Evaporative Drying Induced Self-Assembly of Epicuticular Wax: A Biomimetic Approach in Tuning Surface Roughness.

Epicuticular wax is an example of a naturally created functional material that forms a layer on the outermost surface of plants with the objective to protect them from adverse environmental conditions, such as UV-solar radiation, uncontrolled water loss, microbial attacks, and so forth. Their functionalities are often attributed to the chemical composition of the wax as well as the physical structuration formed by the wax crystals on the surface. With this work, we present a simple, one-step biomimetic approach to replicate similar surface structures, on model substrate, using wax extracted from Euphorbia Cerifera (Candelilla wax). First, we describe formation of structured wax due to self-assembly induced by evaporative drying on quartz plates. Subsequently, we highlight the fundamental physical parameters required to tune the surface morphology. Our experiments reveal that it is possible to achieve considerably diverse surface morphologies depending on the solvent properties and deposition temperature. This diversity is due to the kinetics of recrystallization of wax during evaporation of solvent which, in turn, is primarily driven by the solubility of wax as well as evaporation rate of the solvent. Thus, the final morphology that we obtain is an interplay between recrystallization kinetics and solvent evaporation. Additionally, the degree of crystallinity of the structured films could also be tuned by solvent polarity. Surprisingly, X-ray diffraction indicates that the crystalline structure at the molecular level remains similar to that of bulk Candelilla wax. Our results provide fundamental insights into the replication of epicuticular wax films and identification of tuning parameters to obtain different surface morphologies with the same wax material for potential bioinspired multifunctional coatings in cosmetic applications.

Non-Covalent Integration of a [FeFe]-Hydrogenase Mimic to Multiwalled Carbon Nanotubes for Electrocatalytic Hydrogen Evolution.

Surface integration of molecular catalysts inspired from the active sites of hydrogenase enzymes represents a promising route towards developing noble metal-free and sustainable technologies for H2 production. Efficient and stable catalyst anchoring is a key aspect to enable this approach. Herein, we report the preparation and electrochemical characterization of an original diironhexacarbonyl complex including two pyrene groups per catalytic unit in order to allow for its smooth integration, through π-interactions, onto multiwalled carbon nanotube-based electrodes. In this configuration, the grafted catalyst could reach turnover numbers for H2 production (TONH2 ) of up to 4±2×103 within 20 h of bulk electrolysis, operating at neutral pH. Post operando analysis of catalyst functionalized electrodes revealed the degradation of the catalytic unit occurred via loss of the iron carbonyl units, while the anchoring groups and most part of the ligand remained attached onto multiwalled carbon nanotubes.

Heterogenised Molecular Catalysts for Sustainable Electrochemical CO2 Reduction.

There has been a rapid rise in interest regarding the advantages of support materials to protect and immobilise molecular catalysts for the carbon dioxide reduction reaction (CO2 RR) in order to overcome the weaknesses of many well-known catalysts in terms of their stability and selectivity. In this Review, the state of the art of different catalyst-support systems for the CO2 RR is discussed with the intention of leading towards standard benchmarking for comparison of such systems across the most relevant supports and immobilisation strategies, taking into account these multiple pertinent metrics, and also enabling clearer consideration of the necessary steps for further progress. The most promising support systems are described, along with a final note on the need for developing more advanced experimental and computational techniques to aid the rational design principles that are prerequisite to prospective industrial upscaling.

CO2-Triggered ON/OFF Wettability Switching on Bioinspired Polylactic Acid Porous Films for Controllable Bioadhesion.

Bioinspired honeycomb-like porous films with switchable properties have drawn much attention recently owing to their potential application in scenarios in which the conversion between two opposite properties is required. Herein, the CO2-gas-triggered ON/OFF switching wettability of biocompatible polylactic acid (PLA) honeycomb porous films is fabricated. Highly ordered porous films with diameters between 2.0 and 2.8 µm are separately prepared from complexes of nonresponsive PLA and a CO2-sensitive melamine derivative [N2,N4,N6-tris(3-(dimethylamino)propyl)-1,3,5-triazine-2,4,6-triamine, MET] via the breath figure method. The hydrophilic CO2-sensitive groups can be precisely arranged in the pore's inner surface and/or top surface of the films by simply changing the PLA/MET ratio. The sensitive groups in the pore's inner surface act as a switch triggered by CO2 gas controlling water to enter the pores or not, thus resulting in ON/OFF switching wettability. The largest response of the water contact angle of honeycomb films reaches 35°, from 100 to 65°, leading to an obvious hydrophobic-hydrophilic conversion. The improved surface wettability enhances the interaction between the cell and honeycomb film surface, thus resulting in a better cell attachment. Such smart properties accompanying the biocompatible polymer and biological gas trigger facilitate possible biomedical and bioengineering applications in the future for these films.

Bio-Inspired Silica Films Combining Block Copolymers Self-Assembly and Soft Chemistry: Paving the Way toward Artificial Exosqueleton of Seawater Diatoms.

This review is in line with the principles of bio-inspiration and biomimicry in order to envisage a softer and more environmentally friendly chemistry. Here, the source of inspiration is a microalga from the oceans with the ability to build an exoskeleton of silica under ambient conditions. Following this model, this review is interested in different ways of creating porous silica films with a hierarchical porosity similar to diatoms. For this purpose, polymeric/hybrid/inorganic films structured in honeycomb using the breath figure method are reported. This versatile and easy to implement method based on the principle of rapid evaporation of a solvent in a humid atmosphere is widely used in the formation of structured films with micron-sized pores. In addition to this, the self-assembly of copolymer at the nanoscale can be addressed to obtain a hierarchically structured film. Following this structuration step, the degradation of a sacrificial block is then described from the most energy-intensive to soft process, allowing an added nanoporosity to the micron porosity of the BF method. Finally, hierarchical porous silica films are described using the sol-gel process, which is known as a soft chemistry process.

Microwave-Assisted Ultrafast RAFT Miniemulsion Polymerization of Biobased Terpenoid Acrylates.

There is a growing preference to move away from traditional petrochemical-based polymers toward biobased alternatives. Here, we report the microwave-assisted RAFT polymerization of several terpenoid acrylates (tetrahydrogeraniol, cyclademol, nopol, and citronellol). These biobased monomers give polymers with a broad range of glass transition temperatures and are excellent candidates to substitute oil-based (meth)acrylates in applications such as coatings and adhesives. First, the process was studied in miniemulsion, finding that all terpenoid acrylates showed a substantial increase in both polymerization rate and reaction control when microwave irradiation was applied. These observations were attributed to nonthermal microwave effects, namely, to changes in the kinetic coefficients under irradiation. The reactions were also carried out in solution, where an amplified nonthermal microwave effect was observed. The results indicate that nonthermal microwave effects allow RAFT polymerization of these terpenoid acrylates to proceed with both improved control and at higher polymerization rates compared to using conventional heating.

Core@Corona Functional Nanoparticle-Driven Rod-Coil Diblock Copolymer Self-Assembly.

Herein, a novel strategy to overcome the influence of π-π stacking on the rod-coil copolymer organization is reported. A diblock copolymer poly(3-hexylthiophene)-block-poly(ethylene glycol methyl ether methacrylate) (P3HT-b-PEGMA) was synthesized by the Huisgen cycloaddition, so-called "click chemistry", combining the PEGMA and P3HT blocks synthesized by atom transfer radical polymerization and Kumada catalyst transfer polymerization, respectively. Using a dip-coating process, we controlled the original film organization of the diblock copolymer by the crystallization of the P3HT block via π-π stacking. The morphology of the P3HT-b-PEGMA films was influenced by the incorporation of gold nanoparticles (GNPs) coated by poly(ethylene glycol) ligands. Indeed, the crystalline structuration of the P3HT sequence was counterbalanced by the addition in the film of gold nanoparticles finely localized within the copolymer PEGMA matrix. Transmission electron microscopy and time-of-flight secondary ion mass spectrometry analysis validated the GNP homogeneous localization into the compatible PEGMA phase. Differential scanning calorimetry showed the rod block crystallization disruption. A morphological transition of the self-assembly is observed by atomic force microscopy from P3HT fibrils into out-of-plane cylinders driven by the nanophase segregation.

Renewable Terpene Derivative as a Biosourced Elastomeric Building Block in the Design of Functional Acrylic Copolymers.

In order to move away from traditional petrochemical-based polymer materials, it is imperative that new monomer systems be sought out based on renewable resources. In this work, the synthesis of a functional terpene-containing acrylate monomer (tetrahydrogeraniol acrylate, THGA) is reported. This monomer was polymerized in toluene and bulk via free-radical polymerizations, achieving high conversion and molecular weights up to 278 kg·mol-1. The synthesized poly(THGA) shows a relatively low Tg (-46 °C), making it useful as a replacement for low Tg acrylic monomers, such as the widely used n-butyl acrylate. RAFT polymerization in toluene ([M]0 = 3.6 mol·L-1) allowed for the well-controlled polymerization of THGA with degrees of polymerization (DP n) from 25 to 500, achieving narrow molecular weight distributions ( D̵ ≈ 1.2) even up to high conversions. At lower monomer concentrations ([M]0 = 1.8 mol·L-1), some evidence of intramolecular chain transfer to polymer was seen by the detection of branching (arising from propagation of midchain radicals) and terminal double bonds (arising from ß-scission of midchain radicals). Poly(THGA) was subsequently utilized for the synthesis of poly(THGA)- b-poly(styrene)- b-poly(THGA) and poly(styrene)- b-poly(THGA)- b-poly(styrene) triblock copolymers, demonstrating its potential as a component of thermoplastic elastomers. The phase separation and mechanical properties of the resulting triblock copolymer were studied by atomic force microscopy and rheology.

Direct formation of hydrophilic honeycomb film by self-assembly in breath figure templating of hydrophobic polylacticacid/ionic surfactant complexes.

Honeycomb-patterned porous films with good surface wettability have great potential applications in various areas. However, hydrophilic honeycomb films are difficult to obtain using the direct self-assembly of pure (co)polymers. Thus, additional and special treatments are required to improve film wettability, which makes the procedure complicated and difficult to access. In this study, a facile way to prepare hydrophilic honeycomb-structured porous films is proposed that uses the direct self-assembly of complexes of biocompatible hydrophobic poly(l-lactic acid) and dodecyltrimethylammonium chloride by breath figure templating. The addition of ionic surfactant not only improves film quality but also confers good wettability. The obtained hydrophilic pore arrays were found to effectively promote cell attachment. Such a hydrophilic honeycomb-patterned porous film could find potential applications where pore wetting is required, including tissue engineering, lithography, and nanoparticle embedding.

Directed Self-Assembly in "Breath Figure" Templating of Melamine-Based Amphiphilic Copolymers: Effect of Hydrophilic End-Chain on Honeycomb Film Formation and Wetting.

Amphiphilic copolymers are widely used in the fabrication of hierarchically honeycomb-structured films through a "breath figure" (BF) process because the hydrophilic block plays a key role in stabilising water templating. However, the hydrophilic monomers reported are mainly confined to acrylic acid and its derivatives, which largely limits understanding of the formation of BF arrays and the introduction of additional functions on porous films. The relationship between polymer composition, film microstructure and surface properties are also less documented. Herein, a novel melamine-based hydrophilic moiety, N-[3-({3-[(4,6-bis{[3-(dimethylamino)propyl]amino}-1,3,5-triazin-2yl)amino]propyl}(methyl)amino)propyl]methacrylamide (ANME), was incorporated into polystyrene (PS) chains by combining atom-transfer radical polymerisation and post-modification to afford three well-defined end-functionalised PS-PANME derivatives. These polymers were used to fabricate honeycomb films through the BF technique. Both inner and outer microstructures of the films were characterised by optical microscopy, AFM and SEM. Polymer hydrophilicity is enhanced upon increasing the PANME content, which results in variation of the film microstructure and porosity, and provokes a transition from Cassie-Baxter to Wenzel behaviour. Furthermore, the surface wettability of as-prepared honeycomb films and corresponding pillared films is mainly governed by film morphology, rather than by the properties of the polymers. Knowledge of the relationships between polymer composition and film structure, as well as surface wettability, is beneficial to design and prepare hierarchically porous films with desirable structures and properties.

Hierarchically organized honeycomb films through block copolymer directed self-assembly in "breath figure" templating and soft microwave-triggered annealing.

Hierarchically organized polymer films are produced with a high level of order from the combination of block copolymer nanophase segregation, "breath figure" methodology and microwave irradiation. A block copolymer based on poly(methyl methacrylate) and poly(n-butylacrylate) featuring cylindrical nanopatterns is involved in the "breath figure" process to create a microporous honeycomb structure. These films are submitted to microwave annealing to enhance the degree of ordering of the nano-segregation without the destruction of the honeycomb microstructure, which is not possible by classical thermal or solvent annealing. Ellipsometry, optical and atomic force microscopy are used to study three key parameters; the substrate nature, the film thickness and the microwave irradiation power. The silicon wafer is the substrate of choice to efficiently act as the heating transfer element and 60 seconds at 10 watts are enough to nicely order the 1 µm thick copolymer films. These conditions are eventually applied on hierarchically organized polymer films to obtain a hexagonal array of 100 nm deep holes within a matrix of perpendicularly aligned nano-cylinders.

When block copolymer self-assembly in hierarchically ordered honeycomb films depicts the breath figure process.

Nowadays, a challenge in the preparation of hierarchically ordered materials is the control of concomitant and interacting self-organization processes occurring in time at different length scales. In the present paper, the breath figure process is combined with block copolymer nano-phase segregation to elaborate hierarchically structured honeycomb porous films. Copolymer ordering, at the nanometer length scale, is observed and described in detail with respect to the array of pores of micrometer dimension, hence pointing out the structural interplays between both length-scales. The study is focused on two diblock copolymers made of polystyrene and poly(tert-butyl acrylate) (PS-b-PtBA) with compositions producing lamellae or hexagonal packing of cylinders at thermodynamical equilibrium. Transmission Electron Microscopy completed with Small and Ultra-Small Angle Scattering are performed to evidence the inner morphologies of the honeycomb. The structural data are discussed in the light of the honeycomb film formation process establishing the interest in using kinetically trapped block copolymer self-organization as an imprint to elucidate the complex breath figure process.

Thermodynamics of the multi-stage self-assembly of pH-sensitive gradient copolymers in aqueous solutions.

The self-assembly thermodynamics of pH-sensitive di-block and tri-block gradient copolymers of acrylic acid and styrene was studied for the first time using isothermal titration calorimetry (ITC) and dynamic light scattering (DLS) performed at varying pH. We were able to monitor each step of micellization as a function of decreasing pH. The growth of micelles is a multi-stage process that is pH dependent with several exothermic and endothermic components. The first step of protonation of the acrylic acid monomer units was accompanied mainly by conformational changes and the beginning of self-assembly. In the second stage of self-assembly, the micelles become larger and the number of micelles becomes smaller. While solution acidity increases, the isothermal calorimetry data show a broad deep minimum corresponding to an exothermic process attributed to an increase in the size of hydrophobic domains and an increase in the structure's hydrophobicity. The minor change in heat capacity (ΔCp) confirms the structural changes during this exothermic process. The exothermic process terminates deionization of acrylic acid. The pH-dependence of the ζ-potential of the block gradient copolymer micelles exhibits a plateau in the regime corresponding to the pH-controlled variation of the micellar dimensions. The onset of micelle formation and the solubility of the gradient copolymers were found to be dependent on the length of the gradient block.

Design of smart oligo(ethylene glycol)-based biocompatible hybrid microgels loaded with magnetic nanoparticles.

This article reports a rational strategy for preparing smart oligo(ethylene glycol)-based hybrid microgels loaded with high content of homogeneously distributed preformed magnetic nanoparticles (NPs) (up to 33 wt%). The strategy is based on the synthesis of biocompatible multiresponsive microgels by precipitation copolymerization of di(ethylene glycol) methyl ether methacrylate, oligo(ethylene glycol) methyl ether methacrylate, methacrylic acid, and oligo(ethylene glycol)diac-rylate. An aqueous dispersion of preformed magnetic NPs is straightforwardly loaded into the microgels. Robust monodisperse thermoresponsive magnetic microgels are produced, exhibiting a constant value of the volume phase transition temperature whatever the NPs content. The homogeneous microstructure of the initial stimuli-responsive biocompatible microgels plays a crucial role for the design of unique well-defined ethylene glycol-based thermoresponsive hybrid microgels.

Biomimetic Mussel Adhesive Inspired Anchor to Design ZnO@Poly(3-Hexylthiophene) Hybrid Core@Corona Nanoparticles.

The functionalization of zinc oxide (ZnO) nanoparticles by poly(3-hexylthiophene) (P3HT) brush is completed by the combination of a mussel inspired biomimetic anchoring group and Huisgen cyclo-addition "click chemistry." Herein, the direct coupling of an azide modified catechol derivative with an alkyne end-functionalized P3HT is described. This macromolecular binding agent is used to access core@corona ZnO@P3HT with a stable and homogeneous conjugated organic corona. Preliminary photoluminescence measurement proves an efficient electron transfer from the donor P3HT to the acceptor ZnO nanoparticles upon grafting, thus demonstrating the potential of such a combination in organic electronics.

Terpene and dextran renewable resources for the synthesis of amphiphilic biopolymers.

The present work shows the synthesis of amphiphilic polymers based on the hydrophilic dextran and the hydrophobic terpenes as renewable resources. The first step concerns the synthesis of functional terpene molecules by thiol-ene addition chemistry involving amino or carboxylic acid thiols and dihydromyrcenol terpene. The terpene-modified polysaccharides were subsequently synthesized by coupling the functional terpenes with dextran. A reductive amination step produced terpene end-modified dextran with 94% of functionalization, while the esterification step produced three terpene-grafted dextrans with a number of terpene units per dextran of 1, 5, and 10. The amphiphilic renewable grafted polymers were tested as emulsifiers for the stabilization of liquid miniemulsion of terpene droplets dispersed in an aqueous phase. The average hydrodynamic diameter of the stable droplets was observed at about 330 nm.

Photoactive, porous honeycomb films prepared from Rose Bengal-grafted polystyrene.

Honeycomb-structured porous polymer films based on photosensitizer-grafted polystyrene are prepared through the breath figure process. Rose Bengal (RB) photosensitizer is first attached to a well-defined poly(styrene-stat-4-vinylbenzyl chloride) statistical copolymer, synthesized by nitroxide-mediated radical polymerization. The RB grafted poly(styrene-stat-4-vinylbenzyl chloride) (ca. 20,000 g mol(-1) molar mass, 1.2 dispersity) leads to porous polymer films, with a hexagonal pore pattern, while a simple mixture of poly(styrene-stat-4-vinylbenzyl chloride) and the insoluble RB photosensitizer produced unstructured, nonporous films. The RB-grafted honeycomb films, compared with the corresponding nonporous flat films, are more efficient for oxidation of organic molecules via singlet oxygen production at a liquid/solid interface. The oxidations of 1,5-dihydroxynaphthalene to juglone and α-terpinene to ascaridole are followed in ethanol in the presence of both types of films. Oxidation of the organic molecules is a factor 5 greater with honeycomb compared to the nonporous films. This gain is ascribed to two factors: the specific location of the polar photosensitizer at the film interface and the greater exchange surface, as revealed by fluorescence and scanning electron microscopies.

Water-borne synthesis of multi-responsive and biodegradable chitosan-crosslinked microgels: Towards self-assembled films with adaptable properties.

The present study aims in the synthesis of new biodegradable stimuli-responsive microgels with controllable microstructure and with the ability to form cohesive films. Such self-assembled films by water evaporation at ambient conditions without any chemicals but just physical entanglements between soft colloid shell, present adaptable mechanical, adhesive and mechano-electrical properties. For that, oligo(ethylene glycol)-based stimuli-responsive microgels have been synthesized using biodegradable chitosan-methacrylates (Chi-MAs) with different degree of substitution (DS) as unique cross-linking agents by precipitation polymerization in water, for the first time. In all the cases, the microgels present thermo-responsiveness with hysteresis between heating and cooling cycles. However, this behavior is tuned and controlled using different types and amounts of Chi-MAs. In addition, the type of Chi-MA used can control microgels' microstructure as well as their enzymatic biodegradation. In addition, spontaneous cohesive films formation from colloidal aqueous dispersion with sol-gel transition is demonstrated. The films present tunable mechanical and adhesive properties through microgels' microstructure and enhanced mechano-electrical properties triggered by simple finger pressure (10-15 N). As self-supported films are able to encapsulate different types of active molecules, this study paves the way for suitable self-assembled microgel films for skincare applications as transdermal delivery systems.

Soft Self-Assembled Mechanoelectrical Transducer Films from Conductive Microgel Waterborne Dispersions.

The present study aims in the developing of new soft transducers based on sophisticated stimuli-responsive microgels that exhibit spontaneous self-assembly forming cohesive films with conductive and mechanoelectrical properties. For that, oligo(ethylene glycol)-based stimuli-responsive microgels have been synthesized using bio-inspired catechol cross-linkers by one-step batch precipitation polymerization in aqueous media. Then, 3,4-ethylene dioxyyhiophene (EDOT) has been directly polymerized onto stimuli-responsive microgels using catechol groups as the unique dopant. PEDOT location is dependent on the cross-linking density of microgel particles and EDOT amount used. Moreover, the spontaneous cohesive film formation ability of the waterborne dispersion after evaporation at soft application temperature is demonstrated. The films obtained present conductivity and enhanced mechanoelectrical properties triggered by simple finger compression. Both properties are function of the cross-linking density of the microgel seed particles and PEDOT amount incorporated. In addition, to obtain maximum electrical potential generated and the possibility to amplify it, several films in series were demonstrated to be efficient. The present material can be a potential candidate for biomedical, cosmetic, and bioelectronic applications.