Langmuir Nanoarchitectonics from Basic to Frontier - American

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Langmuir Nanoarchitectonics from Basic to Frontier Katsuhiko Ariga, Taizo Mori, and Junbai Li Langmuir, Just Accepted Manuscript • DOI: 10.1021/acs.langmuir.8b01434 • Publication Date (Web): 28 May 2018 Downloaded from http://pubs.acs.org on May 28, 2018

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Langmuir Nanoarchitectonics from Basic to Frontier Katsuhiko Ariga,1,2,* Taizo Mori1, and Junbai Li3,4 1

WPI-MANA, National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba 305-0044,

Japan. 2

Department of Advanced Materials Science, Graduate School of Frontier Sciences, The

University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa, Chiba 277-8561, Japan. 3

Beijing National Laboratory for Molecular Sciences, CAS Key Lab of Colloid, Interface and

Chemical Thermodynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China.

4

University of Chinese Academy of Sciences, Beijing, 100049, China

KEYWORDS: Nanoarchitectonics, Interface, Molecular Recognition; Molecular Machine, Receptor, Cell Culture

ABSTRACT

ACS Paragon Plus Environment

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Methodology to combine nanotechnology and these organization processes has been proposed as a novel concept of nanoarchitectonics, which can fabricate functional materials with nanolevel units. As one of an instant nanoarchitectonics approach, confining systems within a twodimensional plane to drastically reduce translational motion freedom can be regarded as one of the rational approaches. Supramolecular chemistry, nanofabrication and their related functions at the-air-water interface with the concept of nanoarchitectonics would lead to creation of a novel methodology of Langmuir nanoarchitectonics. In this feature article, we briefly summarize research efforts related with Langmuir nanoarchitectonics including basics for anomaly of molecular interactions such as highly enhanced molecular recognition capabilities. It is also extended to frontiers including fabrications of supramolecular receptors and two-dimensional patterns with sub-nanometer scale structural regulation, manual control of molecular machines and receptors by hand-motion-like macroscopic actions, and regulation of cell fates at nanoarchitected arrays of nanocarbon assemblies and at direct liquid interfaces.

1. Introduction

The devemopment of new functional materials is crucial for various current important issues including

energy

production,

environmental

problems,

sensing/detection,

and

biological/biomedical applications.1-8 For a long time in human history, materials properties for applications have been regulated mainly through design/synthesis of unit molecules and macroscopic manufacturing. However, promoting understanding of structures and phenomena in molecular/atom-scale and nanoscopic regimes by nanotechnology9-12 is now giving us more logical strategies to architect materials through molecular synthesis, nanostructure formation,


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self-assembly/self-organization, and microscopic manipulations aiming to create their functions for desirable purposes including energy creation, environmental remediation, sensing/detection, and biological/biomedical applications.13-21 Methodology to combine nanotechnology and these organization processes has been proposed as a novel concept, nanoarchitectonics, by Masakazu Aono.22,23 Nanoarchitectonics is the conceptual process of combined actions of various unit processes for architecting functional materials with nano-level units, (Figure 1)24-31 including one necessary fact that nanomaterials and nanosystems are architected through organizing nanoscale units even with the inevitable uncertainty and unreliability.32 Unit nanomaterials can be further organized into microscopic and macroscopic materials where novel functions can be created upon mutual interactions of the components and specific structures. Because various disturbances and fluctuations such as thermal and statistical fluctuations always have certain influences properties in nanometer scales, unfixed and dynamic features may remain in functions of materials architected with nanometer-scale units and structures.33 Architected materials would have possibilities of unpredictable surprising functions because of these uncertainties, which have not been fully explored. For more instant understanding on the nanoarchitectonics approaches, confining systems within a two-dimensional plane to drastically reduce translational motion freedom can be regarded as one of the rational approaches. For realization of dynamic features in the nanoarchitectonics concept, interfaces with flexible and soft natures such as gas-liquid and liquid-liquid interfaces might be more appropriate media for nanoarchitectonics34 rather than fixed two-dimensional materials systems such as graphene.35 One of the two-dimensional environments for dynamic nanoarchitectonics would be the air-water interface where well-


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sophisticated systems as Langmuir monolayers and Langmuir-Blodgett films, have been extensively researched.36 Re-consideration of supramolecular chemistry, nanofabrication and their related functions at the-air-water interface with the concept of nanoarchitectonics would lead to creation of a novel methodology, Langmuir nanoarchitectonics. In this feature article, we briefly summarize research efforts related to Langmuir nanoarchitectonics from basic examples far before initiation of nanoarchitectonics. In the initial part of this article, anomalous molecular interactions at the air-water interface are explained as basics of supramolecular chemistry in Langmuir nanoarchitectonics. Enhanced capability of molecular interactions at the air-water interface results in hydrogen-bond-driven molecular recognition even in the presence of water and also results in fabrications of supramolecular receptors and two-dimensional patterns with sub-nanometer scale structural regulation. The latter issue are related with prototype of supramolecular polymers and supra-arrangement of DNA origami pieces. In addition, manual regulation of molecular machines and receptors at the airwater interface are exemplified in the next part. Uneven natures of structural dimensions at dynamic interface lead to coupling macroscopic motions in lateral dimensions and nanoscopic functions in thickness direction, which enables us to control molecular machines and to tune molecular receptors upon hand-motion-like macroscopic actions. In the final part, more much complex matters of living cells are target for scientific challenges, where regulations of cell fates at nanoarchitected arrays of nanocarbon assemblies and liquid interfaces have been investigated. In this feature article, Langmuir nanoarchitectonics is briefly summarized from basics to forefront science.


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2. From Basics of Molecular Recognition to Supramolecular Polymerization at the airWater Interface

Molecular recognitions based on non-covalent molecule-molecule interaction at the air-water interface have different features from those observed in bulk solution media and expected from calculations under ideal vacuum environments. For example, hydrogen-bond-based molecular recognition is very difficult in highly polar media especially in bulk aqueous solutions, but molecular recognition between simple nucleic acid bases becomes possible at the air-water interface as demonstrated in pioneer work by Kitano and Ringsdorf.37 Generality applicability of hydrogen-bond-based molecular recognitions at the air-water interface to various systems including sugars, amino acids, nucleotides, and peptides was established by Kunitake and coworkers.38,39 Molecular recognition as one of the basic processes of nanoarchitectonics from molecular components has to be considered with strong influences from surrounding media.40 Especially interfacial environments having two different dielectric natures would provide an opportunityfor delicate modulations of molecular interactions. Incredibly significant influence of interface types on efficiency of molecular interaction was confirmed through quantification of binding constants for fixed phosphate-guanidinium interaction pairs at molecular, mesoscopic and macroscopic interface (Figure 2A).41 Molecular recognition between phosphate and guanidinium is based on electrostatic hydrogen bonding that is significantly suppressed in bulk water (1.4 M-1).42 Shifting this molecular recognition pair to mesoscopic aqueous interfaces of micelles and lipid bilayers with certain dynamic natures increases the corresponding binding constants to 102-104 M-1 range. Amazingly, the binding constants between phosphate and guanidinium increases to the 106-107 M-1 level.43,44 Molecular


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interaction can be enhanced by millions or tens of millions times only upon changing the nature of the surroundings, which indicates that molecular systems must not be treated only with interacting molecules but have to be interpreted with significant contributions from the surroundings. The latter observation was rationalized by rather simple theoretical calculations as demonstrated by Sakurai and coworkers (Figure 2B).45 A simple structural pair of phosphate and guanidinium derivatives was placed at different positions of interface of high-dielectric phase (water phase) and low-interface phase (lipid phase). With keeping positions of guanidinium at the interface, energy profiles as a function of distance between guanidinium and phosphate were calculated, giving binding constants at particular interfacial positions. This simulation indicated that positions of the interacting pairs relative to the interface significantly affect the binding constants between guanidinium and phosphate. The calculated binding constant was close to zero when the pair was located deep inside of water (high dielectric phase). In contrast, placing it inside of a low-dielectric phase resulted in a high binding constant in the simulation. Binding constant values similar to the experimentally obtained binding constant can be regenerated at the position of guanidinium carbon on the interfacial line. Even when hydrogen bonding sites are surrounded with high-dielectric water media, influences form neighboring low-dielectric media positively support promoted binding between guanidinium and phosphate. It may be one of the important keys for promoted binding constants at the air/lipid-water interface. Hydrogen-bond-based molecular recognition is not limited to simple recognition pairs of one guest and one host. More sophisticated multi-point recognition cavities can be nanoarchitected through self-assembly of receptor components at the air-water interface. As a mimic of binding sites of naturally occurring receptors, where several peptide segments and functional groups


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form multi-point recognition systems, mixed monolayers of a dipeptide amphiphile and a guamidinium-functionalized amphiphile was spread to spontaneously nanoarchitect bindings sites for aqueous guest dipeptides (Figure 3).46 As shown above, the guanidinium functional group strongly binds acid functional groups such as phosphate and carboxylate, the guest dipeptide molecule is supposed to be contacted with the mixed monolayer through interaction between the guest C-terminal and the receptor guanidinium. This binding pair can be supported by protein-second-structure-like hydrogen bonding array with the receptor functional groups. Stabilities of such binding pairs are significantly influenced by several factors including hydrogen bonding modes (parallel or anti-parallel β-sheet like structure), location of hydrophobic side chains of the guest, and its steric hindrance with the receptor dipeptides. In the case of binding of GlyLeu (Figure 3A), various positive factors such as avoidance of unfavorable contact between the guest Leu side chain and bulk water resulted in the high binding constant. Several negative factors in the case of the LeuGly binding (Figure 3B) including disadvantageous location of the guest side chains and steric effect suppress binding constant. Although synthesis of such complicated binding sites by organic chemistry might be a tough task, the nanoarchitectonics approach at dynamic interface can achieve delicate molecular discrimination just through self-assembly of rather simple components. Enhanced capability of molecular recognition at the air-water interface is also useful to transcript molecular information into two-dimensional regular structures with sub-nanometer precision as nanoarchitectonics for two-dimensional molecular patterning. Figure 4 illustrates one typical examples for molecular-level pattern fabrication through emphasized interaction between aqueous template molecules and amphiphile molecules at the air-water interface.47 In this case, one flavine adenine dinucleotide (FAD) as an aqueous template can bind to two


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monoalkyl guanidinium amphiphiles at FAD phosphates and one dialkyl orotate amphiphile at FAD adenine through efficient hydrogen bond formation. Fixing arrangement of these amphiphiles resulted in sub-nanometer-level regular dip patterns upon difference of molecular length of the guanidinium amphiphiles and orotate amphiphile, which was confirmed by observation of the transferred monolayer on a mica surface by atomic force microscopy (AFM). Architecting alternate hydrogen bonding arrays at the air-water interface leads to formation of supramolecular polymers between amphiphilic melamine and aqueous barbiturate (Figure 5A).48 One-dimensional hydrogen-bonded supramolecular polymer chains can run at the air-water interface. The supramolecular polymer structure at their polar heads led to formation of specific alignments of the alkyl chains which was again confirmed by AFM observation. While this simple but pioneering demonstration of supramolecular polymers at Langmuir medium was done in middle of 1990s, supramolecular polymerization of more advanced units, DNA origami squares, has been recently accomplished at the air-water interface.49 Figure 5B depicts one dimensional extension of supramolecular polymerization of DNA origami pieces. DNA origami has been extensively researched for well-designable formation of nano/microstructures and their machine-like functions.50 Beyond individual pieces, methodology for controlled organization of DNA pieces has to be established for advanced applications. In the reported rectangular DNA sheets in size of 90 × 65 nm2 as origami pieces were first complexed with cationic amphiphile molecules for dissolution into organic solvents and subsequent spreading on water. Preservation of the rectangle shape of DNA origami in its transferred monolayer was confirmed by AFM observation. Interestingly, repeated mechanical compressionexpansion cycles for the monolayer of DNA origami drastically induced one-dimensional alignment of the DNA nanosheets while the DNA nanosheets remained independent before the


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mechanical cycles. The formed one-dimensional structures keep the unit width even after the DNA origami supramolecular polymers are grown, indicating that association of the DNA origami pieces occurred only at particular side. In fact, the DNA origami nanosheet possesses single-strand loops at the shorter sides capable for non-base specific hydrogen bonding. Enhanced hydrogen bonding between the single-strand loops at the air-water interface induced the side-specific association and the one-dimensional extension of the DNA origami supramolecular polymers.

3. Recent Progress of Advanced Analysis of Materials Nanoarchitectonics at the Air- Water Interface

Even a few decades after the fundamental findings of various molecular phenomena specific to the air-water interface, unusual properties of molecules embedded at the air-water interface has been paid much attention in recent research. Especially, the interfacial phenomena can now be analyzed by much more advanced techniques. Fayer and coworkers applied two-dimensional infrared vibrational echo spectroscopy to analyze ultrafast to ultraslow dynamics of hydrogen bonding

at

the

air-water

interface

by

using

tricarbonylchloro-9-octadecylamino-4,5-

diazafluorenerhenium(I) as a monolayer component.51 While hydrogen bond rearrangement dynamics is 1.5 ps in bulk water, the corresponding value increased up to 3.1 ps for interfacial water. Fluctuations of the hydrogen bond numbers formed between the monolayer carbonyl and water also induced fluctuations of the monolayers with longer time scale. The measurements revealed elongation of structural randomization time of water hydrogen bonding accompanied


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with concerted hydrogen bond formation/dissociation can be significantly caused by the contact of hydrogen-bond-capable monolayer. Significant shifts in acid dissociation and base protonation were indicated by various analytical methods such as isotherms between surface pressure and molecular area.52 Recently, this kind of phenomenon has been confirmed by Strazdaite et al. using surface analytical method, vibrational

sum-frequency

generation

spectroscopy

and

attenuated

total

reflection

spectroscopy.53 These spectral methods revealed the ionization state of the amino-acids such as L-alanine and L-proline both in bulk water and at the air-water interface. Dissociation of their carboxylic acid groups were observed at significantly higher pH condition at the air-water interface, which can be explained from a difference in solvation between interfacial and bulk environments, the carboxylate ion in bulk water is better solvated than that at the surface. Careful use of traditional methods such as viscoelasticity of the surface can also reveal peculiar phenomena at the air-water interface. Krafft, Tanaka, and coworkers found existence of twodimensional physical gels on water even at zero surface pressure.54 The observed phase was significantly affected by subtle changes in the polymer structure such as the block length ratio, which can be useful for stabilizing microbubbles, emulsions and gels. Fluidic two-dimensional environments such as the air-water interface have been recently paid much attention as media for nanomaterials production as seen in fabrication of two-dimensional metal-organic frameworks of coordination polymers at interfacial media.55-57 Recently, Huang et al.

fabricated

a

free-standing

two-dimensional

coordination

polymer

of

Zn2(benzimidazolate)2(OH)2 at the air-water interface for usages as a charge barrier in Li-S batteries.58 The presence of hydroxyl groups in the fabricated two-dimensional coordination polymers created negative charges to be an effective charge barrier to anion transport under basic


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conditions. This barrier effect softened polysulfide shuttling, resulting efficient improvements of the battery capacity and cycle performance. Fabrication of two-dimensional structures through covalent bonding between well-designed components at the air-water interface has also been investigated. For example, Zheng, Feng, and coworkers reported fabrication of monolayer and multilayers of covalently linked twodimensional polymers upon formation of Schiff’s base between appropriately designed porphyrin derivatives and 2,5-dihydroxyterephthalaldehyde at the air-water interface or water-chloroform interface (Figure 6A).59 Thickness of the formed monolayer is only ca. 0.7 nm while its lateral size corresponds to 4-inch wafer size with preserving Young’s modulus of 267 ± 30 GPa. Multilayer films of 5,10,15,20-tetrakis(4-aminophenyl)-21H,23H-porphyrin-Co(II) can work as active catalysts for hydrogen generation from water. Their performances are better than those observed for molecular catalysts with cobalt-nitrogen coordination on carbon nanotube or graphene oxides. This is also an important examples of two-dimensional soft nanoarchitctonics.60 Another example, two-dimensional films through dynamic imine formation between aromatic triamine and dialdehyde at the air-water interface was also demonstrated by Zhang and coworkers.61 Zenobi, Schlgter, and coworkers fabricated covalently linked monolayer of a bridgehead carboxylic acid with three fluoro-substituted anthracene blades through photoinduced [4+4] cycloaddition of the face-to-face anthracene pairs (Figure 6B).62 The formed twodimensional structures were analyzed by tip-enhanced Raman spectroscopy. Mechanical stability of the monolayer was much improved in the photo-linked monolayer. In concept of molecular paper reported by Payamyar, Schlüter, and coworkers, reversible [4+4]-cycloaddition of diazaanthracene units in the two-dimensional film makes it possible to write information in local


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control of reversible fluorescence quenching.63 In optimized case, written patterns on solid substrates remain unchanged for three months. An interesting proposal by Melosh and coworkers demonstrated control of microscopic motions of microscopic objects as mesoscale artificial clathrin mimics at the air-water interface (Figure 7).64 In this example, three-leg bimetallic structures were self-assembled at liquid interfaces. The assembled structures have dynamic natures and their structural changes and dimensional transformations can be induced by external stimuli such as magnetic fields, sometime resulting in fluidic sampling. As shown in this example, fluidic interfaces such as the air-water interface would be nice media to drive dynamic motions. It may be one important key to explore functions specific to dynamic interfacial media. As pioneering approaches, dynamic controls of molecular machines and molecular receptors at the air-water interface.

4. Molecular Machinery at the Air-Water Interface

Small functional systems and their concerted assemblies are molecular machine. In many biological systems, various machine-like units including proteins, small molecules, and their assemblies are working as molecular-sized machines as independent units or in harmonized relays. Because these biological machine systems can be regarded as ultimately small and highly integrated functional systems, they are nice specimens of final goals of nanoarchitectonics. Powerful chemical approaches to create ultra-small machine-like objects have been also achieved with so-called molecular machine concept.65-67 Control of molecular machineshas traditionally been conducted as solution sciences when evaluation techniques for individual molecules were not well developed. This approach roughly figures out molecular motions as


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averaged states in bulk solution. Recent developments of high-resolution microscopic techniques such as scanning tunneling microscopy (STM) enable us to directly observe changes of molecular shapes on solid interface.68,69 The corresponding research efforts significantly promote understanding of machine motions at interfaces. However, motional and functional controls of molecular machines and deeper understanding of molecular machine properties have not yet been fully accomplished at dynamic interfaces such as the air-water interface. These systems have much larger potentials in sciences and applications due to huge freedom in dynamic motions. As described below, Langmuir nanoarchitectonics can offer nice opportunities to develop molecular machine technologies at dynamic and fluidic interfaces. One of the pronounced features of liquid interfacial media is huge anisotropic nature of motional freedoms of entrapped molecules. A monolayer at the air-water interface can be limitlessly deformed in lateral directions, but molecules confined in the monolayer has subnanometer-level motional freedom in vertical direction. For example, traditional compressionexpansion processes of Langmuir monolayer at the air-water interface couples sub-nm-level molecular orientations with lateral size changes in sub-meter-scale. By applying this specific feature of the air-water interface to molecular machine systems, we can control molecular machine directly by human-level macroscopic mechanical motions.70 One pioneer example of mechanical control of molecular machines at the air-water interface is shown in Figure 8, where reversibly conformational changes between flat form and cavity form of molecular machine, steroid cyclophanes with a 1,6,20,25-tetraaza[6.1.6.1]-paracyclophane cyclic connected with four cholic acid boards through flexible L-lysine arm, can be repeatedly induced in synchronization with macroscopic mechanical actions.71,72 In parallel to the cavity-flat conversion, this molecular machine captures and releases a guest molecules dissolved in aqueous subphase, respectively.


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Capture and release of a target molecule can be desirably controlled through human-motion-like mechanical motions, monolayer compression and expansions in sub-meter-scale. This is one pioneer example to handle molecular machines by macroscopic mechanical forces. In order to further understand conversion of macroscopic mechanical motion to molecular actions at the air-water interface, motions of a model molecular machine, molecular pliers, with much simpler motions have been systematically investigated upon application of macroscopic mechanical stimuli at the air-water interface (Figure 9A).73 The central hinge part of the molecular pliers is made of a chiral binaphthyl attached with two hydrophilic oligo(oxyethylene) chains and two hydrophobic alkyl tails to provide sufficient amphiphilicity for stable formation of its Langmuir monolayer. Structural changes of the molecular pliers, changes in torsional angles in the chiral binaphthyl moiety, were evaluated from shifts and intensity changes of circular dichroism (CD) spectra of the films transferred on a solid surface at various surface pressures. The obtained results were compared with theoretically simulated CD spectra to precisely determine the torsional angles that were used consequently for evaluation of energy gains upon changes of the change of the torsional angle, pliers closing. At the same time, energies given upon the monolayer compressions were calculated through traditional thermodynamic method. Surprisingly, the energy gains for structural changes of the molecular pliers are very similar to the thermodynamic energy supplies to the monolayer, which may corresponds to highly efficient energy conversion. In addition, these processes were actually done with surprisingly small energies and forces. Faint controls of conformational changes of organic molecular machines with delicate force application are possible in mechanical processes at the air-water interface. This nature is totally different from the other conventional controls of molecular machines by photonic and/or electrical stimuli, but is rather similar to biological


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systems where the conformations and functions of many kinds of proteins are controlled with pN-level forces. While the above-mentioned system with the amphiphilic molecular pliers showed continuous analogue changes of its the torsional angle, mixed monolayers of a simple non-tail binaphthyl compound and matrix phospholipids provide discontinuous digital changes of the torsional angle accompanied with reversible formation of two-dimensional crystals upon application of lateral macroscopic mechanical forces (Figure 9B).74 These digital changes correspond to a more substantial reversible cisoid-to-transoid (closed-to-open) transformation with inversion of helicity of the binaphthyl structure (right-handed to left-handed or vice versa) although the former molecular pliers systems were driven within the same helicity. Crystallization/dissolution of quasi-stable binaphthyl crystals within two-dimensional medium would be driven along a double-well potential with a barrier to transition between the two states. These results indicate that mechanical processes in Langmuir films at the air-water interface are delicate enough to modulate molecular conformations in various modes. Mechanical controls on conformations of molecules embedded at the air-water interface can be utilized for faint regulations of molecular-receptor performances with surprisingly improved capability of molecular discrimination. Although changes of molecular structures are not obvious like the flat-cavity conversion, molecular receptors at the air-water interface can be continuously and delicately tuned to optimized structures for particular purpose. For example, a molecular receptor with twisting motion, cholesterol-armed cyclen (a 1,4,7,10-tetraazacyclododecane core with four cholesteric side arms), was structurally tuned at the air-water interface upon lateral mechanical compression of its monolayer (Figure 10A).75 Continuous structural control of this molecular receptor induces exposure of faint and delicate modulation of chiral environments to


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aqueous phase. According to the chiral modulation, chiral selectivity in binding of amino acids can be sensitively shifted. Binding of valine is inverted from its D-isomer at lower pressures to L-isomer at higher pressure. Chiral selectivity of the amino acids can be desirably tuned only with simple macroscopic mechanical compression of the receptor film. Similarly, tuning of twodimensional arrangements of carbonyl groups and ternary amino groups by mechanical compressions of monolayers of another molecular receptor, a cholesterol-substituted triazacyclononane, enables us to delicately tune selective binding of thymine and uracil derivatives (Figure 10B).76 Because these two nucleic acid bases have identical patterns of hydrogen bond arrays, natural nucleic acids, DNA and RNA, cannot distinguish them. In fact, artificial arrays of molecular receptors as its Langmuir monolayer with structurally tuning capability accomplishes biologically impossible substance discrimination. The above-mentioned mode of molecular recognition is fundamentally different from common sense of molecular recognition (Figure 11).77 Basics of molecular recognition are based on formation of complexes between guest and host (receptor) though energy minimization. Therefore, guest binding is solely determined. Structural changes of receptor structure by external stimuli such as photo-isomerization of receptors can create multiple (two, three, ...) possibilities of binding structures.78,79 This is the second generation of molecular recognition modes where molecular recognition states can be switched by external stimuli. This concept was actually used for pioneering examples of molecular machines. Unlike these two initial basic modes of molecular recognition, structural tuning of molecular receptors embedded at the airwater interface upon continuous applications of macroscopic lateral compression utilizes numerous candidate structures of receptors to select optimized answer for particular demands. At dynamic interfacial media, connection between macroscopic mechanical actions and molecular


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motions becomes possible. Unlike input by photonic and electronic stimuli, mechanical stimuli are capable of delicately shifting structures of organic molecules. Similarly, interfacial media such as Langmuir films would be one of the ideal environments for nanoarchitectonics with harmonization of delicate interactions. As mentioned above, actions in Langmuir nanoarchitectonics can be operated only with weak force and low energy comparable with those observed in natural machinery systems such asbiomachines, molecular machines, and molecular cars.80-82 Nanoarchitecting biocomponents and/or biomimetic machines at interfacial media would lead to possible applications of molecular machinery such as nanomotors/biosensors with very delicate inputs.

5. Cell Fate Control with Material Interface and Liquid Interface

One of the important scientific and technological challenges would be understanding biological mechanisms and biomedical applications.83-88 Among various bio-related functions such as drug deliveries and biomolecular regulations, controls of life units, living cells, are attractive targets in current science and technologies. In this section, two examples on cell fate controls using Langmuir nanoarchitectonics are introduced. Mechanical events are very common, and thus living systems are always exposed to certain kinds of mechanical stimuli. Importance of mechanical stimuli in cell activities including proliferation, differentiation and death have initiated a novel research area, mechanobiology,89 which handles responses of biomolecules, cells and tissues upon application of mechanical stresses and under controlled mechanical environments. Surfaces and interfaces consist of welldesigned materials which can act as media appropriate for the exposure of bio-systems to various


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mechanical situations. Langmuir nanoarchitectonics is expected to make significant contributions to mechanobiology by supplying surface materials with controlled mechanical strengths and even as direct cell culture media. The following examples in Langmuir nanoarchitectonics provide some indications of cell fate controls at surfaces with superhard and supersoft properties (Figure 12A). Interfacial assemblies of simple fullerene compounds such as C60, C70, and their derivatives by liquid-liquid interfacial precipitation can give microscopic materials with various shapes.90 Among them fullerene whiskers are known as typical one-dimensional microstructures with superhard mechanical characteristics. The fullerene whiskers were then aligned by a novel technique, the vortex Langmuir–Blodgett (vortex LB) method, in which mechanical rotation of subphase force to align microscopic objects with various curvatures depending on the distance from the rotation center.91 Aligned fullerene whiskers with different curvatures were transferred onto a solid substrate, and human osteoblast cell line MG63 was subjected to the culture on the surfaces of aligned fullerene whiskers. It was observed that the cells bound preferentially to fullerene whiskers probably because of promoted adsorption of extracellular matrix onto the fullerene whiskers through possible electronic interactions. Based on the preferential adhesion of cells to the surface of fullerene whisker, growth of cells occurs along arrays of fullerene whisker. Only limited restraint in the cell growth in this system was observed from the cell proliferation experiments. Therefore, well-designed nanoarchitectonics of fullerene whiskers and related materials can be transcribed to sophisticated cell architectures. Detailed analyses on differentiations of cell adsorbed on arrays of superhard fullerene whiskers were also investigated using mouse skeletal myoblast C2C12 cells.92 Morphology of the cells cultured on the aligned fullerene whiskers were highly elongated with large aspect ratios


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although myoblasts on a bare glass and randomly dispersed fullerene whiskers stayed in polygonal shapes. In addition, myoblast cells cultured on the aligned fullerene whiskers exhibited promoted proliferation behaviors and were fused into myotubes with high fusion index values. The cells on the aligned fullerene whiskers showed 1.35 times higher expression level of MyoD than that for the cells on the bare glass surface. Similarly, 1.43-fold promotion of the myogenin expression for the cells on the fullerene whisker arrays was confirmed. The observed upregulation of the myogenic genes indicates the superhard and oriented environments of the aligned fullerene whiskers induces an acceleration of the early and late stages of myogenic differentiation (Figure 12A). Another challenge to regulate cell fates at Langmuir media is direct cell culture at liquid-liquid interface that is supposed to be supersoft environments. Although few pioneering reports suggest availability of selected organic solvents such as perfluorocarbon for cell culture,93 the detailed behaviors of cell differentiations have not been fully explored. Like significant upregulation of cell differentiation superhard surface, supersoft liquid-liquid interface is expected to show unusual behaviors on cell differentiation as related with its specific natures such as significantly reduced strains between cell and substrate (organic liquid). Successful cultures of C2C12 myoblast cells can be accomplished at liquid-liquid interfaces between water and several perfluorocarbon solvents (Figure 12B).94 These in vitro liquid-liquid culture systems revealed that remarkable attenuation of expression of myogenin, myogenic regulatory factors family gene. The observed unusual regulation of myogenic differentiation would be resulted from supersoft nature of the fluid microenvironment as an interfacial culture medium, which might reduce cell traction forces with the extracellular matrixes. In addition, this liquid-liquid cell culture system can be connected with Langmuir-Blodgett transfer techniques that enables us to prepare LB films


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of living cells. This novel methodology may have potential contributions to the fields of tissue engineering and stem cell research. Although the detailed mechanisms on cell controls are not fully clear in the various surface current stage, various surface chemistry including functional groups and structural orientation would be important keys in addition to bulk mechanical properties.

6. Summary and Perspectives

In this feature article, specific features of interfaces, especially air-water interface, are shortly described, which are summarized below and in Figure 13.

(i) If we look at the air-water interface along the vertical direction, we can find that the airwater interface provides very unique environments with discontinuous change of dielectric constant of surrounding media. Accordingly, a molecule embedded at the dielectrically heterogeneous environments experiences physical factors of low-dielectric nature. Therefore, molecular interaction such as hydrogen-bond-based molecular recognition is much enhanced even though they locate partially at water-surrounding media. Although degree of enhancement of molecular recognition efficiencies much depends on types of interfaces, the same phenomena are universally observed at various aqueous interfaces including surfaces of aqueous lipid assemblies in water and the air-water interface. This specific enhancement of molecular interaction would be key to understand mechanisms of efficient molecular recognition in aqueous biological systems. In addition, specific interactions within two-dimensional media is beneficial to transcript molecular information to nanoscopic structures and patterns. Construction


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of supramolecular receptor structures, two-dimensional molecular patterns, and supramolecular polymers including DNA origami arrays are typical products of Langmuir nanoarchitectonics.

(ii) If we look at the air-water interface along the lateral direction, we can find huge anisotropy of motional freedom, i.e., limitless possibility in motion within lateral direction and nanometerlevel confinements of molecular motions in thickness direction. This anisotropic nature of dynamic interfaces has distinct advantages to connect macroscopic mechanical motions and nanoscopic molecular functions. For example, motions of molecular machines embedded within the air-water interface can be controlled by macroscopic mechanical stimuli. Functions of molecular machines such as reversible capture and release of a guest molecule can be indeed operated by hand-motion-like conventional mechanical actions at the air-water interface. Similarly, structures of molecular receptors can be finely and continuously tuned by application of macroscopic mechanical motions at the air-water interface. This feature enables us to delicately tune receptor structures and select the optimized one among countless numbers of conformer candidates. The latter mechanism is totally different from traditional mechanisms of molecular recognitions.

(iii) In addition to these features of dynamic interfaces, interfacial media are also useful to construct or supply media with various mechanical features, which is powerful nature in controlling biological functions and properties as seen in the examples of cell differentiation regulations in the last section. Dynamic interfaces would be attractive media for develop biorelated functions because the dynamic interfaces can supply several advantageous features


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including enhanced molecular recognition, anisotropic motions, and finely tunable structural characteristics for advanced bio-functions.

By taking account of the above-mentioned characteristics of dynamic interfaces, architecting functional structures including functional biomolecules into integrated functional systems95,96 is attractive ways for future developments of Langmuir nanoarchitectonics. Such efforts have been done through organization of various biocomponents on surface and within membranes that can create remarkable functions as seen self-powered cargo delivery on the surface 97 and promotion of ATP synthesis on the artificial membrane.98 By combining this kind of bio-hybrid design and Langmuir nanoarchitectonics, more sophisticated artificial structures with high-level biofunctional components become possible, which would lead to realistic developments of biofunctioned device technology.99 Nanoarchitectonics concept includes the importance of harmonization of mutual interaction among components that are often under uncertainties with various fluctuations. This intrinsic nature of nanoarchitectonics shares common features with those in biological systems. In actual living systems, various machine-like high-skill molecules are working with certain harmonies with their actions under unavoidable thermal fluctuations. This feature may result in wise and flexible functions in biological systems. The nanoarchitectonics concept using functional molecules and biomolecules within specifically confined media, two-dimensional systems, would lead to powerful approaches toward bio-like clever functional device systems.100 In addition, nanoarchitectonics with non-bio components can create devices with bio-like functions as seen in artificial synapse behaviors of atomic switches.101,102


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ACKNOWLEDGMENT This study was partially supported by JSPS KAKENHI Grant Number JP16H06518 (Coordination Asymmetry) and CREST JST Grant Number JPMJCR1665. The authors appreciate Dr. Daniel Payne for English correction of the manuscript.


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AUTHOR INFORMATION Corresponding Author *E-mail: [email protected] Author Contributions The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. Notes The authors declare no competing financial interest.


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(74) Mori, T.; Ishikawa, D.; Yonamine, Y.; Fujii, Y.; Hill, J. P.; Ichinose, I.; Ariga, K.; Nakanishi, W. Mechanically Induced Opening-Closing Action of Binaphthyl Molecular Pliers: Digital Phase Transition vs. Continuous Conformational Change. ChemPhysChem 2017, 18, 1470-1474. (75) Michinobu, T.; Shinoda, S.; Nakanishi, T.; Hill, J. P.; Fujii, K.; Player, T. N.; Tsukube, H.; Ariga, K. Mechanical Control of Enantioselectivity of Amino Acid Recognition by CholesterolArmed Cyclen Monolayer at the Air-Water Interface. J. Am. Chem. Soc. 2006, 128, 1447814479. (76) Mori, T.; Okamoto, K.; Endo, H.; Hill, J. P.; Shinoda, S.; Matsukura, M.; Tsukube, H.; Suzuki, Y.; Kanekiyo, Y.; Ariga, K. Mechanical Tuning of Molecular Recognition to Discriminate the Single-Methyl-Group Difference between Thymine and Uracil. J. Am. Chem. Soc. 2010, 132, 12868-12870. (77) Shrestha, L. K.; Mori, T.; Ariga, K. Dynamic Nanoarchitectonics: Supramolecular Polymorphism and Differentiation, Shape-Shifter and Hand-Operating Nanotechnology. Curr. Opin. Colloid Interface Sci. 2018, 35, 68-80. (78) Shinkai, S.; Manabe, O. Photocontrol of Ion Extraction and Ion-Transport by Photofunctional Crown Ethers. Top. Curr. Chem. 1984, 121, 67-104. (79) Shinkai, S.; Ikeda, M.; Sugasaki, A.; Takeuchi, M. Positive Allosteric Systems Designed on Dynamic Supramolecular Scaffolds: Toward Switching and Amplification of Guest Affinity and Selectivity. Acc. Chem. Res. 2001, 34, 494-503.


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(80) Shirai, Y.; Minami, K.; Nakanishi, W.; Yonamine, Y.; Joachim, C.; Ariga, K. Driving Nanocars and Nanomachines at Interfaces: From Concept of Nanoarchitectonics to Actual Use in World Wide Race and Hand Operation. Jpn. J. Appl. Phys. 2016, 55, 1102A2. (81) Soe, W.-H.; Shirai, Y.; Durand, C.; Yonamine, Y.; Minami, K.; Bouju, X.; Kolmer, M.; Ariga, K.; Joachim, C.; Nakanishi, W. Conformation Manipulation and Motion of a Double Paddle Molecule on an Au(111) Surface. ACS Nano 2017, 11, 10357-10365. (82) Ariga, K.; Mori, T.; Nakanishi, W. Nano Trek Beyond: Driving Nanocar/Molecular Machine at Interfaces. Chem. Asian J. 2018, 13, 1266-1278. (83) Ariga, K.; Ji, Q.; McShane, M. J.; Lvov, Y. M.; Vinu, A.; Hill, J. P. Inorganic Nanoarchitectonics for Biological Applications. Chem. Mater. 2012, 24, 728-737. (84) Nakanishi, W.; Minami, K.; Shrestha, L. K.; Ji, Q.; Hill, J. P.; Ariga, K. Bioactive Nanocarbon Assemblies: Nanoarchitectonics and Applications. Nano Today 2014, 9, 378-394. (85) Igarashi, C.; Murata, A.; Itoh, Y.; Subekti, D. R. G.; Takahashi, S.; Kamagata, K. DNA Garden: A Simple Method for Producing Arrays of Stretchable DNA for Single-Molecule Fluorescence Imaging of DNA-Binding Proteins. Bull. Chem. Soc. Jpn. 2017, 90, 34-43. (86) Mizutani, Y. Time-Resolved Resonance Raman Spectroscopy and Application to Studies on Ultrafast Protein Dynamics. Bull. Chem. Soc. Jpn. 2017, 90, 1344-1371. (87) Morii, T. A Bioorganic Chemistry Approach to Understanding Molecular Recognition in Protein-Nucleic Acid Complexes. Bull. Chem. Soc. Jpn. 2017, 90, 1309-1317.


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(88) Kashida, H.; Asanuma, H. Development of Pseudo Base-Pairs on D-Threoninol which Exhibit Various Functions. Bull. Chem. Soc. Jpn. 2017, 90, 475-484. (89) Ariga, K.; Minami, K.; Ebara, M.; Nakanishi, J. What Are Emerging Concepts and Challenges

in

NANO?:

Nanoarchitectonics,

Hand-Operating

Nanotechnology,

and

Mechanobiology. Polym. J. 2016, 48, 371-389. (90) Shrestha, L. K.; Ji, Q.; Mori, T.; Miyazawa, K.; Yamauchi, Y.; Hill, J. P.; Ariga, K. Fullerene Nanoarchitectonics: from Zero to Higher Dimensions. Chem. Asian J. 2013, 8, 16621679. (91) Krishnan, V.; Kasuya, Y.; Ji, Q.; Sathish, M.; Shrestha, L. K.; Ishihara, S.; Minami, K.; Morita, H.; Yamazaki, T.; Hanagata, N.; Miyazawa, K.; Acharya, S.; Nakanishi, W.; Hill, J. P; Ariga, K. Vortex-Aligned Fullerene Nanowhiskers as a Scaffold for Orienting Cell Growth. ACS Appl. Mater. Interfaces, 2015, 7, 15667-15673. (92) Minami, K.; Kasuya, Y.; Yamazaki, T.; Ji, Q.; Nakanishi, W.; Hill, J. P.; Sakai, H.; Ariga, K. Highly Ordered One-Dimensional Fullerene Crystals for Concurrent Control of Macroscopic Cellular Orientation and Differentiation towards Large-Scale Tissue Engineering. Adv. Mater. 2015, 27, 4020-4026. (93) Rosenberg, M. D. Cellular control mechanisms and cancer; Emmelot, P., Mohbock, O., Eds.; Elsevier: Amsterdam, Netherlands, 1964; pp 146-164. (94) Minami, K.; Mori, T.; Nakanishi, W.; Shigi, N.; Nakanishi, J.; Hill, J. P.; Komiyama, M.; Ariga, K. Suppression of Myogenic Differentiation of Mammalian Cells Caused by Fluidity of a Liquid–Liquid Interface. ACS Appl. Mater. Interfaces 2017, 9, 30553-30560.


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(95) Matsuura, K. Construction of Functional Biomaterials by Biomolecular Self-Assembly. Bull. Chem. Soc. Jpn. 2017, 90, 873-884. (96) Katayama, Y. Peptide-Grafted Polymers as Artificial Converter of Cellular Signals. Bull. Chem. Soc. Jpn. 2017, 90, 12-21. (97) Jia, Y.; Dong, W.; Feng, X.; Lia, J.; Li, J. A Self-Powered Kinesin-Microtubule System for Smart Cargo Delivery. Nanoscale, 2015, 7, 82-85 (98) Xu, Y.; Fei, J.;

Li, G.; Yuan, T.; Li, Y.; Wang, C.; Li, X.; Li, J. Enhanced

Photophosphorylation of a Chloroplast-Entrapping Long-Lived Photoacid. Angew. Chem. Int. Ed. 2017, 56, 12903-12907. (99) Ariga, K.; Ji, Q.; Mori, T.; Naito, M.; Yamauchi, Y.; Abe, H.; Hill, J. P. Enzyme Nanoarchitectonics: Organization and Device Application. Chem. Soc. Rev. 2013, 42, 6322-6345. (100) Xu, Y.; Fei, J.; Li, G.; Yuan, T.; Li, J. Compartmentalized Assembly of Motor Protein Reconstituted on Protocell Membrane toward Highly Efficient Photophosphorylation. ACS Nano 2017, 11, 10175-10183. (101) Ohno, T.; Hasegawa, T.; Tsuruoka, T.; Terabe, K.; Gimzewski J. K.; Aono, M. Short-Term Plasticity and Long-Term Potentiation Mimicked in Single Inorganic Synapses. Nat. Mater. 2011, 10, 591-595. (102) Ariga, K. Nanoarchitectonics: A Navigator from Materials to Life. Mater. Chem. Front. 2017, 1, 208-211


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Figure 1. Outlines of nanoarchitectonics and Langmuir nanoarchitectonics Figure 2. (A) Efficiency (binding constant) of molecular interaction between phosphate and guanidinium functionalities at interfaces in various sizes. (B) Models for theoretical considerations of molecular interaction between phosphate and guanidinium functionalities at the lipid (air)-water interface.

Figure 3. Multi-point recognition sites within mixed monolayers of a dipeptide amphiphile and a guamidinium-functionalized amphiphile at the air-water interface: (A) GlyLeu binding; (B) LeuGly binding.

Figure 4. Two-dimensional molecular patterning with sub-nanometer precision formed in mixed monolayer of monoalkyl guanidinium amphiphiles and dialkyl orotate amphiphile with a template of flavine adenine dinucleotide (FAD).

Figure 5. Supramolecular polymers at the air-water interface: (A) supramolecular polymer between amphiphilic melamine and aqueous barbiturate; (B) supramolecular polymerization of DNA origami pieces.

Figure 6. (A) Fabrication of covalently linked two-dimensional polymers upon formation of Schiff’s base. (B) Fabrication of covalently linked monolayer of a bridgehead carboxylic acid with three fluoro-substituted anthracene blades through photoinduced [4+4] cycloaddition of the face-to-face anthracene pairs

Figure 7. Control of microscopic motions of microscopic objects as mesoscale artificial clathrin mimics at the air-water interface

Figure 8. Control molecular machine directly by human-level macroscopic mechanical motions. Reversible molecular capture and release of a guest molecule in subphase through conformational changes between flat form and cavity form of molecular machine, steroid cyclophanes with a 1,6,20,25-tetraaza[6.1.6.1]-paracyclophane cyclic connected with four cholic acid boards through flexible L-lysine arm.


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Figure 9. Conformational regulation of a chiral binaphthyl unit through mechanical actions at the air-water interface: (A) continuous changes of amphiphilic molecular pliers; (B) digital changes of a rather simple binaphthyl molecule in matrix lipids.

Figure 10. Molecular recognition by molecular tuning at the air-water interface: (A) chiral discrimination of amino acids through control of twisting motion of cholesterol-armed cyclen (a 1,4,7,10-tetraazacyclododecane core with four cholesteric side arms); (B) selection between uracil and thymine derivatives upon tuning of two-dimensional arrangements of carbonyl groups and ternary amino groups of cholesterol-substituted triazacyclononane receptors.

Figure 11. Representative modes of molecular recognition; (A) one stable-state of host-guest complex; (B) switching of receptor structures; (C) molecular tuning of receptors.

Figure 12. Cell culture with control of cell differentiation at mechanically modified interfaces: (A) superhard surface of fullerene whisker arrays; (B) supersoft interface of water and perfluorocarbon solvent.

Figure 13. Summary of Langmuir nanoarchitectonics


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Figure 1.


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Figure 2.


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Figure 3.


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Figure 4.


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Figure 5.


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Figure 6.


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Figure 7.


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Figure 8.


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Figure 9.


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Figure 10.


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Figure 11.


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Figure 12.


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Figure 13.


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Table of Contents/Abstract Graphic


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Biographies

Katsuhiko Ariga received his PhD degree from Tokyo Institute of Technology in 1990. He joined to the National Institute for Materials Science in 2004. He is currently the leader of the Supermolecules Group and principal investigator of the World Premier International Research Centre for Materials Nanoarchitectonics, NIMS. He is also appointed as a professor of The University of Tokyo. He works for ACS journals as editorial board members of Chemistry of Materials (current), ACS Applied Materials & Interfaces (current), and Langmuir (- 2014).

Taizo Mori is a postdoctoral researcher in the Supermolecules Group at the National Institute for Materials Science (NIMS). He graduated from the Department of Polymer Chemistry at Kyoto University and obtained his doctorate in 2009. He worked as a JSPS fellow and then as a postdoctoral associate of the Liquid Crystal Institute at Kent State University. He won the Michi Nakata Prize for Early Career Award at the International Liquid Crystal Society in 2016.


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Junbai Li obtained his Ph.D. degree in Polymer Science from Jilin University. He then spent several years carrying out postdoctoral work and a joint research project at the interface department in the Max Planck Institute of Colloids and Interfaces in Germany. He is currently a Professor at the Institute of Chemistry in the Chinese Academy of Sciences. His research interests involve molecular biomimetic based on molecular assembly, molecular mechanisms, and structure in assembled biological systems, microcapsules, and nanostructured design.


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Langmuir Nanoarchitectonics from Basic to Frontier - American

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