, including interference lithography, (2) E-beam lithography (3) scanning probe methods including dip-pen lithography, nanoshaving and nanografting, scanning near field, anodization and other electrochemical methods, (4) microcontact printing ,and (5) other patterning techniques which include colloidal, capillary force and nanoimprint lithography as well as Langmuir−Blodgett, laser ablation, and inkjet printing. For each of these different patterning techniques the next sections will highlight several selected examples. 5.1. Photolithography, Including Interference Lithography

Photolithographic techniques are widely used for generating patterned brushes, in particular on silicon surfaces. The feature size for this technique is limited to about half the wavelength of the light used.552 Photopatterning techniques can be used to either pattern a photoresist from which the brush derives its pattern or to directly pattern a surface or a brush. The use of photoresists has become relatively wellestablished since 2009. It has been used in a bottom-up manner to grow homopolymers and block copolymers from a variety of substrates553−557 and has also been exploited to pattern brushes in a top-down approach.365,366,558,559 There is particularly interesting work from Ober and co-workers who used this technique to produce free-standing polymer brushes, which provides an opportunity to study fundamental aspects of the brushes once they are cleaved from the substrate.365,366 The majority of patterned polymer brushes are obtained via direct photopatterning using a photomask to selectively destroy an initiator layer, selectively activating photoiniferters, or selectively generating a functionalizable layer. While in our last review, this was still a nascent field and each technique was used to a roughly equal extent, in the past few years the first technique of irradiating a layer through a photomask to generate a patterned initiator layer for bottom-up patterning is by far the most common method. This speaks to the simplicity of the approach, which is in principle applicable to any type of initiator (ATRP, NMP or RAFT) and can readily be effected with commercially available TEM grids as masks.322,549,551,560−565 This technique has also been shown to be feasible with visible light when used in conjunction with a photoredox catalyst (see section 2.3).134 Even with the relative simplicity of the photomasking technique, complex, threedimensional patterns exhibiting four distinct polymer compositions can readily be formed by exploiting the “living” nature of SI-CRP.356 Hierarchical patterns can also be achieved by combining photomasking with colloidal lithography affording an additional level of control over the surface properties.550,566,567 A new advance for bottom-up patterned brushes on polymer substrates is to apply a photomask during UV

5.2. E-Beam Lithography

Electron-beam (E-beam) lithography is attractive as it allows to generate patterns with feature sizes ranging from micrometers down to sub-100 nm or even sub-10 nm.552 E-beam lithography can be performed both using a mask or by directly “writing” using a focused electron beam. E-beam lithography was one of the most-frequently used patterning techniques in our previous review and continues to be a widely employed technology.578−580 E-beam lithography is frequently employed to bottom-up pattern resists thereby exposing the underlying surface for functionalization with an initiator and subsequent SI-CRP (Figure 9A).581−584 Alternatively, e-beam lithography can also be used to directly pattern polymer brushes postpolymerization.578−580 In this case, an unpatterned brush is first grown and then the e-beam is used to selectively degrade areas of the brush leading to the desired pattern in a top-down approach (Figure 9B). 5.3. Scanning Probe Based Techniques

Scanning probe microscopy (SPM) based techniques provide various possibilities to directly pattern initiator/CTA functionalized substrates or polymer brushes. With these techniques, feature sizes below 50 nm can be achieved.585,586 Over the past years, scanning probe lithography has seen widespread use for the preparation of patterned polymer brushes. One commonly used technique is dip-pen nanodisplacement lithography (DNL), which uses an ATRP initiator-coated AFM tip to displace a SAM of “inert” thiols from a gold surface and replace them with polymerization “active” alkyl halides. Thus, 1177


Table 15. Overview of Patterned Polymer Brushes Prepared by Combination of SI-CRP with Bottom-Up Patterning Techniques


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Table 16. Overview of Patterned Polymer Brushes Prepared by Combination of SI-CRP with Top-Down Patterning Techniques


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Figure 9. Schematic representation illustrating the preparation of patterned polymer brushes via e-beam lithography using (A) a bottom-up approach581 and (B) a top-down approach.579

Figure 10. Bottom-up fabrication of patterned polymer brushes from initiator-functionalized substrates prepared by microcontact printing.

used, where the AFM tip was used to selectively oxidize sections of an octadecyltrichlorosilane-coated silicon wafer.593,594 The thus oxidized regions were then functionalized, e.g. with a trichlorosilane ATRP initiator to selectively grow brushes in this region.594 Interestingly, feature sizes could be controlled by the applied voltage between surface and the AFM probe. Electrochemical methods have also emerged over the last years as a means to pattern brushes. This has been demonstrated with conductive AFM,595 however, the majority of the research has made use of scanning electrochemical microscopy (SECM). In this technique, the probe tip is used to electrochemically etch selected regions and has been demonstrated both in the bottom-up596,597 and top-down manner.598 Hauquier et al. used SECM both in indirect and direct fashion as a bottom-up patterning technique.596 The former was based on reductive debromination of aryldiazonium initiator by a radical anion electrogenerated at the microelectrode tip of SECM. However, the process was quite inefficient, which was hypothesized to be due to limited penetration of the anion species through the multilayer of initiator. More efficient debromination and better pattern resolutions were obtained when direct reduction with the microelectrode was carried out. Nevertheless, this method is limited to conducting substrates, as they have to be used as a working electrode. Ktari et al. used SECM to etch polystyrene brushes with Ag(II) generated by electrochemical oxidation of silver nitrite in dilute nitric acid. Ag2+ ions penetrate gradually the PS layers and oxidize PS brushes to form hydrophilic material having ca. 10% COOH terminations.

subsequent ATRP is only initiated from the areas where the AFM tip has deposited the initiator.587,588 A similar technique is nanoshaving, where inert molecules are also removed with an AFM tip, but instead of immediate replacement it is followed by backfilling with initiator solution.589 Alternatively, the AFM tip may also be used to “scratch” off a resist to selectively expose underlying surfaces with a thick initiator-bearing layer for subsequent ATRP, i.e., so-called molecular scratchcard lithography.590 DNL allows to control grafting density of tethered initiators, which can be useful for obtaining brush features of different heights with the same polymerization time.587 Higher initiator densities can be obtained by higher contact force applied by the AFM probe. An alternative method was exploited by Zheng and co-workers, who used DNL to control the spacing between initiator sites to vary the local grafting density and thereby chain conformation (stretched, semistretched, and collapsed). This in turn allowed tuning of apparent brush height allowing the researchers to gain remarkable control over the three-dimensional features that they could then fabricate.591 This was elegantly demonstrated in their translation of a bitmap image of the Mona Lisa to a gold substrate resulting in a 10 μm × 10 μm image of the da Vinci painting generated from PMETAC brushes with the greyscale derived from the spacing between initiator molecules. In a subsequent paper the same group extended the technique to a process called parallel-DNL in which a multicantilevered AFM was used to produce 18 nanostructures or complex bitmap images concurrently.588 SPM can not only be used to directly write (DPN) or scratch patterns but also represent a powerful tool to chemically pattern surfaces. Zapotoczny et al. used AFM assisted dip-pen nanolithography to form gold nanostructures with HAuCl4, which was locally reduced on the contact with previously hydrogenated silicon surface.592 The resulting features were then used for attachment of disulfide containing iniferter (dithiodiundecane-11,1-diylbis[4-({[(diethylamino)carbonothioyl]thioethyl}phenyl)carbamate]) for subsequent SI-CRP. In another example, scanning probe oxidation was

5.4. Microcontact Printing

Microcontact printing (μCP) represents a very powerful soft lithographic technique that uses soft elastomeric stamps (mostly based on PDMS) to transfer 2D patterns with feature sizes from 30 nm to 100 μm (Figure 10).11,599 Patterned polymer brushes can be obtained via μCP either by first printing a low molecular weight or polymer based initiator or CTA and backfilling the unpatterned areas of the substrate with 1181


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gradient polymer brush microstructures.604 Another interesting result was found when the PDMS stamp was applied with overpressure, swelled in toluene before application or treated with UV-ozone before inking with thiol initiator.605 This strategy extended the patterning available for the original PDMS stamp and allowed to obtain complex microstructures by careful adjustment of μCP parameters. Chen et al. have also demonstrated the facile formation of a polymer brush “anemone” by exploiting the phase separation of initiator and inert alkanethiols and μCP.606 Kelby and Huck have used patterning and substrate etching to fabricate free-standing polymer brushes, which can be used to quantify mechanical stresses in stimuli-responsive brushes.297 While the vast majority of papers employing μCP use a PDMS stamp to generate the patterns, a series of interesting advances in this area has been made by the Zauscher group who use a colloidal arrangement of PS spheres as a stamp.607,608 The process has been shown capable of producing simple, repeating patterns607 inherent to a self-assembled monolayer of microspheres as well as making more complex pattern by varying pressure605 as well as stamp movement604 during the stamping process.

a passive, i.e., nonpolymerization-active low molecular weight or polymer based initiator, or vice versa, followed by growth of the brush. This technique has been frequently applied to prepare a diverse range of patterned polymer brushes (Tables 15 and 16). In addition to its use for the bottom-up fabrication of structured polymer brushes, μCP has also been used to chemically pattern polymer brush films. To this end, the PDMS stamp was used to selectively functionalize areas of PPEGMA brushes with poly-L-lysine or poly-D-lysine in order to direct the growth of cells on the surface.477,600 While silicon and gold are most frequently used, μCP has also been used to prepare patterned brushes from a variety of new substrates including graphene,473 titanium434,525 and ITO.601,602 Hung et al. generated PTMPMA patterns on ITO substrates, by first using PDMS stamps soaked with noctadecylchlorosilane to block some part of the surface and then backfilling the nonprotected spots with (4-(2-bromo-2methyl)propionyloxy)butyltrichlorosilane ATRP initiator.601,602 This sequence was dictated by the lower vapor pressure of the first compound, which was limiting the resolution of generated features. Starting with the ATRP initiator with the higher vapor pressure resulted in migration of the initiator over modified surface and blurry features after the polymerization step. μCP has also been used in conjunction with emerging techniques such as eATRP, which was exemplified by Li et al.118 The authors used ω-mercaptoundecyl bromoisobutyrate as an ATRP initiator, which was transferred to a gold substrate with PDMS stamp. They could obtain well-defined patterns of not only PSPMA and PHEMA homopolymer brushes, but also more complex structures, such as cross-patterns, which were obtained in a two step printing approach. The patterns were also exposed to a second ATRP solution to demonstrate possibility to grow diblock copolymer brushes, e.g., P(HEMAco-SPMA). Interestingly, later Li and Zhou showed that the growth of patterned polymer brushes obtained via eATRP can be in situ followed by AFM.122 Dopamine-based initiators have also been used as μCP “inks” and allow to graft brushes from a wide variety of surfaces.127,355,524 Interestingly, this “universal” initiator can also be used to prepare patterns on top of polymer brushes leading to a stratified brush-on-brush architecture.355 Adding to the versatility of the dopamine initiator is the possibility for incorporating it into oligomeric macroinitiators which may then be used as μCP inks.434,525 Gao et al. patterned both graphene oxide and reduced graphene oxide grafting catechol- and pyrene-terminated macroinitiators prior to SI-ATRP of NIPAM, DMAEMA, SPMA, and METAC.473 They also used copolymers containing both of these functional groups to further enhance the affinity to graphene oxide surface. Finally, they demonstrated that μCP with pyrene-type macroinitiator can also be applied to create polymer brush patterns on reduced graphene oxide substrate. Likewise, Wei et al. used this type of cofunctionalized macroinitiator to generate patterns on Ti substrate using PDMS stamp prior to SI-ATRP of OEGMA.434 Wang et al. created patterned POEGMA and PDMAEMA brushes by using a monofunctionalized catechol-type macroinitiator.525 In terms of architecture, μCP has been used to generate complex, patterned polymer architectures such as hydrogels100,603 or using multistep μCP to generate three-dimensional patterns.128 The Zauscher group also developed dynamic microcontact printing by moving or jumping PDMS stamps over a substrate. This allowed to generate hierarchical or

5.5. Other Patterning Techniques

In addition to the techniques presented in the preceding sections, a variety of other methods has also been used to prepare patterned polymer brushes. One method that is frequently employed is colloidal lithography. In colloidal lithography, patterns are generated using a hexagonally close packed array of self-assembled monodisperse colloidal microspheres. Colloidal lithography has been extensively used to pattern brushes in a bottom-up manner,550,566,567,609 but has also been used for top-down patterning.610 Arrays of colloidal microspheres have been used to mask substrates prior to electrodeposition of CTA172 or evaporative deposition of SiOx.566 Authors have also used colloidal lithography in conjunction with reactive ion etching to fabricate complex architectures such as elliptical brushes609 and nanoposts.567 Nanoimprint lithography (NIL) is a technique for the preparation of nanoscale patterns by first dispensing a curable formulation on a substrate of interest, subsequent application of a mold and final curing the aligned resist.611,612 Authors used UV curing to overcome drawbacks of the typical thermal NIL.613 UV mediated NIL allows to pattern at room temperature, obtain higher throughput and easy optical and high precision alignment owing to transparent templates. This method has been utilized to pattern brushes both in the bottom-up and top-down manner.611,612 Benetti et al. used step-and-flash imprint lithography (SFIL), a UV-NIL variant, to fabricate PEGMA nanostructures (lines or pillars) of sub-100 nm range.611 Moran et al. used easy soft imprint nanolithography (ESINL) to UV-cure resist templates either on top of the initiator SAMs (bottom-up) or polymer brush (topdown) followed by etching of the nonprotected material by oxygen plasma and final lift-off of the resist.612 This allowed the authors to create line gratings with dimensions of 410−480 nm. Another interesting patterning strategy has been reported by Yan et al., who use a zinc wire as a sacrificial anode to derive patterns by the spatial distribution of the electrochemically generated catalyst in a system referred to as sa-ATRP (sacrificial anode-ATRP).120 The authors demonstrate its applicability to a wide range of monomers while using microliters of solution. 1182


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Scheme 8. Post-Polymerization Modification of a Poly(N-hydroxysuccinimide-4-vinyl benzoate) Brush with 1Aminomethylpyrene617

polymer brushes, and (8) (selective) chain end postpolymerization modification of polymer brushes.

Block copolymer micelle lithography is a versatile technique that allows to generate arrays of gold nanoparticles with defined particle sizes and interparticle distances. These arrays of gold nanoparticles have been used by Wang et al. to tether thiol modified ATRP initiators and subsequently produce nanopatterns of PDMAEMA brushes, which were used to study protein adsorption on the nanoscale. Emmerling et al. have used inkjet printing to deposit droplets of HCl or H2SO4 onto an ATRP initiator modified surface. The acid locally renders the ATRP initiator inactive and allows the growth of microstructured PMMA brushes.614

6.1. Postpolymerization Modification of Ester Side-Chain Functionalized Polymer Brushes

Polymer brushes that incorporate ester side-chain functional groups provide various possibilities for PPM. One possibility, which will be discussed in section 6.2, is hydrolysis of the ester bond to afford carboxylic acid side chain functional polymer brushes. Another very attractive and versatile approach relies on the use of polymer brushes that incorporate active ester bearing monomers such as pentafluorophenol 18 5,1 89, 615 and NHS186,616−618 (Scheme 8). These active ester-based or containing brushes are a very versatile platform that can be readily modified with a range of amines. Table 17 provides an overview of side-chain functional polymer brushes, which have been obtained by PPM of active ester containing polymer brush precursor films. Work from our own group has shown that poly(pentafluorophenyl methacrylate) (PPFMA) brushes prepared by S-RAFT polymerization are capable of near-quantitative PPM by a range of sterically unhindered aliphatic primary amines.189 However, when sterically hindered primary amines or secondary amines were used, longer reaction times were required to achieve high degrees of functionalization and when aniline was used as the nucleophile, no functionalization was observed. Parallel work by Arnold et al. investigated the reactivity of poly(pentafluorophenyl acrylate) (PPFPA) toward three amines with strong UV absorbances allowing the authors to follow the functionalization with UV−vis spectroscopy.617 The authors found that the reaction rate constants for the three amines, 1-aminomethylpyrene (AMP), 1-aminopyrene (AP), and bis(2,2′-bipyridine)-(5-aminophenanthroline)ruthenium bis(hexafluorophosphate) (RuA) were as follows: 2.46 × 10−1, 5.11 × 10−3, and 2.59 × 10−3 s−1, respectively. This shows that the aliphatic amine (AMP) was 2 orders of magnitude more reactive toward the PFPA ester than the aromatic amines AP and RuA. However, it is important to note that the authors demonstrated that even with AP and RuA the UV absorbances plateaued after 1 h (while the AMP reaction

6. POSTPOLYMERIZATION MODIFICATION OF POLYMER BRUSHES Postpolymerization modification (PPM) is a powerful technique to introduce functionality into polymer brushes. This is often employed by researchers to incorporate functionalities that are nonorthogonal to the SI-CRP techniques used to fabricate the brushes. In combination with some of the patterning techniques presented in the previous sections, PPM can be used to prepare chemically patterned polymer brushes. The past years have seen a tremendous increase in the use of PPM for the preparation of functional polymer brushes. PPM can either be used to effect changes in the side-chain or the end-group of the polymer brush or both. Each of these modifications can be performed in an almostinfinite variety of ways with various functional groups for a wide range of applications. In an attempt to discuss the various examples in a coherent manner, this section is divided into several parts: (1) postpolymerization modification of ester sidechain functionalized polymer brushes, (2) postpolymerization modification to yield acid side chain functionalized polymer brushes, (3) postpolymerization modification of carboxylic acid side-chain functionalized polymer brushes, (4) postpolymerization modification to yield quaternized polymer brushes, (5) postpolymerization modification of hydroxyl side-chain functionalized polymer brushes, (6) postpolymerization modification of poly(glycidyl methacrylate) polymer brushes, (7) postpolymerization modification of other side-chain functional 1183


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Table 17. Overview of Side Chain Functional Polymer Brushes that Have Been Prepared by Post-Polymerization Modification of Active Ester Based Precursor Brushes

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reached a plateau after ∼15 s) suggesting that quantitative functionalization of the PPFPA brush with aromatic amines was achieved. This is in contrast to experiments with PPFMA brushes, where quantitative active ester group conversion upon PPM with aromatic amines could not be achieved.189 The reaction conditions that were used in the two studies (80−800 mM189 cf. 55 mM617) are analogous to each other suggesting that the pentafluorophenyl acrylate brush is far more reactive than the pentafluorophenyl methacrylate. The methacrylate version of PFPA, however, appears more stable to hydrolytic degradation and has been successfully polymerized with ATRP and postmodified with sterically hindered primary amines to near-quantitative proportions as determined by XPS.615 Thus, there is a trade-off in the choice of PPFPA and PPFMA as a substrate for PPM. The former is more reactive toward functional amines while the later is more hydrolytically stable. The above finding suggests that PPFPA brushes are a very attractive platform for PPM. However, a complication is that the polymerization of the monomer appears to be incompatible with ATRP. Indeed Arnold et al. had to use an azo initiator to effect their polymerization and speculated that the monomer degrades during ATRP yielding an acid, which poisons the

ATRP ligands resulting in brushes less than 5 nm.617 Choi et al. have prepared PPFPA brushes via S-RAFT and successfully modified the brushes with sterically hindered primary amines.185 In addition to pentafluoroesters, another class of active esters that has been used for the postpolymerization modification of polymer brushes are NHS esters. Arnold et al. e.g. studied the postpolymerization modification of P(NHS4VB) brushes and noted that reaction of AMP toward P(NHS4VB) proceeded with a rate constant of 3.49 × 10−3 s−1, which is 2 orders of magnitude lower than PPFPA brushes.617 Further, the P(NHS4VB) brushes could not be functionalized with aromatic amines confirming their lowered reactivity toward active esters. There have, however, been reports of its functionalization with long chain primary amines618 as well as with new methylene blue,616 a sterically hindered aromatic secondary amine (although the last two examples were not quantified and the reactions conducted at harsher reaction conditions). 1186


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Scheme 9. Synthesis of Poly(acrylic acid) Brushes Grafted from Gold Surfaces via Post-Polymerization Modification of (A) Poly(t-butyl acrylate)623,626 and (B) Poly(sodium acrylate) Brushes648

6.2. Postpolymerization Modification to Yield Acid Side Chain Functionalized Brushes

Postpolymerization modification of carboxylic acid side-chain functionalized brushes provides approaches to tune the responsiveness as well as surface properties of these thin films. The pH response of PMAA brushes, for example, can be tuned over a wide range of pH values by PPM with a variety of different amino acids (Scheme 10).647 While a glutamic acidmodified brush shows a response similar to that of an unmodified PMAA brush, a brush modified with 4-aminophenol has a response curve shifted to higher pH due to the higher pKa of the phenolic residues. Not only can PMAA brushes be utilized to generate pH responsive brushes, but also as precursors for postpolymerization modification with 3aminophenyl boronic acid toward glucose-responsive hydraulic flow sensors.665 A variety of carboxylic acid side-chain functionalized brushes including PCAA,557 PCBMA,666 PCBAA,353,354,667 PAA,620,621 and PMAA655 brushes very efficiently prevent nonspecific protein adsorption, which makes them very attractive platforms to generate surfaces that can mediate specific cell adhesion or which can be used for bioanalytical applications. PAA brushes grafted from polyaramide membranes and postmodified with a variety of hydrophilic and hydrophobic alcohols have been investigated with regards to their ability to resist protein fouling. While the resistance to protein binding could be correlated with the surface hydration energy, the release of bound protein was found to be related to surface energy.657 Cell adhesive surfaces have been prepared by postpolymerization modification of carboxylic acid functionalized brushes with, e.g., collagen,656 gelatin,625,658 or RGD.651 In a number of other studies, carboxylic acid functionalized brushes were postmodified to develop bioanalytical interfaces. For example, postpolymerization modification of PCBMA-grafted iron oxide nanoparticles with anti-β-hCG gave greatly improved results in an hCG detection assay at low concentrations (≤15 mIU/ mL)666 while functionalization of PCBAA brushes with an antiTSH antibody allowed antigen detection at a level of 1 ng/ mL.667 Similarly, tuning the ratio of MES to DEAEM in a PMES-co-PDEAEM brush allowed to minimize nonspecific protein absorption while covalent immobilization of an antiTNT analogue on the MES residues allowed TNT detection of 5.7 pg/mL.668 While brushes grafted at a higher density are more effective at preventing nonspecific adhesion of cells and proteins, it is a trade-off between accessibility to postfunctionalization. This is exacerbated by immobilizing large biomolecules such as BSA when a compromise is required between nonfouling properties and functionalizability.621 Two-layer bimodal brushes provide an opportunity to overcome the opposing requirements that nonfouling properties and high

Direct polymerization of acid-functionalized monomers is difficult with ATRP (which in itself is the most widely employed technique for SI-CRP).619 As a consequence, acid side-chain functional brushes are often prepared via SI-CRP of an appropriate precursor monomer followed by a postpolymerization modification to afford the corresponding acid sidechain functionalized polymer brush (Scheme 9). Table 18 provides an overview of different acid side-chain functionalized brushes that have been obtained via postpolymerization modification. The monomers most frequently used to prepare acid sidechain functional polymer brushes are tert-butyl acrylate252,358,423,486,543,620−635 and methacrylate.184,209,551,636−643 While trifluoroacetic acid is commonly used for the cleavage of tert-butyl groups, hydrochloric acid, p-toluenesulfonic acid and trimethylhalosilanes have also been used. Other routes to acid side chain functional poly(meth)acrylic brushes include acid hydrolysis of poly(ethyl acrylate)644 or thermolysis of PtBA.645 An interesting alternative to the deprotection of t-butyl ester (or other side chain protected) polymer brushes is the direct SI-CRP of sodium salts of acrylic acid (sodium acrylate, NaAc)646−651 or methacrylic acid (NaMA)538,652−658 followed by mild PPM to yield the corresponding acidified brushes. Another approach worth mentioning is the photocleavage of side chain protected precursor polymer brushes. This has been demonstrated by Kumar et al.659 and by Cui et al., who both used 4,5-dimethoxy-2-nitrobenzyl ester protected precursor brush films.569 In addition to poly(meth)acrylic based acid sidechain functionalized brushes, PPM has also been used to generate acid side-chain functionalized PS brushes. This can be accomplished either by treating PS based brushes with sulfuric acid (fuming sulfuric acid or sulfuric acid in the presence of phosphorus pentoxide)660−662 or mild acidic treatment of poly(sodium 4-styrenesulfonate).663,664 Carboxylic acid side-chain functionalized polymer brushes are very useful platform for further postpolymerization modification reactions, as will be presented in the next section. 6.3. Postpolymerization Modification of Carboxylic Acid Side-Chain Functionalized Polymer Brushes

Carboxylic acid side-chain functionalized polymer brushes represent a versatile platform for postpolymerization modification. Table 19 presents an overview of side-chain functionalized brushes that have been obtained by PPM of carboxylic acid side-chain functionalized precursors. 1187


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Table 18. Overview of Acid Side Chain Functional Polymer Brushes that Have Been Prepared via Post-Polymerization Modification

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antibacterial properties.223,239,459,519,669−673 Table 20 presents an overview of quaternized polymer brushes that have been obtained via various postpolymerization modification strategies. Quaternization postpolymerization modification is overwhelmingly conducted on PDMAEMA brushes149,239,247,459,504,505,519,561,669−672,674−683 and most frequently involves the use of methyl iodide to form a pendant quaternary ammonium salt (Scheme 11).149,459,460,504,505,561,674−681 However, other approaches have also been reported such as the quaternization of PVAnb-PANI673 and P4VP684 brushes with hexyl bromide, the quaternization of PVBC with tertiary amines203,223 and the quaternization of PDMAEMA with 1,3-propane sultone.685 One interesting study was conducted by Ö zçam et al., who quaternized PDMAEMA brushes with alkyl bromides of varying chain lengths and noted that alkyl chain length is directly proportional to the antibacterial activity of the grafted brush. In this case, the authors noted that the number of colony forming

capacity biomolecule functionalization pose on grafting density. These brushes have been shown to have lower fouling and higher antigen detection than single layer brushes.353,354 This was demonstrated by preparing zwitterionic dual-functional PCB brushes both via SI-ATRP (with an intermediate step of initiator passivation to achieve two-layer brushes)353,354 and SIPIMP354 and high antibody immobilization, which besides increased detection sensitivity, showed potential for applications in diagnostics to medical coatings. Finally, postpolymerization modification of PAA brushes with a fluorescent label has also been instrumental to allow in situ monitoring of the degrafting of polymer brushes by real-time total internal reflection fluorescence microscopy.252 6.4. Postpolymerization Modification to Yield Quaternized Polymer Brushes

Quaternization reactions are widely used for the postpolymerization modification of polymer brushes. Often quaternization reactions are performed to endow polymer brushes with 1190


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Table 19. Overview of Side Chain Functional Brushes that Have Been Obtained by Post-Polymerization Modification of Carboxylic Acid-Side Chain Containing Precursors

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overview of side chain functionalized polymer brushes that have been prepared via postpolymerization modification of hydroxyl functionalized precursors. Often this first postpolymerization modification reaction is followed by a second reaction to introduce the desired functionality onto the brush. From a synthetic point of view, postpolymerization modification reactions of side chain hydroxyl functionalized brushes can be roughly divided into three main categories (Scheme 12).549,687,717−721 The first class of reactions can be considered direct modification reactions, which includes coupling of e.g. alkyl halides,687 organosilanes,688 aromatic halides687,722,723 and isocyanates.724,725 A second class of reactions involves activation of the side chain hydroxyl groups with, e.g., NPC, CDI, DSC, DIPC/DMAP and subsequent reaction of the side chain activated brush with an amine or carboxylic acid. This approach is used for the coupling of biomolecules such as peptides due to the mild reaction conditions and orthogonality to other amino acid functionalities besides amines. The third group of postpolymerization modification reactions are those that involve the transformation of the side-chain hydroxyl groups into aldehyde functionalities. This has been accomplished e.g. using pyridium chloroformate726 or by reacting the hydroxyl group with DMSO thereby yielding an aldehyde group.727 Photochemical approaches have also been used to modify hydroxyl side chain functional polymer brushes. For instance,

units decreased with increasing chain length from butyl bromide > propyl bromide > ethyl bromide.459 In an another study, PDMAEMA brushes postmodified with beta-propiolactone to yield polycarboxybetaine brushes provided surfaces with improved resistance to nonspecific protein adsorption and platelet adhesion.686 In addition to imparting antibacterial properties, postpolymerization quaternization reactions are also used to prepare brushes that can template the growth of nanoparticles such as Au561 and Pd.504 Finally, quaternized PDMAEMA brushes have been shown to have tunable hydrophobicity based on the counterions, with nitrate counterions providing a more hydrophilic brush and Tf2N− counterions forming a more hydrophobic brush,677 to bind and detect femtomolar concentrations of DNA681 as well as to cross-link PDMAEMA brushes with diiodides.674 6.5. Postpolymerization Modification of Hydroxyl Side-Chain Functionalized Polymer Brushes

Polymer brushes that present side chain hydroxyl groups represent an extremely diverse platform for postpolymerization modification. The hydroxyl group is very versatile and can be used for a wide range of postpolymerization modification reactions involving, for example, anhydrides,169,260,322,459,516,594,611,687−695 carbonates,477,550,600,609,687,696−703 acid halides,527,688,689,704−714 or carboxylic acids.181,473,570,572,715,716 Table 21 presents an 1194


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multifunctional organosilanes were incapable of penetrating the brush due to steric hindrance and side-reactions while acyl chlorides were more likely to penetrate the brush and yielded a high proportion of modified PHEMA groups. An interesting report that illustrates the importance of the need to carefully tune the postpolymerization modification reaction conditions for a particular application was published by Lane et al., who functionalized PHEMA brushes with horseradish peroxidase as a model enzyme.696 The authors noted that when a higher concentration of DSC was used to activate the side chain hydroxyl groups, the bound enzyme lost some its catalytic activity. The authors attributed this to the binding of multiple lysine residues of the enzyme to the PHEMA brushes. The resulting structural change of the enzyme lowered its catalytic activity, which was not noted when the DSC concentration was lowered. In a very extensive study, Trmcic-Cvitas et al. screened a variety of coupling reagents and reaction conditions for the immobilization of streptavidin on POEGMA brushes.687 The authors found that DSC coupling was the most efficient method of postpolymerization modification with high levels of functionalization also noted for cyanuric chloride, carbonyldiimidazole and triflic anhydride. Further, the researchers also compared levels of functionalization of brushes with differing lengths of side-chains i.e. PHEMA vs PPEGMA-360 vs PPEGMA-526 and found that while PHEMA brushes afforded streptavidin surface densities of 1.0 μg/cm2, the POEGMA brushes only resulted in streptavidin surface concentration of 190 ng/cm2 due to the lowered DSC functionalization of the longer side-chains. Another example of streptavidin immobilization on hydroxyl functional groups of polymer brushes was carried out generating aldehyde groups on the PDHPA brushes that were obtained by deprotection of the PDMDOMAM precursors.559

the grafting of the photoreactive 2-hydroxy-2-methyl-1-(4vinylphenyl) propan-1-one (HAK) monomer via SI-NMP has been reported. Postpolymerization modification of the resultant brush was effected by the photogeneration of a radical on the side-chain of the brush upon irradiation with an LED light. This radical was subsequently trapped by a range of functional nitroxides present in the irradiated chamber.728 Postpolymerization modification of hydroxyl side-chain functional brushes is also often used as a first step to prepare more complex brush architectures. The hydroxyl side chain functional groups in PHEMA brushes, for example, have been used as an initiator for the ring-opening polymerization of εcaprolactone to form grafted bottle brush polymers.729,730 Functionalization of PHEMA and PPEGMA brushes with BiBB provides access to bottle brush polymers by ATRP.527,705−707,711−713 PHEMA brushes have also been explored as an effective macroinitiator after postmodification to incorporate a Grubbs catalyst. Polymer growth via ringopening metathesis polymerization from the resulting surface was shown to be significantly enhanced when compared to a film grown from a SAM-modified surface.709 Some efforts have also been made to study the influence of grafting density and film thickness on the postpolymerization modification of hydroxyl side chain functional polymer brushes. In one example, PHEMA brushes were modified in a two-step process involving activation with NPC followed by reaction with different deuterated amino acids viz. d-3 serine and d-10 leucine.720 Neutron reflectometry indicated that with a sterically bulky leucine, lowering the grafting density led to a greater level of functionalization beyond the top 200 Å of the polymer brush, while with the less sterically hindered serine the degree of functionalization was not dependent on grafting density. UV−vis spectroscopy, however, also revealed a nonuniform distribution of NPC groups in the activated PHEMA brushes, which adds to the brush thickness and grafting density as well as the nature of the amino acid as

Scheme 10. Post-Polymerization Modification of a Poly(methacrylic acid) Brush with Various Functional Amines (4Aminophenol, Glutamic Acid, and o-Phosphorylethanolamine) Using EDC Coupling Chemistry647

6.6. Postpolymerization Modification of Poly(glycidyl methacrylate) Brushes

variables that influence the final outcome of the postpolymerization modification process. Arifuzzaman et al. grew PHEMA brushes of uniform grafting density and modified them with a range of fluorinated organosilanes, acyl chlorides and trifluoroacetic anhydride.688 The brushes were studied with a range of techniques and it was found that the spatial distribution of the fluorinated moieties depended on the size of the modifying group, its reactivity and the spatial restrictions of the brush. For example, bulky and

In contrast to the preceding sections, which focused on a range of monomers that present a specific modifiable functional group, this section exclusively discusses the post polymerization modification of poly(glycidyl methacrylate) (PGMA) brushes. PGMA brushes are a very versatile platform for postpolymerization modification reactions and have been functionalized with a broad range of small molecules,731,732 macromole1195


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Table 20. Overview of Quarternized Polymer Brushes Prepared via Post-Polymerization Modification

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Scheme 11. Preparation of a Poly(2-(methacroyloxy)ethyl trimethyl ammonium chloride) Brush via Post-Polymerization Quaternization of a Poly(N,N-dimethylaminoethyl methacrylate) Precursor561

cules,733,734 biomolecules,731,732,735−743 and nanoparticles744,745 (Table 22). A common approach is to modify PGMA brushes with mono-,746−748 di-,735,749−752 tri-,753 or tetra-functional amines (Scheme 13).754 This either allows direct incorporation of the desired functionality590,736−738,742,743,746,754,755 into the polymer brush or provides a handle for secondary modification onto the now-pendant amine group.735,752 In a series of papers, Arica and co-workers used this approach to functionalize PGMA brushes with a range of amines including hydrazine,756−758 ethylenediamine,759 agmatine,760 and N,N,N′,N′-tetraethyldiethylenetriamine.761−763 This was done, in most cases, to subsequently immobilize a range of biomolecules such as invertase,757,758,764 lipase,756,761,763 serum albumin,760 catalase,762 protein L,765 papain,766 anti-E. coli,759 and antiSalmonella759 antibodies. A caveat in the modification of PGMA brushes with multifunctional amines is that a certain amount of cross-linking is to be expected since the resulting secondary amines can react further with unconverted epoxide groups. Indeed cross-linking has also been observed even when monofunctional primary amines are used to functionalize the epoxide groups.732,767 In addition to postpolymerization modification with amines, a number of other reactions has also successfully been used to modify PGMA brushes. One interesting example is to react the epoxide groups with sodium azide, which allows further functionalization of the brush with a range of alkynes.768−770 Alternatively, hydrolysis of the epoxide ring to yield two pendant hydroxyl groups (suitable for further postpolymerization modification) is also an often-used modification.755,771−775 PGMA may also be modified with an acid-functionalized alkyl bromide to yield a macroinitiator for bottle-brush synthesis776 or functionalized with an alkoxysilane-functionalized amine to generate macroporous silicas via a sol−gel process.777

metal nanoparticle immobilization and formation and other functionalization reactions. Dimethyl acetal protected PMAIGlc,778 PMAIGal,779 and PDMDOMAM559,780 brushes have been deprotected under acidic conditions to yield the corresponding hydroxyl side chain functional brushes. Acetate protected PAAETAM brushes have been deprotected using 25% sodium methoxide in methanol to afford carbohydrate functional brushes that showed very low protein adsorption against BSA and fibrinogen.272 On the other hand, acidic hydrolysis of side chain silanol functional PTMSPMA670 and PIPSMA781 brushes has been used to introduce cross-linking. In another study, thiol side chain functional brushes were obtained by deprotection of a P(NIPAM-co- N-acryloyl-S-benzyl-L-cysteine) precursor film, which was subsequently derivatized with aspartic acid.278 Amine functionalized brushes have been prepared by deprotection of phthalimide residues on P(PEGMA-r-VBP) brushes,264 by hydrolysis of formamides on PVFAM brushes,782 by acid hydrolysis of BOC protected PBOC-AEMA783 and PNBocHPMA784 brushes or by photodeprotection of PNVOCMA brushes.785 Maleimide side chain functional brushes have been obtained by a thermally induced retro Diels−Alder reaction from a copolymer brush that incorporated a furan-protected maleimide functionalized methacrylate monomer.786 Another broad class of postpolymerization modification reactions are those that involve nucleophilic addition or substitution reactions with an appropriate side-chain functionalized polymer brush. Azlactone side chain functional polymer brushes obtained by SI-ATRP copolymerization of poly(ethylene glycol) methyl ether methacrylate and 2-vinyl-4,4dimethylazlactone have been used for the immobilization of thymine PNA787 and folic acid.788 Surface RAFT copolymerization of N-isopropylacrylamide and acrolein affords aldehyde side chain functional polymer brushes which have been used to immobilize BSA.163,559 Aldehyde functional polymer brushes have also been obtained by successive modification of poly(2chloroethyl acrylate) precursors, which were then used to attach laccase.464 Amino side chain functional P(APMA-coDMA) brushes have been treated with 3-maleimidopropionic acid N-hydroxysuccinimide to introduce maleimide functionalities that were subsequently used to couple KRWRIRVRVIRKC peptide,789,790 dansyl cysteine,790 and mercaptoethanol.790 Masuda et al. modified side chain amino functional poly(NIPAM-co-NAPMAM) brushes with a succinimidyl [Ru(bpy)3] derivative to prepare self-oscillating polymer

6.7. Postpolymerization Modification of Other Side-Chain Functional Brushes

In addition to the polymer brushes that have been discussed in the preceding sections, there is a broad variety of other sidechain functional polymer brushes that have also been used as substrates for postpolymerization modification reactions. These brushes are listed in Table 23. The examples in Table 23 are categorized in five broad groups of postpolymerization modification reactions, viz. deprotection reactions, nucleophilic reactions, Cu-catalyzed azide−alkyne cycloaddition (CuAAC), 1198


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Table 21. Overview of Reactions that Have Been Used to Modify Hydroxyl Side Chain-Functionalized Polymer Brushes

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Scheme 12. Three Examples of Post-Polymerization Modification of a Hydroxyl Side Chain Functionalized Polymer Brush with (A) Pentafluorobenzoyl Chloride,688 (B) GGGRGDS Peptide,549,1577 and (C) 16-mer Probe Oligonucleotides727

brushes.791 Finally, amine functional polymer brushes that incorporate 2-aminoethyl methacrylate have been used to immobilize Staphylococcal Protein A (using a tyrosinase mediated process)792 or to couple the Ac-HWRGWVA peptide under the action of HATU.429 Copper-catalyzed azide−alkyne cycloaddition (CuAAC) reactions are a third group of reactions that are frequently used for the postpolymerization modification of polymer brushes. These postpolymerization modification reactions can be performed using either alkyne or azide functionalized polymer brushes and the corresponding reagents. Polymer brushes that incorporate side chain azide110,111,793−796 or alkyne774,797,798 groups can be obtained via SI-CRP of a variety of methacrylate,110,111,774,793,794,797,798 acrylamide,795 and styrene derivatives.796 Alkyne and azide functional brushes have been successfully used to couple small molecules,793,796,797 macromolecules,774,798 oligomers,110,111,793 DNA sequences,110,111 sugars797 and ferrocene (Scheme 14).794 Postpolymerization modification of azide functional brushes with trifunctional alkynes has been used to introduce crosslinking.774,795 In addition to serving as templates for a variety of postpolymerization modification reactions, polymer brushes are also extensively used as precursors to or templates for the attachment of metal complexes or as templates for the preparation or direct immobilization of metal nanoparticles.

One example for the direct immobilization of nanoparticles is that of Au nanoparticles, which were immobilized via electrostatic interaction on SI-ATRP grown PDMAEMA brushes.799,800 Along the same lines, 3-mercaptopropionic acid stabilized CdSe quantum dots were immobilized in PDMAEMA brushes prepared via S-RAFT.149 Often polymer brush nanoparticle or quantum dot composite films are obtained via reduction of appropriate precursor salts. One strategy to obtain polymer brush films that incorporate metal salts is the polymerization of appropriate metal-containing (methacrylate) monomers.488,801 Specific examples include the SI-ATRP of cadmium488 and lead dimethacrylate801 followed by treatment with H2S to generate the nanoparticle hybrids. Instead of using metal containing monomers, another, more frequently used approach to metal salt loaded brushes, involves the use of appropriate polymer brush films to entrap suitable metal precursor salts. In particular, both quaternized and nonquaternized SI-ATRP grown PDMAEMA brushes have been used as templates for the immobilization of Ag/Pt802 and Au561,610 ions, which were converted to the corresponding nanoparticles and thin films via simple reduction reactions. Other polymer brushes grown via SI-ATRP and used for the immobilization of the metal salts on the side chains are PAM,803 PSPMA804 and PMETAC brushes.804 While the PAM brushes were used to entrap AgNO3, which was subsequently 1204


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Table 22. Overview of Post-Polymerization Modification Reactions that Have Been Used to Derivatize PGMA Brushes

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Scheme 13. Post-Polymerization Modification of a Poly(glycidyl methacrylate) Brush with 1,5,7-Triazabicyclo[4.4.0]dec-5ene746

6.8. (Selective) Chain End Postpolymerization Modification of Polymer Brushes

reduced to Ag nanoparticles in the presence of LiAlH4, PSPMA and PMETAC brushes loaded with HAuCl4 and Pd(NH3)4Cl2 were treated with NaBH4 to generate the corresponding nanoparticles. P4VP brushes have been loaded with Cu2+ to generate antibacterial brushes805 and methyltrioxorhenium(VII) to prepare catalysts for the epoxidation of soybean oil.806 Finally, salen containing copolymer brushes have been used to bind Co3+ and the corresponding polymer brush metal complex film subsequently used to catalyze ring opening of epoxides.807 In addition to the four categories mentioned above, there are a number of other approaches that are worth mentioning as well. A first example are noncovalent postpolymerization modification approaches. Adamantyl-functionalized poly(acrylate) brushes have been used to attach β-cyclodextrinbearing liposomes.290 Second, reversible radical crossover exchange postpolymerization modification with nitroxide functionality forms another type of dynamic covalent bond possessing polymer brushes. For example, the oxidation of grafted poly(2,2,6,6-tetramethylpiperidin-1-oxyl-4-yl methacrylate) (PTMPMA) brushes on PS microspheres with mchloroperoxybenzoic acid yields nitroxide-radical bearing brushes for radical organic batteries.601,602,808−810 Nitroxidebearing polymer brushes have also been synthesized by Sato et al., who demonstrated that these brushes could be postfunctionalized with nitroxide-bearing free polymers to reversibly form bottle-brush polymers.811,812 A final example is the use of thiol−ene radical addition to tether mercaptosuccinic acid to the pendant allyl groups of PAMA brushes which were grafted via S-RAFT from hydroxyapatite nanocrystals and subsequently used to incorporate of cisplatin.224

This final section discusses chemistries that are used to modify the chain-ends of polymer brushes prepared via SI-CRP. Table 24 presents an overview of different approaches that have been used to modify the chain ends of polymer brushes obtained via SI-ATRP, S-RAFT, and SI-PIMP. One of the most common reasons to postmodify chain ends is to deactivate them. This is either done to introduce functional groups for further chain end functionalization reactions, to indiscriminately remove the end groups184,209 or to selectively deactivate a small proportion of them.353,354,646 The latter allows the generation of two layer bimodal brushes via a subsequent polymerization step. End group modification has also been reported, in which a deactivator was used to preserve active end groups that were subsequently used to reinitiate polymer brush growth. This has been demonstrated with the addition of tetraethylthiuram disulfide to SI-PIMP-grown brushes, once again to obtain two layer bimodal brushes.354 The chain ends of polymer brushes grown via SI-ATRP can be deactivated by treatment with SnBu3H or by reaction with NaN3. Chain end deactivation with NaN3 is attractive as it replaces the alkyl halide with an azide functionality, which provides a versatile platform for a wide range of azide−alkyne cycloaddition chemistries to introduce further functionality (Scheme 15).813 Azide end-functionalized polymer brushes have been modified with a range of alkyne modified small molecules, 106,814−817 oligomers, 818,819 and macromolecules819,820 under CuAAC conditions. In addition to reactions with NaN3, the alkyl bromide end group of polymer brushes prepared via SI-ATRP has also been converted into amines via 1208


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Table 23. Overview of Post-Polymerization Modification Reactions that Have Been Used to Post-Modify Side ChainFunctionalized Polymer Brushes Other than Those Presented in Tables 17−22

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the Gabriel synthesis.821−823 Alternatively, the alkyl bromide chain end can be treated with a variety of nucleophiles to directly introduce the desired functionality.821−823 This approach has been used to modify polymer brush chain ends with, e.g., pyrene,824 TREN,825 naphthalene,710 cysteamine,113 and collagen,826 Chain ends of polymer brushes grown by S-RAFT can be deactivated by reaction with AIBN.184,209 Most often, however, chain ends of polymer brushes obtained via S-RAFT are converted into a thiol groups either via aminolysis or reduction reactions (Scheme 16).139,142,161,165,174,201,225 A last method used to modify chain ends of S-RAFT grafted polymer brushes is amidation of carboxylic acid chain end group which is introduced by CTA.156 In this part, carboxyl acid end groups of PEGMEMA brushes were functionalized with biotin molecules via an EDC/NHS coupling reaction. End group modification of SI-PIMP-grown brushes can be carried out either via hydrolysis of morpholine dithiocarbamate (MDC) groups to the thiol groups782 or transforming radical chain ends to amines which can be coupled further with carboxyl modified quantum dots.354,827 Accurately and quantitatively monitoring the progress and outcome of chain end postpolymerization reactions is challenging due to the low surface concentration of chain ends. As they are UV-active, removal/displacement of RAFTchain ends can sometimes be monitored spectroscopically. Alternatively, the incorporation of fluorescent moieties (e.g., pyrene) in the reagents that are used to deactivate or modify chain ends also provides semiquantitative insight into chain end functionality.225,710,824 Another technique to monitor the modification of polymer brush end groups is

XPS,106,113,201,813,825 which often indicates complete conversion (for example by the disappearance of the Br 3d peak and/or appearance of the azide N signal in ATRP- or SET-LRPprepared brushes106,813,825). Another technique used for monitoring functionality of the end groups before and after modification is FTIR spectroscopy. This technique has been used in several instances to monitor modification of chain ends of polymers produced by SI-ATRP with sodium azide.814,816,817 It is important to note, however, that both for XPS and FTIR spectroscopy the peak intensities of the end groups are often at the limits of detection of these techniques.

7. CHARACTERIZATION OF POLYMER BRUSHES The most important characteristics of polymer brushes are the film thickness, as well as the chemical composition, molecular weight, dispersity and grafting density of the surface-tethered polymer chains. Film thicknesses on planar surfaces are easily determined by ellipsometry, although it does not provide direct information about polymer molecular weight and dispersity. As mentioned in section 2.7, molecular weights of surface-tethered polymers are often determined by GPC analysis of free polymers generated by the use of sacrificial initiators/CTAs during SI-CRP. While in several instances the molecular weights of the free polymers have been shown to be in relatively good agreement with that of the surface-tethered chains, this is, however, not always the case. Obtaining accurate molecular weight information requires cleavage of the surfacetethered polymers followed by GPC analysis. Determination of the grafting density of polymer brushes is another challenge. In the following sections, we will first discuss some of the 1216


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Scheme 14. Two Examples of Copper-Catalyzed Alkyne-Azide Cycloaddition Post-Polymerization Modification of Polymer Brushesa

a

(A) Modification of a poly((poly(ethylene glycol) methyl ether methacrylate)-co-(2-propynyl methacrylate)) brush with 3-azido-7hydroxycoumarin797 and (B) modification of a poly(2-azidoethyl methacrylate) brush with ethynyl ferrocene.794.

where t is the brush thickness on a spherical substrate of radius r, ϕ is the polymer mass fraction, and ρp and ρb are the particle and polymer densities, respectively. Cheesman et al.294 used eq 2 to relate the dry film thickness of a brush grafted from a spherical substrate (t) to the dry film thickness of a brush grown under the same reaction conditions from a planar substrate (tp)

conventional, well-established techniques for the characterization of polymer brush film thickness and grafting density. After that, a number of more advanced methods will be presented, which can be used to evaluate the chemical composition and physical properties of polymer brushes. 7.1. Characterization of Polymer Brush Thickness and Grafting Density

⎤ ⎡ 3t p t = r⎢ 3 + 1 − 1⎥ ⎢⎣ r ⎦⎥

Ellipsometry is widely utilized to determine polymer brush thicknesses on planar substrates.5,7,8,13,14,17,21 Alternatively, AFM analysis of patterned polymer brushes will also provide an estimate of film thickness, however compression of polymer brushes by the AFM tip can lead to an underestimation, especially when brushes swollen in a good solvent are investigated.828−830 The film thicknesses of polymer brushes grafted from spherical particles can be determined using dynamic light scattering (DLS) and thermogravimetric analysis (TGA). Dynamic light scattering provides the hydrodynamic thickness of polymer brush layers grafted from spherical particles.92−94,831−833 TGA analysis of polymer brush-modified particles provides access to the overall mass fraction of polymer,831,834 from which the dry brush thickness can be calculated according to294 ⎡ ϕ(ρ − ρ ) + ρ ⎤ p b p ⎢ 3 − 1⎥ t=r ⎢ ⎥ − (1 ) ρ ϕ b ⎣ ⎦

(2)

where t is the predicted brush thickness on a curved substrate of radius r and tp is a prescribed brush thickness on a planar substrate. The conformation of polymers grafted from surfaces is determined by the grafting density (σ), i.e., the average number of surface-tethered polymer chains per unit surface area and the molecular weight of the surface grafted polymers. Taking PAM brushes as an example, with a Mn of 17 kDa and dispersity of 1.7, the mushroom-to-brush transition occurs at ∼0.06 chains/ nm2.835,836 The grafting density (in chains/nm2) is commonly obtained from the following equation:543,837−841

σ=

hρNA Mn

(3)

where h is the dry film thickness of the polymer brush, ρ is the polymer density, NA is Avogadro’s constant, and Mn is the number-average molecular weight of the surface-tethered

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Table 24. Overview of Post-Polymerization Modification Reactions that Have Been Used to (Selectively) Modify the Chain Ends of Polymer Brushes Prepared via SI-CRP

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where W60−730 is the weight loss (g) between 60 and 730 °C corresponding to the decomposition of the silane, initiator/ CTA, or polymer, M is the molar mass of the degradable portion of the grafted molecule, Sspec is the specific surface area of silica particles, and Wsilica is the weight loss of silica determined before surface modification. Polymer brush grafting densities can also be obtained from neutron reflectometry (NR) experiments. This was demonstrated by Deodhar et al.,845 who used this technique to determine the water content in surface-grafted polyelectrolyte brushes. The authors described a method to unambiguously determine the dry polymer mass density, layer thickness and brush profiles in solutions of various pH by modeling multiple data sets.

polymers. Ideally, Mn is determined by analysis of polymers cleaved from the substrates. Molecular weight, however, is also often obtained by analysis of free polymers produced via sacrificial initiators/CTAs during SI-CRP, since it is difficult to produce sufficient amounts of sample by cleaving brushes from planar substrates. The recent work of Patil et al.842 has provided the means to quantitatively obtain the molecular weight and grafting density of PMMA brushes cleaved from planar substrates by GPC through the use of a high-sensitivity differential refractive index detector. As noted earlier, it is important to keep in mind that analysis of free polymers can provide skewed results in comparison to cleaved brush analysis (see Tables 6−8). If determining the brush film thickness is complicated or not possible, but surface tethered polymers can be cleaved and the total mass and molecular weight can be determined, then the grafting density can also be calculated using the following equation:95 σ=

WNA M nA

7.2. Chemical Characterization

A number of tools is available for the chemical characterization of polymer brushes. Routine techniques that are commonly used include FTIR spectroscopy,91,189,508,543,846−848 elemental analysis70,99,239,433,472,849,850 and XPS. The following sections will highlight some more recent work in which XPS (section 7.2.1) and mass spectrometric techniques (section 7.2.2) have been used to address some more advanced analytical questions related to, e.g., distribution of functional groups in polymer brushes, nature of chain end functional groups, as well as the presence of trace impurities of catalyst. 7.2.1. X-ray Photoelectron Spectroscopy (XPS). X-ray photoelectron spectroscopy (XPS) is a technique routinely used for the characterization of polymer brushes. XPS provides a convenient way to probe the elemental composition of the top 5−10 nm of a surface154,217 and has been used to determine the presence of ATRP initiators,172,529,851 RAFT agents (see refs 154, 155, 163, 170, 172, 180, 185, 189, 198, 210, 216, 217, 219, 224, and 852), NMP initiators,728,853 PIMP initiators,357,854,855 azo-initiators,138,856 as well as to confirm the chemical structure of the polymers grown from those initiator modified substrates (see refs 138, 146, 154, 155, 170, 172, 177, 185, 189, 198, 210, 217, 357, 732, 851, 852, 855, and 857). XPS has also been used to confirm the presence of polymerization active end groups at the termini of surface grafted polymer chains. There are several reports, for example, in which XPS analysis allowed to detect the sulfur signal of the RAFT agent present in brush grown via S-RAFT polymeriza-

(4)

where W is the weight of the cleaved polymer, NA is Avogadro’s constant, Mn is the number-average molecular weight of cleaved polymers, and A is the surface area of the substrate. The total amount of grafted material can be determined by GPC analysis of the cleaved polymer using, e.g., a calibrated RI detector.95 Alternatively, grafted amounts of polymer brushes can be obtained from FTIR analysis.144 In this case, calibration curves were first obtained with known quantities of polymers cast onto initiator-immobilized surfaces. TGA is a very convenient technique to determine grafting densities, in particular for brushes grown from nanoparticles.70,302,320,389,843,844 The grafting densities of PS brushes grown via SI-NMP from silica nanoparticles was determined via TGA as follows:70,844

( σ(μmol/m ) = 2

W60 − 730 100 − W60 − 730

) × 100 − W

MSspec × 100

silica

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tion.154,180,217,219 XPS analysis has also been used to detect the bromine end groups of thin (∼55 nm) PS brushes grown via SI-ATRP.57 XPS analysis can also be used to monitor postpolymerization modification reactions on brushes, for example, by monitoring the disappearance of a fluorine signal from pentafluorophenyl containing brushes 185,189 or the appearance of nitrogen,185,728,732 sulfur,728 fluorine,177 platinum,224 oxygen,728 or europium169 signals resulting from the postpolymerization modification reaction. By combining XPS with soft sputtering methods, this technique can not only be used to (semi-) quantitatively monitor postpolymerization modification reactions, but can also provide insight into the distribution and localization of functional groups in the modified brushes. This approach has been used to investigate the postpolymerization modification of poly(glycidyl methacrylate) brushes with ethanolamine or BSA. Depth profiling experiments using a C60 cluster ion gun revealed that the distribution of ethanolamine throughout the

100 nm thick brush depended on and could be tuned by the reaction time. The sterically hindered BSA, on the other hand, was shown to be localized only on the topmost layer of the brush,732 independent of the reaction time that was used for the postpolymerization modification reaction. 7.2.2. Matrix-Assisted Laser Desorption Ionization Time-of-Flight (MALDI-ToF) and Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS). Mass spectrometric techniques also represent powerful tools for polymer characterization. MALDI-ToF MS, for example, has been used to analyze PS,302 PMMA,302 PBA,340 PtBA,423 PDMAEMA,839 and PAM brushes.287 One advantage of MALDI-ToF MS is that it allows to directly analyze surface grafted polymers from the substrate, without the need to cleave chains. Chirowodza et al. used MALDI-TOF MS to analyze poly(butyl acrylate) brushes grown via S-RAFT from clay nanoparticles. The authors found that the number-average molecular weight (Mn) of the grafted polymer as determined by

Scheme 15. Derivatization of the Bromine End-Group of an SI-ATRP Grown Poly(3-(methacryloylamino)propyl]dimethyl(3sulfopropyl)ammonium hydroxide) Brush with Sodium Azide Followed by CuAAC with a Strained Cyclooctyne-Biotin Conjugate813

Scheme 16. Aminolysis of the Trithiocarbonate End-Group of a S-RAFT Grown Polymer Brush with Ethanolamine Followed by Michael Addition of the Resulting Thiol with 3-Maleimidopropionic Acid142

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MALDI-ToF MS and 1H NMR spectroscopy are in good agreement.340 MALDI-ToF MS has also been used to probe the nature of the chain ends of PS and PMMA brushes grafted from mesoporous particles via SI-ATRP.302 To this end, PS and PMMA brushes were cleaved from the particles using HF. The authors were able to observe both aliphatic and unsaturated chain-ends produced and concluded that the low molecular weight fraction of chains were indeed due to termination reactions.302 Interestingly, in both cases for PS and PMMA, the termination reactions were due to disproportionation rather than combination. Another mass spectrometric technique that has been used to characterize polymer brushes is time-of-flight secondary ion mass spectrometry (ToF-SIMS). This technique has been used for the characterization of PNIPAM,858 PHEMA,859 PNAM101 and PNaSS860 brushes, among others. While most of the time this technique has been used to monitor initiator immobilization or brush growth,101,859,860 it has been also used to detect crosslinking as well as the presence of copper and ascorbic acid residues in PNIPAM brushes prepared via SI-ARGET ATRP.858 Atmane et al. investigated the functionalization of aluminum nanoparticles with 4-[(diethylcarbamothioyl)thio] methylbenzenediazonium tetrafluoroborate, an SI-PIMP initiator.855 The authors found that the aryl radicals appeared to be connected to the surface via covalent Al−O−C bonds suggesting that the diazonium salts react spontaneously with the native aluminum oxide layer on the nanoparticles.855

deflection of NCS arrays was also correlated to the LCST of PNIPAM chains, as demonstrated by Bradley et al.872 7.3.2. Silicon Photonic Microring Resonators. Limpoco and Bailey325 reported a novel technique to rapidly screen various SI-ATRP reaction conditions in real time on a single substrate consisting of arrays of silicon photonic microring resonators.873 Such sensing devices are of great promise for label-free biosensing. They consist of arrays of micron-sized ring-shaped optical waveguides etched into silicon-on-insulator (SOI) chips and their resonance wavelengths supported by microcavities shift upon adsorption of molecular species due to changes in optical density at their surfaces. With this technology, SI-ATRP of SBMA was monitored in real time and different resonance wavelength shifts were observed by changing polymerization conditions, such as ligand and copper halide activator. Comparison of brush growth profiles obtained with the silicon photonic microring resonators with those determined by ex situ ellipsometry revealed that the growth rates measured in real time were observed to decline more rapidly in situ, however, likely caused by the presence of flow, which has been shown to limit brush thickness.229,294 In addition to monitoring of brush growth and screening reaction conditions, this technique was also used to study the nonfouling properties of the PSBMA brushes in the presence of serum proteins. 7.3.3. Tilted Fiber Bragg Gratings (TFBG). Pilate et al.874 explored tilted fiber Bragg gratings (TFBG)875 to monitor the growth of polymer brushes via SI-ATRP. TFBGs are sections of a single-mode optical fiber where the core is permanently and periodically modulated. TFBG sensing relies on the perturbation of the period or refractive index of the grating inscribed in the fiber core upon attachment of molecules. In comparison to silicon photonic microring resonators, TFBG does not require an advanced microfluidic system. SI-ATRP of DMAEMA was carried out from the surface of an initiator-functionalized glass optical fiber modified with a TFBG in a polymerization reactor, without flow or agitation. Growth of the PDMAEMA brushes was then followed in situ with an optical spectrum analyzer. The growth of the polymer brush chains resulted in refractive index changes surrounding the TFBG. The brush growth profiles measured by TFBG were in good agreement with those determined by ex situ ellipsometry on planar substrates. Interestingly, with known grafting density, dry thickness, and monomer size by volume, the authors were able to determine the degree of polymerization without cleaving brushes or analysis of free polymers via sacrificial initiators. 7.3.4. Neutron Reflectometry (NR) and Small-Angle Neutron Scattering (SANS). Neutron reflectometry (NR) and small-angle neutron scattering (SANS) are effective methods to characterize the structure of polymer brushes, including thickness, density, and roughness.301,876,877 The main advantages of neutron versus X-ray diffraction are the ability to label with isotopes and sensitivity toward lighter elements. While NR is typically used to probe polymer brushes grafted from planar substrates,877,878 SANS can be utilized to elucidate the structure or assembly of “hairy” particles in liquid media.879−882 Akgun et al.883 resolved the internal structure of dPS-b-PMA and PMA-b-dPS brushes by NR measurements. The authors found that for sufficiently thin brush films, a lamellar morphology was adopted regardless of differences in block chain length, while at higher thicknesses, the internal structure no longer fitted to lamellar models. Under good solvent

7.3. Physical Characterization

There is a broad and ever increasing range of techniques that can be used to study the structure and physical properties of polymer brushes. The following sections will highlight some selected examples of new or more established techniques that have been used to study the structure or mechanical, adhesive or tribological properties of polymer brushes. In addition to the methods discussed in this section, there are various other powerful tools, such as scanning probe microscopies (SPM), surface plasmon resonance (SPR) and surface forces apparatus (SFA), among others, which are also frequently used for the physical characterization of polymer brushes. The application of SPM, SPR and SFA to the characterization of polymer brushes is not formally discussed here, but has been reviewed elsewhere.5,16,841,861−863 7.3.1. Nanomechanical Cantilever Sensor Arrays (NCS). The lubrication properties of polymer brushes depend highly on their chemical structure, architecture and conformation.309,674,864−867 Most methods available to characterize the mechanical behavior of polymer brushes rely on the influence of external shearing fields.868 In efforts to understand the collapse-swelling transition of polymer brushes in the absence of external fields, and therefore, to make direct correlations to molecular structure, Lenz et al.869 applied nanomechanical cantilever sensor (NCS) arrays870 to study PMMA mechanics during the collapse-swelling transition upon altering solvent quality. NCS bending experiments provided insight into the lateral forces within the polymer brush, e.g., interchain entanglements in bad solvents and osmotic pressure upon swelling in a good solvent. Overall, PMMA brush swelling lead to lower surface stress as a result of chain disentanglements and softening. SI-ATRP of MMA was recently applied to nanocantilever sensors with high sensitivity and selectivity toward polar analytes in the vapor phase.871 Furthermore, 1223


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conditions, PS brushes have been shown to be highly stretched at moderate molecular weight and with increasing numberaverage molecular weight (Mn), there is a higher degree of entanglements causing deviation from density profiles.884 NR has also been used to investigate chain mixing between surfacetethered PS brushes grown via SI-ATRP and free dPS in both wet and dry states with varying dispersities.885 As predicted theoretically, intermixing between brushes and matrix did not occur with low dispersity brushes after thermal annealing, while high brush dispersity resulted in better intermixing with the external matrix. As a consequence, polydisperse brushes are expected to improve adhesion in composite materials. Similarly, Rodriguez et al.886 demonstrated with NR that a PMMA brush gate dielectric penetrates active P3HT layers in all-polymer field-effect transistors after thermal annealing at temperatures as low as 40 °C. Dunlop et al.887 examined the structure of PMETAC brushes grafted from sapphire in pure heavy water and in the presence of electrolytes. In pure heavy water, PMETAC brushes adopted a two-region structure of different densities, while upon addition of electrolytes, to screen electrostatic interactions, partial collapse was observed. Addition of sodium dodecyl sulfate destroyed the two-region structure as a result of complete charge neutralization. Similar results were obtained by Kobayashi et al.,888 where the effect of NaCl on PMETAI and PMPC brushes was investigated. However, in this case, a negligible effect of ionic strength on the structure of PMPC and PMETAI brushes was observed.680 Yamaguchi et al.889 studied the aggregation states of PHDFDA brushes during the sorption of supercritical CO2. The authors determined that supercritical CO2 sorption led to a large expansion of polymer chains resulting in highly ordered aggregation states. The collapse of thermoresponsive PMEO2MA-co-PPEGMA brushes upon increased temperature and ionic strength was also investigated by NR measurements.890 Similarly, the pHresponsive behavior of PDMAEMA brushes was determined to be highly dependent on temperature and grafting density. Lower grafting density brushes showed a more pronounced response to pH changes and, at pH 10, a partial collapse was observed above 30−40 °C.839 Moglianetti et al.891 investigated PDMAEMA brushes grown from sapphire via adsorbed polyanionic macroinitiators. PDMAEMA brushes were welldescribed by Gaussian density profiles with the exception of a spike caused by a thin, dense layer close to the liquid interface for thicker brushes at pH 7 and 9. Upon complete swelling of the PDMAEMA brushes at pH 3, this spike in density profile disappeared, due to the contribution of counterions to the osmotic pressure. The collapse-swelling transition of PMMA brushes upon gradual addition of solvent mixtures also showed that osmotic pressure dominates over the enthalpy of polymer−solvent interactions.869 Not only can changes in pH lead to changes in the density profile of PDMAEMA brushes, but also changes in electric fields between brush substrates and parallel electrodes.892 In the latter case, PDMAEMA brushes were stretched nearly to their contour length at very high positive voltage, before being detached from the substrate. NR has also been combined with in situ ATR-FTIR to evaluate the pH-responsive behavior of PDEAEMA brushes, allowing simultaneous measurement of brush density profiles, degree of protonation and heavy water concentration at the brush interface.846 The degree of hydration of PMAA and PMAA-coPHEMA brushes and physical properties of polyelectrolyte brush layers were also determined by NR.845

In addition to investigating the structure and conformational changes of surface-tethered polymer brushes, NR has also been utilized to study postpolymerization modification reactions of polymer brushes. In model experiments with PHEMA brushes, which were subjected to an NPC-mediated PPM with deuterated amino acids, it was found that the penetration of reactants into brush films was highly dependent on thickness, grafting density, and molar mass of deuterated amino acids.720 SANS can provide information on the structure of polymer brushes grafted from particles when carried out in deuterated solvents642 or using deuterated particles.893 By conducting SANS experiments in deuterated solvents and star model fits of scattering signals, Gal et al.642 determined particle size and number of chains per nanoparticle, and thus, grafting density of PtBMA brushes. Furthermore, radius of gyration and molecular weight (Mw) of polymer brushes was determined by SANS of hairy particles at different concentrations without the need of cleaving. Mazurowski et al.893 also examined the structure of PS brushes grafted from fully deuterated PS latex nanoparticles produced by SI-NMP, which provided excellent contrast in SANS experiments conducted in deuterated toluene. 7.3.5. Colloidal Probe Microscopy (CPM). Quantification of the interfacial forces between polymer brush layers and opposing surfaces is of great relevance for accurate control over adhesion, viscosity, and lubrication behavior.894 Advances in scanning probe microscopy have greatly facilitated investigations of film thickness, surface morphology, mechanical properties and stimuli-responsive behavior of surface-tethered polymers.861,862 AFM is routinely employed to characterize interaction forces of polymer brushes95,335,559,566,569,776,780,895−904 and even to monitor brush growth in situ.122 Typical AFM cantilever tips are sharp and pyramidal in shape and could potentially penetrate the spaces between adjacent surface-tethered polymers, depending on their grafting density.861 This could complicate the interpretation of force curves, or brush compression, based on the application of Alexander,330 de Gennes,331 or MilnerWitten-Cates905 theories and the Derjaguin approximation.906 This will be outlined further in section 8. The use of colloidal probe microscopy (CPM),907,908 which typically utilizes a microsphere of 1−30 μm radius glued to the cantilever, provides a way to directly measure the colloidal forces in air or in a liquid medium. Since CPM only measures the relative displacement of the cantilever and not the actual distance between the probe and the surface, methods have been developed to determine the contact point with polymer brushes.271 CPM has been applied to probe the adhesion and friction properties of polymer brushes in dry conditions,909,910 but the exemplary properties of polymer brushes are better manifested under wet (swollen) conditions.271,419,531,655,680,867,911−917 Coad et al.531 examined the interaction between PPEGMEMA brushes grafted from silicon wafers with a 2 μm silica colloidal probe in PBS and found a distinct dependence on grafting density. For low grafting density brushes, polymer chains had more entropic freedom to form bridges with the colloidal probe, however at high grafting densities, the high packing of polymer chains forced highly extended conformations near their contour length, thus displaying purely repulsive forces with the colloidal probe. The onset of repulsive forces was also utilized to calculate equilibrium brush thicknesses in different solvent mixtures. Adhesion and lateral (friction) forces were also evaluated with a 50 μm silica bead for PMPC brushes 1224


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in different solvents and at various NaCl concentrations.680 In bad solvents, both adhesion and friction forces were greater than in pure water, but ionic strength had little impact. CPM was also used to study the lubrication properties of PS brushes in toluene/2-propanol mixtures. The observed frictional forces with a 5 μm silica probe were found to reveal two distinct lubrication mechanisms: boundary and hydrodynamic depending on solvent quality.867 Kutnyanszky and Vancso655 grafted PMAA brushes from colloidal gold probes by SI-ATRP, followed by functionalization with RGD peptides. These probes were used to study interactions with PMAA brushes grafted from planar substrates. The authors determined grafting densities by applying a “boxlike” polymer brush model based on de Gennes theory,331 which afforded grafting densities of 0.11 and 0.053 chains/nm2 for PSBMA and PMAA, respectively. The authors determined that polymer brushes with similar charge and grafting density showed similar elastic properties upon compression with the colloidal probe. Sakata et al. probed the interaction forces between five types of polymer brushes (PMPC, PSPMA, PHEMA, PBMA, and PMETAC) and different functional groups present in proteins, using 20 μm diameter silica beads covered with a carboxylic acid, amine, or methyl terminated self-assembled monolayer.913 The weakest interactions were observed in the case of PMPC, while high adhesion was obtained between oppositely charged functional groups and between amines and PBMA. In addition to interaction forces between particles and flat surfaces, CPM can also be used to measure interaction forces between oppositely charged particles grafted with polyelectrolytes, as demonstrated by Spruijt et al.914 In this case, PS colloids were grafted with PMETAC or PSPMA by SI-ATRP, which were subsequently immobilized on AFM cantilevers. The authors determined that the attraction between oppositely charged particles increases over time due to interpenetration of the polyelectrolyte brushes driven by complexation. Another powerful application of CPM lies in the determination of collapse-swelling transitions of stimuliresponsive polymer brushes, such as PNIPAM.419,911,915−917 By varying the ionic strength of the liquid medium, partial collapse of PNIPAM brushes grafted from cellulose nanocrystals was observed at room temperature, as indicated by decreased steric repulsion forces.419 Furthermore, pull-off forces were of higher magnitude at lower ionic strength, possibly due to increased bridging in extended PNIPAM brushes. Vancso et al.911,915 used CPM to measure friction forces, Young’s moduli,915 collapse of PNIPAM brushes in water/MeOH mixtures at three different grafting densities. Low friction was observed in pure water; however, it was greatly increased in water/MeOH and for higher grafting densities. Moreover, the process was completely reversible. Young’s modulus of swollen high density brushes was four times lower than the same brushes in the collapsed state.915 In addition to PNIPAM, Synytska et al.916,917 probed the adhesion properties of PPEGMEMA-co-PMEO2MA and PPEGMEMA-co-PPGMA brushes grafted from both the planar surface and the colloidal probe. They found that all thermoresponsive polymer brushes were essentially nonadhesive below the LCST, but adhesive above.917 Moreover, the adhesion of PNIPAM brushes was highest in magnitude, while PPEGMEMA-co-PPGMA brushes exhibited the lowest adhesion forces. The authors also examined the effect of substrate roughness, in which higher adhesion was obtained with brushes grafted from flat surfaces

than those grafted from microstructured substrates, due to reduced contact area with the colloidal probe.916 7.3.6. In Situ Ellipsometry. In situ ellipsometry has, in recent years, emerged as a powerful technique to investigate the swelling behavior of polymer brushes. This method, for example, has been used to study the pH-responsive behavior of PMAA, 199,359,918 PDEAEMA, 919−922 PDMAEMA, 923 PDPAEMA,921 PEAA199 and PAA199,924 brushes, as well as the temperature-response of PNIPAM199,911,917,925,926 brushes and the ionic-strength dependent response of PMETAC927 and PDEAEMA922 brushes. Borozenko et al. used in situ ellipsometry to study the interaction of PS-b-PAA brushes with various mono- and divalent cations. It was found that while monovalent sodium and cesium ions caused stretching of the brushes, divalent calcium ions induced chain collapse.924 Conformational changes in a PDMAEMA brush were also brought about using an applied voltage while the swelling was measured in situ.892 Similarly, it was shown that an electrode in proximity to a pH-responsive polymer brush can be used to trigger the brush response via the pH change induced in the medium by the electrolysis of water.919 Thus, waves of acidic or alkaline solution pH could be generated triggering the swelling or collapse of the grafted PDEAEMA brush, which was concurrently measured by in situ ellipsometry. Another detailed study undertaken using in situ ellipsometry investigated the solvency of PMPC brushes in a variety of solvents. It was found that while PMPC brushes were highly swollen in pure water or ethanol, in ethanol-rich cosolvent compositions, they deswelled. This was also noted with water/ 2-propanol mixtures, however, surprisingly this phenomenon was not noted in methanol/water mixtures in which the brushes were well swollen at all solvent compositions.928 The authors also attempted fitting the ellipsometric data to model the density profile of the brushes and found that an exponential decay model of the density away from the surface yielded the best fits. Interestingly methanol/water was also used as a cononsolvent for another study on PNIPAM brushes.911 In this case the swelling was not as pronounced in methanol/water as it was in pure water. Interestingly, the data in this case suggest that the layer close to the substrate remains partially hydrated while the outer layer experiences full collapse. Kooij et al. have used in situ spectroscopic ellipsometry to model PNIPAM brushes as a two-layer system: a dense layer in proximity to the substrate and a more dilute layer further away with a gradient density profile. The dilute layer shows gradual changes in the temperature range 25−30 °C with complete collapse noted at 30−33 °C (the temperature typically associated with the temperature response of PNIPAM).925 At this range the dense layer close to the substrate also experiences a marked increase in density. Cheesman et al. used in situ ellipsometry and QCM to study the pH-dependent swelling of PDEAEMA brushes grown via ARGET ATRP.920 Upon changing the pH from pH 4 to pH 9, the authors noted a hysteresis in brush thickness in response to increasing acidity on the first ramp. This did not materialize in subsequent cycles and the authors attributed this to the disentanglement of the as-prepared polymer chains on the first protonation allowing them to trap more solvent on subsequent cycles. Another report also used in situ ellipsometry to study the response of PDEAEMA brushes between pH 4 and 9 as well as changes in ionic strength (between 0.1 to 500 mM of 1225


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KNO3).922 In the case of the pH responsiveness, a hysteresis was noted in the swelling and collapse, which the authors attributed to the formation of a dense “skin” on the outer region of the brush, which retards solvent egress during collapse. This hysteresis is not noted in response to ionic strength suggesting that the mechanism for this conformational change is different from that of the pH response. 7.3.7. Quartz Crystal Microbalance with Dissipation Monitoring (QCM-D). Quartz crystal microbalance with dissipation monitoring (QCM-D) is a convenient method for in situ monitoring of the viscoelastic properties of polymer thin films. The resonance frequency f and energy dissipation D of a QCM sensor chip are sensitive to changes in the mass as well as the viscoelastic properties of the surface-bound layers e.g. a surface grafted polymer brush.929,930 As a consequence, QCMD experiments, in principle, can provide insight both in adsorption/binding and desorption/release of molecules or ions from polymer brushes and can also be used to monitor collapse/swelling of surface-tethered polymers. In practice, however, swelling/collapse transitions are often accompanied by uptake or release of solvent molecules, which can make interpretation of the experimental results challenging. QCM-D, nevertheless, is widely used to monitor polymer brush growth kinetics,121,318,577,927,931,932 to characterize stimuli-responsive brushes,288,569,603,647,785,840,920,933−936 and to study adsorption532,648,847,937−939 or binding events290,291,429,692,940 onto or within polymer brush films. Chernyy et al.318 used QCM-D to study the ATRP of PMMA brushes grafted from gold substrates modified with a diazonium based initiator layer. First, they observed large decreases of resonance frequency as a result of CuBr/PMDETA adsorption onto initiator-modified QCM sensors. Further decreases in frequency were noted during PMMA brush growth, the magnitude of which depended on the grafting density. To follow the growth of PHEMA brushes produced via SI-eATRP, Hosseiny et al.121 applied electrochemical QCM. The eQCM technique is a QCM device integrated with an electrochemical cell. Growth of PMETAC brushes by SI-ATRP from gold was monitored in situ in a single device integrating QCM-D and ellipsometry.927 This combination of techniques provided a unique way to determine the amount of solvent released upon collapse of the PMETAC brushes in the presence of NaCl solutions. In situ QCM-D measurements have also been used to follow the photopolymerization kinetics of PMAA brushes produced by SI-PIMP.931 These experiments revealed a nearly linear decrease in resonance frequency beyond 45 min of UV exposure, suggesting continuous polymer growth. In contrast, ellipsometry showed slower growth after 45 min. This was likely caused by effects of solvation of polymer brushes during the growth detected by QCM-D. Cheesman et al.920 monitored the adsorption of cationic poly(2-(dimethylamino)ethyl methacrylate-stat-glycerol monomethacrylate) macroinitiators by QCM-D and the subsequent pH-response of PDEAEMA brushes grown via SI-ARGET ATRP from the macroinitiator modified QCM-D sensors. Using the Sauerbrey equation, dry brush thicknesses were determined, however, values were 30−50% larger than those determined by ellipsometry, likely caused by the assumptions of film rigidity and uniformity required to satisfy Sauerbrey’s equation.929,930 The pH-response of PDEAEMA brushes in QCM-D was interpreted solely based on uptake or expulsion of solvent and counterions. It was found that the swelling of

PDEAEMA brushes due to solvent uptake and protonation is about eight times faster than the expulsion of solvent and counterions upon brush collapse, in agreement with in situ ellipsometry. Thermoresponsive kinetics of PNIPAM hydrogel brush films cross-linked with two PPEGDMA comonomers was evaluated by QCM-D and higher water content was determined for the higher molar mass cross-linker.603 Huang and He933 monitored the viscoelastic properties and water adsorption on the surface of hydrophobic PMMA-b-PDFHMA brushes synthesized by SI-ATRP from silica nanoparticles by drop casting onto QCM sensors. The wettability of PNIPAM copolymer brushes containing phenylthiourea and phenylboronic acid units changed upon adsorption of nucleotides, as determined by QCM.288 Furthermore, the LCST of PNIPAM brushes, as measured by QCM-D, was highly dependent on grafting density, due to increased lateral aggregation of PNIPAM chains at lower interchain distances.840 Similar conclusions have been made regarding the pH response of PMAA brushes, which was not only dependent on grafting density, but also brush thickness.647 In that case, at high PMAA grafting densities, the apparent pKa differed from free PMAA in solution and spanned a wider pH range. With a combination of QCM-D and equilibrium contact angle measurements, Laloyaux et al.935 were able to decouple the collapse of the bulk of PPEGMEMA-co-PMEO2MA brushes versus chain-ends exposed at the surface. It was found that chains collapsed at lower temperature in the bulk of the brush compared to those at the outer surface. Cui et al.569,785 followed the response of PNVOCMA569 and PNVOCAMA785 brushes during light irradiation and pH cycles. Removal of the photolabile NVOC groups generated pH-responsive PMAA or PAEMA brushes and resulted in swelling in water. Not only is QCM-D sensitive to liquid phase solutes, but also adsorption of dissolved gases. For example, CO2-responsive PDEAEMA brushes were synthesized by SI-ATRP, which could be reversibly switched by passing inert N2.934 CO2 adsorption into the brushes caused cationization of tertiary amine groups. The subsequent collapse of neutral PDEAEMA brushes upon addition of N2 also allowed reversible adsorption of proteins. QCM-D is also a useful method to study the interactions of polymer brushes with biomolecules and to evaluate their nonfouling properties. Coad et al.532 utilized QCM-D to investigate the adsorption of human serum albumin on PDMAM brushes grafted via SI-ATRP and demonstrated the nonfouling nature of these surface grafted polymer layers. Reduction of protein adsorption from fetal bovine serum onto a series of polymer brushes including PMPC, PCBMA, PSBMA and PHEMA was also evaluated by QCM.937 It was determined that the mass of proteins adsorbed was 10 times more on thick polymer brush layers bearing hydroxyl groups, in comparison to those bearing phosphorylcholine groups. Rastogi et al. used QCM-D to investigate the nonspecific adsorption of IgG antibodies on 2,4-dinitrophenyl (DNP) modified PAA brushes, which were grown via ATRP from gold substrates with different thiol based initiators.648 Thiol-based initiators containing OEG spacers resulted in lower IgG adsorption than a conventional initiator with only an alkyl chain. PPEGMA-co-PHEMA brushes postfunctionalized with rabbit IgG not only resisted nonspecific protein adsorption, but at the same time also showed high binding capacity of goat antirabbit IgG, a well-known bait and prey pair.692 Furthermore, Zhang et al.429 evaluated the binding of human IgG and nonspecific protein resistance of PAEMA-coPHEMA brushes grafted from cellulose nanofibrils and 1226


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postmodified with an IgG-specific peptides. Kimura et al. used QCM to evaluate the sensing properties of PDMAEMA brushes modified with metal-substituted phthalocyanines toward a range of volatile organic compounds.940 Molecular recognition between β-cyclodextrin (CD) coated liposomes and adamantane-functionalized (PAD-TEGA-co-PHEA) brushes produced by SI-NMP was also supported by QCM measurements.290 QCM-D based ion sensors were synthesized for the selective detection of potassium by crown-ether functionalized polymer brushes, which bound potassium even in the presence of interfering Na+ ions.291 Furthermore, their sensitivity could be fine-tuned by adjusting polymer brush thickness.

Steric interaction forces between polymer brush-coated crossed cylinders were first elucidated by direct surface force measurements by Taunton et al.,946 which provided quantitative agreement with the predictions of AdG models. The case of force per unit area (F) from repulsive pressure (P) between two crossed cylinders was extended to flat surfaces with adsorbed or grafted polymer brushes, given by the following AdG equation947 F = P(D) =

(10)

where kB is the Boltzmann constant, T is the temperature, s is the mean spacing between grafting points, D is the distance between two surfaces, and h is the equilibrium brush thickness. Since surface force measurements are typically conducted between curved surfaces, eq 10 is applicable after applying the Derjaguin approximation to account for curvature effects.947 Although more accurate and complex expressions for force-laws have been derived (see section 8.2), this simple model often predicts force vs distance (F vs D) profiles of polymer brush interfaces reasonably well, especially at large separation distance.897 The partial collapse of PNIPAM brushes upon increasing ionic strength measured by CPM was fitted by the AdG equation, providing qualitative evidence of repulsive steric forces between spherical silica probes and PNIPAM brushes grafted from cellulose nanocrystals.419 Moreover, extensions of the AdG equation have been fitted to CPM force curves to determine grafting density of polymer brushes.655 An example F vs D profile fitted by the AdG equation is shown below in Figure 11. Finally, Van Lehn and Alexander-Katz948 reported a novel combination of Flory−Huggins and AdG theories to simulate the lateral phase separation of mixed polymer brushes with mobile grafting points.

8. POLYMER BRUSH THEORY Theoretical descriptions are of great use for interpreting experimental observations and further tailoring of polymer brush properties. Mathematical models of polymer brushes in-6 and out-of-equilibrium,28 as well as computer simulations of surface-initiated polymerizations232 have been authoritatively reviewed in great detail elsewhere. Therefore, the following sections will not attempt to provide rigorous derivations of the rich theoretical framework of polymer brushes, but give a brief introduction to prominent theoretical developments, their key concepts and examples of how they have been (or could be) applied by experimentalists to explain common experimental observations. Here, Alexander-de Gennes (AdG) scaling, selfconsistent field (SCFT) and density functional (DFT) theories, Monte Carlo and Molecular Dynamics (MD) simulations of polymer brushes will be briefly introduced. As these topics were not addressed in our previous review,5 the first developments of each theory in the field of tethered polymer brushes are discussed. Although not strictly addressed in the following sections, single chain mean field (SCMF) theory of polymer brushes has also led to improvements to some of these traditional models.941−944

8.2. Self-Consistent Field Theory (SCFT)

Pioneered independently by Milner et al.905 and Zhulina et al.,949 the self-consistent field (SCFT) approach to polymer brushes, also known as mean field theory (MFT), provides a more detailed description of the polymer brush structure than the AdG theory.330,331 The SCFT approach typically considers a large quantity of small individual components that interact with each other, in which the effects of all the other individuals on any given individual is approximated by a single averaged effect, or the mean field approximation. In contrast to AdG scaling methods, SCFT formulates the statistical mechanics of a single polymer chain under the influence of an effective field from other polymer chains that is computed self-consistently. One of the most important initial results of the SCFT approach is that monomer density profiles are parabolic functions and not stepwise as suggested by AdG theory.905,945 In this case, the equilibrium brush height (h) becomes905

8.1. Alexander−de Gennes (AdG) Theory

Due to their conceptual simplicity, polymer brushes are an interesting model for theoretical studies toward understanding many facets of polymer and (bio)interface science.945 The work of Alexander330 and de Gennes331 provided the foundation for polymer brush theory, which has since flourished, especially in terms of computer simulation methods.6,28 The structure and dynamics of polymer brushes can be studied experimentally by techniques such as small-angle neutron scattering (SANS), neutron reflectivity and ellipsometry (see section 7), thus providing a means for comparisons to theoretical descriptions. In the AdG scaling model, equilibrium polymer brush height (h) is obtained by a balance of the free energy of stretching of “blobs” with excluded volume interactions, or the Flory argument.330,331 It does not consider details of polymer chain conformations or the monomer density profile at a defined distance from the surface. Thus, the argument suggests a stepfunction density profile or that any chain behaves the same way as any other, which can be calculated without lengthy computations. Equilibrium brush height (h) then becomes a function of the number of blobs and their diameter, or number of monomer units (N) of size (a), grafting density (σ), and Flory exponent (v = 3/5) as in6 h ≈ Na(σa 2)1/3

kBT ⎡⎛ 2h ⎞9/4 ⎛ D ⎞3/4 ⎤ ⎢⎜ ⎟ − ⎜ ⎟ ⎥ for D < 2h ⎝ 2h ⎠ ⎥⎦ s 3 ⎢⎣⎝ D ⎠

⎛ 12 ⎞1/3 h = N ⎜ 2 ⎟ (σw)1/3 ⎝π ⎠

(11)

where w is the excluded volume parameter. Using SCFT, the force-law (F(D)/R), normalized by radius R, as a function of distance D between two crossed cylinders with adsorbed or grafted polymer brushes can be written as950 F(D) = 4π (f (h) − f (h0)) R

(9) 1227

(12) DOI: 10.1021/acs.chemrev.6b00314 Chem. Rev. 2017, 117, 1105−1318

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where f(h) is the free energy per unit area of a compressed brush an h0 is the uncompressed height. The free energy per unit area for a monodisperse brush is given as f (u) =

⎛5⎞ ⎛1 u5 ⎞ ⎜ ⎟f ⎜ + u2 − ⎟ 0 ⎝9⎠ ⎝u 5⎠

model of a polydisperse brush based on AdG theory that agreed well with the SCFT model. This model was later utilized to study the effect of dispersity on the nonfouling properties of neutral polymer brushes955 and grafted comb-polymers.956 Since the development of early SCFT models,905,949 SCFT treatments have been used to study polymer brushes within the worm-like chain model,957 polymer brush-modified vesicles,958 brush interactions with colloids,959 polyelectrolyte brushes,960 mixed homopolymer brushes, 961,962 block copolymer brushes,963 and the collapse of stimuli-responsive brushes.964,965 Extensions of SCFT theory have also led to design rules and theoretical insights into the culturing of cells on thermoresponsive PNIPAM brushes.966,967 O’Driscoll et al.968 applied SCFT models to explain experiments on microphase separation of block copolymer brushes. Lastly, lateral microphase separation experiments of mixed homopolymer brushes were in agreement with simulations predicted by SCFT theory.969

(13)

where u = h/h0 and f 0 is the free energy per unit area of the uncompressed brush. The SCFT approach defines h0 and f 0 as h0 =

⎛ 12 ⎞1/3 1/3 1/3 −1/3 ⎜ ⎟ Nσ w v ⎝ π2 ⎠

(14)

1/3 ⎛ 9 ⎞⎛ π 2 ⎞ 5/3 2/3 1/3 ⎜ ⎟⎜ ⎟ Nσ w v ⎝ 10 ⎠⎝ 12 ⎠

(15)

and f0 =

where w is the excluded volume parameter and v is a constant which depends on polymer mechanical properties. With the help of mean field treatments, the SCFT model of polymer brushes at large separation distances has also been extended to take into account chain dispersity.950 The authors found excellent agreement between the SCFT model and the direct surface force measurements of end-grafted polymer chains by Taunton et al.946 Mendez et al.897 compared the SCFT model and the AdG model to force vs distance profiles of PNIPAM brushes and found good agreement at large separation distance. Although more accurate than the AdG eq 10,947 the SCFT model is more computationally demanding. It should be noted that, like AdG theory, the SCFT model was derived in the infinite-stretching limit, meaning the brush thickness is infinitely greater than the unperturbed radius of gyration and ignores fluctuations about the most probable chain trajectories.951,952 Thus, Netz and Schick derived an approximation of the full SCFT without the infinite stretching assumption, which included a component for the entropy related to the distribution of end points, of relative weight β‑1.951,952 Depending on the value of β‑1, the density profile of brushes in finite stretching deviates from the parabolic form proposed by Milner et al.905 and Zhulina et al.,949 however, disappears in the infinite stretching limit, β‑1 → 0, therefore reduces to the SCFT model, albeit an improved overall description. Furthermore, Kim and Matsen953 showed that upon comparing SCFT predictions with experimental compressive force data from two brush-coated cylinders,946 whereas dispersity effects seemed relatively small, effects of chain fluctuations were too large to be ignored. The theoretical framework presented in eqs 9−15 has been developed for the case of monodisperse polymer brushes. This assumption is obviously unrealistic for polymer brushes produced via SI-CRP. Descriptions of polydisperse brush models can be found in the review by Binder and Milchev.6 When polydispersity was introduced in SCFT models, for example, by de Vos and Leermakers,954 parabolic density profiles progressively changed to linear and then concave, where the concave density profile suggests an exponential decrease in density (Figure 12A). The authors further observed that the maximum in end-point distribution moves closer to the grafting interface upon increasing dispersity (Figure 12B). Average brush height also increased with higher dispersity, while brush stretching decreased. In contrast, the scaling exponents of the AdG model were nearly independent of dispersity, thus de Vos and Leermakers proposed a simpler

8.3. Density Functional Theory (DFT)

Density functional theory (DFT) of polymer brushes treats polymer chains without explicitly describing intermolecular interactions at the atomistic level, but with an effective external field to account for effects of the surrounding medium.970,971 DFT uses mathematical functionals of electron densities to determine the properties of systems composed of many electrons. It has also been used to describe the thermodynamic properties, microscopic structure and phase behavior of confined fluids, while being more computationally efficient than simulation. Thus, solvent molecules can be considered by including a separate field that interacts with the polymer and the monomers in DFT, which gives information on the solvent density distribution within polymer brush chains. In contrast to AdG and SCFT theories, DFT can address the case of relatively thin brushes of high density, in which the monomer distribution near the substrate wall should be well-defined.6 Examples of the use of DFT models applied to polymer brushes can be found elsewhere.970,971 The reader is also directed to a recent review of DFT applied to macromolecular systems, including polymer brushes, by Emborsky et al.972 Borówko et al.973−980 have provided insights into multiple aspects of polymer brush structure by DFT approaches. These include changes in brush structure at different grafting density,973 in binary solvent mixtures,980 and adsorption of small molecules974,978 and oligomers975,976,979 on polymer brush interfaces. The same group further developed DFT models for solvation forces between brush-modified surfaces981,982 and retention in chromatography considering polymer brush modified stationary phases.977 DFT calculations have also proven useful to study the solvent-responsive behavior of binary brushes, 983 block copolymer brushes984 and the thermoresponsive behavior of PNIPAM brushes.985 A DFT study on the conformation and structure of “hairy” particles under good solvent conditions further revealed that with higher chain lengths, monomer density profiles displayed a transition from flat brush behavior to that of a star polymer, in agreement with molecular dynamics (MD) simulations.986 The authors further proposed this model to aid in interpreting light scattering from spherical micelles. By a combination of SCFT and DFT, Zhu et al.987 investigated the self-assembly of “hairy” nanoparticles grafted with block copolymers. Xu et al.988 applied DFT to study the effect of polymer brush architecture on the adsorption of colloids on brush interfaces. Toward modeling thermodynamics within 1228


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nanocomposite materials, Jain et al.989 provided an extension of DFT, known as interfacial statistical associating fluid density theory (iSAFT), to calculate surface interaction forces between brush-modified interfaces in the absence and presence of free polymer melts. In the absence of free polymers, surface interactions were purely repulsive, however attractive in the presence of free polymer, depending on the ratio of chain lengths of free polymer vs polymer brushes. Finally, free energy calculations by DFT were used to predict the electron-beam sensitivity of various methacrylate brushes.580 Therein, Rastogi et al. found good agreement between polymer brush e-beam sensitivity and the calculated free energies for methacrylate main chain radicals.

weight PS matrices, which was supported by MC simulations.183 Jalili et al.1006 examined the interaction forces between polydisperse “living” brushes grown in situ and a piston mimicking an AFM tip via coarse-grained off-lattice MC simulations. Results of MC simulations were compared to CPM experiments of PNIPAM brushes and previous SFA measurements1007 and found to be in excellent agreement. 8.4.2. Monte Carlo Simulations of SI-CRP Reactions. Genzer231 reported computer simulations of the SI-CRP process, which used MC methods. Therein, the molecular weight and dispersity of polymer brushes compared to bulk polymers were investigated as a function of reaction conditions, such as initiator grafting density and monomer concentration. The results of MC simulations showed that polymer brushes

8.4. Monte Carlo and Molecular Dynamics Simulations

Computer simulation has become an essential tool to solve complex problems in polymer science.990 It provides a powerful method to model many-body systems in great detail, especially when the mathematical approximations often implied in mean field theoretical approaches are no longer valid. Computer simulations, such as Monte Carlo and Molecular Dynamics, have been applied to predict polymer brush properties, like structure, surface interaction forces, such as van der Waals, electrostatic or steric forces, as well as the kinetics of SIP reactions. In the following sections, these two classes of computer simulations and their application to the study of both the structure of polymer brushes and SIP reaction kinetics will be briefly presented. 8.4.1. Monte Carlo Simulations of Polymer Brush Structure. The Monte Carlo (MC) simulation method generates probability distributions for structural observables, consistent with the thermodynamic boundary conditions, by generating a sequence of random moves that preserve detailed balance.990 In the simplest form, MC simulations of polymer brushes are carried out by generating large samples of selfavoiding walks (SAWs) on a cubic lattice, as first reported by Cosgrove et al.991 In this case, the authors studied single chain conformations and used periodic boundary conditions to mirror grafting density effects. Chakrabarti and Toral992 used MC simulation to determine the density profile of many tethered polymer chains at different chain lengths and grafting densities. The monomer density profiles obtained by these MC simulations were in agreement with SCFT approaches,905 and showed the expected deviation from a parabolic form near the grafting surface where there is a depletion layer. The fluctuations about the most probable chain trajectories that are ignored by AdG and SCF theories951,952 have been quantified by MC simulations.993 The surface interaction forces between brush-modified interfaces have also been modeled by MC simulation.994 MC simulations have been further utilized to model polymer brush structure at various chain lengths,995 stiffness,996 grafting densities,995,997 and upon addition of crosslinkers.998 Other simulation studies focused on the structure999 and mechanical properties1000 of polymer melt/brush-interfaces, interactions between “hairy” particles grafted with polyelectrolytes,1001 polymer brushes and magnetic particles,1002 and brush infiltration by colloids.1003,1004 MC simulations have further suggested that anisotropic selfassembled structures, consisting of “hairy” nanoparticles in solvents, readily form when nanoparticle size is similar to polymer chain radius of gyration.1005 Moreover, a variety of anisotropic self-assemblies of spherical silica particles grafted with PS brushes formed when dispersed in high molecular

Figure 11. (a) Approach curves as measured by CPM on PSBMA brushes with polymer coated and unmodified probes and (b) log−log plot with corresponding fitting according to the AdG equation. Reprinted with permission from ref 655. Copyright 2012 Elsevier.

were prone to early terminations causing higher dispersity as compared to bulk polymers, which was supported by other models.231,303,304,306 Early terminations were even more pronounced at high grafting densities and poor solvent conditions.233 Turgman-Cohen and Genzer234,235 reported results of MC simulations in which polymer brushes have lower molecular weight and higher dispersity than bulk 1229


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rates of polymerization. As described in section 2.7.2, Liu et al.298 showed that brush dispersity was also dependent on surface curvature with MD simulations.

polymers, especially at high grafting density. As alluded to in section 2.7.4, some of the experimental observations of cleaved brushes versus free polymers (see Tables 6−8) have demonstrated different trends, which suggests that additional factors might play a role. 8.4.3. Molecular Dynamics Simulations of Polymer Brush Structure. Molecular Dynamics (MD) simulations model the motion of individual atoms and molecules by numerically solving Newton’s equations of motion.990 The interaction forces between particles and the potential energy within the system are defined by molecular mechanics force fields and interatomic potentials. MD simulations of tethered polymer brushes under good solvent conditions were first described by Murat and Grest,1008,1009 in which each monomer was weakly coupled to a heat bath in order to maintain constant temperature. Monomer density profiles were parabolic for intermediate grafting density, in good agreement with SCFT models,905 rather than AdG theory,330,331 but deviated from parabolic form at higher grafting densities. As in the case of the SCFT model,950 the interaction forces between opposing brush-modified surfaces modeled by MD1008 were also in agreement with the experiments of Taunton et al.946 The interpenetration in compressed brushes was also quantified and shown to be described by a simple scaling form. More recently, MD simulations have been applied to structural studies of polymer brushes including PS,1010,1011 PMMA,1012 block copolyelectrolytes,1013 PAAEE,1014 and PEGbased brushes.1015,1016 More advanced simulations have been developed to study the structure of “hairy” particles,1017,1018 capillary rise in brush-modified nanotubes,1019 diffusion of colloids within polymer brush films,1020,1021 and brush-modified nanochannels.1022−1024 Furthermore, MD models of frictional forces between opposing polymer brushes,1025 compressioninduced phase transitions,1026 liquid flow over polymer brush films,1027 and even postpolymerization modification reactions1028 have been realized. Elliott et al.301 have recently reviewed the consistencies between MD simulations and neutron reflectivity experiments. MD simulations have provided especially useful information for the production of nanocomposites, specifically the dispersion of brush-modified colloids in polymer matrices.1029 Smith et al.1030 demonstrated with MD simulations that repulsive interactions between nanoparticles dispersed in a high molecular weight polymer matrix can be achieved with relatively thin and low density polymer brushes, in contrast to larger colloids. However, Shen et al.1031 found that increasing the thickness or grafting density of polymer brushes grafted from nanoparticles led to better dispersion in polymer matrices but was dependent on the molecular weight of the matrix. Interaction forces of opposing polymer brushes was examined by Elliott et al.,300 in which high interpenetration of brushes was observed in MD simulations. 8.4.4. Molecular Dynamics Simulations of SI-CRP Reactions. As in the case of MC simulations,231,233−235 MD can also model the SI-CRP process. Liu et al.1032 demonstrated the importance of a slow-moderate rate of polymerization to maintain good control, i.e., low dispersity. Control of SI-CRP in their model was also highly dependent on the initiator grafting density. Higher initiator efficiencies were obtained at lower initiator grafting density, but upon increased initiator grafting density, slower polymerization rates were required to retain high efficiencies. The authors found this a result of excluded volume effects, which could be circumvented at low-moderate

9. PROPERTIES AND NOVEL APPLICATIONS The past decade has seen remarkable advances both in the fundamental understanding of the structure and properties of surface grown polymer brushes as well as in terms of potential application of these thin films. This holds especially true for applications in the biomedical field,5,14,16,18,23,25 functional nanomaterials and nanofabrication,2,11,20,21,24 which have already been the subject of other review articles. This section will highlight some other novel properties and potential applications of polymer brush films, which have emerged or received particular attention over the past decade.3,16,17,21

Figure 12. (A) Overall volume fraction φ(z) profile for brushes with increasing dispersity as indicated. Nn = 100, σ = 0.01, dispersity with Schulz−Zimm distribution. Cutoff chain length NI = 1000. (B) The corresponding overall distribution of end points φe(z). Reprinted with permission from ref 954. Copyright 2009 Elsevier. 1230


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systems.1049 Further dual-responsive plasmonic gold nanoparticles were synthesized via grafting of PMEO2MA-coPPEGMEMA.438 Interestingly, ATRP initiators were covalently bound by an adsorbed layer of BSA. Toward new ionresponsive membrane adsorbers, Yang and Ulbricht1050 grafted zwitterionic PSBMA brushes from PET membranes via SIATRP. Membrane flux, and thus adsorption of human IgG, was well-controlled by addition of various salts that altered PSBMA brush conformation and followed the empirical Hofmeister classification of ions in the order of their ability to salt out or salt in IgG. As an example of redox-responsive interfaces, self-oscillating polymer brushes were recently developed by Masuda et al.,791 based on PNIPAM-co-PNAPMAM brushes postmodified with [Ru(bpy)3]. Here, the authors took advantage of the Belousov−Zhabotinsky (BZ) reaction that autonomously generates redox oscillation and thus, chemical waves. Propagation of the chemical wave was observed within a glass capillary by fluorescence microscopy confirming the spontaneous generation of periodic changes on the surface. Photoresponsive graphene nanosheets were fabricated by SIATRP of EPAEMA, followed by postpolymerization modification with the diazonium salt of 4-aminobenzonitrile via azocoupling.474 The diffraction efficiency of photoinduced surfacerelief gratings (SRGs) on azo molecular glass films was significantly enhanced when doped with as little as 0.5% wt. of azo polymer brush-functionalized graphene nanosheets.

9.1. Stimuli-Responsive Surfaces and Colloids

SI-CRP represents a powerful toolbox for the preparation of stimuli responsive thin films that can undergo (reversible) changes in conformation and structure upon exposure to external stimuli.5,12,16,22,24,385,1033−1035 Such tethered stimuliresponsive polymers can produce responsive drug delivery systems, biointerfaces and catalysts, actuators, self-healing coatings and controllable colloidal stability, to name a few. Recent reviews have further focused on stimuli-responsive polymer brushes to control flow through nanopores,1036 thermoresponsive chromatography,1037 hydrophilic stimuliresponsive brushes1038 and responsive nanocomposites.1039 Polymer brushes can be designed to respond to light, temperature, mechanical stress or a variety of chemical stimuli such as changes in solvent, pH, ionic strength or redox stimuli. The synthesis, properties and applications of stimuli-responsive polymer brushes have been covered in detail in recent reviews.5,12,16,22,24,385,1033−1035 This section will highlight a few examples of promising applications of stimuli-responsive polymer brushes toward reversibly switchable interfaces. Thermoresponsive polymers exhibit an upper and/or lower critical solution temperature (UCST or LCST), which causes coil−globule conformational transitions. By far still the most widely studied thermoresponsive polymer is PNIPAM which has an LCST of ∼32 °C in water.278,288,439,606,643,795,815,915,1040−1045 PNIPAM brushes are promising for biomedical applications, such as cell sheet engineering5,16,1046 and protein purification.1047 These applications often rely on the fact that above the LCST of PNIPAM it allows nonspecific adhesion of cells and biomaterials, while below the LCST it can display nonfouling behavior. Interestingly, PNIPAM brushes grown from substrates that present nanoscale topography have been reported to possess nonfouling properties both below and above the LCST.643,1040 Qing et al. have developed PNIPAM based brushes, the wettability of which can be manipulated isothermally and which respond to nucleotide solutions.288 In addition to biomedical applications, the LCST behavior of PNIPAM has also been explored for other applications. Thermoresponsive plasmonic devices were fabricated based on PNIPAM brushes grafted from planar gold to which gold nanoparticles were immobilized via click chemistry.815 Superhydrophobic surfaces have been fabricated based on copolymers of NIPAM, cysteine and aspartic acid.278 Various PEG-based brushes, such as PPEGMA and PPEGMEMA, display similar thermoresponsive behavior and have received increasing attention in the past years.1048 pH-responsive polymer brushes are typically based on carboxylic acid-functional monomers, such as MAA or AA, or tertiary amine-functional monomers, such as DMAEMA and DEAEMA. Such polymers display pH- or counterion-dependent conformational transitions. In addition to pH-dependent conformational transitions, the responsive behavior of tertiary amine-functional polymers, such as PDEAEMA, can also be triggered by gas adsorption.934 Kumar et al. for example, demonstrated reversible adsorption and release of proteins from PDEAEMA brushes triggered by bubbling of N2 and CO2, respectively. Tertiary amine groups of PDEAEMA brushes reacted with CO2 in water to form charged ammonium bicarbonate inducing extended conformations that could then be reversed by passing N2. Plasmonic vesicles based on gold nanoparticles grafted with PMMA-co-P4VP brushes showed pH-dependent self-assembly.258 The same group later exploited these vesicles for targeting cancer cells and drug delivery

9.2. Brush-Modulated Gating through Nanopores and Nanochannels

Precise control over the transport of ions and molecules is essential in separation science1051 and biosensing applications,1052 among others. Inspiration for synthetic gating membranes consisting of nanoscale pores and channels has been taken from biology, in which membrane proteins control transport of ions and molecules across the cell membrane to regulate membrane potential, cell volume and deliver nutrients. The ability of surface-tethered polymers to undergo reversible conformational transitions from a collapsed to an extended state and the possibilities to modulate this behavior by engineering chemical composition, grafting density, and film thickness makes polymer brushes very attractive candidates for the fabrication of nanopores or nanochannels that allow gated control of fluid flow or the transport of molecules and ions.385,1053 Li et al.1054 grafted PNIPAM brushes from anodic aluminum oxide (AAO) membranes in order to control the diffusion of vitamin B12 via reversible temperature switching through the LCST. Above the LCST of the PNIPAM brushes, vitamin B12 diffusion was higher than below the LCST due to the collapsed conformation of the surface grafted polymer chains. Similarly, AAO substrates grafted with PNIPAM brushes acted as nanovalves to control the capture and release of calcein molecules from within nanopores.1043 Polyimide membranes with conical pore morphologies were also modified with PNIPAM brushes and K+ and Cl− ion flux could be varied by temperature cycles.1045 Stimuli-responsive gating nylon membranes based on PNIPAM-b-PMAA brushes allowed temperature-, pH-, and ion-dependent flux of citric acid/disodium hydrogen phosphate buffer solutions.1055 pH-responsive PDMAEMA brushes were grafted from freestanding colloidal membranes (nanofrits), which allowed acid modulated control of transport of Fe(bpy)32+ and ferrocene.1056 1231


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based synthesis were used to site-specifically grow PNIPAM brushes via SI-ATRP.1067 Tanaka et al.1068 reported an alternative strategy, which involved the preparation of poly(methyl methacrylate)/poly(styrene-2-(2-bromoisobutyryloxy) ethyl methacrylate) Janus particles via internal phase separation induced by solvent evaporation. The resulting particles displayed ATRP initiator groups on one side, which were then used to grow PDMAEMA brushes leading to brush modified Janus particles displaying pH-1068 and dual-responsive behavior.1069

The same group also previously demonstrated the pHresponsive gating of PMAA brushes when grafted from nanoporous silicon nitride films.1057 Fortin and Klok665 developed polypropylene hollow fiber-based hydraulic flow glucose sensors by surface grafting PMAA brushes followed by postpolymerization modification with 3-aminophenyl boronic acid (PBA). The PBA functionalized PMAA brushes allowed controlled hydraulic permeability upon exposure to glucose due to swelling of the brush coating. Elbert et al.1058 recently reported a redox-mediated strategy to control transport of Fe(CN6)3− and Ru(NH3)63+ through mesoporous silica membranes. The authors investigated both grafting to of polyvinylferrocene and SI-ATRP of poly(2(methacryloyloxy) ethyl ferrocenecarboxylate) and found substantial differences in ionic permselectivity. In this case, the authors obtained more efficient coating throughout the mesoporous silica membranes by the SI-ATRP method, which also showed improved permselectivity compared with the grafting to method. This was due to better shielding of electrostatic interactions between the ions and mesoporous silica interfaces.

9.4. Pickering Emulsion Systems

The strong adsorption of solid particles at the oil−water interface is critical in the stabilization of surfactant-free emulsions, or so-called Pickering emulsions,1070 which have been applied to cosmetics, food products and biomedical devices.1071 The high stability of emulsions stabilized by colloidal particles is derived from the energy barrier required to remove the particles from the interface in order to facilitate droplet coalescence. Pickering emulsions have a number of advantages over traditional surfactant-stabilized emulsions related to reduced tissue irritation and their easily adjustable viscosity.1072 Although solid particles may inherently act as amphiphiles and spontaneously assemble at oil−water interfaces, grafting of surface-active polymer brushes can penetrate the interface leading to decreased interfacial tension and reduced Ostwald ripening.1073 Furthermore, Pickering emulsion interfaces can be used to initiate CRP reactions toward the formation of hollow capsules or “colloidosomes”.1074 Saigal et al.1073 reported an in-depth study on the characteristics of Pickering emulsions stabilized by PDMAEMA grafted silica nanoparticles. Such thermoresponsive “hairy” nanoparticles were used to stabilize xylene-in-water and cyclohexane-in-water Pickering emulsions. The authors investigated the effect of PDMAEMA brush grafting density and molecular weight in addition to pH, ionic strength and temperature on emulsion stability and qualitative models of the interfacial region were proposed. Overall, Pickering emulsifiers consisting of low grafting density brushes were the most robust to changes in the solution conditions and were stable for over 13 months under ambient conditions. However, due to the thermoresponsive behavior of PDMAEMA brushes, the emulsions could be rapidly broken when heated above the critical flocculation temperature. Thermoresponsive 1-octanolin-water Pickering emulsions were also made from PDMAEMA grafted “mushroom-like” Janus particles.1069 Cellulose nanocrystals (CNCs) grafted with PNIPAM brushes stabilized heptane-in-water emulsions.420 As a result of their rod-like shape, grafted CNCs formed anisotropic “nematic-like” assemblies at the oil−water interface, which were also rapidly broken upon heating above their LCST. Similarly, ferritin grafted with PNIPAM brushes stabilized perfluorodecalin-inwater Pickering emulsions.439 Incorporation of UV-crosslinkable 2-(dimethyl maleinimido)-N-ethyl-acrylamide in the PNIPAM grafts allowed the formation of droplets that were stable to addition of ethanol, which is otherwise known to break Pickering emulsions. Not only have thermoresponsive polymer brushes been applied to stabilize Pickering emulsions, but also ion-responsive PMETAC brushes.1075 Dodecane-in-water Pickering emulsions, for example, were stabilized with PMETAC grafted silica nanoparticles. At sufficient concentrations of perchlorate ions, “hairy” nanoparticles formed stable emulsions and increased

9.3. Janus Particles

Janus particles are micro/nanoobjects that provide different chemical or physical properties in an asymmetric fashion.1059 The broken symmetry in these particles provides unique opportunities for the preparation of complex self-assembled materials. In a number of reports, SI-CRP has been explored to generate polymer brush modified Janus particles. A key challenge in the synthesis of such nanoparticles is the desymmetrization of the particles to allow immobilization of initiators/CTAs on opposing sides of the (nano)particles and subsequent grafting of polymer brushes by SI-CRP. Li and coworkers have explored polymer single crystals to template the formation of Janus nanoparticles. In one example, the feasibility of this approach was demonstrated by first immobilizing gold nanoparticles on thiol end functionalized PEO single crystals followed by grafting of a thiol modified ATRP initiator on the “free” side of the surface bound gold nanoparticles and subsequent SI-ATRP of MMA or tBA.1060 By using alkoxysilane terminated poly(ε-caprolactone) single crystals as the template, the same group later utilized the same strategy to produce thermoresponsive silica Janus particles by SI-ATRP of NIPAM.1061 The LCST of the PNIPAM brush Janus particles was found to be around 4 °C lower than symmetric “hairy” nanoparticles. Liu et al.1062 prepared PS colloid particles that were decorated with Au nanoparticles via an interface directed self-assembly strategy. Modification of the Au nanoparticles with an ATRP initiator, ATRP of DMAEMA and dissolution of the PS cores with THF afforded PS/PDMAEMA modified Janus particles, which displayed pH-responsive emulsification properties. Magnetic Janus particles were also synthesized via immobilization of amine-terminated Fe3O4 nanoparticles on anionic mica surfaces.1063 ATRP initiators were then grafted to exposed amine groups for subsequent SI-ATRP of NIPAM. The authors went on to produce bicompartmental PMAA and PNIPAM-b-PMAA brushes by a second SI-ATRP, in which one particle hemisphere contained PMAA and the other contained PNIPAM-b-PMAA. Fixation at solid and Pickering emulsion interfaces has been explored in a number of other examples as well to prepare nanoparticles that are asymmetrically modified with initiator/CTAs.1064−1067 For example, dumbbell-shaped colloids consisting of distinct lobes produced by emulsion1232


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presence of unattached polymers, as in the case of thermal selfinitiation of styrene.307,342 PS-grafted Fe2O3 nanoparticles were incorporated into thin PBMA-b-PS copolymer films that maintained their selfassembled lamellar structures and enhanced optical reflectivity.1088 Nanocomposite systems toward hybrid electronics were based on conductive fillers/polymers such as graphene oxide nanosheets grafted with PtBA brushes486 and silica nanoparticles grafted with P4VTPA.1089 The latter were used in combination with hole-conductors as a capping layer at a dye/ TiO2 interface in solid-state dye-sensitized solar cells while the former was uniformly blended with a polythiophene in an electronic memory device. Electrical conductivity of polypropylene was improved by the incorporation of poly(dodecyl acrylate) and poly(octadecyl acrylate) modified MWCNTs at low loading, while better dispersion was observed with PDDA grafted MWCNTs.1090 Moreover, MWCNTs grafted with PS brushes improved their dispersion in polystyrene-b-polyisoprene-b-polystyrene matrices toward photoactuators.1091 Although uniform nanoparticle distributions are often desirable in polymer matrices, anisotropic nanoparticle assemblies can lead to beneficial direction-dependent properties. Akcora et al.183 developed a strategy to produce a range of anisotropic superstructures of spherical silica nanoparticles dispersed in PS matrices via grafting of PS brushes. Supported by MC simulations, their self-assembly was suggested to result from the balance between entropy of polymer brush distortion and energy gain upon interparticle approach.

particle concentrations led to smaller droplets and higher stability. In contrast, the presence of NaCl did not lead to stable emulsions, which demonstrated the ion-specific emulsification properties of the PMETAC brushes. Halloysite nanotubes modified with PS-b-P4VP and P4VP-bPS grafts stabilized emulsions of water and soybean oil, depending on brush architecture.168 An interesting approach to generate Pickering emulsions stabilized by amphiphilic nanoparticle complexes was reported by Tian et al.161 The authors synthesized thiol-terminated PS brushes grafted from Fe3O4 nanoparticles that were first well-dispersed in toluene. Upon mixing with an aqueous dispersion of citrate-stabilized gold nanoparticles, stable emulsions were prepared in which thiolterminated PS brushes formed a bridge between Fe3O4 and gold nanoparticles that could assemble at the toluene-water interface. 9.5. Polymer Nanocomposites

Nanoparticles of various morphologies can provide significant enhancements in the thermomechanical, optical and electrical properties of polymer matrices.1029,1076,1077 One of the primary challenges, however, is control over the dispersion and spatial organization of nanoparticles within the matrix such that the desired macroscale properties are realized. In addition to techniques such as surfactant adsorption, grafting small molecules and polymers to nanoparticle surfaces, grafting polymers from nanoparticles via SI-CRP provides an alternative strategy to control surface chemistry. Not only can polymer brushes improve nanoparticle miscibility within polymer melts,1078 but also allow quasi-one-component nanocomposites with unique properties upon optimization of brush thickness and grafting density.98,1079−1083 The mechanical reinforcement mechanism of polymer grafted nanoparticles was elucidated by Moll et al.,202 who showed that nanoparticle percolation is essential for stress propagation and that brush−brush entanglements allow a percolating network at lower loadings. Choi et al.1084 established the existence of a transition from particle-like to polymer-like deformation of particle brush solids with increasing degree of polymerization of PS and PMMA chains grafted from silica nanoparticles. Furthermore, an order of magnitude increase in the fracture toughness of particle brush solids was observed as the degree of polymerization exceeded a threshold value. The miscibility of nanocomposite blends depends on the molecular weight of the polymer brush in comparison to the polymer matrix. Ojha et al.1085 elucidated the compatibility of PMMA grafted silica nanoparticles and PMMA matrices. The authors found better uniformity when polymer brush molecular weight was comparable or higher than that of the polymer matrix, although this had little importance in the case of PS-coPAN modified silica nanoparticles dispersed in PMMA. On the other hand, PS-co-PAN modified silica nanoparticles dispersed in PMMA displayed the advantage of high optical transparency, even with the use of large particles (500 nm diameter).1086 The latter is due to favorable interactions between the grafted polymer chains and the polymer host.262 Goel et al.1087 demonstrated that a high degree of crystallinity can still be obtained in PBA blends with as low as 0.7% vol. silica nanoparticles grafted with PBA brushes. Grafting of PMMA from clay nanotubes improved their dispersion in PVC matrices, while observing temperature dependent interfacial adhesion.255 The thermomechanical properties of “hairy” particle composite films are also dramatically impacted by the

9.6. Catalysis

Surface-initiated polymerization reactions provide manifold opportunities to enhance the performance of catalysts. Modification of TiO2 nanoparticles with PNIPAM brushes, for example, has shown to stabilize the nanoparticles while retaining their catalytic activity. Moreover, the LCST properties of PNIPAM allow to control catalytic activity via temperature.1092 Similarly, grafting PNIPAM and PSBMA from chymotrypsin was shown to increase the temperature stability of the enzyme while maintaining enzyme activity.441 While these two examples represent two possible applications of SICRP reactions to catalysis, polymer brushes are more commonly used as supports for the immobilization of catalysts. Table 25 presents an overview of catalysts immobilized on polymer brush modified supports or polymer brush based catalysts prepared via SI-CRP, which includes (bi)metallic nanoparticles,214,470,505,697,1093−1095 the catalysts listed in Table 25 included organometallic catalysts, 710,806,807,820,1096 bases, 74 6,807, 1097 acids, 487, 660, 663,6 64,109 8,109 9 and enzymes.662,696,737,756,757,761−763,766,1100−1103 These catalysts are used for a range of reactions, most commonly oxidation,505,696,820,1094,1095,1100,1102 reduction, 470,1093 hydrolysis 660,662,697,737,756,757,761,766,1097,1099,1101 and esterification487,663,761−763,1098 reactions. There are also reports of the brush-supported catalysts being used for Suzuki crosscoupling,710 Knoevenagel condensation,746,807 epoxidation,806 ring-opening,807 (photo)degradation,214,762 dehydration,664 hydrogenation,1096 and azide−alkyne cycloaddition1104 reactions, which elegantly demonstrates the range of reactions possible using these methodologies. Ag, Pd, Pd/Au, Au, Pt, ZnO/ZnS/Ag2S, and Ni are the most commonly used (bi)metallic catalytic nanoparticles that are presented on polymer brush modified supports obtained via surface-initiated controlled radical polymerization. Costantini et 1233


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precursor with tetra-n-butyl titanate.1123 PDMAEMA brushes grown via SI-ATRP from gold substrates have been used to guide the formation of thin micropatterned titanium dioxide1124 and silica films.1125,1126 Tugulu et al. have prepared photolithographically patterned PMAA brushes via SI-ATRP which were subsequently used to fabricate 3D microstructured calcite films.1127

al. used a carboxylic acid modified brush for the in situ formation of Ag and Pd nanoparticles as a catalytic coating on the inner wall of glass microreactors. These catalytic microreactors were applied for the reduction of 4-nitrophenol and for the Heck reaction.1093 In another example, 4-diphenylphosphine styrene brushes were grown from silica nanoparticles, which were subsequently used for the immobilization of Wilkinson’s catalyst.1096 The use of magnetic nanoparticles is attractive as it facilitates removal of the catalyst. This was demonstrated by Gill et al., who grafted PS brushes that incorporate Co(III) salen or piperazine side chains via SIATRP from Fe3O4 nanoparticles.807 Li et al. prepared sodium p-styrenesulfonate brushes via SI-ATRP and transformed them to poly(p-styrenesulfonic acid) brushes. Catalytic performance of brushes was tested by esterification of lauric acid with ethanol and acid exchange capacity was found to be in the range of 0.20−0.60 mmol H+g−1.1098

9.8. Chiral Polymer Brushes

Over the past years, a number of reports have described the preparation of chiral polymer brushes, which have been explored as substrates in cell culture experiments as well as for the separation of enantiomers. Wang et al. reacted L- and Dvaline with acryloyl chloride to give the corresponding acrylamido monomers, which were subsequently polymerized from a silicon wafer by SI-ATRP to generate 10−14 nm thin chiral brush films. The brushes were then used as substrates to culture COS-7 and bEnd.3 cells and it was found that in each case, the cells adhered to and proliferated better on the Lbrushes.279 It is worth noting that the brush surfaces were identical in terms of their thickness, smoothness and water contact angle and thus the difference in cell behavior was attributed to the stereochemistry of the monomers. The group extended the work to other monomers, which incorporate Land D-alanine and leucine instead of valine. The hydrophobicity of these monomers increases in the order alanine > valine > leucine, which translates into an increase in water contact angle of the corresponding brushes, which were determined to be 42°, 52°, and 57° respectively.280 The authors also studied and compared the behavior of COS-7 and bEnd.3 cells cultured on these brushes. It was found that for the monomers with larger (more hydrophobic) side groups, the difference in the cell behavior on the two substrates was pronounced (with the Lbrushes once again being preferred). This difference was not significant for brushes based on the N-acryloyl-L(D)-alanine monomers. Chiral polymer brushes have also found utility in the chromatographic separation of enantiomers. In an initial report, Wang et al. demonstrated this using a PGMA brush grafted silica stationary phase, which was postmodified with βcyclodextrin. This stationary phase was useful to resolve enantiomers of chlorthalidone, aminoglutethimide, chlorpheniramine, ibuprofen, amlodipine and benzoin.734 Since β-cyclodextrin can couple to the PGMA brushes via any of the hydroxyl groups at the 2-, 3-, and 6- positions, the authors went on to modifying the silica stationary phase with brush layers that incorporated 2-methyl-3-butyn-2-ol methacrylate. This enables side selective CuAAC coupling of β-cyclodextrin and result in better separation of the enantiomers (lower Rs values) as well as separation of the enantiomers of mandelic acid and chlorthalidone in a sample of human plasma spiked with the analytes.733,774,798 Choi and co-workers prepared chiral stationary phases by SIATRP of vinylated cellulose 2,3-bis(3,5-dimethylphenylcarbamate). These polymer brushes were grown either directly from silica276 or from silica grafted with an initial polystyrene block.277 The authors demonstrated enantiomer separation of stilbene oxide, benzoin, 2-phenylcyclohexanone, cobalt(III) trisacetylacetonate, D,L-sec-phenylethyl alcohol, Tröger’s base, 2,2,2-trifluoro-1-(9-anthryl)ethanol and flavanonein.

9.7. Brush-Assisted Synthesis of Metallic and Inorganic Nanoparticles and Thin Films

Polymer brushes grafted from silicon/ SiO x , 198 ,5 61, 795 ,1 093 ,1 105 −110 7 gold, 109 5, 110 8−11 10 polymer,1111−1114 carbohydrate-based,1115 carbon-based,470,488,1116 iron-,1117 and titanium-oxide504,1118 substrates have been used to template the formation of a variety of metal nanoparticles including silver,198,795,1093,1109,1118 gold,198,470,561,1106,1113,1114 platinum, 1095,1106 copper, 1105,1107,1108,1110−1112,1115 nickel,1108,1111,1112,1115 palladium,470,504,561,1093 PbS,1117 and CdS(/CdSe).488,1116 Table 26 presents an overview of the different metal nanoparticles that have been prepared using polymer brush templates. Most often, the templates that are used to produce metal nanoparticles are carboxylic acid side chain functionalized brushes (such as PHEMA postfunctionalized with succinic anhydride)1093,1109,1119 or basic brushes such as PDMAEMA, 470,504,561,1113,1114 its quaternized analogue PMETAC1108,1110,1112 or P4VP.198,1095,1105 The metallic precursors are typically introduced into the brushes by impregnating them with an aqueous solution of metallic salt. Nanoparticles will be formed after chemical reduction of the metallic salt. Then by removing the brush template, the metallic films will be prepared.198,504,561,1107,1114,1118 There are also other ways to make metallic films, one of the most commonly used way is electroless plating (via a PdCl42− precursor).1105,1108,1110−1112,1115 Grafting the polymer brush template from a particle instead of a planar substrate allows access to more complex architectures. For example, removing the silica core onto which the nanoparticle-templating brush has been formed yields a hollow particle with a nanoparticle-impregnated polymer shell.795 In addition to metallic nanoparticles, polymer brushes can also be used to template the formation of nonmetallic inorganic nanoparticles and thin films. For example, PEGMEMA brushes have been used as a template for the formation of TiO2 films462 and PNIPAM brushes have been used as to template the formation of vaterite crystal thin films.1120 Taniguchi et al. have reported on the use of a polymer brush-grafted polystyrene particle to template the condensation of TEOS precursor to silica. The polystyrene core can then be removed either via calcination1121 or dissolution in THF1122 to yield raspberryshaped hollow nanoparticles. The authors have also demonstrated that the process is applicable to the formation of a hollow titania-shell raspberry particle by substituting the TEOS 1234


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Table 25. Overview of Catalysts Immobilized on Polymer Brush Modified Supports or Polymer Brush Based Catalysts Prepared via Surface-Initiated Controlled Radical Polymerization

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Table 25. continued

9.9. High Binding Capacity Layers for Biomolecular Mass Spectrometry

allowed for the identification, via LC-MS/MS of 2447 unique phosphopeptides from the tryptic digest of Arabidopsis.1129 In a similar vein to the above reports polymer brushes have also been used for glycoprotein enrichment. In this case, PGMA brushes were grafted onto silica particles and subsequently derivatized with lectin. The thus-functionalized particles were shown to specifically adsorb glycoproteins from a solution containing high amounts of nonglycoproteins (BSA) leading to enrichment prior to MALDI-TOF MS analysis.275 Magnetic, silica coated Fe2O3 nanoparticles modified with aldehyde functionalized PGMA brushes were used to digest BSA, IgG, or protein extracts from Thermoanaerobacter tengcongensis. Remarkably, digestion times of only 1−2 min were required using the trypsin-functionalized particles whereas using free trypsin, the digestion time is usually ∼16 h for identical concentrations of BSA.752

Polymer brushes produced by SI-CRP have also been explored as high binding capacity coatings on MALDI-TOF MS sample plates to allow enrichment of the analytes. This was first demonstrated by Dunn et al., who grafted PHEMA brushes on a gold substrate, which were subsequently functionalized with nitrilotriacetate-Fe(III) complexes to allow selective binding of phosphopeptides.1128 Thus, phosphopeptides could be enriched on the MALDI plate allowing the detection of femtomole quantities of the peptide. Other approaches for the enrichment of phosphopeptides take advantage of their affinity to metal oxides (TiO2) or metal ions (Fe3+, Zr2+, and Ti4+). Qin and co-workers prepared ZrPO3 loaded PGMA brush-based enrichment capillary columns, which were used to provide online enrichment prior to MS analysis of a tryptic digest of α-Casein leading to the identification of 22 phosphopeptides.735 In another example, Ti4+ loaded PPEGMA brushes were grafted from Fe2O3/SiO2 core−shell nanoparticles which allowed the particles bearing the phosphopeptides to be magnetically separated from the nonphosphopeptide-containing supernatant. Remarkably, the methodology

9.10. Liquid Crystalline Brushes

One example of a liquid crystalline polymer brush by Wei et al. used silica particles grafted with a mesogenic polymer brush as a stationary phase for liquid chromatography.1130 The thus synthesized brushes were shown capable of separating isomers of carotene (α- vs β-) and polyaromatic hydrocarbons (i.e., 1236


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Table 26. Overview of Metallic Nanoparticles that Have Been Prepared Using Polymer Brush Templates Obtained via SI-CRP

stopped and only reverted to the original form on exposure to visible light. The photoisomerization of azo-benzene units has also been explored by Wang et al. In their work, graphene oxide modified with an azobenzene brush was used as a filler to enhance the diffraction efficiency (DE) of photoinduced surface-relief gratings (SRGs) on azo molecular glass films.474 In a series of reports, Haque et al. have investigated the structure and dynamics of surface-grafted azobenzene containing polymer brush thin films.253,1132,1133 In an initial study, the advantages of isolating the mesogen-bearing block from the

phenanthracene vs anthracene, benz(a)anthracene vs chrysene and benzo(a)pyrene vs perylene). In the same year, Naka et al. demonstrated the formation of reversible photomobile films by grafting azo-benzene monomers from a cross-linked polybutadiene film.1131 Reversible isomerization of the azo-benzene moieties on irradiation with UV and visible light was demonstrated. When exposed to linearly polarized UV light, the films showed slight bending along the direction of polarization toward the actinic light source. The films maintained their bent shape even once the irradiation was 1237


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underlying (quartz) substrate using an initial block of poly(hexyl methacrylate) was demonstrated.1132 This allowed for more efficient orientation of the mesogens as well as a narrower temperature range in which the induction of anisotropy was optimized. The effect was attributed to the fact that in-plane rotations (which lead to anisotropy) are more readily achieved in the presence of an underlying flexible block. The importance of the flexibility of the underlying block was further emphasized in a following publication, which revealed that using polymers with a higher glass transition temperature leads to brushes which are incapable of adopting a highly ordered conformation.253 Further, the authors also demonstrated that increasing the length of the underlying flexible block also facilitates radiation-induced isomerization.1133

the dyes1134,1135 while maintaining high photoluminescent quantum yields (up to 0.90).1135 Polymer brush coated nanoparticles have also been used as precursors to colloidal crystals.204,246,466,1139−1141 A series of papers from the laboratories of Tsujii and Ohno have demonstrated the formation of colloidal crystals from a range of silica-core, polymer-shell hybrid nanoparticles.204,246,466,1139,1140,1142,1143 These so-called “semisoft” colloidal crystals demonstrate remarkable interparticle longrange order and offer the opportunity to tune a number of parameters. In particular, the chain length of the grafted brush,1140,1143 nature of the grafted polymer,204,1140 and the substrate size,246 composition and geometry can all be tuned to dictate the properties of the final crystal.

9.11. Polymer Brushes for Photonic Applications

9.12. Proton Conducting Membranes

Polymer brushes have found varied usage in photonic applications. One approach involves the use of the polymer brush to attach photoluminescent moieties. 645,695,744,801,817,1044,1134,1135 Alternatively, polymer brushes can be grafted directly from photoluminescent nanoparticles.1136,1137 The later approach has been shown to improve the dispersion and near-band-edge emission of nanoparticles.1137 Further, the intrinsic processability of the grafted polymer allows incorporation of fluorescent moieties into functional materials such as polystyrene-grafted fluorescent carbon nanoparticles being electrospun into a fiber mat.1138 The functionality of a polymer brush can also be used to tune the properties of the resultant hybrid. For example, grafting pH responsive brushes to gold nanoparticles allows the plasmonic resonance of the resultant suspension to be changed in response to changes in the pH and nature of the solvent.1136 Similarly, using thermoresponsive brushes such as PNIPAM allows modulation of the spatial distribution of nanoparticles attached to brushes which in turn allows a thermo-reversible surface plasmon absorbance band shift.817 The thermoresponsive properties of PNIPAM brushes have also been exploited in photonic applications where the dye is attached to the polymer brush. This was elegantly demonstrated by Wu et al. to tune the fluorescence resonance energy transfer (FRET) efficiency of silica particles grafted with FRET donor− acceptor pairs. In this case, the authors copolymerized NIPAM with a FRET donor 4-(2-acryloyloxyethylamino)-7-nitro-2,1,3benzoxadiazole (NBDAE) and a photoswitchable acceptor, 1′(2-methacryloxyethyl)-3′,3′-dimethyl-6-nitro-spiro(2H-1benzo-pyran-2,2′-indoline) (DNSMA), via SI-ATRP from silica nanoparticles.1044 Under UV irradiation the DNSMA underwent photoisomerization from the nonfluorescent spiropyran form to the fluorescent merocyanine form. This transformation was reversible under visible light irradiation. Thus, the authors were able to construct silica−polymer hybrid nanoparticles where the FRET process could be turned on or off via UV (respectively visible) radiation while the FRET efficiency could be controlled via the temperature-induced swelling/collapse of the PNIPAM brush. Fluorescent quaternary ammonium tetraphenylethylene derivatives attached to brushes were shown to have their photoluminescence quenched in the presence of 2,4,6trinitrotoluene (TNT). This quenching was shown to have a high sensitivity leading to the detection of concentrations as low as 0.1 ppb of TNT in water.645 Incorporating photoluminescent dyes into polymer−clay hybrid materials has also been shown to improve the thermal and chemical stabilities of

SI-CRP reactions also provide opportunities to generate proton conducting hybrid materials. This section as an example will highlight the proton conductivity properties of PSS and PAMPS brushes grafted from nanoparticles and macroporous silicon channels. Proton conductive membranes have been prepared by blending brush-grafted nanoparticles into an inert polymer matrix. This has been demonstrated with silica nanoparticles grafted with PSS, which were blended into a poly(vinylidene fluoride-co-hexafluoropropylene) matrix. The proton conductivity of the composite membrane was found to depend on the loading of the hybrid nanoparticles. A maximum of 0.1 S/cm was achieved with 60 wt % of the particles and 10 mS/cm at 30 wt %.1144 Proton conductive membranes have also been made by grafting PSS brushes on TiO2 nanoparticles and blending the particles into a poly(vinylidene fluoride-co-chlorotrifluoroethylene)-graf t-poly(styrene sulfonic acid) film.1145 In this case, the authors were able to achieve proton conductivities of 4−5 × 10−2 S/cm with the addition of 2−8 wt % of the brush-grafted nanoparticles, although it should be noted that membranes without nanoparticles also had a proton conductivity of approximately 3.8 × 10−2 S/cm. An alternative approach was reported by Yameen et al., who developed proton conducting membranes by filling the pores of porous silicon scaffold via SIATRP with 100 nm thick poly(sodium 2-acrylamide-2methylpropanesulfonate) brush layer. In this way, the authors generated polyelectrolyte microdomains oriented normal to the plane of the membrane with conductivities in the range of 1 × 10−2 S/cm.1146 9.13. Polymer Brushes for Field Effect Transistors and Photovoltaic Devices

One interesting application of SI-CRP in the pursuit of allpolymer field-effect transistors is in the generation of polymer brush-based gate dielectrics. The ease of device preparation and the avoidance of expensive fabrication facilities are primary advantages of all-polymer field-effect transistors. In one study, the performance of a device consisting of a poly(3hexylthiophene) active layer on a PMMA brush was studied. It was demonstrated that the PMMA gate dielectric penetrated the P3HT active layer after annealing at 40 °C, with lower molecular weight P3HT demonstrating larger mobilities than higher molecular weight samples.886 Moreover, PS brushes grafted from SiO2 surfaces via SI-ATRP have also been shown to perform as gate dielectrics in devices that used pentacene as active organic semiconductor. The capacity of the device was found to vary with film thickness. While 12.5 nm thick brushes 1238


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yielded a capacitance of 11.5 nF/cm2, for 113 nm thick brushes a capacitance of 7.5 nF/cm2 was determined.1147 The hole-transporting properties of polymer brushes have also been exploited to demonstrate proof-of-concept organic photovoltaic devices. In one example, poly(N-vinylcarbazole) (PVK) brushes were grafted onto ITO surfaces and showed comparable performance to standard PEDOT:PSS-based devices (photoconversion efficiency of 2.3% cf. 2.1%). The authors postulate that the lack of an insulating layer and acid dopant in the PVK device should result in a more robust device with regards to humidity and oxygen exposure which are detrimental contributors to the lifetime of an organic photovoltaic device.175 Polymer brushes have also demonstrated utility in the fabrication of TiO2 electrodes for dyesensitized solar cells. In this case, PEGMEMA brush-grafted aluminum oxide particles were used to template the formation of crack-free, organized mesoporous TiO2 films with good interconnectivity between the pores. The high surface areas and interconnectivity were crucial for improving dye adsorption and pore infiltration of the solid polymer electrolyte and facilitated electron transfer resulting in an energy conversion efficiency of 7.3% at 100 mW/cm2.462 Silica particles grafted with poly(4vinyl-triphenylamine) (PVTPA) brushes have also been used in dye-sensitized solar cells. In this case, the particles were added into a solar cell based on the common hole conductor spiroMeOTAD (2,2′,7,7′-tetrakis(N,N-di-p-methoxyphenylamine)9,9′-spirobifluorene). The authors found that incorporating the brush-grafted silica particles at a 1:1 weight ratio to the spiro-MeOTAD resulted in a 26% improvement in photocurrent over the pure spiro-MeOTAD device.1089

increase in high-energy storage densities such as 21.51 J/cm3 at 3 MV/cm with respect to bulk PGMA 5.86 J/cm3 at 5 MV/ cm. Qiao et al. investigated grafting monomers with pendant oligothiophene units to BaTiO3 particles using S-RAFT polymerization resulting in composite materials with high permittivity (∼20) and low dielectric losses ( PGMA > PHEMA while the leakage currents were in the order of PHEMA > PMMA > PGMA. This work reinforces the point that, while materials with high dielectric currents have high storage capabilities, materials with high leakage currents have high dielectric loss and low breakdown strengths. Thus, an optimal material for energy storage would be one with a high dielectric constant and low leakage current. SI-CRP can also be used to generate thin-film electrodes for organic radical batteries as has been demonstrated in a series of papers by Lee et al.601,602,808,809 The authors reported on the use of nitroxide-bearing polymer brushes as cathodes for organic radical batteries. In the first report, the authors used a combination of μCP, SI-ATRP and postpolymerization modification to obtain patterned nitroxide brushes on ITO and ITO/PET surfaces. The latter served as a demonstration of the technique to obtain flexible thin-film electrodes while the former was used to store charge. The recorded discharge capacities at 10, 20, and 50 C were 97, 87, and 74 mA h g−1 respectively and the brushes had a thickness of 11.3 nm (as measured by AFM).602 The group went on to further investigate the effect of brush thickness on the capacity of the batteries by studying brushes with film thicknesses of 28, 47, 55, 68, and 84 nm. Comparison of the different brushes at a discharge rate of 20 C revealed a discharge capacity of 90 mA h g−1 for film thickness of 20, 47, 55 nm. For thicker films, in contrast, there was a sharp drop-off in capacity as at these thicknesses, the postpolymerization oxidation of the precursor polymer to the nitroxide did not take place at the base of the brush, which resulted in a barrier to charge propagation.601 Lee and co-workers also grafted nitroxide brushes from silica particles of different sizes and used these particles in conjunction with conductive carbon to form electrodes. In this case, the authors noted that the discharge capacity of the composite electrode depended on the size of the silica particle. For example electrodes with 400 nm particles had a discharge capacity of 121 mA h g−1 at 10 C while electrodes with 40 and 15 nm particles had discharge capacities of 94 and 84 mA h g−1 respectively.809 The best results were achieved with 400 nm silica core particles, which had discharge capacities of 102 and 95 mA h g−1 at 30 and 50 C respectively. In a final example, Lee and co-workers reported the preparation of three-dimensionally ordered macroporous nitroxide brush electrodes, which were prepared via SI-ATRP of 2,2,6,6-tetramethyl-4-piperidinyl methacrylate (TMPMA) and subsequently postpolymerization

9.14. Energy Storage

Polymer brush-derived nanocomposites have attracted significant interest in the area of energy storage to alleviate difficulties like low breakdown strength and processing difficulties encountered with traditional ferroelectric ceramic materials such as BaTiO3.1148 Polymer brushes can provide an elegant solution to the problem of incompatibilities between the ceramics and the polymer matrix leading to inhomogeneous mixing. Yang et al. for example have shown that BaTiO3 nanoparticles modified with a RAFT grown poly(1H,1H,2H,2H-heptadecafluorodecyl acrylate) brush can be solution blended with poly(vinylidene fluoride-co-hexafluoropylene) to form nanocomposite films, which can withstand a high electric field and exhibit significantly enhanced energy storage capability in comparison with the pure fluoropolymer.213 Furthermore, the incorporation of the fluoropolymer grafted nanoparticles into the film reduces their dielectric loss and thus may be a potentially promising material for energy storage. Paniagua et al. investigated a one-component nanocomposite dielectric material composed of barium titanate nanoparticles modified with a PMMA brush generated by ARGET ATRP.1083 The PMMA modified barium-titanate nanoparticles were found to possess approximately twice the extractable energy density (2 J/cm3) as compared to a similar material wherein the PMMA and BaTiO3 were simply mixed together. Similarly, Xie et al. have shown that BaTiO3/PMMA nanocomposites showed both higher dielectric constants and lower losses than bulk PMMA in a wide range of frequencies.1081 A recent study investigating PGMA modified BaTiO3 nanocomposites to improve dielectric properties was carried out by Grayson and co-workers.1149 Therein, 20 nm PGMA grafted BaTiO3 nanoparticles exhibited significant 1239


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may be SET-LRP/SARA ATRP. Indeed while this is already used quite extensively, there have been synthetic developments in recent years that bring new insight into how to perform ultrafast polymerizations83 and polymerizations initiated by household lamps,136 for example, which will likely have high impact in the field of SI-CRP. A challenge that remains is the precise and facile determination of initiator and polymer brush grafting density and, thus, initiator efficiency. This challenge is particularly important as several studies have shown the effects of differences in grafting density on the properties of the polymer brush. To establish accurate composition-property relationships it would be important to have a simple, versatile and accurate technique for determining the number of initiator units per square nanometer of substrate. Often, brush grafting densities are calculated based on the number-average molecular weight of free polymers produced simultaneously with sacrificial initiators. However, a survey of the literature indeed shows that the molecular weight of polymers grafted from surfaces and synthesized in solution are not always identical (section 2.7.4). Opportunities in this field are varied and numerous as evidenced by the extensive applications above. Although the utility of polymer brushes via SI-CRP in fields such as separation science, biosensors, and nonfouling coatings is well-established, research in polymer brushes toward organic electronics is still in its infancy. Another opportunity that has seen an increasing amount of research effort is the field of photovoltaic applications. Although not a topic addressed here, another emerging application of polymer brushes is anti-icing coatings.1162,1163 Overall, the broadened scientific interest in SI-CRP is predicted to provide answers to some of the remaining fundamental questions of surface-tethered polymers as well as new applications that have yet to be demonstrated. There are a substantial number of groups working in the field worldwide and the opportunities for interdisciplinary collaboration to meet these fundamental challenges and address application-focused questions are almost innumerable. We have presented a comprehensive overview of the past few years in this review, and we expect even more growth and diversity in the field in the coming years.

modification from polypyrrole inverse opal substrates. The discharge of these electrodes was found to increase with increasing polymerization time to 0.17 μA h g−1 at 5 C at 6 h and then remained more or less constant. This capacity was 40 times higher than that of the planar electrode.808 The nitroxide polymer brushes also had excellent retention of function after several cycles with the brushes on ITO maintaining 97.3% efficiency after 100 cycles,601 those on silica particles maintaining 96.3% efficiency after 300 cycles,809 and the three dimensionally ordered brushes retaining 96.1% efficiency after 250 cycles.808 Good cycling stability (87% after 200 cycles) and specific capacity (85% of theoretical capacity) was also demonstrated for nanocomposites composed of MWCNTs grafted with nitroxide polymer brushes.1153 PMMA brushes have also been used as surface-grafted nanodielectrics by Li et al. For PMMA brushes with a film thickness of 10 nm, a maximum capacitance of 220 nF/cm2 and low leakage density (2 × 10−8 to 6 × 10−8 A/cm2 at 2 MV/cm) as well as an effective dielectric constant of 3.1, which is slightly smaller than that of spin coated PMMA(εpb= 3.5) were found. By combining these polymer brush based nanodielectrics with copper phtalocyanine single crystalline nanoribbons, the authors fabricated battery-drivable organic single-crystalline transistors.1154 In another example, the same authors used these PMMA brush-based nanodielectrics to build a variety of OFET devices using a range of semiconductors (pentacene, vanadyl phthalocyanine, perfluorinated copper phthalocyanine).1155 Ma et al. demonstrated that PMMA brushes can be charged both positively and negatively by means of conductive microcontact printing and AFM lithography. The charge storage performance of these PMMA brush electrets is almost the same as that of bulk PMMA thin films. There are several advantages related to the use of the PMMA brush electrets as compared with bulk PMMA thin films. First of all, the PMMA brushes allow the fabrication of uniform charge patterns on nonplanar surfaces which is hardly to realize by using bulk PMMA thin films. Second, the charge stability of PMMA brushes in organic solvent is higher than PMMA bulk materials, which will be dissolved in a good solvent.595

10. CONCLUSIONS, OPPORTUNITIES, AND CHALLENGES Since our last review, over 1500 articles have been published covering research involving SI-CRP. Surely, this is even underestimated. We have attempted to be comprehensive, however, a few articles might have been unintentionally overlooked in our review of the literature solely due to the vast applicability of SI-CRP in multiple research fields. Nevertheless, this rapid pace is exciting and reflects the broad scientific interest in the use of SI-CRP to generate functional surfaces and interfaces. One of the advances in the field is the emergence of RAFT as a powerful technique to generate surface-grafted polymer brushes. Indeed, while SI-ATRP is still the predominant technique in the field, the adaptability of RAFT to a range of polymerization conditions is certainly a powerful incentive for researchers to look at it as a promising methodology. Particular advancements in RAFT polymerization made in recent years such as the ability to synthesize multiblock copolymers with a high degree of fidelity,1156,1157 the ability to work in the presence of oxygen1158,1159 and its compatibility with a broad range of functional groups1160,1161 are attractive to those working in the field of SI-CRP. Another promising technique

AUTHOR INFORMATION Corresponding Author

*E-mail: harm-anton.klok@epfl.ch. Phone: + 41 21 693 4866. Fax: + 41 21 693 5650. Notes

The authors declare no competing financial interest. Biographies Justin Zoppe was born in Flint, Michigan (USA) in 1983 and graduated from the University of North Carolina at Wilmington with a Bachelor of Science degree in Chemistry and a minor in Mathematics. He was awarded a Ph.D. in 2011 from the Department of Forest Biomaterials at North Carolina State University under the supervision of Prof. Orlando Rojas. He then joined the Polymer Technology group of Prof. Jukka Seppälä at Aalto University as a postdoc before working as a Research Scientist at Clariant Specialty Chemicals in Frankfurt, Germany in 2013. Dr. Zoppe moved to the Polymers Laboratory of Prof. Harm-Anton Klok at EPFL in 2014 and is currently an EPFL Fellow cofunded by Marie Curie working on the synthesis of multivalent cellulose nanocrystals for application as viral entry 1240


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kindly providing Figure 11, and Dr. Ioana Konz for proofreading the manuscript.

inhibitors. In addition to biomedical applications of cellulose nanomaterials, he is interested in the fundamentals of transition metal-mediated SI-CRP carried out in polar media, surface forces, and self-assembly of lyotropic liquid crystals.

ABBREVIATIONS 2VP 2-vinylpyridine 3HT 3-hexylthiophene 3VP 3-vinylpyridine 4VP 4-vinylpyridine 4VTPA 4-vinyltriphenylamine AA acrylic acid AAb acrylated antibody AACFPC acrylamide fluorinated phosphatidylcholine AAEE N-acryloylaminoethoxyethanol AAETAM 2′-acrylamidoethyl-2,3,4,6-tetra-O-acetyl-αD-mannopyranoside AAO anodic aluminum oxide AAEP 2′-acrylamidoethyl D-pyranosides AAPBA 3-(acrylamido)phenylboronicacid AASOPC 9-(2-amino-ethylcarbamoyl)-nonyl-1-phosphatidycholineacrylamide ABA azobenzeneacrylate ABC N-acryloyl-S-benzyl-L-cysteine ABTS 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonicacid) AcGEMA 2-(2,3,4,6-tetra-O-acetyl-β-D-glucosyloxy)ethyl methacrylate ADA 1-adamantan-1-ylmethyl acrylate AdG Alexander−deGennes AD-TEGA adamantane-functionalized tetraethylene glycol acrylate AEMA 2-aminoethyl methacrylatehydrochloride (also listed as 2-aminoethyl methacrylate) AETAC (2-(acryloyloxy)ethyl)trimethylammonium chloride AFM atomic force microscopy AGA N-acryloylglucosamine AGMA dimethyl-(4-methacryloyloxy)phenylsulfoniumtriflate AIBN 2,2′-azobis(2-methylpropionitrile) AL acrolein AM acrylamide AMA allyl methacrylate aminobutyl NTA Nα,Nα-bis(carboxymethyl)-L-lysinehydrate AMP 1-aminomethylpyrene AMPS 2-acrylamido-2-methyl-1-propanesulfonatesalts AMPSA acrylamido-2-methylpropanesulfonicacid AN acrylonitrile AnMA 9-anthracenylmethyl acrylate anti-β-hCG anti β subunit of human chorionic gonadotrop AP 1-aminopyrene APTES (3-aminopropyl)triethoxysilane AO acrydite-modified oligonucleotides APBA-PA 3-(2-azido-acetylamino)phenylboronicacidpropargyl acrylate APMA N-(3-aminopropyl)methacrylamidehydrochloride APTAX 3-acrylamidopropyltrimethylammoniumsalts APTMS 3-aminopropyltrimethoxylsilane A(R)GET activators (re)generated by electron transfer AS acetoxystyrene

Nariye Cavusoglu Ataman was born in Kardzhali (Bulgaria) in 1986. She obtained her M.Sc. degree in the group of Prof. E. Acar in Chemistry Department at Bogazici University (Istanbul, Turkey) in 2011. She completed her Ph.D. studies under the supervision of Prof. H.-A. Klok at the Ecole Polytechnique Federale de Lausanne (EPFL, Switzerland) in 2016. Piotr Mocny was born in Tczew (Poland) in 1989. He received his B.S. degree in double majors of chemical technology and physics at Gdansk University of Technology. He continued studies in chemical technology and graduated with M.Sc. degree in 2013. He is currently working as a Ph.D. student with H.-A. Klok at the École Polytechnique Fédérale de Lausanne (EPFL). Jian Wang was born in 1989 in Jilin Province, China. He received his B.Sc. from the College of Chemistry, Jilin University, in 2012. After that, he became a master student under the guidance of Professor Yapei Wang at the Department of Chemistry, Renmin University of China. In 2015, he joined Professor H.-A. Klok’s group in École Polytechnique Fédérale de Lausanne, Switzerland as a Ph.D. student. John Moraes completed his undergraduate and Masters at Victoria University of Wellington, New Zealand (under the supervision of Prof. Jim Johnston, Prof. Peter Northcote, and Dr. Thomas Borrmann). He then spent three years teaching English at public schools in rural Japan and a year working at Schering-Plough in New Zealand. He started his Ph.D. studies in 2009 and completed his dissertation under the supervision on Prof. Sébastien Perrier and Prof. Thomas Maschmeyer at the University of Sydney, Australia. This included a collaboration with Prof. Kohji Ohno and Yoshinobu Tsujii at the University of Kyoto, Japan. Following this, he was a postdoc in the group of Prof. Harm-Anton Klok in Lausanne, Switzerland where he received an EPFL fellowship to study the coating of semiconductor surfaces with polymers and silver nanoparticles. His previous research projects have focused on surface-initiated RAFT polymerization, polymer and surface characterization, wet-air oxidation, conducting polymer-paper composites, and organic deprotection chemistry and have led to 14 research papers. Harm-Anton Klok is a Full Professor at the Institutes of Materials and Chemical Sciences and Engineering at the École Polytechnique Fédérale de Lausanne (EPFL, Switzerland). He was born in 1971 and studied chemical technology at the University of Twente (Enschede, The Netherlands) from 1989 to 1993. He received his Ph.D. in 1997 from the University of Ulm (Germany) after working with M. Möller. After postdoctoral research with D. N. Reinhoudt (University of Twente) and S. I. Stupp (University of Illinois at Urbana− Champaign), he joined the Max Planck Institute for Polymer Research (Mainz, Germany) in early 1999 as a project leader in the group of K. Müllen. In November 2002, he was appointed to the faculty of EPFL.

ACKNOWLEDGMENTS Financial support from the Swiss National Science Foundation (SNF), the EPFL Fellows Marie Curie COFUND program (EU FP7 grant agreement no. 291771; J.Z. and J.M.) as well as the China Scholarship Council (J.W.) is gratefully acknowledged. The authors would like to thank Prof. Michele Ceriotti (EPFL) and Prof. Stefano Angioletti-Uberti (Imperial College) for their helpful comments regarding the section on polymer brush theory, Prof. Julius Vancso (University of Twente) for 1241


Chemical Reviews ATEA ATPP-PF6 ATRA ATR-FTIR ATRP AzAMA AzEMA AzPAM AzPMA BA BAEA BBEA BCNF BiBA BiBB BiBMS BIEMA BIMHFP BMA BMDO BMPUS Boc Boc-AEMA BPEA Bpy BpyClCl BSA BZ BzA BzMA CA CAA CB CBAA CBAM CBMA CBMAM CD CDI CDMA CDMPCA CDTP CEMA CHMA CMA CMF CMS CNC CNF CNT COEMA CPB CPM

Review

CPPUA

adamantyltriethoxyethyl acrylate allyltriphenylphosphoniumhexafluorophosphate atom transfer radical addition attenuated total reflectance-Fourier transform infrared spectroscopy atom transfer radical polymerization azidoalkyl methacrylate azidoethyl methacrylate 3-azidopropylacrylamide azidopropyl methacrylate n-butyl acrylate 2-(bromoacetyloxy)ethyl acrylate 2-((bromobutyryl)oxy)ethyl acrylate bacterial cellulose nanofibrils α-bromoisobutyric acid α-bromoisobutyryl bromide p-(2-bromoisobutyloylmethyl)-styrene 2-(2-bromoisobutyryloxy)ethyl methacrylate 2-(1-butylimidazolium-3-yl)ethyl methacrylatesalts N-butyl methacrylate 5,6-benzo-2-methylene-1,3-dioxepane [11-(2-bromo-2-methyl)propionyloxy]undecyltrichlorosilane tert-butyloxycarbonyl protecting group butoxycarbonylaminoethyl methacrylate 2-(2-bromopropionyloxy)ethyl acrylate 2,2′-bipyridine N-benzyl-N′-(4-vinylbenzyl)-4,4′-bipyridiumdichloride bovine serum albumin Belousov−Zhabotinsky benzyl acrylate benzyl methacrylate cellulose acetate 2-carboxyethyl acrylate carboxybetaine carboxy betaine acrylamide carboxy betaine-derivatized acrylamide carboxy betaine methacrylate carboxy betaine methacrylamide β-cyclodextrin 1,1′-carbonyldiimidazole cadmium dimethacrylate cellulose2,3-bis(3,5-dimethylphenylcarbamate)-6-acrylate 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoicacid 2-(N-carbazolyl)ethyl methacrylate cyclohexyl methacrylate 7-(2-methacryloyloxyethoxy)-4-methyl-coumarin cellulose microfibrils 4-chloromethylstyrene cellulose nanocrystals cellulose nanofibrils carbon nanotube 2-cinnamoyloxyethyl methacrylate concentrated polymer brush colloidal probe microscopy

CRP CTA CuAAC CyPAM DADMAC DCC DCM DDA DDMA DDMAT DE DEAEA DEAEMA DEGMA DEMM-TFSI DEPN DFHMA DFT DHPA DHPMA DIPC DLS DMAEMA DMAM DMAP DMAPAM DMAPMAM DMAPS DMDOMAM DMF DMIAM DMIPMA DMMA DMPST DMSMA DMSO DMVSA DNA dNbipy DNL DNP DNSMA DOPA DPAEMA 1242

11-(4′-cyanophenyl-4″-phenoxy)undecyl acrylate controlled radical polymerization chain transfer agent Cu-catalyzed azide−alkyne cycloaddition N-cyclopropylacrylamide diallyldimethylammonium chloride N,N′-dicyclohexylcarbodiimide dichloromethane dodecyl acrylate (also known as LA) dodecyl methacrylate 2-(dodecylthiocarbonothioylthio)-2-methylpropionicacid diffraction efficiency N,N-diethylaminoethyl acrylate 2-(diethylamino)ethyl methacrylate di(ethylene glycol)methyl ethermethacrylate N,N-diethyl-N-(2-methacryloylethyl)-Nmethylammoniumbis(trifluoromethylsulfonyl)imide N-tert-butyl-N-[1-diethylphosphono-(2,2dimethylpropyl)]nitroxide dodecafluoroheptyl methacrylate density functional theory N-(2,3-dihydroxypropyl)acrylamide 2,3-dihydroxypropyl methacrylate N,N′-diisopropylcarbodiimide dynamic light scattering 2-(dimethylamino)ethyl methacrylate N,N-dimethylacrylamide 4-(dimethylamino)pyridine N-(3-(dimethylamino)propyl)acrylamide N-[3-(dimethylamino)propyl]methacrylamide N , N - d i m e t h y l - ( m e t h a c r y l o y le t h y l ) ammonium propane sulfonate [(2,2-dimethyl-1,3-dioxolane)methyl]acrylamide dimethylformamide 2-(dimethylmaleinimido)-N-ethylacrylamide 2,3-dimethylmaleicimidopropyl methacrylate (2,2-dimethyl-1,3-dioxolan-4-yl)methyl methacrylate dimethyl-(4-methacryloyloxy)phenylsulfoniumtriflate(alsoknownasAGMA) 3-[poly(dimethylsiloxy)silyl]propyl methacrylate dimethyl sulfoxide N,N-dimethyl-N-(p-vinylbenzyl)-N-(3sulfopropyl)ammonium deoxyribonucleic acid 4,4′-dinonyl-2,2′-dipyridyl dip-pen nanodisplacement lithography 2,4-dinitrophenyl 1′-(2-methacryloxyethyl)-3′,3′-dimethyl-6nitro-spiro(2H-1-benzo-pyran-2,2′-indoline) dopamine 2-(diisopropylamino)ethyl methacrylate DOI: 10.1021/acs.chemrev.6b00314 Chem. Rev. 2017, 117, 1105−1318

Chemical Reviews DPPS dPS DPVB DSC DTBE DTT DVB EA EAA eATRP EBiB EDC EDOT EDTA EEMA EG EGDA EGDMA EGMASA EHA EHMA EMA EMEICl EMOMA EO EPAEMA eQCM ESINL ETEA EtOH FA FcMA FMA FMMA FMS FRET FRP FTIR GAMA GINAEMA GL GMA GMAG GMHP GO GOD GPC GUMA HAEMA HAK HAM

Review

HATU

4-diphenylphosphinestyrene deuterated polystyrene 2,5-dioxopyrrolidin-1-yl-4-vinylbenzoate N,N′-disuccinimidyl carbonate or differential scanning calorimetry 2,2′-dithiobis[1-(2-bromo-2methylpropionyloxy)]ethane 1,4-dithiothreitol divinylbenzene ethyl acrylate 2-ethylacrylicacid electrochemically mediated atom transfer radical polymerization ethylα-bromoisobutyrate N-(3-(dimethylamino)propyl)-N′-ethylcarbodiimidehydrochloride 3,4-ethylenedioxythiophene ethylenediaminetetraacetic acid 1-ethoxyethyl methacrylate ethylene glycol ethylene glycoldiacrylate ethylene glycoldimethacrylate ethylene glycolmethacrylatesuccinoylalkyne 2-ethylhexyl acrylate 2-ethylhexyl methacrylate ethyl methacrylate 1 - et h y l3 - ( 2 -m et h ac r y lo y l o x y et h y l) imidazolium chloride 3-ethyl-3-(methacryloyloxy)-methyloxetane ethylene oxide 2-(ethyl(phenyl)amino)ethyl methacrylate electrochemical quartz crystal microbalance easy soft imprint nanolithography pentaerythritoltetraacrylate ethanol fluoresceinacrylate 2-(methacryloyloxy)ethylferrocenecarboxylate 2-(perfluoroalkyl)ethyl methacrylate ferrocenylmethyl methacrylate 4-(perfluoroalkyl)-oxymethylstyrene fluorescence resonance energy transfer free radical polymerization Fourier transform infrared spectroscopy 2-gluconamidoethyl methacrylate 2-O-(N-acetyl-β-D-glucosamine)ethyl methacrylate tert-butoxy-vinylbenzyl-polyglycidol glycidyl methacrylate 2-methyl-acrylic acid 3-(2,4,5-trihydroxy-6hydroxymethyl-tetrahydro-pyran-3-ylamino)-propylester 3-(N-glucidol-N-methyl)amino-2-hydroxypropyl methacrylate graphene oxide glucose oxidase gel permeation chromatography glucosylureaethyl methacrylate 2-(bis(2,3-dihydroxypropyl)amino)ethyl methacrylate 2-hydroxy-2-methyl-1-(4-vinylphenyl)propan-1-one N-hydroxymethylacrylamide

hCG HDDA HDFDA HE HEA HEAAM HEBAMA HECBMA HEMA HF HFBA HFBMA hIgG HMA HMAM HMTA HMTETA HNPANA HosMA HPEMA HPG HPhMAM 2HPMA 3HPMA HPMAM HRP HTMA I IA IBMA iBoMA IgG IPSMA iSAFT ISET ITO LA LAMA LbL LDMA LC-MS/MS LCST LED LMA μCP MA MAA Mad MADIX MAECTMP

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1-[bis(dimethylamino)methylene]-1H1,2,3-triazolo[4,5-b]pyridinium3-oxidhexafluorophosphate human chorionic gonadotrophin 1,6-hexanedioldiacrylate heptadecafluorodecyl acrylate halide exchange 2-hydroxyethyl acrylate N-hydroxyethylacrylamide 2-(4-(2-hydroxyethylamino)-4oxobutanamido)ethyl methacrylate hydroxyethyl-derivatized carboxy betaine methacrylate 2-hydroxyethyl methacrylate hydrofluoric acid 2,2,3,3,4,4,4-heptafluorobutyl acrylate 2,2,3,3,4,4,4-heptafluorobutyl methacrylate human immunoglobulin G hexyl methacrylate N-hydroxymethylacrylamide hexamethylenetetramine 1,1,4,7,10,10-hexamethyltriethylenetetramine 9-(4-(4′-(9-hydroxynonyloxy)phenylazo)phenoxy)nonyl acrylate hostasol-derivatized methacrylate 4-hydroxyphenylethyl methacrylate hyperbranched polyglycidol N-(2-hydroxyphenyl)methacrylamide 2-hydroxypropyl methacrylate 3-hydroxypropyl methacrylate N-(2-hydroxypropyl)methacrylamide horseradish peroxidase 2-hydroxyl-3-(4-(hydroxymethyl)-1H-1,2,3triazol-1-yl)propyl2-methacrylate isoprene itaconic acid isobutyl methacrylate isobornyl methacrylate immunoglobulinG 3-(triisopropyloxy)silylpropyl methacrylate interfacial statistical associating fluid density theory inner sphere electron transfer indium tin oxide lauryl acrylate 2-lactobionamidoethyl methacrylate layer-by-layer assembly lead dimethacrylate liquid chromatography−mass spectrometry lower critical solution temperature light-emitting diode lauryl methacrylate micro contact printing methyl acrylate methacrylic acid 5′-methacryloyladenosine macromolecular design via the interchange of xanthates 4-(2′-methacryloyloxyethylcarbamyl)-1((1′-phenylethyl)oxy)-2,2,6,6-tetramethylpiperidine


Chemical Reviews

Review

MTEP

MAHOBA

4-((4-((6-(methacryloyloxy)hexyl)oxy)phenyl)diazenyl)benzoicacid MAIGal 6-O-methacryloyl-1,2:3,4-di-O-isopropylidene-D-galactopyranose MAIGlc 3-O-methacryloyl-1,2:5,6-di-O-isopropylidene-D-glucofuranose MA-L-Ala-OMe N-methacryloyl-L-alaninemethylester MA-L-Ala-iPA N-methacryloyl-L-alanineisopropylamide MALDI-TOF-MS matrix-assisted laser desorption/ionization time-of-flight mass spectrometry MAM methacrylamide MAn maleicanhydride MANi methacrylonitrile MAPMA 2-(N-methyl-N-(4-pyridyl)amino)ethyl methacrylate MAPTAC (3-(methacryloylamino)propyl)trimethylammonium chloride MBL α-methylene-γ-butyrolactone MBAM N,N′-methylenebis(acrylamide) MBMA 2-methyl-3-butyn-2-olmethacrylate MC Monte Carlo MCPT 4-(2′-methacryloyloxyethylcarbamyl)-1((1′-phenylethyl)oxy)-2,2,6,6-tetramethylpiperidine MD molecular dynamics MDC morpholine dithiocarbamate MDMA 2-(2-methoxyethoxy)ethyl methacrylate MDPAB 4-(10-methacryloydecyloxy)-4′-pentylazobenzene Me4Cyclam 1,4,8,11-tetraaza-1,4,8,11-tetramethylcyclotetradecane Me6TREN tris[2-(dimethylamino)ethyl]amine MEAM methoxyethyl acrylamide MEMA 2-methoxyethyl methacrylate MEO2MA di(ethylene glycol)methyl ethermethacrylate MeOEGMA monomethoxyoligo(ethylene glycol) methacrylate MeOH methanol MEP 2-(methacryloyloxy)ethylphosphate MES mono-2-(methacryloyloxy)ethylsuccinate METAC 2 -(m et h a cr y lo y lo xy )e t h y lt rim et h y lammonium chloride METAI 2-(methacryloyloxy)ethyltrimethylammoniumiodide MFT mean field theory MIPS molecularly imprinted polymer sensor MMA methyl methacrylate MMAZO 6-[4-(4-methoxyphenylazo)phenoxy]hexyl methacrylate MMT montmorillonite Mn number-average molecular weight Mw weight-average molecular weight Mw/Mn dispersity MPC 2-(methacryloyloxy)ethylphosphorylcholine MPCS 2,5-bis((4-methoxyphenyl)oxycarbonyl)styrene MPDSAH (3-(methacryloylamino)propyl)-dimethyl(3-sulfopropyl)ammoniumhydroxide MPPM microporous polypropylene membrane MS mass spectrometry MSN mesoporous silica nanoparticles MSt 4-methylstyrene

MTMA Mur MWCNT N-BocAEMA N-BocAHAM N-BocHPMA NAAa NaAc NABC NAM NaMA NAPD NAPMA NAPMAM NAS NaSS NBA NBDAC NBDAE NCS NHS NHSMA NHS4VB NIL NIPAM NMEMA NMP NMR NPA NPC NPMA NR NTA NTBAM NVBP NVCL NVF NVI NVOC NVOCAMA NVOCMA NVP OA ODA ODMA ODVBPheA OEA OEG OEGMA OEGMEMA 1244

5-(2-(trimethylsilyl)ethynyl)pyridin-2-yl2methylprop-2-enoate 3-methylthienyl methacrylate 5′-methacryloyluridine multi walled carbon nanotubes N-butoxycarbonylaminoethyl methacrylate N-(6-(N-tert-butoxy-carbonylaminooxy)hexyl)acrylamide N-butoxycarbonylhydroxyproline methacrylate N-acryloyl-L(D)-amino acids sodiumacrylate N-acryloyl-S-benzyl-L-cysteine N-acryloylmorpholine sodiummethacrylate N-acryloyl-pyrrolidine-2,5-dione 2-((naphthalen-1-ylcarbamoyl)oxy)ethyl methacrylate N-3-(am inopropyl)methacrylam ide(hydrochloride) N-(acryloyloxy)succinimide sodiumstyrenesulfonicacid 4,5-dimethoxy-2-nitrobenzyl acrylate trans-3,6-endomethylene-1,2,3,6-tetrahydrophthaloyl chloride 4-(2-acryloyloxyethylamino)-7-nitro-2,1,3benzoxa-diazole nanomechanical cantilever sensor N-hydroxysuccinimide N-hydroxysuccinimide methacrylate N-hydroxysuccinimide-4-vinylbenzoate (also referred to as DPVB) nanoimprint lithography N-isopropylacrylamide 2-(N-morpholino)ethyl methacrylate nitroxide-mediated polymerization nuclear magnetic resonance spectroscopy p-nitrophenyl acrylate p-nitrophenylchloroformate neopentyl methacrylate neutron reflectometry nitrilotriacetate N-tert-butylacrylamide N-(p-vinylbenzyl)-phthalimide N-vinylcaprolactam N-vinylformamide N-vinylimidazole 6-nitroveratryloxycarbonyl 2-((4,5-dimethoxy-2-nitrobenzyl)carbonyl)aminoethyl methacrylate 4,5-dimethoxy-2-nitrobenzyl methacrylate N-vinyl-2-pyrrolidone octyl acrylate octadecyl acrylate (also known as SA) octadecyl methacrylate (also referred to as SMA) N′-octadecyl-N α-(4-vinyl)-benzoyl-L-phenylalanineamide N-(2-oxoethyl)acrylamide oligo(ethylene glycol) oligo(ethylene glycol)methacrylate oligo(ethylene glycol)methyl ether methacrylate DOI: 10.1021/acs.chemrev.6b00314 Chem. Rev. 2017, 117, 1105−1318

Chemical Reviews OFET OMA OMS OSET PAGMA PANI PAS PBA PBS PC PDMS PDSM PE PEDOT PEEK PEGA PEGASF PEGDMA PEG400DMA PEG600DMA PEGEEA PEGMEAM PEGMEMA PEGEEMA PEGMA PEGMAN PEGMEA PEMA PeMMA PEO PET PF-in PFMA PFOMA PFPA PFS PIMP PLLA PMA PMDETA PMPI PNA POSSMA PP PPGMA PPM PPMA PRE PTFE PU PVC PVDF PVOH PyMA PyMMA

Review

organic field-effect transistors octyl methacrylate ordered mesoporous silica outer sphere electron transfer dimethyl-(4-methacryloyloxy)phenylsulfoniumtriflate polyaniline piperazine-derivatized styrene 3-aminophenyl boronic acid phosphate-buffered saline polycarbonate polydimethylsiloxane pyridyldisulfideethyl methacrylate polyethylene poly(3,4-ethylenedioxythiophene) poly(etheretherketone) poly(ethylene glycol)acrylate poly(ethylene glycol)acrylatesuccinylfluorescein poly(ethylene glycol)dimethacrylate poly(ethylene glycol) 400 dimethacrylate poly(ethylene glycol) 600 dimethacrylate poly(ethylene glycol)ethyl ether acrylate poly(ethylene glycol)methyl ether acrylamide poly(ethylene glycol)methyl ether methacrylate poly(ethylene glycol)ethyl ether methacrylate poly(ethylene glycol)methacrylate azide-functionalizedpoly(ethylene glycol)methacrylate poly(ethylene glycol)methyl ether acrylate 4-hydroxyphenylethyl methacrylate 3-perylenylmethyl methacrylate poly(ethylene oxide) polyethylene terephthalate pentafluoropropyl acrylate pentafluorophenyl methacrylate 1H,1H,2H,2H-perfluorooctyl methacrylate pentafluorophenyl acrylate pentafluorostyrene photoiniferter-mediated polymerization poly(L-lactide)heptadecyl methacrylate 2-propynyl methacrylate N,N,N′,N″,N″-pentamethyldiethylenetriamine N-(p-maleimidophenyl)isocyanate peptide nucleic acid heptaisobutyl POSS-derivatized propyl methacrylate polypropylene poly(propylene glycol)methacrylate postpolymerization modification 2-propynyl methacrylate persistent radical effect polytetrafluoroethylene polyurethane polyvinyl chloride polyvinylidene difluoride poly(vinyl alcohol) 1-pyrenylmethyl acrylate 1-pyrenylmethyl methacrylate

QCM-D QRAMA RAFT RGD rhBMP-2 RI RM488 RuA S SA sa-ATRP SA-LbL SAM SANS SARA ATRP SAW SBMA SBMAM SCFT SCMF Sd8 SDPB SECM SEMA SerMA SERS SET-LRP SFA SFIL S-Fl3 SIP SI-ATRP SI-CRP SI-FRP SI-NMP SIPGP SI-PIMP SI-ROP SOI SLS SMA SP SPA 1245

quartz crystal microbalance with dissipation monitoring quaternary ammonium resin acid-functionalized methacrylate reversible addition−fragmentation chain transfer arginine-glycine-aspartic acid tripeptide recombinant human bone morphogenetic protein-2 refractive index mesogen-functionalized acrylate bis(2,2′-bipyridine)-(5aminophenanthroline)rutheniumbis(hexafluorophosphate) styrene stearyl acrylate sacrificial anode-atom transfer radical polymerization spin-assisted layer-by-layer assembly self-assembled monolayer small-angle neutron scattering supplemental activator and reducing agent atom transfer radical polymerization self-avoiding walk sulfobetaine methacrylate (also known as DMAPS) sulfobetaine methacrylamide self-consistent field theory single chain mean field theory deuterated styrene semidilute polymer brush scanning electrochemical microscopy 2-sulfatoethyl methacrylate serine methacrylate surface-enhanced Raman spectroscopy single electron transfer-living radical polymerization surface forces apparatus step-and-flash imprint lithography 9,9-dioctyl-2-(9,9-dioctyl-2-(9,9-dioctyl-2(4-vinylphenyl)-9H-fluoren-7-yl)-9H-fluoren-7-yl)-9H-fluorene surface-initiated polymerization surface-initiated atom transfer radical polymerization surface-initiated controlled radical polymerization surface-initiated free radical polymerization surface-initiated nitroxide-mediated polymerization self-initiated surface photopolymerization and photo grafting surface-initiated photo iniferter-mediated polymerization surface-initiated ring-opening polymerization silicon-on-insulator salen ligand-derivatized styrene stearyl methacrylate spirobenzopyran-functionalized methacrylate spiropyran-functionalized acrylate


Chemical Reviews SPEG Spiro-MeOTAD SPM SPMA SPR SPS S-RAFT SRG SS SSNa Sulfo-SANPAH SWCNT TA TAMT tBA tBAAm tBAEMA TBAF tBMA TCT TEA TED TEGMMA TEM TEMPO TEOS TFA TFBG TFEA TFEMA TFMAA TFMPAM TFPT TGA THEBMA THF TIRF TMA TMI TMPMA TMSA TMSBr TMSI TMSMA TMSPMA TMSSPMA TNT TOF-SIMS TPAA TPMA TPSPMA

Review

TREN Tris TSH UCST UV VA VAc VAn VBAz VBBIX VBC VBCB VBEC

4-(poly(ethylene glycol)methyl ether)styrene 2,2′,7,7′-tetrakis(N,N-di-p-methoxyphenylamine)-9,9′-spirobifluorene scanning probe microscopy 3-sulfopropyl methacrylate potassium salt (also known as SPMA(K)) surface plasmon resonance styrene-p-salen surface-reversible addition−fragmentation chain transfer polymerization surface-relief grating 4-styrene sulfonic acid 4-styrene sulfonic acid sodium salt (also know as SS(Na) and NaSS) 1−6-[4′-azido-2′-nitrophenylamino]hexanoate single-walled carbon nanotubes tannic acid 2,4,6-trisacrylamido-3,5-triazine tert-butyl acrylate tert-butylacrylamide 2-(tert-butylamino)ethyl methacrylate tetra-n-butylammoniumfluoride tert-butyl methacrylate 1,3,5-trichlorotriazine triethylamine tetraethylthiuram disulfide methoxytri(ethylene glycol) methacrylate transmission electron microscopy (2,2,6,6-tetramethylpiperidin-1-yl)oxyl tetraethylorthosilicate trifluoroacetic acid tilted fiber Bragg gratings 2,2,2-trifluoroethyl acrylate 2,2,2-trifluoroethyl methacrylate 2-(trifluoromethyl)acrylic acid trifluoromethylphenylthiourea acrylamide (trifluoromethyl)phenylthiourea acrylamide thermo gravimetric analysis 3,4,5-tris(2-(2-(2-hydroxylethoxy)ethoxy)ethoxy)benzyl methacrylate tetrahydrofuran total internal reflection fluorescence microscopy thymyl methacrylate m-isopropenyl-α,α′-dimethyl-benzylisocyanate 2,2,6,6-tetramethylpiperidin-4-yl methacrylate trimethylsilyl acrylate trimethylsilyl bromide iodotrimethylsilane trimethylsilyl methacrylate 3-(trimethoxy-silyl)propyl methacrylate 3-[tris(trimethylsiloxy)silyl]propyl methacrylate 2,4,6-trinitrotoluene time-of-flight secondary ion mass spectrometry triphenylamine acrylate tris(2-pyridylmethyl)amine 3-(tri-2-propoxysilyl)propyl methacrylate

VBIMC VBIPS VBK VB(Na) VBP VBPT VBSAELA VBSAEZ VBTAC VBTMAX VC VDMA VFAM VK VPBA VQ VT VTPA XPS ZFM

tris(2-aminoethyl)amine tris(hydroxymethyl)aminomethane thyroid stimulating hormone upper critical solution temperature ultraviolet 4-vinylaniline vinylacetate 4-vinylaniline 4-vinylbenzylazide 1-(4-vinylbenzyl)-3-butyl-imidazoliumsalts 4-vinylbenzyl chloride 4-vinylbenzocyclobutene 9-(2-(4-vinyl(benzyloxy)ethyl)-9H-carbazole) 1-vinyl-3-butylimidazolium chloride 3-(1-(4-vinylbenzyl)-1H-imidazol-3-ium-3yl)propane-1-sulfonate 9-(4-vinylbenzyl)-9H-carbazole sodium4-vinylbenzoate N-(p-vinylbenzyl)-phthalimide 10-(4-vinylbenzyl)-10H-phenothiazine N -2−4-(vinylbenzenesulfonamido)ethyllactobionamide 4-vinylbenzenesulfonamidoethyl L-thio-β-Dsaccharides (ar-vinylbenzyl)trimethylammonium chloride (p-vinylbenzyl)trimethylammonium salts vinyl chloride 2-vinyl-4,4-dimethylazlactone vinylformamide N-vinylcarbazole (4-vinylphenyl)boronic acid vinyl quinoline derivative 5-vinyltetrazole 4-vinyltriphenylamine X-ray photoelectron spectroscopy zonyl fluoromonomer

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Chemical Reviews

Review

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