Control of electro‐osmotic flow by mixed polymer brushes: Molecular dynamics simulations

Molecular dynamics simulations of electro‐osmotic flow through a channel coated by a mixed polymer brush reveal the modulation of electro‐osmotic flow. The mixed polymer brush consists of two types of neutral chains, denoted as PA and PB chains, respectively. The effect of the interaction strength between PA and PB monomers on fluid transport is studied. It was found that the PA‐PB interaction plays an important role in controlling the flow. The mixed polymer brush adopts a layered structure owing to the difference in solvent‐polymer interactions. Stronger shear force from the solvent flow leads to larger extension of polymer chains on the top layer (or PA chains). Such layering structure also causes different coupling between polymer conformational dynamics and fluid dynamics. At high grafting densities, there are remarkable differences in the velocity profiles for different PA‐PB interactions. For repulsive and attractive interactions, the increase of grafting density leads to reduced fluid transport. However, when the attraction between PA and PB interactions becomes stronger, the flow behavior is more complicated depending on the grafting density. Our simulation results indicate the change of ionic distribution induced by the conformational transition due to the PA‐PB interaction has significant contributions to the flow controlling. POLYM. ENG. SCI., 57:1293–1300, 2017. © 2017 Society of Plastics Engineers     

Self-reorganization of mixed poly(methyl methacrylate)/polystyrene brushes on planar silica substrates in response to combined selective solvent treatments and thermal annealing

This article reports reversible changes in surface morphology and surface wettability of mixed poly(methyl methacrylate) (PMMA)/polystyrene (PS) brushes with PS M_n slightly lower than that of PMMA in response to combined selective solvent treatments and thermal annealing. The mixed brushes were synthesized from asymmetric difunctional initiator-terminated monolayers by controlled radical polymerizations. Two sets of experiments were performed. The first set involved treating the samples with glacial acetic acid (AA), a selective solvent for PMMA, followed by treatment with cyclohexane, a selective solvent for PS, or thermal annealing. The surfaces were rough and composed of relatively ordered nanodomains after AA treatment. Subsequent cyclohexane treatment or thermal annealing made the surfaces flattened and surface analysis indicated that the outermost layers were occupied by PS. The second set of experiments involved treating the samples with cyclohexane or thermal annealing, followed by AA treatment. The surfaces were smooth after cyclohexane treatment or thermal annealing and became very rough in the subsequent AA treatment. The nanodomains formed in AA treatment were speculated to be micelles with PS forming the core shielded by PMMA chains.     

Glycopolymer brushes with specific protein recognition property

Here, we report the synthesis of glycopolymer brushes on the silicon substrate by interface‐mediated reversible addition‐fragmentation chain transfer polymerization of pentafluorophenyl acrylate as well as subsequent attachment of d ‐glucosamine to determine specific and nonspecific protein interactions. The root‐mean‐square roughness of the glycopolymer brushes is only about 3.1 nm, indicating unstable distribution of the collapsed glycopolymer chains on the surface. The water contact angle of glycopolymer brush was determined as ～53° indicating a hydrophilic behavior. The results of fluorescence microscopy studies indicated that the glycopolymer brushes have specific interaction with fluorescence‐labeled Concanavalin A and nonspecific interaction with fluorescence‐labeled bovine serum albumin. The glycopolymer brushes tested here are hoped to enlarge to our knowledge of recognition phenomena at the surface of polymer brushes. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45238.     

Cross-linked polymer brushes. II. Formation and properties of poly(isobutyl vinyl ether)-b-poly[2-(vinyloxy)ethyl cinnamate] brushes

A diblock copolymer, i.e., poly(isobutyl vinyl ether)-b-poly[2-(vinyloxy)ethyl cinnamate] (PIBVE-b-PVEC), has been shown to form polymer brushes quickly on the surface of solid substrates by deposition from a solvent selectively poor for PVEC. The resultant brush could be cross-linked photochemically by initiating the dimerization between VEC groups of different polymer chains and the cross-linking was extremely efficient. Crosslinked polymer brushes, as expected, were resistant to organic solvent, such as chloroform, and nitric acid attacks. Important industrial applications are expected of cross-linked brushes. © 1994 John Wiley & Sons, Inc.     

Molecular dynamics simulation of a flexible polymer network in a liquid crystalline solvent; dynamical properties

Molecular dynamics simulation was performed for the systems consisting of a flexible regular tetrafunctional polymer network and a low molecular liquid crystal (LC) solvent. The LC solvent comprises of anisotropic rod-like semiflexible linear molecules composed of beads bonded by a FENE potential. Rigidity was induced by a bending potential, proportional to the cosine of the angle between neighbouring valence bonds. All interactions between non-bonded beads are described by the repulsive part of the Lennard–Jones potential. For comparison the simulations of the system of flexible polymer chains in a low molecular LC solvent and a system of pure low molecular LC solvent were also carried out. The influence of the network and linear chain polymer on the translational and rotational mobility of low molecular LC solvent was studied. The influence of the LC solvent ordering on the local translational mobility of the polymer chains was also observed.     

Nanopatterns of poly(styrene-block-butyl acrylate) block copolymer brushes on the surfaces of exfoliated and intercalated clay layers

We report a study of poly(styrene-block-butyl acrylate) (PSBA) block copolymer brushes on the surfaces of intercalated and exfoliated silicate (clay) layers. The PSBA/clay nanocomposite was synthesized by in situ atom transfer radical polymerization (ATRP) from initiator moieties immobilized within the silicate galleries of the clay particles. Transmission electron microscopy (TEM) analysis showed the existence of both intercalated and exfoliated structures in the nanocomposite. Block copolymer brushes on the surface of exfoliated or intercalated clay layers were found to create nanopatterns after treatment in different solvents. For the block copolymer brushes after treatment in THF, uniform collapsed brush layers are observed. After treatment in acetone, a selective solvent for PBA, wormlike surface aggregates are observed. After treatment in methanol, a precipitant for both of the blocks, micelles as well as wormlike aggregates can be observed. Furthermore, the polymer brushes tend to aggregate together and change their nanopatterns at an elevated temperature.     

Ordering of Polystyrene Nanoparticles on Substrates Pre-Coated with Different Polyelectrolyte Architectures

Adjusting the inter-particle distances in ordered nanoparticle arrays can create new nano-devices and is of increasing importance to a number of applications such as nanoelectronics and optical devices. The assembly of negatively charged polystyrene (PS) nanoparticles (NPs) on Poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) brushes, quaternized PDMAEMA brushes and Si/PEI/(PSS/PAH)₂, was studied using dip- and spin-coating techniques. By dip-coating, two dimensional (2-D), randomly distributed non-close packed particle arrays were assembled on Si/PEI/(PSS/PAH)₂ and PDMAEMA brushes. The inter-particle repulsion leads to lateral mobility of the particles on these surfaces. The 200 nm diameter PS NPs tended to an inter-particle distance of 350 to 400 nm (center to center). On quaternized PDMAEMA brushes, the strong attractive interaction between the NPs and the brush dominated, leading to clustering of the particles on the brush surface. Particle deposition using spin-coating at low spin rates resulted in hexagonal close-packed multilayer structures on Si/PEI/(PSS/PAH)₂. Close-packed assemblies with more pronounced defects are also observed on PDMAEMA brushes and QPDMAEMA brushes. In contrast, randomly distributed monolayer NP arrays were achieved at higher spin rates on all polyelectrolyte architectures. The area fraction of the particles decreased with increasing spin rate.     

Influence of poly(acrylic acid) grafting density on switchable protein adsorption/desorption of poly(2-methyl-2-oxazoline)/poly(acrylic acid) mixed brushes

Poly(dopamine) is employed as an anchor to obtain a series of poly(acrylic acid) (PAA) and poly(2-methyl-2-oxazoline) (PMOXA) mixed brush coatings by sequential grafting to methods with PAA chains longer than PMOXA chains. Then, the prepared mixed brush coatings are rigorously characterized. The results show that the grafting density of PAA in mixed brushes could be well adjusted by changing the concentration of PAA solution used for the preparation of mixed brush coatings and the amounts of lysozyme adsorbed on PMOXA/PAA mixed brushes increase with increasing the grafting density of PAA chains while the desorption amounts decrease significantly when the grafting density of PAA is higher than one-half of PMOXA chains. When the grafting density of PAA is about one-half of PMOXA chains, the mixed brush could absorb high amounts of lysozyme (898.4 ng cm⁻²), and then more than 90% of adsorbed proteins could be released sharply by changing pH and ionic strength (I). © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48135.     

Properties of branched polymer chains adsorbed on a patterned surface

The aim of this study was to investigate the properties of polymer chains strongly adsorbed on a planar surface. Model macromolecules were constructed of identical segments, the positions of which were restricted to nodes of a simple cubic lattice. The chains were in good solvent conditions, thus, the excluded volume was the only interaction between the polymer segments. The polymer model chain interacted via a simple contact potential with an impenetrable flat surface with two kinds of points: attractive and repulsive (the latter being arranged into narrow strips). The properties of the macromolecular system were determined by means of Monte Carlo simulations with a sampling algorithm based on the local conformational changes of the chain. The structure of adsorbed chains was found to be strongly dependent on the distance between the repulsive strips, whenever this distance was very short. The mobility of the chains was also studied and it was found that diffusion across repulsive strips was suppressed for large distances between the strips.     

Dependence of thin polystyrene films stability on the thickness of grafted polystyrene brushes

We investigate the stability of thin polystyrene (PS) films on chemically identical grafted brushes of various thickness and grafting density. We observe an essential influence of the brush thickness on the stability of the PS films. For brushes with a thickness of 20-35 nm no de-wetting of the PS film occurs, while considerably thicker or thinner PS brushes lead to de-wetting of the PS top layer. We suggest that in the thin brush-like layers, the unfavorable interactions with underlying silica favor de-wetting. The tendency to de-wet is reduced once the brush is sufficiently thick to insulate the free PS layer from the surface. Beyond that point, the de-wetting process speeds up as the brush becomes thicker and has a higher grafting density with a substantial increase of the interfacial tension between the brush and the free polymer.     

Effect of solvent balance on the surface properties of poly(vinyl chloride)

Films of poly(vinyl chloride) have been cast from solutions of varying thermodynamic quality and the film properties studied by inverse phase gas chromatography. The solvents included tetrahydrofuran, cyclohexanone, and mixtures of toluene with both tetrahydrofuran and cyclohexanone. The solvent composition was followed during evaporation and film formation for the mixed solvents, and it was shown that the slower evaporating solvent component has the greatest effect on the surface properties of the films. The porosity of the polymer film surfaces is interpreted in terms of the mobility of the polymer chains during film formation. At high concentrations, polymer chain–polymer chain interactions become stronger when thermodynamically less powerful solvents are used or are last to leave during film formation; therefore, the solvent balance has a critical influence on the film surface properties. Annealing the poly(vinyl chloride) above the glass transition temperature reduces the surface porosity of the cast polymer.     

Architecture of prototype copolymer brushes composed of alternating structure and intramolecular phase separation of side chains in solution

Atom transfer radical polymerization (ATRP) was applied to the synthesis of prototype copolymer brushes composed polystyrene/poly(t‐butyl methacrylate) (PS/PBMA) alternating structure. Dilute solution properties of prototype copolymer brush were investigated by static and dynamic light scattering (SLS and DLS) in tetrahydrofuran (THF). As a result, such prototype copolymer brush composed of short aspect ratio formed a star‐like single molecule in THF. To discuss the intramolecular phase separation of PS/PBMA brushes in solution, we determined the radius of gyration (R_g) and cross‐sectional radius of gyration (R_g,c) of prototype copolymer brush by small‐angle X‐ray scattering (SAXS) using Guinier's plots in THF and styrene. We used styrene as solvent to cancel each other out with the electron density of PS side chains. Both R_g and R_g,c obtained in styrene decreased drastically compared with those obtained in THF. These results indicated strongly that PS and PBMA side chains of prototype brushes formed intramolecular phase separation even in good solvent. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Highly efficient synthesis of cylindrical polymer brushes with various side chains via click grafting-onto approach

Though much attention has been paid to synthesis of cylindrical polymer brushes, it is still not easy to prepare well-defined brushes by a general approach. Herein, well-defined cylindrical polymer brushes with various side chains were synthesized via grafting-onto approach by CuAAC click chemistry. Narrowly dispersed polymer backbones functionalized with azide groups were obtained by post-modification of poly(glycidyl methacrylate) (PGMA) which was prepared by reversible addition-fragmentation chain transfer (RAFT) mediated radical polymerization. The alkyne-terminated side chains, polystyrene, polyacrylates, polymethacrylates and poly(N-alkyl acrylamide)s, were synthesized by RAFT mediated radical polymerization with alkyne-containing chain transfer agents (CTAs). The CuAAC reactions between the backbone and side chain polymers were conducted with an equivalent feed of alkyne-terminated side chains and azide groups under mild conditions. Influences of reaction conditions and chemical composition of polymer side chains on grafting efficiency and molecular weight distribution of the polymer brushes were investigated. It is demonstrated that the side chains of polystyrene, polyacrylates and poly(N-alkyl acylamide)s were grafted at a density above 85% while that of polymethacrylates decreased to ca. 50%. The polymer brushes synthesized under the optimized reaction conditions had well-defined chemical composition and narrow distribution of molecular weight, and their wormlike morphology was visualized by atomic force microscopy (AFM).     

Structure of bimodal and polydisperse polymer brushes in a good solvent studied by numerical mean field theory

We apply a lattice-based self-consistent mean field theory in order to investigate poly-disperse polymer brushes dissolved in good solvent. The systems investigated consist of asymmetric poly(dimethylsiloxane)-polystyrene di-block copolymers near air-ethylbenzoate interface and of diblock copolymer polystyrene-poly(ethyl oxide) deposited on a air-water interface. Our results have been compared to experimental data from neutron reflectivity experiments and have shown very good agreement. We have also systematically studied the structure of the bi-disperse and tri-disperse brush for various values of the molar fraction of the chains and of the overall surface densities. In addition, we have investigated the behavior of the brushes in other type of solvents.     

Mechanism of nanoparticle actuation by responsive polymer brushes: from reconfigurable composite surfaces to plasmonic effects

The mechanism of nanoparticle actuation by stimuli-responsive polymer brushes triggered by changes in the solution pH was discovered and investigated in detail in this study. The finding explains the high spectral sensitivity of the composite ultrathin film composed of a poly(2-vinylpyridine) (P2VP) brush that tunes the spacing between two kinds of nanoparticles-gold nanoislands immobilized on a transparent support and gold colloidal particles adsorbed on the brush. The optical response of the film relies on the phenomenon of localized surface plasmon resonances in the noble metal nanoparticles, giving rise to an extinction band in visible spectra, and a plasmon coupling between the particles and the islands that has a strong effect on the band position and intensity. Since the coupling is controlled by the interparticle spacing, the pH-triggered swelling-shrinking transition in the P2VP brush leads to pronounced changes in the transmission spectra of the hybrid film. It was not established in the previous publications how the actuation of gold nanoparticles within a 10-15 nm interparticle distance could result in the 50-60 nm shift in the absorbance maximum in contrast to the model experiments and theoretical estimations of several nanometer shifts. In this work, the extinction band was deconvoluted into four spectrally separated and overlapping contributions that were attributed to different modes of interactions between the particles and the islands. These modes came into existence due to variations in the thickness of the grafted polymeric layer on the profiled surface of the islands. In situ atomic force microscopy measurements allowed us to explore the behavior of the Au particles as the P2VP brush switched between the swollen and collapsed states. In particular, we identified an interesting, previously unanticipated regime when a particle position in a polymer brush was switched between two distinct states: the particle exposed to the surface of the collapsed layer and the particle engulfed by the swollen brush. On average, the characteristic distance between the particles and the islands increased upon the brush swelling. The observed behavior was a result of the anchoring of the particles to polymeric chains that limited the particles' vertical motion range. The experimental findings will be used to design highly sensitive optical nanosensors based on a polymer-brush-modulated interparticle plasmon coupling.     

Molecular dynamics simulation of a flexible polymer network in a liquid crystal solvent; structure and equilibrium properties

A flexible regular tetrafunctional polymer network containing a low molecular liquid crystal (LC) solvent was simulated with molecular dynamics. The LC solvent comprises of anisotropic rod-like semi-flexible linear molecules composed of beads bonded by a FENE potential. Flexibility was induced by a bending potential proportional to the cosine of the angle between neighbouring valence bonds. All interactions between non-bonded beads are described by the repulsive part of the Lennard-Jones potential. The average length of the network chain was chosen to be close to the length of a mesogen. The number of network cells was constant and the simulated systems differ from each other by the number of LC layers. The simulations of a system of flexible polymer chains in a low molecular LC solvent and a system of pure low molecular LC solvent were also carried out. Increasing the density of the composite system the LC solvent experiences the same phase transition as the pure LC: isotropic, nematic and smectic. The presence of the network shifts the isotropic-nematic transition to higher densities but does not significantly change the position of nematic-smectic transition. Transition of the LC solvent into the smectic state changes the morphology of the network. The periodicity of LC phase determines the number of network layers. The presence of linear chains in the LC solvent decreases the number of LC layers in the smectic phase.The LC order induces some stretching of the network chains along the direction of orientation and at the same time causes shrinkage in the perpendicular direction especially in the smectic phase.     

Effect of miscibility on migration of third component in star‐like co‐continuous and disperse‐within‐disperse mixed brushes

Novel ternary mixed‐brush single crystals were designed with disperse‐within‐disperse and star‐like co‐continuous morphologies based on poly(ethylene glycol) (PEG)‐b‐polystyrene (PS)/PEG‐b‐poly(methyl methacrylate) (PMMA)/PEG‐b‐polyaniline (PANI) and PEG‐b‐PS/PEG‐b‐PMMA/PEG‐b‐(poly(?‐caprolactone) (PCL) or poly(l ‐lactide) (PLLA)) block copolymers, respectively. In the disperse‐within‐disperse ternary mixed brushes, PANI nanorods were dispersed within the matrix (PS)–dispersed (PMMA) amorphous brushes. The flexibility and rigidity of brushes mainly affected the ultimate morphology and arrangement of amorphous coiled brushes in the vicinity of PANI nanorods. In addition, the migration of PCL and PLLA crystallizable brushes was evident into PMMA phases dispersed in the PS matrix, leading to star‐like co‐continuous patterns of PCL and PLLA brushes. This phenomenon was related to the miscibility of crystallizable PCL and PLLA brushes with the PMMA phase. The migration of crystallizable PCL and PLLA brushes increased the size of PMMA domains in the star‐like co‐continuous patterns. Despite the larger osmotic pressure of PLLA brushes, their higher miscibility with PMMA chains reflected the greater PMMA dispersal and wider PLLA star‐like branches. © 2017 Society of Chemical Industry     

Influence of solutes on hydration and lubricity of dextran brushes

The characteristic lubricity and non-fouling behavior of polymer brushes is critically dependent on the solvation of the polymer chains, as well as the chain-chain interactions. Dextran brushes have shown promise as non-toxic aqueous lubricant films, and are similar in composition to natural lubricating systems, while their comparative simplicity allows for controlled preparation and fine characterization. This project entails measuring the solvation and lubricity of dextran brushes in the presence of additives which modify the inter-chain hydrogen bonding. The thickness and refractive index of the film were measured during adsorption of the brush layer onto a silica substrate and the subsequent immersion in solutions of potassium sulfate and α, α-trehalose. We also studied the lubricity of the system as a function of normal loading using colloidal-probe AFM. Both solutes are shown to have a minimal effect on the hydration of the brush while significantly reducing the brush lubricity, indicating that inter-chain hydrogen bonding supports the load-bearing capacity of polysaccharide brushes.     

Modification of side chain terminals of PEGylated molecular bottle brushes—A toolbar of molecular nanoobjects

Water soluble molecular brush with poly(glycidyl methacrylate) (PGMA) as the main chain and mono-allyl terminated poly(ethylene glycol) (PEG) as the densely grafted side chains was efficiently synthesized via grafting-onto approach by copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction. Then highly efficient post-modification of the ends of the side chains was realized through UV light induced thiol–ene radical addition. Thus polymer brushes with various side chain terminal functional groups including hydroxyl group, carboxyl group, amino group, amino acid, sulfonic group and glucose unit were obtained.     

Homo- and mixed polymer brushes prepared by surface-grafting of asymmetric non-sticky/sticky diblock copolymers and their stimuli–responsive behaviors

We synthesize a non-sticky/sticky diblock copolymer, poly[styrene-b-3-(trimethoxysilyl)propylmethacrylate], to produce polymer brushes using the grafting-to technique. Uniform coatings of the polymer brushes are efficiently produced because of the multiple reactive groups offered by the sticky block, and the surface coverage and nanoscopic morphology of the brush layer are adjusted by varying the concentrations of the immersion polymer solutions and the immersion time of the substrate. The nanoscopic pattern of the polymer brushes is subsequently utilized to produce mixed polymer brushes. The resulting homo- or mixed polymer brushes change their nanoscopic morphology in response to external stimuli of temperature and solvent. The results indicate that grafting of the asymmetric non-sticky/sticky block copolymer is an efficient method for producing a surface of polymer brushes with nanoscopic chemical heterogeneity.