Diblock Copolymer Brushes Research Articles

Inhibition of bacteria adhesion and biofilm formation using a precisely structured nitric oxide-releasing coating with repeatedly renewing antimicrobial and antifouling ability

Bacterial adhesion and colonization usually causes the formation of biofilm that cannot be easily eradicated by common antibiotics and disinfectants. Surface covalent immobilization of nitric oxide (NO)-releasing polymer is an effective surface modification strategy to combat the threat from bacteria. Although surface covalent strategy avoided the leaching of toxic NO donors, the existence of hydrophobic NO donors on topsurface could inevitably accelerate the microorganism adhesion and accumulation, and the NO-releasing period of time was still very limited. In this work, we prepared an antimicrobial and antibiofilm surface via tethering a precision-structured NO-releasing copolymer brush to an organic-inorganic hybrid hard coating (> 5H pencil hardness) on one end. The precision-structured diblock copolymer brush was composed of a surface antifouling block and a subsurface antimicrobial block of NO-releasing units. A typical effect of “kill two birds with one stone” was observed, the NO releasing subsurface segment within a polymeric matrix prolongs NO release while also preventing surface fouling caused by hydrophobic NO donors on top surface. The impacts of polymer architecture on bioactivity was detailed investigated, and the block copolymer brush exhibited the optimal inhibitory effects against bacteria colonization and biofilm formation. The developed bioactive diblock copolymer brush was grafted from a hard hybrid persistent coating that embeds considerable initiation sites for surface modification. Thanks to the presence of initiator throughout the hybrid network, the initiation layer could initiate polymerization repeatedly after the polymer brushes are worn off at high pressure. Thus, the coating exhibited repeatedly renewing antimicrobial and antifouling ability after multiple abrasion cycles. This work not only developed a novel strategy for regulating NO releasing via modulating the polymer architecture, but provided a feasible route for obtaining a robust initiator layer for synthesizing polymer brush for antimicrobial and antifouling applications.

PH-Mediated Size-Selective Adsorption of Gold Nanoparticles on Diblock Copolymer Brushes.

Precise control of nanoparticles at interfaces can be achieved by designing stimuli-responsive surfaces that have tunable interactions with nanoparticles. In this study, we demonstrate that a polymer brush can selectively adsorb nanoparticles according to size by tuning the pH of the buffer solution. Specifically, we developed a facile polymer brush preparation method using a symmetric polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) block copolymer deposited on a grafted polystyrene layer. This method is based on the assembly of a PS-b-P2VP thin film oriented with parallel lamellae that remains after exfoliation of the top PS-b-P2VP layer. We characterized the P2VP brush using X-ray reflectivity and atomic force microscopy. The buffer pH is used to tailor interactions between citrate-coated gold nanoparticles (AuNPs) and the top P2VP block that behaves like a polymer brush. At low pH (∼4.0) the P2VP brushes are strongly stretched and display a high density of attractive sites, whereas at neutral pH (∼6.5) the P2VP brushes are only slightly stretched and have fewer attractive sites. A quartz crystal microbalance with dissipation monitored the adsorption thermodynamics as a function of AuNP diameter (11 and 21 nm) and pH of the buffer. Neutral pH provides limited penetration depth for nanoparticles and promotes size selectivity for 11 nm AuNP adsorption. As a proof of concept, the P2VP brushes were exposed to various mixtures of large and small AuNPs to demonstrate selective capture of the smaller AuNPs. This study shows the potential of creating devices for nanoparticle size separations using pH-sensitive polymer brushes.

Graphene Oxide-Grafted Hybrid Diblock Copolymer Brush (GO-graft-PEG6k-block-P(MA-POSS)) as Nanofillers for Enhanced Lithium Ion Conductivity of PEO-Based Nanocomposite Solid Polymer Electrolytes.

Nanocomposite solid polymer electrolytes (NSPEs) with PEO as the matrix and (i) GO or (ii) GO-graft-PEG6k or (iii) GO-graft-PEG6k-block-P(MA-POSS) as nanofillers have been fabricated to elucidate the impact of the filler morphology on the lithium ion conductivity. GO-graft-PEG6k was obtained by grafting PEG6k onto GO via esterification. GO-graft-PEG6k-block-P(MA-POSS) was prepared via surface-initiated atom transfer radical polymerization. Fourier-transform infrared spectroscopy revealed enhanced salt dissociation and complexation between the filler and PEO host that could be attributed to Lewis acid-base interactions. Electrochemical impedance spectroscopy revealed the improved ion conductivity of the fabricated NSPEs as compared with the pristine PEO-LiClO4. As an example, at 50 °C, the ion conductivity increased to 4.01 × 10-5 and 6.31 × 10-5 S cm-1 with 0.3% GO and 0.3% GO-graft-PEG6k, respectively, from 2.36 × 10-5 S cm-1 of PEO-LiClO4, suggesting that the filler with brush-like architecture (GO-graft-PEG6k) is more efficient in enhancing the ion conductivity. Further increase in filler content resulted in lowering of the ion conductivity that could be ascribed to aggregation of the filler. The most dramatic impact on conductivity was observed with the incorporation of brush-like GO-graft-PEG6k-block-P(MA-POSS) as a nanofiller (3.0 × 10-4 S cm-1 at 50 °C with 1.0 wt % filler content). The increase in ion conductivity in the current systems, as opposed to the conventional view, could not be correlated with the content of the amorphous phase of the matrix. The conduction mechanism is still unclear; nevertheless, it could be assumed that in addition to the ion conduction through the PEO matrix, the filler forms additional low-energy ion conducting channels at its interface with the matrix. The pendent POSS nanocages of GO-graft-PEG6k-block-P(MAPOSS) might probably increase the free volume at the interface with the matrix that is associated with higher chain and ion mobility, thus further enhancing the ion conductivity as compared with GO and GO-graft-PEG6k. The faster ion dynamics in 1.0 wt % GO-graft-PEG6k-block-P(MAPOSS) NSPEs has also been verified by the dielectric relaxation studies. Thus, integration of both the PEG and POSS nanocages into GO-grafted brush-like architecture offers a new tool for tuning the lithium ion conductivity for potential Li ion battery applications.

Thermoresponsive, Pyrrolidone‐Based Antifouling Polymer Brushes

AbstractCommonly, modification of surfaces with thermoresponsive polymers is performed using poly(N‐isopropylacrylamide) (poly(NIPAM)). However, integration of poly(NIPAM) with a second polymer to obtain more complex copolymer structures has proven challenging due to inherently poorly controllable polymerization characteristics of acrylamides. In this study, (N‐(2‐methacryloyloxyethyl)pyrrolidone (NMEP) is synthesized and polymerized under controlled conditions from silicon oxide substrates via surface‐initiated atom transfer radical polymerization (SI‐ATRP) to produce thermoresponsive poly(NMEP) brushes. The livingness of the brushes is demonstrated by reinitiation of poly(NMEP) brushes using oligo(ethylene glycol) methyl ether methacrylate to obtain diblock copolymer brushes. Following extensive characterization, the reversible thermoresponsive behavior of these poly(NMEP) brushes is demonstrated using phase‐controlled AFM topography measurements in an aqueous liquid environment. These measurements indicate that at 27 °C the poly(NMEP) brushes are solvated and extend away from the surface, whereas at 60 °C the polymers are insoluble and reside in a collapsed conformation. Finally, to investigate the potential applicability of poly(NMEP) brushes in biomedical devices, the antifouling properties of the coating are tested in aqueous media containing BSA, fibrinogen, or 10% diluted human serum using quartz crystal microbalance with dissipation monitoring (QCM‐D). These measurements reveal very good antifouling properties, even when exposed to 10% diluted human serum.

Cell Adhesion and Migration on Thickness Gradient Bilayer Polymer Brush Surfaces: Effects of Properties of Polymeric Materials of the Underlayer.

In the field of tissue engineering and biomaterials, controlling the surface properties and mechanical properties of scaffold materials is crucial and has attracted much attention. Here, two types of bilayer polymer brushes composed of a hydrophilic underlying layer and a cationic surface layer [made of poly(2-aminoethyl methacrylate)] with a thickness gradient were prepared by surface-initiated atom-transfer radical polymerization. To investigate the influence of the stiffness as a mechanical property of the polymer brush on cell behavior, the underlayer was prepared from either 2-methacryloyloxyethyl phosphorylcholine or oligo(ethylene glycol) methyl ether methacrylate, with the bilayers designated as gradient poly(2-methacryloyloxyethyl phosphorylcholine)-block-poly(2-aminoethyl methacrylate) [grad-pMbA] and gradient poly(oligo[ethylene glycol] methyl ether methacrylate)-block-poly(2-aminoethyl methacrylate) [grad-pEGbA], respectively. Characterization of these surfaces was performed by spectroscopic ellipsometry, X-ray reflectivity, and determination of the zeta potential, static contact angle, and force curve. These diblock copolymer brushes with a thickness gradient helped to distinguish the effects of the mechanical and surface properties of the brushes on cell behavior. The attachment and motility of L929 fibroblasts and epithelial MCF 10A cells on the fabricated brushes were then assessed. L929 cells had a round shape on the thin surface layer of grad-pMbA and spread well on thicker areas. In contrast, MCF 10A cells spread well in areas of any thickness of either grad-pMbA or grad-pEGbA. Single MCF 10A cells migrated randomly on grad-pMbA, whereas grouped cells started to climb up along the thickness gradient of grad-pMbA. In contrast, both single and grouped MCF 10A cells migrated randomly on grad-pEGbA. These thickness gradient diblock copolymer brushes are simple, reproducible, and reasonable platforms that can facilitate practical applications of biomaterials, for example, in tissue engineering and biomaterials.

Diblock and Random Antifouling Bioactive Polymer Brushes on Gold Surfaces by Visible‐Light‐Induced Polymerization (SI‐PET‐RAFT) in Water

AbstractSurface‐initiated photoinduced electron‐transfer‐reversible addition–fragmentation chain transfer (SI‐PET‐RAFT) is, for the first time, used for the creation of antifouling polymer brushes on gold surfaces based on three monomers: oligo(ethylene glycol) methyl ether methacrylate (MeOEGMA), N‐(2‐hydroxypropyl) methacrylamide (HPMA), and carboxybetaine methacrylamide (CBMA). These coatings are subsequently characterized by X‐ray photoelectron spectroscopy (XPS) and ellipsometry. The living nature of this polymerization allows for the creation of random and diblock copolymer brushes, which are based on HPMA (superb antifouling) and CBMA (good antifouling and functionalizable via activated ester chemistry). The polymer brushes demonstrate good antifouling properties against undiluted human serum, as monitored by quartz crystal microbalance with dissipation (QCM‐D) and surface plasmon resonance (SPR) spectroscopy in real time. The amount of immobilization of bioactive moieties, here an antibody immobilized using N‐succinimidyl ester–1‐ethyl‐3‐(3‐dimethylaminopropyl)carbodiimide hydrochloride (NHS–EDC) coupling, in the diblock and random copolymer brushes is monitored by SPR, and is analyzed with respect to the brush structure, and is shown to be superior in the diblock copolymer brush. This approach represents a scalable, robust, mild, oxygen‐tolerant, and heavy‐metal‐free route toward the production of antifouling and functional copolymer brushes (on gold surfaces) that open up applications in biosensing and tissue engineering.

Ultrathin Yet Robust Single Lithium-Ion Conducting Quasi-Solid-State Polymer-Brush Electrolytes Enable Ultralong-Life and Dendrite-Free Lithium-Metal Batteries.

Quasi-solid-state polymer electrolytes are one of the most promising candidates for long-life lithium-metal batteries. However, introduction of plasticizers for high ion conductivity at room temperature inevitably gives rise to poor mechanical strength and requires a very thick electrolyte membrane, which is detrimental to safety and energy density of the batteries. Herein, inspired by tube brushes coupling hardness with softness, a novel superstructured polymer bottlebrush BC-g-PLiSTFSI-b-PEGM (BC = bacterial cellulose; PLiSTFSI = poly(lithium 4-styrenesulfonyl-(trifluoromethylsulfonyl) imide); PEGM = poly(diethylene glycol monomethyl ether methacrylate)) with a hard nanofibril backbone and soft functional polymer side-chains is reported as an effective strategy to well balance the mechanical strength and ion conductivity of quasi-solid-state polymer electrolytes. The resulting single lithium-ion conducting quasi-solid-state polymer-brush electrolytes (SLIC-QSPBEs) integrate the features of the ultrathin membrane thickness (10µm), the nanofibril backbone-strengthened porous nanonetwork (Young's modulus = 1.9GPa), and the high-rate single lithium-ion conducting diblock copolymer brushes. As a result, the ultrathin yet robust SLIC-QSPBEs enable ultralong-term (over 3300 h) reversible and stable lithium plating/stripping in Li/Li symmetrical cell at a current density of 1mA cm-2 for lithium anode. This work affords a promising strategy to develop advanced electrolytes for solid-state lithium-metal batteries.

Grafting density induced reentrant disorder-order-disorder transition in planar di-block copolymer brushes.

By means of multiscale molecular simulation, we show that solvophilic-solvophobic AB diblock copolymer brushes in the semi-dilute regime present a re-entrant disorder/order/disorder transition. The latter is fully controllable through two parameters: the grafting density and the solvophobic to solvophilic ratio of the tethered macromolecules. Upon increasing density, chains first aggregate into patches, then further order into a crystalline phase and finally melt into a disordered phase. We demonstrate that the order/disorder transition can be explained through the peculiar properties of the aggregates: upon increasing density, the aggregation number grows as expected. On the contrary, their projection on the plane shrinks, thus melting the emergent ordered phase. Such a density dependent shrinkage, seen for the first time as the cause to an order/disorder phase transition, is as a consequence of the entropic/enthalpic competition that characterises the hierarchical self-assembly of the brush.

Precisely Structured Nitric-Oxide-Releasing Copolymer Brush Defeats Broad-Spectrum Catheter-Associated Biofilm Infections In Vivo.

Gram-negative bacteria cannot be easily eradicated by antibiotics and are a major source of recalcitrant infections of indwelling medical devices. Among various device-associated infections, intravascular catheter infection is a leading cause of mortality. Prior approaches to surface modification, such as antibiotics impregnation, hydrophilization, unstructured NO-releasing, etc., have failed to achieve adequate infection-resistant coatings. We report a precision-structured diblock copolymer brush (H(N)-b-S) composed of a surface antifouling block of poly(sulfobetaine methacrylate) (S) and a subsurface bactericidal block (H(N)) of nitric-oxide-emitting functionalized poly(hydroxyethyl methacrylate) (H) covalently grafted from the inner and outer surfaces of a polyurethane catheter. The block copolymer architecture of the coating is important for achieving good broad-spectrum anti-biofilm activity with good biocompatibility and low fouling. The coating procedure is scalable to clinically useful catheter lengths. Only the block copolymer brush coating ((H(N)-b-S)) shows unprecedented, above 99.99%, in vitro biofilm inhibition of Gram-positive and Gram-negative bacteria, 100-fold better than previous coatings. It has negligible toxicity toward mammalian cells and excellent blood compatibility. In a murine subcutaneous infection model, it achieves >99.99% biofilm reduction of Gram-positive and Gram-negative bacteria compared with <90% for silver catheter, while in a porcine central venous catheter infection model, it achieves >99.99% reduction of MRSA with 5-day implantation. This precision coating is readily applicable for long-term biofilm-resistant and blood-compatible copolymer coatings covalently grafted from a wide range of medical devices.

Antifouling thin-film composite membranes with multi-defense properties by controllably constructing amphiphilic diblock copolymer brush layer

We developed a novel amphiphilic copolymer architecture for thin-film composite (TFC) membranes to integrate “resistant” and “release” strategies against membrane fouling. Two materials were sequentially grafted on TFC reverse osmosis membrane surfaces via dual surface-initiated atom transfer radical polymerization (SI-ATRP): zwitterionic polymer, poly[2-(methacryloyloxy)ethyl-dimethyl-(3-sulfopropyl) ammonium hydroxide] (pMEDSAH) with strong hydrophilicity and poly(2,2,2-trifluoroethyl methacrylate) (pTFEMA) with low surface energy. According to MD simulation and theoretical quantification, the p(MEDSAH-b-TFEMA)-grafted membranes (i.e. amphiphilic TFC membranes) possess not only strong hydration, but also lower surface energy, which yield the features of both fouling resistant and fouling release properties. The superiority of possessing multi-defense properties was further confirmed by the long-term, multi-cycle membrane fouling and cleaning filtration. Compared with pristine TFC and hydrophilic TFC membranes, the amphiphilic TFC membranes showed not only less water flux decline during the fouling filtration, but also higher water flux recovery after cleaning by water. Both theoretical and experimental results strongly suggest that the amphiphilic TFC membrane is a novel candidate for improving membrane antifouling properties.

Controlled grafting of polymer brush layers from porous cellulosic membranes

Dense polymer brushes on porous supports present powerful routes toward fouling-resistant coatings and ultra-thin, mechanically-stable selective layers. However, characterization of polymer chains grafted from nonideal, planar substrates often relies on indirect methods to determine the length, density, and location of polymeric brushes. In this study, we explore new methods to control and characterize the properties of polymer brush layers. Starting from hand-cast cellulose films and commercial cellulose membranes, we use surface-initiated atom transfer radical polymerization to graft polymeric chains. We tailor brush density and simultaneously stabilize the support by varying the proportions of initiator and crosslinker esterified to the cellulose substrate. On films with grafted polyacrylic acid (PAA) chains, we use the silver-binding method to determine brush density. We analyze brush growth behavior by directly cleaving chains from the surface of films for analysis by size exclusion chromatography, uniquely observing the divergence of two distinct populations of differing length beyond a certain molecular weight. Such behavior would be important to consider if the alignment of block copolymer layers is absolutely necessary in an application. By controlled contact of polymerization solution with the top surface, we show that brush growth can be partially directed to the top surface for asymmetric cellulose membranes with relatively low molecular weight cutoffs. In a semi-quantitative method to locate brush growth, depleted uranium was bonded to grafted PAA chains, and targeted emission x-ray spectroscopy was conducted for comparison of uranium content in various regions. Finally, we used our developed methods and findings to inform the synthesis of homopolymer and diblock copolymer brush layers, which we then used as selective layers in pressure-driven filtration and diffusion cell experiments.

The synthesis of bottlebrush cellulose-graft-diblock copolymer elastomers via atom transfer radical polymerization utilizing a halide exchange technique.

A novel kind of bottlebrush cellulose-graft-diblock copolymer thermoplastic elastomer (Cell-g-PBA-b-PMMA) was synthesized by grafting from cellulose backbones via surface-initiated atom transfer radical polymerization (ATRP). The mechanical properties of the bottlebrush copolymer elastomers can be adjusted by controlling the block lengths and composition of the side chains.

Tethering solvophilic blocks to the ends of polymer brushes: an effective method for adjusting surface patterns.

The effect of different lengths of solvophilic A and C blocks on the assembled configuration of intermediate solvophobic B-blocks in both ABA and ABC polymer brush systems is investigated via dissipative particle dynamics simulations. For the AB diblock copolymer brush with solvophilic A-blocks being grafted to the surface, B-blocks self-assemble into spherical micelle structures that are immersed in a layer formed by the A-blocks. Tethering a very small solvophilic block A(C) at the free end of the polymer brush pulls the B-blocks toward the polymer brush/solvent interface and increases their local density which can significantly change the B-block self-assembled structure from spherical micelles to ripples. By increasing the length of the outermost solvophilic blocks, the lateral density distribution of B-blocks can be further changed, resulting in the domain size of the ripple structure first decreasing and then increasing. Compared to the ABA system, the incompatibility between the A and C blocks can effectively reduce the vertical domain separation caused by the fusion of the upper and lower A blocks. Then, based on an AB diblock copolymer brush system with self-assembled spherical micelles, we introduce extremely short free solvophilic blocks A(C) in dilute solution that can be tethered to the free ends of the polymer brush by using a reaction model [Liu et al., J. Chem. Phys., 2007, 127, 144903]. We find that the micelles' coalescence is mainly affected by the content of tethered reactive solvophilic blocks, and only weakly affected by the reaction rate of the reversible reactions. This strategy of tethering solvophilic blocks to the ends of polymer brushes can be an effective way for the fabrication of stimuli-responsive surfaces and for adjusting nanoscopic surface patterns.

Enhanced Stability of Surface-Tethered Diblock Copolymer Brushes with a Neutral Polymer Block and a Weak Polyelectrolyte Block: Effects of Molecular Weight and Hydrophobicity of the Neutral Block

We study the stability of diblock copolymer brushes featuring a bottom neutral block, poly(methyl methacrylate) (PMMA) or poly(poly(ethylene glycol) methacrylate) (PPEGMA), and a top poly(acrylic acid) (PAA) block on flat silicon substrate. The polymer brushes are prepared by surface-initiated atom transfer radical polymerization (SI-ATRP). We use a combinatorial design featuring a molecular weight gradient in the bottom neutral block to investigate systematically the effect of the molecular weight of that block on the stability of the copolymer brush. We measure variations in dry thickness of the diblock copolymer brush by ellipsometry after different incubation times in aqueous buffer (pH = 9.0) as a function of thickness of the neutral block, indicating degrafting of the mechanically activated copolymer chains via hydrolysis of ester groups in the initiator and/or Si–O bonds that attach the polymer to the substrate. The stability of the diblock copolymer brushes is higher than that of PAA homopolymer b...

Exploring the wetting properties of diblock copolymer brushes with a hydrophobic block of poly([formula omitted]H,[formula omitted]H,[formula omitted]H,[formula omitted]H-Perfluorodecyl acrylate)-(PPFDA) and a Thermoresponsive block of poly(N-isopropylacrylamide)-(PNiPAM) synthesized by RAFT polymerization

Polymer brushes have a great potential for controlling surface wetting properties. In this work we study the surface wettability in respect to water of diblock copolymer brushes with an outer block of the thermoresponsive poly(N-isopropylacrylamide) (PNiPAM) polymer and an inner hydrophobic block of 1H 1H 2H 2H-perfluorodecyl Acrylate (PPFDA) and with variable block lengths. Block copolymer brushes are synthesized by reversible addition–fragmentation chain transfer (RAFT) polymerization. The conditions of synthesis; polymerization time of NiPAM, grafting density of change transfer agent (CTA) on the surface, amount of initiator and monomers were varied to produce brushes with different ratios of PNiPAM and PPFDA. Diblock copolymer brushes are characterized by Raman, XPS and Atomic Force Microscopy. Brushes with contact angles from 28 to 85 degrees are produced. The brushes with longer PPFDA blocks are the more hydrophobic. Contact angle values increase when raising temperature from 20 °C to 40 °C as for PNiPAM but always to higher contact angles than for the PNiPAM brush.

Cooperative Interactions between Different Classes of Disordered Proteins Play a Functional Role in the Nuclear Pore Complex of Baker's Yeast.

Nucleocytoplasmic transport is highly selective, efficient, and is regulated by a poorly understood mechanism involving hundreds of disordered FG nucleoporin proteins (FG nups) lining the inside wall of the nuclear pore complex (NPC). Previous research has concluded that FG nups in Baker’s yeast (S. cerevisiae) are present in a bimodal distribution, with the “Forest Model” classifying FG nups as either di-block polymer like “trees” or single-block polymer like “shrubs”. Using a combination of coarse-grained modeling and polymer brush modeling, the function of the di-block FG nups has previously been hypothesized in the Di-block Copolymer Brush Gate (DCBG) model to form a higher-order polymer brush architecture which can open and close to regulate transport across the NPC. In this manuscript we work to extend the original DCBG model by first performing coarse grained simulations of the single-block FG nups which confirm that they have a single block polymer structure rather than the di-block structure of tree nups. Our molecular simulations also demonstrate that these single-block FG nups are likely cohesive, compact, collapsed coil polymers, implying that these FG nups are generally localized to their grafting location within the NPC. We find that adding a layer of single-block FG nups to the DCBG model increases the range of cargo sizes which are able to translocate the pore through a cooperative effect involving single-block and di-block FG nups. This effect can explain the puzzling connection between single-block FG nup deletion mutants in S. cerevisiae and the resulting failure of certain large cargo transport through the NPC. Facilitation of large cargo transport via single-block and di-block FG nup cooperativity in the nuclear pore could provide a model mechanism for designing future biomimetic pores of greater applicability.

Preparation of plasmonic vesicles from amphiphilic gold nanocrystals grafted with polymer brushes.

Gold nanovesicles contain multiple nanocrystals within a polymeric coating. The strong plasmonic coupling between adjacent nanoparticles in their vesicular shell makes ultrasensitive biosensing and bioimaging possible. In our laboratory, multifunctional plasmonic vesicles are assembled from amphiphilic gold nanocrystals (such as gold nanoparticles and gold nanorods) coated with mixed hydrophilic and hydrophobic polymer brushes or amphiphilic diblock co-polymer brushes. To fulfill the different requirements of biomedical applications, different polymers that are either pH=responsive, photoactive or biodegradable can be used to form the hydrophobic brush, while the hydrophilicity is maintained by polyethylene glycol (PEG). This protocol covers the preparation, surface functionalization and self-assembly of amphiphilic gold nanocrystals grafted covalently with polymer brushes. The protocol can be completed within 2 d. The preparation of amphiphilic gold nanocrystals, coated with amphiphilic diblock polymer brushes using a 'grafting to' method or mixed hydrophilic and hydrophobic polymer brushes using tandem 'grafting to' and 'grafting from' methods, is described. We also provide detailed procedures for the preparation and characterization of pH-responsive plasmonic gold nanovesicles from amphiphilic gold nanocrystals using a film-rehydration method that can be completed within ∼3 d.

Cleavage of diblock copolymer brushes in a selective solvent and fusion of vesicles self-assembled by pinned micelles.

Lipid membrane fusion is a fundamental process in nature. In the fusion process two distinct bilayers merge the hydrophobic layers, and an interconnected structure is produced. In this research, the fusion of polymer membrane self-assembled by cleaved pinned micelles is investigated. Disulfide-tethered poly(tert-butyl acrylate-block-styrene) diblock copolymer brushes on the surfaces of silica particles were prepared by the "grafting to" or "grafting from" method. In acetone, the diblock copolymer brushes self-assemble into pinned micelles. Upon cleavage from the surfaces of the silica particles with n-tributylphosphine, the pinned micelles self-assemble into vesicles. In the meanwhile, thiol groups at the ends of the block copolymer brushes were produced in the cleavage reaction. Because of the oxidation of the thiol groups and the formation of the disulfide bonds, the vesicle structures are fused into bigger hollow structures and fiber-like structures. The further fusion of the fiber-like structures results in precipitation of the polymer from the solution.

Hierarchical antifouling brushes for biosensing applications

In this report, hierarchically structured diblock copolymer brushes are shown as an effective alternative to limit the increase in fouling caused by the activation of functional groups for the attachment of biorecognition elements. The growth of antifouling diblock copolymer brushes containing hydroxyl- and carboxy-functional top blocks was enabled by the utilization of surface-initiated atom transfer radical polymerization. The fouling from blood plasma is minimized, which is an essential property for the applications of these surfaces in label-free affinity biosensors for medical diagnostics and other fields that involve complex biological matrices. Furthermore, the increase in fouling associated with the activation of functional groups was significantly lowered. The use of a top block consisting of poly(carboxybetaine acrylamide) displays improved performance relative to a hydroxyl-bearing polymer after activation. A biosensor able to detect a targeted protein spiked in undiluted blood plasma is presented as a proof of concept.

Binary hairy nanoparticles: Recent progress in theory and simulations

ABSTRACTBinary polymer brushes, including mixed homopolymer brushes and diblock copolymer brushes, are an attractive class of environmentally responsive nanostructured materials. Owing to microphase separation of the two chemically distinct components in the brush, multifaceted nanomaterials with functionalized and patterned surfaces can be obtained. This review summarizes recent progress on the theory and simulations related to binary polymer brushes grafted to flat, spherical, and cylindrical substrates, with a focus on patterned morphologies of multifaceted hairy nanoparticles, an intriguing class of hybrid nanostructured particles (e.g., nanospheres and nanorods). In particular, powerful field theory and particle‐based simulations suitable for revealing novel structures on these patterned surfaces, including self‐consistent field theory and dissipative particle dynamics simulations, are emphasized. The unsolved yet critical issues in this research field, such as dynamic response of binary polymer brushes to environmental stimuli and the hierarchical self‐assembly of binary hairy nanoparticles, are briefly discussed. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014, 52, 1583–1599