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Interface-Rich Materials and Assemblies

Synergistic Effect of Granular Seed Substrates and Soluble Additives in Structural Control of Prismatic CaCO3 Thin Films Bingjun Wang, Li-Bo Mao, Ming Li, Yupeng Chen, Mingfeng Liu, Chuanlian Xiao, Yuan Jiang, Shutao Wang, Shu-Hong Yu, Xiang Yang Liu, and Helmut Cölfen Langmuir, Just Accepted Manuscript • DOI: 10.1021/acs.langmuir.8b02072 • Publication Date (Web): 23 Aug 2018 Downloaded from http://pubs.acs.org on August 30, 2018

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Synergistic Effect of Granular Seed Substrates and Soluble Additives in Structural Control of Prismatic CaCO3 Thin Films Bingjun Wang†,[+], Li-Bo Mao§,[+], Ming Li†, Yupeng Chen‡, Ming-Feng Liu†, Chuanlian Xiao†, Yuan Jiang†*, Shutao Wang‡,⊥, Shu-Hong Yu§*, Xiang Yang Liu†,¶, Helmut Cölfen#

†

College of Materials, Research Institute for Soft Matter and Biomimetics, Fujian

Provincial Key Laboratory for Soft Functional Materials Research, Xiamen University, Xiamen 361005, China

§

Division of Nanomaterials & Chemistry, Hefei National Research Center for

Physical Sciences at the Microscale, CAS Center for Excellence in Nanoscience, Collaborative Innovation Center of Suzhou Nano Science and Technology, Department of Chemistry, University of Science and Technology of China, Hefei, 230026, China

1 ACS Paragon Plus Environment

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‡

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CAS Key Laboratory of Bio-inspired Materials and Interfacial Science, CAS Center

for Excellence in Nanoscience, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, China

⊥

¶

University of Chinese Academy of Sciences, Beijing 100049, P. R. China

Department of Physics, Faculty of Science, National University of Singapore,

117542 Singapore, Singapore

#

Physical Chemistry, University of Konstanz, Konstanz 78457, Germany

Abstract

In biomineralization and bioinspired mineralization, substrates and additives function synergistically in providing structural control of the mineralized layers including their orientation, polymorph, morphology, hierarchical architecture, etc. Herein, a novel type of granular aragonitic CaCO3-poly(acrylic acid) (PAA) substrates guides the mineralization of prismatic CaCO3 thin films of distinct morphology and polymorph in the presence of different additives including organic compounds and polymers. For instance, weakly-charged amino acids lead to columnar aragonite overlayers, 2 ACS Paragon Plus Environment

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while their charged counterparts and organic acids/bases inhibit the overgrowth. Employment of several specific soluble polymer additives in overgrowth instead results in calcitic overlayers with distinct hierarchical architecture, good hardness/Young's modulus, and under-water superoleophobicity. Interestingly, self-organized patterns in the CaCO3-poly(L-glutamic acid) overlayer are obtained under proper mineralization conditions. We demonstrate that the granular seed comprised of mineralized and polymeric constituents is a versatile platform for obtaining prismatic CaCO3 thin films, where structural control can be realized by the employment of different types of additives in overgrowth. We expect the methodology to be applied to a broad spectrum of bioinspired, prismatic-type crystalline products, aiming for the development of high-performance hybrids.

Introduction

A challenging issue in crystallization is the exploration of sustainable approaches for transforming various compounds to engineering/functional materials with preferred structural form, therefore with satisfying properties and good performance.1-4


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Nevertheless, current methods of crystal engineering remain empirical in controlling important structural characters, such as nucleation number density, orientation, morphology, and polymorph of crystalline products, leading to impediment in realizing their functional outcomes.1,5 As a comparison, biominerals exhibit fascinating structural functions mainly due to their hierarchical architecture.1,6,7 Replication of the structural essence of biominerals would therefore provide rational approaches to bioinspired crystalline products with intriguing functions.1,2,4,8,9 Among model compounds for bioinspired mineralization studies, CaCO3 has received increasing attention because the mineral plays an important role in biomineralization process and has widespread applications in industry.10-12 Meanwhile, its precipitation has a profound impact on the carbon cycle, as it is the most abundant biomineral in the biosphere.13

Many CaCO3 biominerals found in mollusk shells,14,15 avian shells,16 sea turtle shells,17 and exoskeleton shells of lobsters and crabs18 are (thin) films distinct in hierarchical

architecture.

Previous

studies

have

shown

that

insoluble

biomacromolecular substrates in the presence of soluble additives play a key role in 4 ACS Paragon Plus Environment

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controlling the structural characters of these biogenic products including their morphological, polymorphic, and orientational outcomes19-22. Hence, various substrates including Langmuir-Blodgett (L-B) membranes,23-26 self-assembled monolayers,27-29 and semicrystalline polymers19,20 have been employed for producing CaCO3 thin films, where the synergistic effect of insoluble biomacromolecular substrates and soluble additives was assumedly responsible for the structural outcomes.8,19,22,23,28,30 Nonetheless, most of related mineralization studies are incapable of producing continuous CaCO3 thin films carrying distinct mesostructural architecture. Hence, few synthetic CaCO3 thin films exhibit comparable structural functions, such as remarkable mechanical performance or superwetting behaviors, to their biological counterparts. In the last few years, researchers found that a novel type of substrates comprised of granular CaCO3-polyelectrolyte (i.e. poly(acrylic acid) (PAA) and poly(aspartic acid)) hybrids can lead to uniform, prismatic CaCO3 thin films.4,31,32 However, these studies were mainly about the morphosyntheses of thin films. To date, no systematic study has been focused on the structural control of


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prismatic CaCO3 thin films provided by the synergistic effect of these granular seed substrates and soluble additives.

Herein, we report that granular aragonitic CaCO3-PAA seed layers and soluble additives can function synergistically in providing structural control of prismatic CaCO3 thin films. With organic compounds including organic acids/bases, amino acids, and branched polyethylenimine (PEI), the overgrowth on the seed layer can be either promoted or inhibited, leading to columnar aragonitic overlayers in different morphological

characters.

As a

comparison,

employment

of

poly(sodium

4-styrenesulfonate) (PSS), poly(L-glutamic acid) (PGlu), or silk fibroin (SF) in overgrowth caused polymorphic transformation from the aragonitic seed layer to the calcitic overlayer, accompanied by the prismatic nature and distinct hierarchical architectures. Interestingly, CaCO3 overlayers with the micro-/nano-architecture exhibited structural functions such as good hardness/Young’s modulus and under-water superoleophobicity. The granular seed layers, combined with the presence of soluble additives, realized the structural control in overgrowth of prismatic CaCO3 thin films. This strategy can lead to prismatic thin films with 6 ACS Paragon Plus Environment

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specific mesostructural architecture, which has enormous potential in fabrication of hybrid thin coatings exhibiting extraordinary structural functions.

Experimental Section A three-step mineralization process is listed in sequence.

Step 1. Coating of polymer substrates Poly(vinyl alcohol) (PVA, the average Mw = 1.5–1.9 × 105 g mol-1, 87–89% hydrolyzed, Sigma-Aldrich) was used as the substrate for CaCO3 mineralization. The PVA thin film was prepared as follows. A volume of 30 µL 2 wt% PVA aqueous solution was dropped on a hydrophilic cover glass (1.2 cm × 1.2 cm, pretreated with Piranha solution) and spread uniformly, followed by either a two-step spin-coating process (3000 rpm for 15 s followed by 5000 rpm for 45 s) or a drop casting process in vacuum to evaporate the solvent and yield the PVA thin film. Afterwards, PVA thin films were annealed at 160˚C for 1 h before use.

Step 2. Deposition of the granular seed layer In a typical procedure to achieve the seed layer, the mineralization was conducted above the PVA thin films by the slow diffusion of CO2 (g) (based on the slow decomposition of NH4HCO3 (powders, AR, Sinopharm Chemical Reagent)) in a volume of 4 mL 20 mM CaCl2 (aq) (AR, Sinopharm Chemical Reagent) in the presence of 4.0 × 10-3 wt% poly(acrylic acid sodium salt) (PAA, partial sodium salt 7 ACS Paragon Plus Environment

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solution, average Mw = 2.1 × 103 g mol-1, 61-65 wt% in water, Sigma-Aldrich) as the additive in a closed desiccator for 48 h, based on a previous study.31 Subsequently, the hybrid thin film was removed and rinsed twice with degassed water (obtained from Millipore, Direct-Q3 and boiled for 0.5 h to remove CO2 before use) before being used for characterization or further overgrowth.

Step 3. Overgrowth of prismatic CaCO3 thin films

For the overgrowth on the aragonitic seed layer in the presence of silk fibroin (SF; from cocoons of the silkworm Bombyx mori), the solution was prepared using a CaCl2–SF solution, where the concentration of SF was between 1 g L-1 and 6 g L-1. The exterior morphologies of the overlayer varied moderately by using different SF concentration values. Purification of SF was based on the standard procedure provided by Kaplan and coworkers34. In terms of branched polyethylenimine (PEI, branched, average Mw = 800 g mol–1, Sigma-Aldrich), its concentration range was between 0.005 g L-1 and 0.5 g L-1, and no overgrowth was observed on the seed layer. The concentrations of both poly(sodium 4-styrenesulfonate) (PSS; Mw = 2.1 × 103 g mol–1, Sigma-Aldrich) and poly(L-glutamic acid) (PGlu, Mw = 3-15 × 103 g mol–1, Sigma-Aldrich) were between 0.01 g L-1 and 5 g L-1. Regarding small molecule 8 ACS Paragon Plus Environment

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additives (organic acids and bases and several amino acids, all from Sigma-Aldrich), the concentration of each was between 10 mM and 50 mM. For evaluation of the acceleration effect of amino acids, the concentration value of 50 mM was used in the overgrowth for comparisons; otherwise, the evaluation based on SEM imaging of the exterior morphologies was difficult due to insignificant overgrowth. The concentration of Ca2+ was constant at 20 mM for all overgrowth experiments, according to previous studies.21,31,33 The overgrowth procedure was completed by immersing the seed layer in 4 mL CaCl2-additive solution, which was exposed to the NH4HCO3 vapor in a closed desiccator for 72 h.

Characterization

SEM images were collected using a Hitachi SU-70 electron microscope. Samples were prepared by breaking the thin film into pieces, and then by sticking them onto double-side conducting adhesive tape. Samples were coated with a thin layer of gold using a sputter coater for 30 s (i.e. for SEM acquisition at 15 kV). An Olympus BX53 optical microscope equipped with polarizers was used for the OM & POM observation. X-ray diffraction patterns were collected using an X’pert PRO, 9 ACS Paragon Plus Environment

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PANalytical, X-ray diffractometer with Cu-Kα radiation. Diffraction patterns were generated under machine operation at 40 mA and 40 kV and using a step size at 0.016°, and calculation of peak ratios was based on the peak height. Raman spectra were recorded using a Labram HR Evolution system (Horiba) equipped with a 532 nm laser. The laser power and beam size were approximately 0.25 mW and 1 µm, respectively. The polymorphic assignment of CaCO3 was verified according to a reference35. The ATR-FTIR spectra from 4,000 to 500 cm−1 were collected on a Nicolet iS10 FTIR spectrometer (Thermo Scientific). A Zeiss Neon 40EsB was used to prepare the TEM samples. To protect the surface during milling and lift-out, a bar of SiO2 was deposited on the sample using gas-assisted deposition. After lift-out and transfer onto the TEM grid, the sample was polished to the final thickness using a 50 pA current. A FEI Talos F200S transmission electron microscope (200kV) was employed to examine the morphology, structure, and chemical components. The relatively large collection angle (54–200 mrad) of the HAADF-STEM detector allowed the acquisition of images with excellent atomic-number (Z) sensitivity. TEM and selected area electron diffraction (SAED) tests were also performed using a


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JEOL-2010 device (200kV). Samples were prepared by breaking columnar thin films into small pieces followed by dispersion in ethanol, and drop-casting of the dispersed solution onto a carbon-coated copper TEM grid.

For the determination of mechanical properties, a Nano Indenter (Agilent G200, US) with a Berkovich diamond probe was utilized to perform the nanoindentation tests on the specimens. To ensure that the indentations were performed on calcium carbonate spherules, the indentation locations were selected manually under an optical microscope at a magnification factor of 1000. With a theoretical displacement resolution of 0.01 nm, the indentation tests were performed with an indentation depth of 500 nm. During the loading process, the strain rate was controlled to be constant at 0.5 nm/s with a loading resolution of 50 nN.

The under-water contact angle was measured using an OCA 20 machine (Data-Physics, Germany) at ambient temperature. The membrane was first immersed in water, and then an oil droplet (1,2-dichloroethane, 3 µL) was squeezed slowly onto the membrane and the contact angle was measured. The result was the average value of three measurements detected at different positions of the same sample. The 11 ACS Paragon Plus Environment

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adhesion force between oil droplet and CaCO3 membrane was detected using a high-sensitivity micro-electro-mechanical balance system (Data-Physics DCAT11, Germany) by controlling an oil droplet (1,2-dichloroethane, 10 µL) contact with the membrane and leave in water environment. The force during the process was recorded.

Results and Discussion

Overview. The three-step approach to prismatic CaCO3 thin films is summarized in Scheme 1. PVA, a synthetic polymer rich in hydroxyl groups, was selected as the insoluble matrix for growing continuous seed layers granular in nature. A PVA thin film was obtained by using a drop casting method and annealed at 160˚C for 1h before the growth of the seed layer. As a comparison, discontinuous sperulitic aragonitic CaCO3 domains were observed on the polymer surface without annealing (Figure S.I. 1a-b). Next, deposition of a granular seed layer was proceeded by exposing an aqueous solution containing CaCl2 and PAA to ammonium bicarbonate vapor.31 A continuous thin film composed of spherulitic polydomains was obtained after 48 h, as detected under the polarizer (Figure 1a). Both POM imaging and the 12 ACS Paragon Plus Environment

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XRD pattern verify that the vast majority of spherulitic polydomains are aragonitic CaCO3, coexisting with the slight contribution of spherulitic vateritic and calcitic domains (Figure 1b). The Raman microscopy scanning unambiguously confirms polymorphic information in both aragonitic and vateritic spherulitic polydomains (Figure 1c-d).35 The coexistence of the two polymorphs can be attributed to their close kinetics of heterogeneous nucleation on the PVA substrate.21 An atomic force microscopy (AFM) image verifies the granular nature of the aragonitic domain (Figure 1e). Moreover, a cross-section SEM image evidences that the aragonitic seed layer 1-3 µm in thickness is composed of tilted aragonitic nanorods (Figure 1f), which is in accordance with previous studies.32,36 Next, the granular aragonitic thin films were employed as the seed layer for structural control of the overlayer in the presence of different types of additives.

Scheme 1. Summary of the three-step procedure in mineralization of CaCO3 thin films and list of the additives used for studying the additive effect in three categories. Overgrowth in the presence of different additives leads to different structural characters of the overlayer. The values in the brackets are hydropathy indices based on the Kyte & Doolittle model.37


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Figure 1. Characterization of the aragonitic seed layer with multiple tools. a-b, POM image (a) and XRD pattern (b) of a CaCO3-PAA seed deposited on a PVA substrate, where abbreviations “A”, “C”, and “V” in image b represent aragonite (PDF#41-1475), calcite (PDF#47-1743), and vaterite (PDF#33-0268), respectively. c-d, Raman spectra confirm the aragonitic nature of the same seed layer. e-f, AFM (e) and side-view SEM (f) images of the seed layer grown on a PVA thin film.


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Overgrowth of the prismatic CaCO3 thin films aims at disclosing the correlations between the structural character of the overlayer and the synergetic effect of the seed layer and the soluble additives used in overgrowth. The candidates of soluble additives include organic acids/bases, amino acids, positively- and negatively-charged polyelectrolytes, and a biomacromolecule – SF. The screening tests evidenced that the presence of various additives had a tremendous effect on the morphological and polymorphic outcomes of the overlayer. These additives are hence classified into three categories according to their performance (Scheme 1). Amino acids possessing proper hydropathy indices (according to the Kyte & Doolittle model37) promoted the overgrowth of the columnar aragonitic layer effectively. In contrast, charged organic compounds, hydrophilic amino acids, and PEI inhibited the nucleation of the overlayer. Besides, polymorphic transformation from an aragonitic seed layer to a calcitic overlayer was detected by using PSS, PGlu, or SF as an additive.

Promotion/Inhibition Effects. Employment of hydrophobic amino acids in CaCO3 mineralization (Scheme 1) promoted the overgrowth of the columnar layer on the granular seed layer. We note that the term "hydrophobic amino acids" means amino 16 ACS Paragon Plus Environment

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acids with their hydropathy indices higher than -1, based on the Kyte & Doolittle model37. The promotion degree, provided by different hydrophobic amino acids, can be evaluated by the morphological outcome of the columnar aragonitic overlayer. L-serine (Ser) exhibited the most pronounced promotion ability among candidates employed in the current study, leading to a continuous, highly-oriented columnar aragonitic thin film (Figure 2a-b). As a comparison, the presence of glycine (Gly) caused a continuous columnar thin film composed of spherulitic polydomains with the decreased columnar number density (Figure 2c-d). Employment of hydrophobic amino acids with high positive hydropathy values such as L-valine (Val), L-alanine (Ala), and L-phenylalanine (Phe) led to overgrowth of spherulitic polydomains on the seed layer (Figure 2e-f). In the control experiment, sporadic spherulitic polydomains were observable under the guidance of seeded mineralization in the absence of an additive (Figure S.I. 2a-b). According to heterogeneous nucleation theories, the decrease of columnar number density roughly reflects the increase of the heterogeneous nucleation barrier in overgrowth. It is important to note that the columnar number density correlates well with the sequence of hydropathy indices of


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above amino acids. The correlation can be explained by considering the amphiphilic molecular structures of the amino acids employed and their interactions with the seed layer. The polar amine groups facilitate their approach to the seed layer, as the latter is characteristic of being rich in carboxyl groups due to the occlusion of the PAA constituents. Subsequently, the short molecular chains lead to the rapid, reversible adsorption because of the relatively small molecular size. It is hypothesized that the amino acids rich in hydroxy groups such as Ser and Gly can displace the water molecules adsorbed on the seed layer by perturbations.38,39 Hence, the H-bonding interactions can decrease the magnitude of diffusive barrier effectively and therefore, lead to the reduction of the energy barrier for attaching Ca2+ to the seed layer. Next, the adsorbed Ca2+ can occupy these positions for further overgrowth owning to the reversibility of the adsorption/desorption process. From this explanation, it can be seen that the proper hydrophobicity of the amino acid additive is critical in terms of promoting the overgrowth process. Therefore, when we consider different amino acid additives in the Kyte & Doolittle model,37 hydrophobicity,

which is a scale to evaluate the

the amino acids with hydropathy indices between -1 and 0 possess


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the ability to accelerate the overgrowth of CaCO3 in the current study. As a comparison, very hydrophobic amino acids are ineffective in breaking the water layer to facilitate the interactions between Ca2+ and the seed layer. In short, the promotion effect provided by the abovementioned amino acids causes the distinct structural character of the overlayers, as the additives exhibit different levels of capability in breaking the water absorbed on the seed layer and in decreasing the heterogeneous nucleation barrier in the overgrowth process.


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Figure 2. Comparison of the morphological characters of overlayers obtained in the presence of different additives. Top-view SEM images show the overlayers obtained in the presence of Ser (a-b), Gly (c-d), and Ala (e-f), respectively, in accordance with the sequence of the decline in the promotion effect to the overgrowth. The overgrowth proceeded in the presence of 50 mM amino acids.

Cross-sectional SEM images provide the detailed information of the columnar layer obtained

in

the

presence

of

Ser

(Figure

3a-b),

which

is

a

typical 20

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overgrowth-promoting additive. SEM images confirm the formation of a continuous, densely-packed columnar overlayer on the seed layer, where the interface between the two layers is clearly visible (Figure 3b). The unidirectional growth direction of the columnar overlayer is reflected in an XRD pattern, where the aragonitic (012) peak of CaCO3 dominates (Figure 3c). Regarding the crystallographic information of each rod in the overlayer, transmission electron microscopy (TEM) and the related data of selected area electron diffraction (SAED) confirm that a typical aragonitic rod grows along the [001] direction (Figure 3d-e), which is favored in typical aragonitic CaCO3 crystals as well. Both pieces of crystallographic information are in accordance with the tilted aragonitic rods in the overlayer, as shown in both SEM images (Figure 3a-b). The calculation of the tilted angle is 19.82°, according to the crystallographic information of aragonitic CaCO3 (Figure 3f). This value is in accordance with the average angle measured in the SEM images.


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Figure 3. Characterization of an overlayer obtained in the presence of Ser with multiple tools. a-b, Cross-section SEM images provide an overview (a) and the interface between the seed layer and overlayer (b). c, Typical XRD pattern of the overlayer, where abbreviations “A” and “V” represent aragonite (PDF#41-1475) and vaterite (PDF#33-0268), respectively. d-e, TEM image (d) and SAED pattern (e) of a typical aragonitic column. (f), Model of an aragonitic column in the overlayer, showing the crystallographic relations between the seed layer and the columnar overlayer. The overgrowth proceeded in the presence of 50 mM Ser. In images a & b, dash lines highlight the interface between the seed layer and overlayer, respectively. The white arrows in image b indicate two tilted columns.

With this detailed information, we now can discuss the structural control of the overlayer provided by the seed layer beneath. An interesting question is orientational transformation from a polycrystalline seed layer to a highly-oriented columnar


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overlayer. Unlike the exterior layer characteristic of well-aligned columns, inclined rods can be detected in the overlayer close to the seed layer (Figure 3a-b). It is deemed that the poor orientation in the initially-grown overlayer reflects the polycrystalline nature of the seed layer underneath (Figure 1b), where the epitaxial overgrowth starts. In addition to orientational preference, the overgrowth also accompanied the increase in the size of columns and correspondingly the decrease in the crystal number density (Figure 3a). The gradual changes of orientational and structural forms in the overlayer hint that a "competition growth route"40 was involved in overgrowth. As densely-packed aragonitic rods grew, those that were not aligned along the tilted direction were soon impeded by adjacent crystals, and had limited room for further growth41. The highly-oriented overlayer was hence produced under the guidance of the crystallization habit of aragonitic rods and the "competition growth" model, showing close relationship in structural characters with the seed layer.

Organic acids/bases, hydrophilic amino acids (five charged amino acids listed in Scheme 1, L-asparagine (Asn), L-glutamine (Gln), and L-proline (Pro)), and a positively-charged polyelectrolyte – branched PEI exhibited the inhibition ability in 23 ACS Paragon Plus Environment

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the overgrowth procedure (Scheme 1 & Figure 4a-d). The seed layer remained spherulitic in structural character under the polarizer with no evidence of overgrowth (Figure 4a). The failure in overgrowth was reconfirmed by a side-view SEM image, where no detectable increase in thickness was observed (Figure 4c). The concentration effect of inhibitors was considered next. Regarding organic compounds, no overgrowth was observed when the concentration of the additive was between 10 and 50 mM. Decreasing the concentration further left the observation of the inhibition effect difficult, as the overgrowth led to sporadic spherulitic domains. The presence of a small amount of PEI ([EI] = 0.12 mM; the concentration of the repeating structural unit ethylene imine (EI) instead of PEI was employed for a better understanding of the molar ratios between Ca2+ and PEI) inhibited the overgrowth completely. Hence, PEI is a relatively strong inhibitor42 of the overgrowth on the seed layer compared with abovementioned organic compounds. By contrast, PEI can be an effective soluble additive for obtaining CaCO3 precipitates with distinct microstructures and polymorphs43. The additive effect can be attributed to the primary amine groups, which complex with carbonate anions in the solution phase.


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Figure 4. Characterization of the hybrid thin film obtained after an overgrowth in the presence of ethylenediamine at a concentration of 50 mM. a-b, POM (a) and SEM (b) images indicating an overview of the upper layer after overgrowth. c-d, Cross-section (c) and top-view (d) SEM images showing the structural character of the exterior mineralized layer.

Though all selected additives exhibited the effective inhibition ability in overgrowth, they functioned via different principles. Regarding negatively-charged organic compounds, they can form pairs with Ca2+, decreasing the supersaturation level in the reacting mother liquor.44-46 As a comparison, amine-rich molecules are strongly adsorbed on the substrate with limited selectivity and reversibility. For instance, the adsorption of ethylenediamine on the seed layer was evidenced by ATR-FTIR 25 ACS Paragon Plus Environment

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spectroscopy (Figure S.I. 3). The strong and irreversible adsorption of candidates such as organic bases, basic amino acids, and branched PEI on the seed layer hence hampers the attachment of Ca2+ on the seed layer, ceasing in-situ mineralization of a CaCO3 thin film. As to hydrophilic amino acids, though they have good tendency to approach to the seed layer, their improper hydrophobicity disallowed them to break the local water layer and hence, overgrowth was failed to initiate.44,46 In a word, the improper hydrophilicity/hydrophobicity of the overgrowth-inhibiting additives leads to unfavored interaction, in terms of triggering crystallization, between these additives and the seed layer, which is the key reason of the inhibited overgrowth.

Polymorphic Transformation. PGlu,21,47 SF,48 and PSS49 are typical soluble polymer additives employed in morphosynthetic studies of CaCO3 mineralization.31 In the current study, it is worth noting that the overlayers achieved from the aragonitic seed layer were calcitic CaCO3 in the presence of these three additives, and this polymorphic transformation was confirmed by XRD patterns (Figure 6b). Moreover, these polymeric additives led to continuous overlayers with specific hierarchical architecture (Figure 5a-f, S.I. 4a-c). For instance, the calcite-SF overlayer constitutes 26 ACS Paragon Plus Environment

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block-shaped rhombohedral calcitic microcrystals (Figure 5a-b). As a comparison, cross-lamellar calcitic microdomains were obtained by using PSS as the additive (Figure 5c-d). Nevertheless, lamellae are not highly-oriented owing to the polycrystalline nature of the seed layer. In addition, overgrowth in the presence of PGlu led to raspberry-shaped microdomains comprised of nanocrystalline structural units (Figure 5e-f). The prismatic calcitic CaCO3-PGlu overlayer shows the ultimate morphological similarity to the eggshells of sea turtles close to the membrane area.17 These morphologies were also obtainable in our previous study.31 Though the seed layers in the two studies are different in polymorphic form, the overgrowth in the presence of the same polymeric additive can lead to the same calcitic hierarchical architecture.


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Figure 5. Top-view SEM images of calcitic overlayers obtained in the presence of SF (i.e. [SF] = 6 g L-1) (a-b), PSS (i.e. [PSS] = 0.5 g L-1) (c-d), and PGlu (i.e. [PGlu] = 0.01 g L-1) (e-f) in low and high magnification, respectively.

More intuitively, a cross-sectional SEM image clearly shows that when SF was applied as the additive, microdomains close to the bottom area of the overlayer are characteristic of densely-packed, block-shaped microcrystals deposited on the seed layer (Figure 6a). Microcrystals high in packing density are rhombohedral in shape, in 28 ACS Paragon Plus Environment

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accordance with the structural character of single crystalline calcitic CaCO3. The orientational preference in the CaCO3-SF overlayer is confirmed, as the (104) peak in its XRD pattern is relatively dominant in comparison to that in the XRD pattern of calcitic powders (Figure 6b). Hence, doping SF in the seeded overgrowth procedure led to the continuous, oriented hierarchical architecture composed of rhombohedral microcrystals (Figure 5a-b). Unlike PGlu and PSS, SF provides the moderate effect in shaping rhombohedral calcite microcrystals. A previous study highlighted that biomacromolecules can play a similar role in promotion of faceted growth of rhombohedral calcite microcrystals in bioinspired mineralization due to the presence of their aggregates.50 It is hence assumed that the nanoaggregates of SF might guide the formation of the continuous overlayer comprising stacks of calcitic microcrystals. Such high number density of microcrystals in the exterior layer highly increases the surface roughness of the overlayer, which is the prerequisite for its superwetting behavior.51

Next, the TEM technique was employed for the detailed structural analyses of the same sample. The clear interface between the aragonitic seed layer and the calcitic 29 ACS Paragon Plus Environment

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overlayer is visible in a TEM image (Figure 6c; the sample was prepared by a focused ion beam treatment). Such an abrupt aragonite-calcite interface has been reported in previous studies.52,53 An HRTEM image shows that the seed layer is composed of granular aragonitic nanocrystals lacking orientational preference (Figure 6d). Therefore, the polycrystalline nature of the seed layer from the HRTEM result is in line with the XRD pattern (Figure 1b). As a comparison, a rhombohedral microcrystal in the overlayer composed of nanocrystalline calcitic CaCO3 diffracts in a similar way as a single crystal, suggesting that the nanocrystals in the same microcrystal exhibit the same growth direction (Figure 6e-f). Thus, each microcrystal is mesocrystalline in nature,11,54 owning to the additive effect of the SF constituents during overgrowth.


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Figure 6. Characterization of the calcitic overlayer obtained in the presence of SF (i.e. [SF] = 6 g L-1). a, Cross-section SEM image showing the structural details of the product. b, XRD patterns of the overlayer (top) and calcite powders (bottom), where the abbreviation “C” represents calcite (PDF#47-1743). c, TEM image showing the interface between the aragonitic seed layer and the calcitic overlayer, where the two layers are highlighted by arrows. d, High-resolution TEM images of the aragonitic seed layer. e-f, High-resolution TEM images of the calcitic overlayer, where the inserted pattern in image e is the responding SAED pattern of the same domain. The 31 ACS Paragon Plus Environment

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sample for the TEM measurement was treated with the focused ion beam technique. Dash lines in images a and c highlight the interface between the seed layer and the overlayer.

Interestingly, overgrowth in the presence of PGlu (i.e. [PGlu] = 0.05 g L-1) at 25˚C caused an overlayer constituted by concentric ring patterned polydomains, as shown in an SEM image (Figure 7a). Each periodic ring is composed of one layer of densely-packed raspberry-shaped microdomains (Figure 7b). Moreover, the distance between adjacent grooves is about 2-3 µm, equivalent to the diameter of a typical spherulitic microdomain. A close scan (Figure 7b) indicates that the self-organized overlayer is characterized of the "Turing pattern."55 Instead of being a concentric ring with constant distance between adjacent grooves, the width of gaps is slightly inconsistent in several different directions. Hence, it is more reliable that each concentric ring is composed of several periodic polydomains propagating independently along the radial direction. In each periodic polydomain, the equal distance between adjacent rings signifies the oscillating character of the precipitation of the Belousov-Zhabotinsky type.56 Specifically, the formation of periodic polydomains hypothetically endured a coupled reaction-diffusion process. It is 32 ACS Paragon Plus Environment

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assumed that the preadsorption of the reacting PGlu and Ca2+ constituents on the seed layer could form a thin hydrogel matrix dynamically, where the oscillating reaction usually occurred during the diffusion of the HCO3- components.57,58 Additionally, the active role of precursors like nanocomplexes,59 amorphous CaCO3 nanoparticles,60 or liquid precursors comprising amorphous CaCO3 nanoparticles as structural units61 in a coupled reaction-diffusion process should be crucial for controlling the growth kinetics of the periodic polydomains, according to previous studies. When the precursor components were consumed to deposit CaCO3, their local concentration was decreased so that the deposition was halted. Apparently, the lack of the nucleation driving force led to the formation of the valley domains. Until the local supersaturation was restored by lateral diffusion of precursor particles, deposition of another ring-like layer could occur. The circling of the coupled process eventually led to periodic patterns. It is noteworthy that periodic patterns also exist in bioinspired minerals58,62 and biominerals, the inner surface of growing nacre, for example.63,64 Nature also employs the oscillating reactions on different length scales to produce materials with unique appearances and functions.65,66


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Figure 7. Top-view SEM images (a-b) of a self-organized overlayer obtained in the presence of PGlu (i.e. [PGlu] = 0.05 g L-1). The white circle in image b denotes a typical "Turing pattern."

Functionalities of calcitic CaCO3 thin films. CaCO3-based biogenic thin films are characterized by their remarkable mechanical properties due to their hierarchical architecture.14,67 The synthetic prismatic-type CaCO3 thin films obtained in the current study possess distinct micro-/nano-textures, and hence, could be good candidates regarding mechanical properties. Nanoindentation measurements verified excellent mechanical properties of the calcitic overlayer obtained in the presence of PGlu and PSS. Hardness (H) and Young’s modulus (E) values of the CaCO3-PGlu overlayer are 1.04 ± 0.22 and 22.0 ± 4.0 GPa (N = 15), respectively. As a comparison, both values of the CaCO3-PSS overlayer are 0.85 ± 0.12 and 20.8 ± 2.4 GPa (N = 11), respectively. The mechanical properties of the CaCO3-SF overlayer were not


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measured, as the exterior surface was too rough. These values are shown together with several categories of synthetic and biogenic materials in an Ashby plot (Figure 8). It is evident that the synthetic thin films possess comparable mechanical properties with prismatic-type biominerals.14 Remarkably, both values are higher than those of human bone, a typical biomineral with excellent mechanical properties. It is promising that mechanical properties could be modified further by employing other well-designed polymer additives and by doping with shape-anisotropic colloids. The significant mechanical performance of the synthetic prismatic-type CaCO3 thin film can be convincingly attributed to the high reinforcement orientation between densely-packed columns in each spherulitic microdomain.14,68


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Figure 8. Ashby plot showing the mechanical properties of the prismatic-type, calcitic CaCO3-PGlu (denoted by the solid star) and CaCO3-PSS overlayers (denoted by the solid sphere) as well as some synthetic and biogenic materials. (i.e. [PGlu] = 0.05 g L-1; [PSS] = 0.50 g L-1).

It is worth to mention that synthetic prismatic-type CaCO3 thin films possess a remarkable wetting behavior, which can also be found in numerous biominerals due to the similar hierarchical exterior textures.69 The calcitic CaCO3-SF, CaCO3-PGlu, and CaCO3-PSS exhibited excellent under-water superoleophobicity with static under-water oil (1,2-dichloroethane) contact angles of 155.5 ± 3.6°, 153.4 ± 1.5°, and


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160.5 ± 2.5° (N = 3), respectively. An exemplary image shows the under-water superoleophobicity with static under-water oil – 1,2-dichloroethane – of the CaCO3-SF overlayer (Figure 9a). Moreover, oil droplets show ultralow adhesion force on the CaCO3-SF overlayer. When an oil droplet was controlled to contact to and then to lift from the thin film, there remained no residual oil on the surface and the force in this process was as low as 21.3 ± 3.7 µN (N = 3) (Figure 9c-d). Consequentially, an oil droplet could roll away easily from the CaCO3-SF overlayer when the membrane leaned an angle of 3.5 ± 0.4° (N = 3) (Figure 9b). The low rolling angle can be attributed to under-water superoleophobicity and the low oil adhesion force of the synthetic prismatic-type CaCO3 thin film. Hence, a green approach, based on the synergistic effect of granular seed substrates and soluble additives, to such a bioinspired thin film composed of a cheap engineering material – CaCO3 could provide a competitive alternative to current commercial materials with the under-water superoleophobic property.


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Figure 9. Under-water superoleophobicity of an SF-doped prismatic-type calcitic thin film (i.e. [SF] = 6 g L-1). a-b, Photographs of an oil droplet (1,2-dichloroethane, 3 µL) dropped on a CaCO3 thin film with a static under-water contact angle (a) and rolling angle (b), separately. c-d, two typical images during the lifting of the oil droplet show the ultralow adhesion force between the oil and the overlayer both emerged in water. Abbreviations “W” and “O” in all images represent water and 1,2-dichloroethane, respectively.

Conclusions

To summarize, granular aragonitic CaCO3–PAA layers provide a novel but versatile platform for structural control of prismatic CaCO3 thin films in the presence of 38 ACS Paragon Plus Environment

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different additives. By rationally using the synergistic effect of these two factors, we can tune the nucleation number density, morphology, and polymorph of the CaCO3 overlayer, under specific conditions endowing it with intriguing structural function(s). Therefore, CaCO3, a typical sustainable engineering material, shows great potential on becoming a functional materials, which can find widespread applications in the fabrication of biomedical coatings and oil-water separation membranes, etc. Moreover, extending this method to functional compounds can lead to hierarchical thin films, which can display the unprecedented performance due to the coupling of both inherent and emerging properties.

ASSOCIATED CONTENT

Supporting Information. The supporting information is available free of charge, in which a detailed mechanical calculation process, the FTIR spectra of the seed layer and the layer obtained in the presence of ethylenediamine and the POM images of the calcitic overlayers are listed.

AUTHOR INFORMATION


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Corresponding Author

*E-mail: [email protected] (Y.J.), *E-mail: [email protected] (S.-H.Y.).

Author Contributions [+]

B.W. and L.-B.M. contributed equally to this work.

The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript.

Funding Sources

Y.J. acknowledges financial support from the National Natural Science Foundation of China (NSFC; 21303144, 21875193) the Fundamental Research Funds for the Central Universities (20720162013, 20720180066). S.-H.Y acknowledges the funding support from NSFC (21431006, 21761132008). X.Y.L thanks the 111 Project (B16029).

Notes

The authors declare no competing financial interest.

ACKNOWLEDGMENT


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This work was supported by the Training Program of Innovation and Entrepreneurship for Undergraduates of Xiamen University and the Fundamental Research Funds for the Central Universities (No. 20720162013). Y.J. acknowledges financial support from the National Natural Science Foundation of China (NSFC; 21303144) the Fundamental Research Funds for the Central Universities (20720180066). S.-H.Y acknowledges the funding support from NSFC (21431006, 21761132008). X.Y.L thanks the 111 Project (B16029). Prof. Ruikang Tang, Prof. Haihua Pan, Prof. Zhiyang Yu, Dr. Da Zhan, Xiuming Zhang, Xinyu Liu, and Zihao Lu are acknowledged for characterization assistance and discussion.

ABBREVIATIONS CaCO3, calcium carbonate; PAA, poly(acrylic acid); PGlu, poly(L-glutamic acid); PAsp,

poly(L-aspartic

acid);

PEI,

polyethylenimine;

PSS,

poly(sodium

4-styrenesulfonate); SF, silk fibroin; PVA, poly(vinyl alcohol); FIB, focused ion beam;

Ser,

L-serine;

Gly,

glycine;

Val,

L-valine;

Ala,

L-alanine;

Phe,

L-phenylalanine. REFERENCES


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