Adsorption Of Block Copolymers Research Articles

Block Copolymer Adsorption on the Surface of Multi-Walled Carbon Nanotubes for Dispersion in N,N Dimethyl Formamide

This research aims to characterize the adsorption morphology of block copolymer dispersants of the styrene-block-4-vinylpyridine family (S4VP) on the surface of multi-walled carbon nanotubes (MWCNT) in a polar organic solvent, N,N-dimethyl formamide (DMF). Good, unagglomerated dispersion is important in several applications such as fabricating CNT nanocomposites in a polymer film for electronic or optical devices. Small-angle neutron scattering (SANS) measurements, using the contrast variation (CV) method, are used to evaluate the density and extension of the polymer chains adsorbed on the nanotube surface, which can yield insight into the means of successful dispersion. The results show that the block copolymers adsorb onto the MWCNT surface as a continuous coverage of low polymer concentration. Poly(styrene) (PS) blocks adsorb more tightly, forming a 20 Å layer containing about 6 wt.% PS, whereas poly(4-vinylpyridine) (P4VP) blocks emanate into the solvent, forming a thicker shell (totaling 110 Å in radius) but of very dilute (<1 wt.%) polymer concentration. This indicates strong chain extension. Increasing the PS molecular weight increases the thickness of the adsorbed layer but decreases the overall polymer concentration within it. These results are relevant for the ability of dispersed CNTs to form a strong interface with matrix polymers in composites, due to the extension of the 4VP chains allowing for entanglement with matrix chains. The sparse polymer coverage of the CNT surface may provide sufficient space to form CNT-CNT contacts in processed films and composites, which are important for electrical or thermal conductivity.

Assembly of polyelectrolyte star block copolymers at the oil-water interface.

To understand and resolve adsorption, reconfiguration, and equilibrium conformations of charged star copolymers, we carried out an integrated experimental and coarse-grained molecular dynamics simulation study of the assembly process at the oil-water interface. This is important to guide development of novel surfactants or amphiphiles for chemical transformations and separations. The star block copolymer consisted of arms that are comprised of hydrophilic-hydrophobic block copolymers that are covalently tethered via the hydrophobic blocks to one point. The hydrophobic core represents polystyrene (PS) chains, while the hydrophilic corona represents quaternized poly(2-vinylpyridine) (P2VP) chains. The P2VP is modeled to become protonated when in contact with an acidic aqueous phase, thereby massively increasing the hydrophilicity of this block, and changing the nature of the star at the oil-water interface. This results in a configurational change whereby the chains comprising the hydrophilic corona are significantly stretched into the aqueous phase, while the hydrophobic core remains solubilized in the oil phase. In the simulations, we followed the kinetics of the anchoring and assembly of the star block copolymer at the interface, monitoring the lateral assembly, and the subsequent reconfiguration of the star via changes in the interfacial tension that varies as the degree-of-protonation increases. At low fractions of protonation, the arm cannot fully partition into the aqueous side of the interface and instead interacts with other arms in the oil phase forming a network near the interface. These insights were used to interpret the non-monotonic dependence of pH with the asymptotic interfacial tension from pendant drop tensiometry experiments and spectral signatures of aromatic stretches seen in vibrational sum frequency generation (SFG) spectroscopy. We describe the relationship of interfacial tension to the star assembly via the Frumkin isotherm, which phenomenologically describes anti-cooperativity in adsorbing stars to the interface due to crowding. Although our model explicitly considers long-range electrostatics, the contribution of electrostatics to interfacial tension is small and brought about by strong counterion condensation at the interface. These results provide key insights into resolving the adsorption, reconfiguration, and equilibrium conformations of charged star block copolymers as surfactants.

Polymer Concentration Maximizes Encapsulation Efficiency in Electrohydrodynamic Mixing Nanoprecipitation

Encapsulation in self-assembled block copolymer (BCP) based nanoparticles (NPs) is a common approach to enhance hydrophobic drug solubility, and nanoprecipitation processes in particular can yield high encapsulation efficiency (EE). However, guiding principles for optimizing polymer, drug, and solvent selection are critically needed to facilitate rapid design of drug nanocarriers. Here, we evaluated the relationship between drug-polymer compatibility and concentration ratios on EE and nanocarrier size. Our studies employed a panel of four drugs with differing molecular structures (i.e., coumarin 6, dexamethasone, vorinostat/SAHA, and lutein) and two BCPs [poly(caprolactone)-b-poly(ethylene oxide) (PCL-b-PEO) and poly(styrene)-b-poly(ethylene oxide) (PS-b-PEO)] synthesized using three nanoprecipitation processes [i.e., batch sonication, continuous flow flash nanoprecipitation (FNP), and electrohydrodynamic mixing-mediated nanoprecipitation (EM-NP)]. Continuous FNP and EM-NP processes demonstrated up to 50% higher EE than batch sonication methods, particularly for aliphatic compounds. Drug-polymer compatibilities were assessed using Hansen solubility parameters, Hansen interaction spheres, and Flory Huggins interaction parameters, but few correlations were EE observed. Although some Hansen solubility (i.e., hydrogen bonding and total) and Flory Huggins interaction parameters were predictive of drug-polymer preferences, no parameter was predictive of EE trends among drugs. Next, the relationship between polymer: drug molar ratio and EE was assessed using coumarin 6 as a model drug. As polymer:drug ratio increased from &amp;lt;1 to 3–6, EE approached a maximum (i.e., ∼51% for PCL BCPs vs. ∼44% PS BCPs) with Langmuir adsorption behavior. Langmuir behavior likely reflects a formation mechanism in which drug aggregate growth is controlled by BCP adsorption. These data suggest polymer:drug ratio is a better predictor of EE than solubility parameters and should serve as a first point of optimization.

Thermoresponsive Poly(glycidyl ether) Brush Coatings on Various Tissue Culture Substrates-How Block Copolymer Design and Substrate Material Govern Self-Assembly and Phase Transition.

Thermoresponsive poly(glycidyl ether) brushes can be grafted to applied tissue culture substrates and used for the fabrication of primary human cell sheets. The self-assembly of such brushes is achieved via the directed physical adsorption and subsequent UV immobilization of block copolymers equipped with a short, photo-reactive benzophenone-based anchor block. Depending on the chemistry and hydrophobicity of the benzophenone anchor, we demonstrate that such block copolymers exhibit distinct thermoresponsive properties and aggregation behaviors in water. Independent on the block copolymer composition, we developed a versatile grafting-to process which allows the fabrication of poly(glycidyl ether) brushes on various tissue culture substrates from dilute aqueous-ethanolic solution. The viability of this process crucially depends on the chemistry and hydrophobicity of, both, benzophenone-based anchor block and substrate material. Utilizing these insights, we were able to manufacture thermoresponsive poly(glycidyl ether) brushes on moderately hydrophobic polystyrene and polycarbonate as well as on rather hydrophilic polyethylene terephthalate and tissue culture-treated polystyrene substrates. We further show that the temperature-dependent switchability of the brush coatings is not only dependent on the cloud point temperature of the block copolymers, but also markedly governed by the hydrophobicity of the surface-bound benzophenone anchor and the subjacent substrate material. Our findings demonstrate that the design of amphiphilic thermoresponsive block copolymers is crucial for their phase transition characteristics in solution and on surfaces.

Transport of Flexible, Oil-Soluble Diblock and BAB Triblock Copolymers to Oil/Water Interfaces.

The connection between block copolymer architecture and adsorption at fluid/fluid interfaces is poorly understood. We characterize the interfacial properties of a well-defined series of polyethylene oxide/polydimethyl siloxane (PDMS) diblock and BAB triblock copolymers at the dodecane/water interface. They are oil-soluble and quite flexible because of their hydrophobic PDMS block. Rather than relying on equilibrium interfacial measurements for which it is difficult to mitigate experimental uncertainty during adsorption, we combine measurements of steady-state adsorption, dilatational rheology, and adsorption/desorption dynamics. Steady-state interfacial pressure is insensitive to interfacial curvature and mostly agrees with theory. Adsorption does not occur in the diffusive limit as is the case for many aqueous, small-molecule surfactants. Dilatational rheology reveals differences in behavior between the diblocks and triblocks, and all interfaces possess elasticities below the thermodynamic limit. Desorption dynamics show that material exchange between the interface and the neighboring fluid occurs too slowly to relax dilatational stresses. The mechanism of relaxation occurs at the interface, likely from the reorientation of adsorbed chains.

Tailoring Rheological Properties of Thermoresponsive Hydrogels through Block Copolymer Adsorption to Cellulose Nanocrystals.

This study investigates the adsorption of a block copolymer composed of a poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) cationic polyelectrolyte and a poly(di(ethylene glycol) methyl ethermethacrylate) (PDEGMA) on oxidized cellulose nanocrystals (TO-CNCs) to produce hydrogels. PDMEAMA- b-PDEGMA was synthesized by atom-transfer radical polymerization. The extent and dynamics of the adsorption of PDMAEMA- b-PDEGMA on TO-CNCs were determined by electromechanical microbalance and optical techniques. Electrostatic adsorption was identified on TO-CNCs with the quaternized block copolymer. Small-angle neutron scattering experiments were performed to investigate the polymer behavior on the TO-CNC surfaces. Depending on the temperature, block copolymer induces the aggregation of nanocrystals after adsorption by connecting CNCs bundles with block copolymer chains. A reversible liquid-to-gel transition, triggered by temperature, was clearly detected by rheological measurements for the copolymer-CNC mixtures. At the optimal copolymer to CNC ratio the viscosity increased by 4 orders of magnitude at low shear rates. These stimuli-responsive CNC-based materials could be used as injectable biomedical systems.

Dynamics of amphiphilic block copolymers in an aqueous solution: direct imaging of micelle formation and nanoparticle encapsulation.

Micelles formed through the aggregation of amphiphilic block copolymers are ideal drug nanocarriers. Despite their importance in nanomedicine, the detailed mechanisms through which micelles form and copolymers encapsulate the target nanomaterials are unclear. Here, using in situ liquid cell transmission electron microscopy imaging, we capture both the dynamics of micelle formation and their encapsulation of gold nanoparticles (NPs) in an aqueous solution. Our observations reveal that the amphiphilic block copolymers aggregate and rearrange to form a micelle with a hydrophobic and rigid core, surrounded by a corona of hydrophilic blocks that extend into the solution. These micelles are stable against coalescence, and once mature, they do not merge. We also show that the encapsulation of hydrophobic NPs is a self-limiting process, which occurs through gradual adsorption of block copolymers; the growth of a polymeric shell around the NPs, shielding them from water, ceases when the NPs are fully covered by the adsorbed copolymers. The insights from these observations are of fundamental importance for the design of biocompatible soft materials.

Functional Modification of Silica through Enhanced Adsorption of Elastin-Like Polypeptide Block Copolymers.

A powerful tool for controlling interfacial properties and molecular architecture relies on the tailored adsorption of stimuli-responsive block copolymers onto surfaces. Here, we use computational and experimental approaches to investigate the adsorption behavior of thermally responsive polypeptide block copolymers (elastin-like polypeptides, ELPs) onto silica surfaces, and to explore the effects of surface affinity and micellization on the adsorption kinetics and the resultant polypeptide layers. We demonstrate that genetic incorporation of a silica-binding peptide (silaffin R5) results in enhanced adsorption of these block copolymers onto silica surfaces as measured by quartz crystal microbalance and ellipsometry. We find that the silaffin peptide can also direct micelle adsorption, leading to close-packed micellar arrangements that are distinct from the sparse, patchy arrangements observed for ELP micelles lacking a silaffin tag, as evidenced by atomic force microscopy measurements. These experimental findings are consistent with results of dissipative particle dynamics simulations. Wettability measurements suggest that surface immobilization hampers the temperature-dependent conformational change of ELP micelles, while adsorbed ELP unimers (i.e., unmicellized block copolymers) retain their thermally responsive property at interfaces. These observations provide guidance on the use of ELP block copolymers as building blocks for fabricating smart surfaces and interfaces with programmable architecture and functionality.

Thermosensitive silica-pluronic-starch model coating dispersion-part I: The effect of Pluronic block copolymer adsorption on the colloidal stability and rheology

The colloidal stability of a model paper coating dispersion consisting of silica particles, Pluronic F127, starch and glycerol was studied with respect to PF127 temperature responsiveness and its adsorption on the silica surface. Rheological characterization of this system in order to extract structural information for the wet suspension state was accomplished in terms of rotational tests. The analysis, done by Krieger-Dougherty model and the elastic floc model for all flow curves at three different temperatures, 20°C, 25°C and 30°C, and at different particle volume fractions (Ͽ between 0 and 0.31), revealed that the structure of the system changes. Two regions with different behaviour and a plateau region at particle volume fraction of Ͽ⿼0.16 were observed. At Ͽ⿤0.16 temperature was affecting the suspension structure. By rising the temperature the well dispersed suspension at 20°C transformed to flocculated one, where the higher the temperature was, more open floc structures were detected in terms of degree of flocculation parameter, Cfp, but at the same time with increasing the particle concentration the flocs got denser according to the calculated. At Ͽ⿥0.16, there were not detected major structural differences by changing temperature or particle concentration. At Ͽ⿼0.16 a plateau in yield stress values was observed. The behaviour of the investigated model coating suspension was discussed in terms of shear stresses andCfp.

Role of block copolymer adsorption versus bimodal grafting on nanoparticle self-assembly in polymer nanocomposites.

We compare the self-assembly of silica nanoparticles (NPs) with physically adsorbed polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) copolymers (BCP) against NPs with grafted bimodal (BM) brushes comprised of long, sparsely grafted PS chains and a short dense carpet of P2VP chains. As with grafted NPs, the dispersion state of the BCP NPs can be facilely tuned in PS matrices by varying the PS coverage on the NP surface or by changes in the ratio of the PS graft to matrix chain lengths. Surprisingly, the BCP NPs are remarkably better dispersed than the NPs tethered with bimodal brushes at comparable PS grafting densities. We postulate that this difference arises because of two factors inherent in the synthesis of the NPs: In the case of the BCP NPs the adsorption process is analogous to the chains being "grafted to" the NP surface, while the BM case corresponds to "grafting from" the surface. We have shown that the "grafted from" protocol yields patchy NPs even if the graft points are uniformly placed on each particle. This phenomenon, which is caused by chain conformation fluctuations, is exacerbated by the distribution function associated with the (small) number of grafts per particle. In contrast, in the case of BCP adsorption, each NP is more uniformly coated by a P2VP monolayer driven by the strongly favorable P2VP-silica interactions. Since each P2VP block is connected to a PS chain we conjecture that these adsorbed systems are closer to the limit of spatially uniform sparse brush coverage than the chemically grafted case. We finally show that the better NP dispersion resulting from BCP adsorption leads to larger mechanical reinforcement than those achieved with BM particles. These results emphasize that physical adsorption of BCPs is a simple, effective and practically promising strategy to direct NP dispersion in a chemically unfavorable polymer matrix.

Role of textile substrate hydrophobicity on the adsorption of hydrosoluble nonionic block copolymers

The adsorption of polyalkylene glycols and co-polymers of ethylene oxide and propylene oxide on substrates relevant to textiles with varying surface energies (cellulose, polypropylene, nylon and polyester) was studied by using quartz crystal microgravimetry. Langmuirian-type isotherms were observed for the adsorption profiles of nonionic block polymers of different architectures. The affinity with the surfaces is discussed based on experimental observations, which highlights the role of hydrophobic effects. For a given type of block polymer, micellar and monomeric adsorption is governed by the balance of polymer structure (mainly, chain length of hydrophobic segments) and substrate’s surface energy.

Mono- and Di-valent Salts as Modifiers of PEO-PPO-PEO Block Copolymer Interactions with Silica Nanoparticles in Aqueous Dispersions

Colloidal stabilization of nanoparticle dispersions is central to applications including coatings, mineral extraction, and dispersion of oil spills in oceanic environments, which often involves oil-mineral-aggregates (OMAs). We have an ongoing interest in the modulation of amphiphile micellization and adsorption behavior in aqueous colloidal dispersions in the presence of various additives. Here we evaluate the effect of added salts CaCl2, MgCl2, and NaCl on the micellization and adsorption behavior of the poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer Pluronic P105 (EO37PO56EO37). In 0.10 wt% silica nanoparticle (10.6 nm average diameter) dispersion, adsorbed block copolymer layer formation begins at a critical surface micelle concentration (csmc) of 0.02 wt%, well below the critical micellization concentration of Pluronic P105 in water. Dye solubilization experiments demonstrate an increase in the csmc upon addition of each salt. Each added salt reaches a level of maximum effectiveness in its ability to disfavor Pluronic P105 adsorption at the silica surface. These peak levels occur at concentrations of 0.005, 0.03, and 0.05 M for CaCl2, MgCl2, and NaCl, respectively, in the presence of 0.10 wt% silica nanoparticles. We explain these results in the context of an electrostatic displacer mechanism and discuss possible connections to OMA-dispersant formation.

Fabrication of latex rubber reinforced with micellar nanoparticle as an interface modifier

Reinforced latex rubbers were fabricated by incorporating small amount of nanoparticles as interface modifier. The rubbers were fabricated in a compression mold at 130 °C. The incorporated nanoparticles were prepared from wheat protein (gliadin) and ethyl cyanoacrylate (ECA). These nanoparticles were disintegrated to the constituent amphiphilic block copolymers while mixing with latex suspension and adsorbed on the surface of latex particles. The disintegration of nanoparticles and adsorption of the constituent amphiphilic block copolymers on the surface of latex particles were investigated by dynamic light scattering. The improved mechanical properties of the produced reinforced latex rubbers were characterized by mechanical analysis (stress–strain) and hardness test. Incorporation of nanoparticle into latex improved most of the mechanical properties, such as tensile strength, % elongation, energy at break, and toughness by 30% to 300%. On the other hand, tensile modulus and hardness were not much affected by the incorporation of nanoparticles. This research showed that the optimum percentage of nanoparticle is 2%, and the optimum gliadin:ECA weight ratio is 3:1.

Adsorption of block copolymers on solid surfaces: A Monte Carlo study.

Using hyper-parallel tempering Monte Carlo simulation, multiple histogram reweighting method, and finite size scaling, we investigate the adsorption of fully flexible and rod-coil chains on the square lattice. We find that the phase behaviour changes with the chain length and flexibility. For homonuclear rod-coil chains, the phase diagram consists of only gas-disorder liquid critical point. Weakening of the interaction energy between the segments belonging to two different subunits gives rise to an order-disorder transition. The topology of the resulting phase diagram depends on the chain length and flexibility. For short chains, both fully flexible and rod-coil diblock copolymers form lamellar ordered phase with fully stretched chains, and the order-disorder transition is of the first order. The phase diagrams are similar for both chain architectures and consist of two binodals meeting in the triple point. When the chain length increases the order-disorder transition becomes second-order and the difference in the phase behaviour between the fully flexible and the rod-coil diblock copolymers becomes more pronounced. While for the former chain architecture the topology of the phase diagram involves a λ-line which meets the gas-disordered liquid binodal in the critical end-point, in the latter case the λ-line meets the gas-disordered liquid critical point and forms the tricritical point. We trace back these changes to the change in the morphology of the ordered phase. The mechanism of the order-disorder transition involves the formation of domains resembling those observed during the spinodal decomposition process. The domains subsequently merge and arrange into lamellae. These observations are supported by integral geometry analysis.

Kinetics of Preferential Adsorption of Amphiphilic Star Block Copolymers that Tether by Their Corona Blocks at the Solid/Fluid Interface

The kinetics of preferential adsorption of a series of amphiphilic star block copolymers having cores made of polystyrene, PS, and coronas made of poly(2-vinylpyridine), PVP, have been studied using in situ phase modulated ellipsometry. The stars have, on average, either 26 or 40 PS-b-PVP diblock copolymer arms with PS/PVP molecular weight ratios (S/V) of 1/1, 5/1, or 9/1. Preferential adsorption from dilute toluene solutions onto silicon surfaces tethers these topologically complex star copolymers through their PVP blocks, yielding an interfacial structure resembling a dome. The adsorption kinetics are concentration dependent and show two distinct regimes: an initial rapid adsorption is followed by a slow approach toward equilibrium that is dominated by relaxations and rearrangements. For all PS/PVP ratios studied, star copolymers having 40 arms exhibit greater final adsorbed amounts compared to those having 26 arms. A kinetics model that considers diffusion of molecules at the solid/fluid interface as well as surface relaxation/reorganization events is used to characterize the adsorption process. In general, while both processes are necessary to describe the kinetics of preferential adsorption of these materials, surface rearrangements dominate for the two stars having the largest size and number of arms. It is also found that star block copolymers having symmetric arms (PS/PVP = 1/1) approach adsorption equilibrium in agreement with random sequential adsorption (RSA) model kinetics, attaining final adsorbed amounts that are close to those predicted for RSA processes. In contrast, the asymmetric stars having PS/PVP = 9/1 and 5/1 are able to rearrange on the surface, reaching final adsorbed amounts that are greater than those predicted for RSA processes, suggesting surface relaxation/reorganization and possible stretching due to confinement occurring at the solid/fluid interface. The results reported provide key insights as to how composition and connectivity of highly branched soft materials impact their self-assembly and interfacial structure.

Block‐Copolymer‐Mediated Nanoparticle Dispersion and Assembly in Polymer Nanocomposites

A individual nanoparticle (NP) dispersion in polymer nanocomposites has been obtained through the adsorption of PSbP2VP block copolymer (BCP) at the NPs' surface in solution. The adsorbed block increases the minimum inter-NP distance, while the non-adsorbed block has favourable entropy of mixing with the matrix polymer with the same chemical structure. Physical adsorption of BCP provides a simple, robust means of organizing NPs in a chemically unfavourable polymer.

Two Non-covalent Methods to Decorate Nanoparticles with Block Copolymers

The physical adsorption of block copolymers is a simple and reliable approach to functionalize the surface of organic or inorganic nanoparticles. This article presents two novel methods of particle coating with block copolymers that may apply to various aqueous colloidal dispersions. The first method relies on the use of charged block copolymers having two adsorbing blocks, which can adopt a typical anchor-buoy conformation at the particle surface when proper conditions are used. The second approach consists of self-assembling a bilayer of amphiphilic block copolymers around charged nanoparticles. In both cases, a special emphasis is placed on the process used to control and orient the molecular interactions between the copolymer and the particles.

Surface and Adsorption Parameters of Water Soluble Polymeric Surfactants Based on Ethoxylated Schiff Base Polymers in Aqueous Medium

This work aims to measure the adsorption and micellization parameters of new water soluble nonionic amphiphilic block and graft copolymers based on hydrophilic poly (ethylene glycol) (PEG) and hydrophobic poly (propylene oxide) (PPO) at ambient temperature and normal atmospheric pressure. The chemical composition and molecular weights of the prepared copolymers were determined from 1H NMR analyses. The surface properties of the prepared surfactants were determined by measuring the surface tension at different temperatures. The surface tension, critical micelle concentration and surface activities were determined at different temperatures. Surface parameters such as surface excess concentration, the area per molecule at interface and the effectiveness of surface tension reduction were determined from the adsorption isotherms of the prepared surfactants. Some thermodynamic data for the adsorption and micellization process were calculated and are discussed.

Fabrication of composite thin films with microstructures of honeycomb, foam, and nanosphere arrays through adsorption and self-assembly of block copolymers at the liquid/liquid interface

The adsorption and self-organization behaviors of two kinds of block copolymers, polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) and poly(4-vinylpyridine)-block-polystyrene-block-poly(4-vinylpyridine) (P4VP-b-PS-b-P4VP), at planar liquid/liquid interfaces were investigated. A gel film decorating with honeycomb-like microstructures forms at the liquid/liquid interface between PS-b-P4VP chloroform solution and chloroauric acid aqueous solution. However, foam films were developed when the chloroauric acid aqueous solution was replaced by a chloroplatinic acid solution or a silver nitrate solution. Furthermore, a free-standing film containing the ordered arrays of nanospheres appeared at the liquid/liquid interface between P4VP-b-PS-b-P4VP chloroform solution and chloroauric acid aqueous solution. The formation of these microstructures was attributed to the adsorption of polymer molecules, combining with inorganic ions and the self-assembly of the composite species at the interface. The doped metal ions and complex ions were transformed to metal nanoparticles after further treatment. This is a facile and convenient method to prepare polymer/inorganic nanoparticle composites. These results also indicate the great influences of the polymer structures and the inorganic species in the aqueous phases on the self-assembly behaviors of the polymers at the interfaces, the final morphology, and structure of the composites. In addition, the formed thin composite films doped with well-dispersed, homogeneous small noble metal nanoparticles exhibit great and durable catalytic activities for the reduction of 4-nitrophenol (4-NP) by potassium borohydride.

Adsorption of Pluronic block copolymers on silica nanoparticles

Polymers on the surface of nanoparticles are of great scientific and technological importance since they dictate many important properties and functions of dispersed systems. We investigate here the organization of a representative poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) (PEO–PPO–PEO) block copolymer on silica nanoparticles dispersed in water. Pluronic P105 (EO36PO56EO36) adsorbs on protonated silica and starts forming hydrophobic domains above a certain bulk polymer concentration, called critical surface micelle concentration (csmc), which is lower than the critical micelle concentration (cmc) of Pluronic P105 in plain water. The csmc decreases with increasing particle concentration and decreasing particle size. Below its csmc, the PEO–PPO–PEO block copolymer adsorption on protonated silica nanoparticles is similar to the adsorption of PEO homopolymers. Above the csmc, the block copolymers form micelle-like aggregates on protonated silica nanoparticles, as suggested by the adsorbed layer thickness, adsorbed polymer amount, and presence of hydrophobic domains.