Nanoscale Structure-Property Relations in Self-Regulated Polymer-Grafted Nanoparticle Composite Structures.

Using a model system of poly(methyl methacrylate)-grafted silica nanoparticles (PMMA-NP) and poly(styrene-ran-acrylonitrile) (SAN), we generate unique polymer nanocomposite (PNC) morphologies by balancing the degree of surface enrichment, phase separation, and wetting within the films. Depending on the annealing temperature and time, thin films undergo different stages of phase evolution, resulting in homogeneously dispersed systems at low temperatures, enriched PMMA-NP layers at the PNC interfaces at intermediate temperatures, and three-dimensional bicontinuous structures of PMMA-NP pillars sandwiched between two PMMA-NP wetting layers at high temperatures. Using a combination of atomic force microscopy (AFM), AFM nanoindentation, contact angle goniometry, and optical microscopy, we show that these self-regulated structures lead to nanocomposites with increased elastic modulus, hardness, and thermal stability compared to analogous PMMA/SAN blends. These studies demonstrate the ability to reliably control the size and spatial correlations of both the surface-enriched and phase-separated nanocomposite microstructures, which have attractive technological applications where properties such as wettability, toughness, and wear resistance are important. In addition, these morphologies lend themselves to substantially broader applications, including: (1) structural color applications, (2) tuning optical adsorption, and (3) barrier coatings.

Colloidal Crystals of Charged-Polymer-Brush-Decorated Hybrid Particles in Low-Polarity Solvents.

Colloidal crystals are self-assembled systems that are suitable as models for studying crystallization; they are also attractive as nanostructures with a periodic arrangement of materials that have different refractive indices. Here, we present a method of constructing colloidal crystals in an organic solvent using charged-polymer-brush-decorated core-shell-type hybrid particles synthesized by surface-initiated living radical polymerization. The core-shell-type hybrid particles consisted of a silica particle core surrounded by a shell of polymer brushes obtained by the polymerization of methyl methacrylate and a small amount of a cationic monomer, [2-(methacryloyloxy)ethyl]trimethylammonium chloride. When the core-shell-type hybrid particles were dispersed in a low-polarity solvent with a dielectric constant of ∼11, colloidal crystals formed when the particle volume fraction exceeded a certain threshold, and remarkably, the interparticle distance in the colloidal crystal reached more than several micrometers under certain colloidal crystallization conditions. The colloidal crystallization behavior depended upon the surface charge density of the hybrid particles, ionic strength of the suspension, and dielectric constant of the solvent. The proposed method to construct colloidal crystals using electrostatic interactions between charged polymer brushes will promote the development of systems exhibiting particle self-assembly.

Grafted Nanoparticle Surface Wetting during Phase Separation in Polymer Nanocomposite Films.

Wetting of polymer-grafted nanoparticles (NPs) in a polymer nanocomposite (PNC) film is driven by a difference in surface energy between components as well as bulk thermodynamics, namely, the value of the interaction parameter, χ. The interplay between these contributions is investigated in a PNC containing 25 wt % polymethyl methacrylate (PMMA)-grafted silica NPs (PMMA-NPs) in poly(styrene-ran-acrylonitrile) (SAN) upon annealing above the lower critical solution temperature (LCST, 160 °C). Atomic force microscopy (AFM) studies show that the areal density of particles increases rapidly and then approaches 80% of that expected for random close-packed hard spheres. A slightly greater areal density is observed at 190 °C compared to 170 °C. The PMMA-NPs are also shown to prevent dewetting of PNC films under conditions where the analogous polymer blend is unstable. Transmission electron microscopy (TEM) imaging shows that PMMA-NPs symmetrically wet both interfaces and form columns that span the free surface and substrate interface. Using grazing-incidence Rutherford backscattering spectrometry (GI-RBS), the PMMA-NP surface excess (Z*) initially increases rapidly with time and then approaches a constant value at longer times. Consistent with the areal density, Z* is slightly greater at deeper quench depths, which is attributed to the more unfavorable interactions between the PMMA brush and SAN segments. The Z* values at early times are used to determine the PMMA-NP diffusion coefficients, which are significantly larger than theoretical predictions. These studies provide insights into the interplay between wetting and phase separation in PNCs and can be utilized in nanotechnology applications where surface-dependent properties, such as wettability, durability, and friction, are important.

Controlling the Thermally Induced Phase Separation of Polymer/Ionic Liquid Blended Films with Concentrated-Polymer-Brush-Decorated Hybrid Particles.

The development of quasi-solid electrolytes for electrical devices operating at high voltages is important for addressing future energy storage requirements. Here, we report a new method to fabricate quasi-solid electrolytes through the thermally induced phase separation of a polymer/ionic liquid (polymer/IL) blend. In a polymer/IL blend that exhibits lower critical solution temperature-type phase separation, we demonstrate that the addition of silica particles decorated with concentrated polymer brushes (CPB-SiPs) can prevent macroscopic phase separation after heating, resulting in a quasi-solid electrolyte with a continuous IL phase. This is due to the adsorption of CPB-SiPs onto the polymer/IL interface in the phase-separated structure. We also reveal a relationship between the molecular weight of the CPB and the phase-separated structure. Namely, a quasi-solid film with a bicontinuous phase-separated structure is formed only when polymers with an appropriate molecular weight are grafted on the CPB-SiPs. The resulting quasi-solid film exhibits a relatively high ionic conductivity, owing to the existence of a continuous ion-conductive phase solely consisting of IL. In addition, we fabricated a quasi-solid electrolyte with the blended film and successfully applied it to an electric double-layer capacitor operating at a high voltage, owing to the wider potential window of the IL employed herein.

Polymer-Brush-Decorated Graphene Oxide: Precision Synthesis and Liquid-Crystal Formation.

Given the specificity of the structure and function of graphene oxide (GO), hybridization with a variety of compounds will further extend its applications. To that end, we examined a new method for introducing a polymer brush onto the GO surface. In this method, GO was surface-modified with 2-((3-((2-bromo-2-methylpropanoyl)oxy)propyl)thio)ethylamine hydrochloride, which is a newly synthesized compound that contains an initiating group for atom transfer radical polymerization (ATRP) and an amino group for reacting with the epoxy groups on the GO surface. The ATRP-initiator-functionalized GO was then used as a substrate for the surface-initiated ATRP of methyl methacrylate (MMA), which produced graft polymers of poly(MMA) (PMMA) with targeted molecular weights and narrow molecular weight distributions; the average graft density was ∼0.06 chains/nm2. Because of their high dispersibilities and structural anisotropies, the PMMA-brush-decorated GOs formed lyotropic liquid crystals in their suspensions. In addition, similar suspensions with relatively high hybrid concentrations exhibited structural color that depended on the concentration.

Structure and dynamics in suspensions of soft core-shell colloids in the fluid regime.

We report on a detailed experimental study of the structure and short-time dynamics in fluid-regime suspensions of soft core-shell spherical particles with different molecular weights of the chains forming the soft outer shell, and therefore different degrees of particle softness, using 3D dynamic light scattering (3D-DLS). Owing to the particle softness, the liquid-crystal coexistence regime is found to be broader than that of hard-sphere (HS) suspensions. Static light scattering in the dilute regime yields form factors that can be described using a spherical core-shell model and second virial coefficients A2 > 0 indicative of purely repulsive interactions. The particle-particle interactions are longer ranged for all considered systems except those of the smaller molecular weight chain grafted particles which show a HS-like behavior. 3D-DLS experiments in the concentrated regime up to the liquid-crystal transition provide the short-time diffusion function, D(q), in a broad range of scattering wavenumbers, q, from which the structural (cage) and short-time self-diffusion coefficients D(qm) and DS = D(q ≫ qm), respectively, are deduced as functions of the effective particle volume fraction, ϕ = c/c*, where c* is the overlap concentration, calculated using the hydrodynamic particle radius, RH. The size of the nearest-neighbor cage of particles is characterized by 2π/qm, with D(q) and the static structure factor S(q) attaining at qm the smallest and largest values, respectively. Experimental data of D(qm) and DS are contrasted with analytic theoretical predictions based on a simplifying hydrodynamic radius model where the internal hydrodynamic structure of the core-shell particles is mapped on a single hydrodynamic radius parameter γ = RH/Reff, for constant direct interactions characterized by an (effective) hard-core radius Reff. The particle softness is reflected, in particular, in the corresponding shape of the static structure factor, while the mean solvent (Darcy) permeability of the particles related to γ is reflected in the dynamic properties only. For grafted particles with longer polymer chains, D(qm) and DS are indicative of larger permeability values while particles with shorter chains are practically nonpermeable. The particle softness is also evident in the effective random close packing fraction estimated from the extrapolated zero-value limit of the cage diffusion coefficient D(qm).

Control of Phase Separation in Polystyrene/Ionic Liquid-Blended Films by Polymer Brush-Grafted Particles.

Immiscible composite materials with controlled phase-separated structures are important in areas ranging from catalysis to battery. We succeeded in controlling the phase-separated structures of immiscible blends of polystyrene (PS) and two ionic liquids (ILs), namely, N, N-diethyl- N-(2-methoxyethyl)- N-methylammonium bis(trifluoromethylsulfonyl)imide (DEME-TFSI) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, by adding precisely designed concentrated polymer brush-grafted (CPB-grafted) silica nanoparticles (CPB-SiPs) prepared by surface-initiated atom-transfer radical polymerization. We discuss relationships between chemical species and molecular weights of the CPB and phase-separated structures. When the CPB was composed of a PS homopolymer of an appropriate molecular weight, the IL phase formed a continuous structure and a quasi-solid-blended film was successfully fabricated because the CPB-SiPs were adsorbed at the PS/IL interface and prevented macroscopic phase separation. We propose that CPB-SiP adsorption and the fabrication of quasi-solid films are governed by the degree of penetration of the matrix PS chains into the CPB and deformability of the CPB-SiPs. We found that the DEME-TFSI domain size can be controlled by the CPB-SiP content and that only 1 wt % of the CPB-SiPs was needed to fabricate a quasi-solid film. In addition, we investigated the ionic properties of the quasi-solid PS/DEME-TFSI-blended film. Owing to continuous ion channels composed only of DEME-TFSI, the film exhibited an ionic conductivity of 0.1 mS/cm, which is relatively high compared to previously reported quasi-solid electrolytes. Finally, we demonstrated that an electric double-layer capacitor fabricated using this film as the electrolyte exhibited high charge/discharge cycling stability and reversibility.

Grafting of Polymer Brushes from Xanthate-Functionalized Silica Particles.

Monodisperse silica particles (SiPs) were surface-modified with a newly designed silane coupling agent comprising a triethoxysilane and an alkyl halide, namely, 6-(triethoxysilyl)hexyl 2-bromopropionate, which was further treated with potassium O-ethyl dithiocarbonate (PEX) to immobilize xanthate molecules on the particle surfaces. Surface-initiated macromolecular design via interchange of xanthates (MADIX) polymerization of vinyl acetate (VAc) was conducted with the xanthate-functionalized SiPs. The polymerization was well controlled and produced SiPs coated with poly(vinyl acetate) (PVAc) with a well-defined target molar mass and a graft density of about 0.2 chains nm-2 . Dynamic light scattering and TEM measurements revealed that the hybrid particles were highly dispersible in good solvents without any aggregation. The PVAc brushes were hydrolyzed with hydrochloric acid to produce poly(vinyl alcohol) brushes on the SiP surfaces. In addition, the number of xanthate molecules introduced on the SiP surfaces could be successfully controlled by adjusting the concentration of PEX. Thus, the SiPs have two functionalities: xanthates able to act as a MADIX chain-transfer agent and alkyl bromide initiation sites for atom transfer radical polymerization (ATRP). By using these unique bifunctional particles, mixed polymer brushes were constructed on the SiPs by MADIX of VAc followed by ATRP of styrene or methyl methacrylate.

Measuring the Interactions between Protein-Coated Microspheres and Polymer Brushes in Aqueous Solutions.

Hydrophilic or zwitterionic polymer-functionalized surfaces have become attractive biomaterials in bioscience and technology due to their excellent protein-resistant ability. Understanding the fundamental interactions between proteins and polymers plays an essential role in the surface design of biomaterials. In this work, we studied the interactions between bovine serum albumin (BSA) and two sorts of polymer brushes including zwitterionic poly(carboxybetaine methacrylate) (PCBMA) and hydrophilic poly[oligo(ethylene glycol) methyl ether methacrylate] (POEGMA) in NaCl aqueous solutions directly with a self-established total internal reflection microscope (TIRM) to provide a better understanding of the underlying nonfouling mechanism of polymers. Our results indicate that both the surface charge and brushes length can affect protein adsorption through electrostatic and steric repulsions, respectively. Both PCBMA- and POEGMA-coated surfaces display negative charge properties due to incomplete coverage and ionic adsorption. As a result, strong electrostatic repulsions between proteins and negatively charged polymer-coated surfaces could contribute to the resistance of protein-coated particles in solutions with low ionic strength (0.1, 0.5, and 1 mM) and disappear in solutions with high ionic strength (10 mM). The measured interaction profiles demonstrate that PCBMA brushes could provide apparent steric forces only at high ionic strength (10 mM), where zwitterionic brushes exhibit a relatively extended conformation with a lack of electrostatic forces between intra- and interpolymers. In contrast, the steric repulsion between proteins and POEGMA brushes appears when particles diffuse at low positions in all salt concentrations (0.1-10 mM) with similar steric decay lengths, which results from the unresponsiveness of POEGMA brushes to the salt stimulus.

Magnetically Responsive Assemblies of Polymer-Brush-Decorated Nanoparticle Clusters That Exhibit Structural Color.

The development of new magnetic materials for applications such as magnetic-driven drug delivery, next-generation display materials, and magnetic resonance imaging is an important objective. To that end, we synthesized monodispersed, magnetically responsive particles grafted with well-defined polymer brushes and investigated the formation of their ordered arrays in organic solvents in response to a magnetic field. To achieve this, we prepared monodispersed magnetic nanoparticle clusters (MNCs) composed of large numbers of superparamagnetic ferrite ZnFe2O4 nanoparticles. The MNCs were subsequently coated with thin silica layers through the hydrolysis of tetraethoxysilane. The colloidal particles were surface-modified with initiating groups for atom transfer radical polymerization (ATRP) using a triethoxysilane derivative with an ATRP initiation site. To demonstrate the ability of the synthesized particles to produce well-defined polymer brushes on their surfaces, the ATRP-initiator-functionalized silica-coated MNCs were subjected to surface-initiated ATRP with methyl methacrylate. This polymerization proceeded in a living fashion to produce graft polymers with targeted molar masses and narrow molar mass distributions. The average graft density was determined to be 0.65 chains/nm2, which confirms the formation of concentrated polymer brushes on the MNCs. The hybrid particles were analyzed by dynamic light scattering and transmission electron microscopy techniques, which revealed excellent uniformity and solvent dispersibility. A suspension of the polymer-brush-decorated MNCs in acetone quickly developed intense structural color in response to approaching a magnet that depended on the strength of the magnetic field.

USAXS analysis of concentration-dependent self-assembling of polymer-brush-modified nanoparticles in ionic liquid: [I] concentrated-brush regime.

Using ultra-small angle X-ray scattering (USAXS), we analyzed the higher-order structures of nanoparticles with a concentrated brush of an ionic liquid (IL)-type polymer (concentrated-polymer-brush-modified silica particle; PSiP) in an IL and the structure of the swollen shell layer of PSiP. Homogeneous mixtures of PSiP and IL were successfully prepared by the solvent-casting method involving the slow evaporation of a volatile solvent, which enabled a systematic study over an exceptionally wide range of compositions. Different diffraction patterns as a function of PSiP concentration were observed in the USAXS images of the mixtures. At suitably low PSiP concentrations, the USAXS intensity profile was analyzed using the Percus-Yevick model by matching the contrast between the shell layer and IL, and the swollen structure of the shell and "effective diameter" of the PSiP were evaluated. This result confirms that under sufficiently low pressures below and near the liquid/crystal-threshold concentration, the studied PSiP can be well described using the "hard sphere" model in colloidal science. Above the threshold concentration, the PSiP forms higher-order structures. The analysis of diffraction patterns revealed structural changes from disorder to random hexagonal-closed-packing and then face-centered-cubic as the PSiP concentration increased. These results are discussed in terms of thermodynamically stable "hard" and/or "semi-soft" colloidal crystals, wherein the swollen layer of the concentrated polymer brush and its structure play an important role.

Unusual photoresponses in the upper critical solution temperature of polymer solutions mediated by changes in intermolecular interactions in an azo-doped liquid crystalline solvent.

Photoinduced changes in the upper critical solution temperature (UCST) were investigated for polymer solutions in an azobenzene-doped liquid crystal solvent. The UCST of poly(methyl methacrylate) (PMMA) and polystyrene (PS) solutions dropped upon irradiation with UV light, which induces trans-cis photoisomerization of the doped azo dye. In the case of PMMA solutions, the photoinduced drop in UCST was significantly larger than that expected from previous studies using azo-based polymers and common solvents. Moreover, the UCST of PS solutions also decreased under photoirradiation, in a direction opposite to that expected from the contribution of polarity. X-ray diffraction data of the solvent suggest that the decreased intermolecular interaction in the solvent (i.e. larger distance between the solvent molecules) is responsible for the photoresponsive behavior of the UCST. The proposed mechanism is consistent with the Flory-Huggins theory. Using such photoresponses in the UCST, the isothermal transition between 2-phase and 1-phase states by photoirradiation was demonstrated.

A novel approach for UV-patterning with binary polymer brushes.

A mixed self-assembled monolayer (SAM) of an initiator (3-(2-bromo-2-isobutyryloxy)propyl triethoxysilane) for atom transfer radical polymerization (ATRP) and an agent (6-(triethoxysilyl)hexyl 2-(((methylthio)carbonothioyl)thio)-2-phenylacetate) for reversible addition-fragmentation chain transfer (RAFT) polymerization was constructed on the surface of a silicon wafer or glass plate by a silane coupling reaction. When a UV light at 254nm was irradiated at the mixed SAM through a photomask, the surface density of the bromine atom at the end of BPE in the irradiated region was drastically reduced by UV-driven scission of the BrC bond, as observed by X-ray photoelectron spectroscopy. Consequently, the surface-initiated (SI)-ATRP of 2-ethylhexyl methacrylate (EHMA) was used to easily construct the poly(EHMA) (PEHMA) brush domain. Subsequently, SI-RAFT polymerization of a zwitterionic vinyl monomer, carboxymethyl betaine (CMB), was performed. Using the sequential polymerization, the PCMB and PEHMA brush domains on the solid substrate could be very easily patterned. Patterning proteins and cells with the binary polymer brush is expected because the PCMB brush indicated strong suppression of protein adsorption and cell adhesion, and the PEHMA brush had non-polar properties. This technique is very simple and useful for regulating the shape and size of bio-fouling and anti-biofouling domains on solid surfaces.

Semisoft Colloidal Crystals in Ionic Liquids.

Here, we introduce a technique for the direct formation of semisoft colloidal crystals of hybrid particles in nonvolatile ionic liquid (IL) solvents. The hybrid particles are comprised of a silica core and a densely grafted polymer brush shell, which were synthesized by surface-initiated living radical polymerization. A phase transition of the suspensions from a disordered fluid to a crystallized system was observed within a narrow concentration range. Confocal laser scanning microscopy observation and ultraviolet-visible light (UV-vis) spectrometry confirmed the highly ordered structure of the hybrid particles in ionic liquids. The effect of the hybrid particle structure on the photonic band gap of the colloidal crystals was investigated, and the band gaps varied by changing graft chain lengths. In addition, the colloidal crystal suspensions were successfully immobilized in ILs.

Grafted polymer chains suppress nanoparticle diffusion in athermal polymer melts.

We measure the center-of-mass diffusion of poly(methyl methacrylate) (PMMA)-grafted nanoparticles (NPs) in unentangled to slightly entangled PMMA melts using Rutherford backscattering spectrometry. These grafted NPs diffuse ∼100 times slower than predicted by the Stokes-Einstein relation assuming a viscosity equal to bulk PMMA and a hydrodynamic NP size equal to the NP core diameter, 2Rcore = 4.3 nm. This slow NP diffusion is consistent with an increased effective NP size, 2Reff ≈ 20 nm, nominally independent of the range of grafting density and matrix molecular weights explored in this study. Comparing these experimental results to a modified Daoud-Cotton scaling estimate for the brush thickness as well as dynamic mean field simulations of polymer-grafted NPs in athermal polymer melts, we find that 2Reff is in quantitative agreement with the size of the NP core plus the extended grafted chains. Our results suggest that grafted polymer chains of moderate molecular weight and grafting density may alter the NP diffusion mechanism in polymer melts, primarily by increasing the NP effective size.

Polymer-brush-afforded SPIO Nanoparticles Show a Unique Biodistribution and MR Imaging Contrast in Mouse Organs.

INTRODUCTION: To investigate the biodistribution and retention properties of the new super paramagnetic iron oxide (new SPIO: mean hydrodynamic diameter, 100 nm) nanoparticles, which have concentrated polymer brushes in the outer shell and are difficult for phagocytes to absorb, and to compare the new SPIO with clinically approved SPIO (Resovist: mean hydrodynamic diameter, 57 nm). MATERIALS AND METHODS: 16 male C57BL/6N mice were divided in two groups according to the administered SPIO (n = 8 for each group; intravenous injection does, 0.1 ml). In vivo magnetic resonance imaging (MRI) was performed before and one hour, one day, one week and four weeks after SPIO administration by two dimensional-the fast low angle shot (2D-FLASH) sequence at 11.7T. Ex vivo high-resolution images of fixed organs were also obtained by (2D-FLASH). After the ex vivo MRI, organs were sectioned and evaluated histologically to confirm the biodistribution of each particle precisely. RESULTS: The new SPIO was taken up in small amounts by liver Kupffer cells and showed a unique in vivo MRI contrast pattern in the kidneys, where the signal intensity decreased substantially in the boundaries between cortex and outer medulla and between outer and inner medulla. We found many round dark spots in the cortex by ex vivo MRI in both groups. Resovist could be detected almost in the cortex. The shapes of the dark spots were similar to those observed in the new SPIO group. Transmission electron microscopy revealed that Resovist and the new SPIO accumulated in different cells of glomeruli, that is, endothelial and mesangial cells, respectively. CONCLUSION: The new SPIO was taken up in small amounts by liver tissue and showed a unique MRI contrast pattern in the kidney. The SPIO were found in the mesangial cells of renal corpuscles. Our results indicate that the new SPIO may be potentially be used as a new contrast agent for evaluation of kidney function as well as immunune function.

Three Gel States of Colloidal Composites Consisting of Polymer-Brush-Afforded Silica Particles and a Nematic Liquid Crystal with Distinct Viscoelastic and Optical Properties.

Colloidal composites consisting of polymer-brush-afforded silica particles (P-SiPs) and a nematic liquid crystal (LC) exhibited three gel states with distinct viscoelastic and/or optical properties depending on temperature: (1) opaque hard gel, (2) translucent hard gel, and (3) translucent soft gel. We demonstrated that the transitions of the optical property and the hardness of the gels were due to the phase transition of the LC matrix and the glass transition of the grafted polymers of P-SiPs, respectively. We then revealed that the gelation (the formation of the translucent soft gel) was caused by the phase separation of P-SiPs and LC matrix in an isotropic phase based on spinodal decomposition. In addition, the particle concentration and molecular weight of the grafted polymer of P-SiPs were observed to significantly affect the elastic moduli and thermal stability of the composite gels. By the addition of an azobenzene derivative into an LC matrix, we achieved photochemical switching of the transparency of the composites based on the photoinduced phase transition of LCs, while keeping self-supporting ability of the composite gel.

Gradation of proteins and cells attached to the surface of bio-inert zwitterionic polymer brush.

A self-assembled monolayer (SAM) of a 2-bromoisobutyryl end group-carrying initiator for atom transfer radical polymerization (ATRP) was constructed on the surface of silicon wafer or glass substrates via a silane-coupling reaction. When the initiator SAM was irradiated with UV light at 254nm, the surface density of bromine atoms was reduced by the scission of CBr bonds as observed by XPS. With the surface-initiated ATRP of the zwitterionic vinyl monomer, carboxymethyl betaine (CMB), the surface density of PCMB brushes could be easily varied by changing the irradiation period of UV light prior to the polymerization. Furthermore, by using a UV-cut shutter sliding above the initiator SAM-modified substrate at a constant speed, the degree of bromine atom removal could be linearly varied along the direction of movement of the shutter. Consequently, the amount of both proteins adsorbed and cells adhered to the PCMB brush-covered substrate could easily be controlled by the gradation of the surface density of PCMB brushes, which suppressed protein adsorption and cell adhesion. Such a technique is very simple and useful for the regulation of the surface density of adsorbed proteins and adhered cells on an originally bio-inert surface.

Dispersion of PMMA-grafted, mesoscopic iron-oxide rods in polymer films.

This study investigates the parameters that affect the dispersion of polymer grafted mesoscopic iron-oxide rods (FeMRs) in polymer matrices. FeMRs (212 nm long by 36 nm in diameter) are grafted with poly(methyl methacrylate) (PMMA) at three different brush molecular weights: 3.7 kg mol(-1), 32 kg mol(-1), and 160 kg mol(-1). Each FeMR sample was cast in a polymer thin film consisting of either PMMA or poly(ethylene oxide) (PEO) each at a molecular weight much higher or much lower than the brush molecular weight. We find that the FeMRs with 160 kg mol(-1) brush disperse in all matrices while the FeMRs with 32 kg mol(-1) and 3.7 kg mol(-1) brushes aggregate in all matrices. We perform simple free energy calculations, taking into account steric repulsion from the brush and van der Waals attraction between FeMRs. We find that there is a barrier for aggregation for the FeMRs with the largest brush, while there is no barrier for the other FeMRs. Therefore, for these mesoscopic particles, the brush size is the main factor that determines the dispersion state of FeMRs in polymer matrices with athermal or weakly attractive brush-matrix interactions. These studies provide new insight into the mechanisms that affect dispersion in polymer matrices of mesoscopic particles and therefore guide the design of composite films with well-dispersed mesoscopic particles.

Silica core-polystyrene shell nanoparticle synthesis and assembly in three dimensions.

Monodisperse silica nanoparticles (SiNPs) grafted with well-defined and highly dense polystyrene brushes are used as building blocks for the formation of three-dimensional (3D) colloidal crystals. By adjusting the refractive indices and the density of the hybrid particles with those of mixed solvents, iridescent microcrystals were formed throughout the entire suspension which were characterised by confocal laser microscopy. These core-shell hybrid particles are not charged and the driving force of the crystallization relies on repulsive forces between the polymer brushes with high grafting density. The interparticle distance is correlated to Bragg's Law and can be controlled by manipulating the grafting density and the length of the polymer brushes. Finally, the uniformity of these unique core-shell particles was exploited to generate 3D assemblies by a rapid and simple process based on centrifugation.