Transport-Limited Adsorption of Plasma Proteins on Bimodal Amphiphilic Polymer Co-Networks: Real-Time Studies by Spectroscopic Ellipsometry

Traditional hydrogels are commonly limited by poor mechanical properties and low oxygen permeability. Bimodal amphiphilic co-networks (β-APCNs) are a new class of materials that can overcome these limitations by combining hydrophilic and hydrophobic polymer chains within a network of co-continuous morphology. Applications that can benefit from these improved properties include therapeutic contact lenses, enzymatic catalysis supports, and immunoisolation membranes. The continuous hydrophobic phase could potentially increase the adsorption of plasma proteins in blood-contacting medical applications and compromise in vivo material performance, so it is critical to understand the surface characteristics of β-APCNs and adsorption of plasma proteins on β-APCNs. From real-time spectroscopic visible (Vis) ellipsometry measurements, plasma protein adsorption on β-APCNs is shown to be transport-limited. The adsorption of proteins on the β-APCNs is a multistep process with adsorption to the hydrophilic surface initially, followed by diffusion into the material to the internal hydrophilic/hydrophobic interfaces. Increasing the cross-linking of the PDMS phase reduced the protein intake by limiting the transport of large proteins. Moreover, the internalization of the proteins is confirmed by the difference between the surface-adsorbed protein layer determined from XPS and bulk thickness change from Vis ellipsometry, which can differ up to 20-fold. Desorption kinetics depend on the adsorption history with rapid desorption for slow adsorption rates (i.e., slow-diffusing proteins within the network), whereas proteins with fast adsorption kinetics do not readily desorb. This behavior can be directly related to the ability of the protein to spread or reorient, which affects the binding energy required to bind to the internal hydrophobic interfaces

Direct Immersion Annealing of Thin Block Copolymer Films

We demonstrate ordering of thin block copolymer (BCP) films via direct immersion annealing (DIA) at enhanced rate leading to stable morphologies. The BCP films are immersed in carefully selected mixtures of good and marginal solvents that can impart enhanced polymer mobility, while inhibiting film dissolution. DIA is compatible with roll-to-roll assembly manufacturing and has distinct advantages over conventional thermal annealing and batch processing solvent-vapor annealing methods. We identify three solvent composition-dependent BCP film ordering regimes in DIA for the weakly interacting polystyrene–poly­(methyl methacrylate) (PS–PMMA) system: rapid short-range order, optimal long-range order, and a film instability regime. Kinetic studies in the “optimal long-range order” processing regime as a function of temperature indicate a significant reduction of activation energy for BCP grain growth compared to oven annealing at conventional temperatures. An attractive feature of DIA is its robustness to ordering other BCP (e.g. PS-P2VP) and PS-PMMA systems exhibiting spherical, lamellar and cylindrical ordering

Role of Amphiphilic Block Copolymer Composition on Pore Characteristics of Micelle-Templated Mesoporous Cobalt Oxide Films

Block copolymer templating is a versatile approach for the generation of well-defined porosity in a wide variety of framework chemistries. Here, we systematically investigate how the composition of a poly­(methoxy poly­[ethylene glycol] methacrylate)-<i>block</i>-poly­(butyl acrylate) (PMPEG-PBA) template impacts the pore characteristics of mesoporous cobalt oxide films. Three templates with a constant PMPEG segment length and different hydrophilic block volume fractions of 17%, 51%, and 68% for the PMPEG-PBA are cooperatively assembled with cobalt nitrate hexahydrate and citric acid. Irrespective of template composition, a spherical nanostructure is templated and elliptical mesostructures are obtained on calcination due to uniaxial contraction of the film. The average pore size increases from 11.4 ± 2.8 to 48.5 ± 4.3 nm as the length of the PBA segment increases as determined from AFM. For all three templates examined, a maximum in porosity (∼35% in all cases) and surface area is obtained when the precursor solids contain 35–45 wt % PMPEG-PBA. This invariance suggests that the total polymer content drives the structure through interfacial assembly. The composition for maximizing porosity and surface area with the micelle-templating approach results from a general decrease in porosity with increasing cobalt nitrate hexahydrate content and the increasing mechanical integrity of the framework to resist collapse during template removal/crystallization as the cobalt nitrate hexahydrate content increases. Unlike typical evaporation induced self-assembly with sol–gel chemistry, the hydrophilic/hydrophobic composition of the block copolymer template is not a critical component to the mesostructure developed with micelle-templating using metal nitrate–citric acid as the precursor

Mesoporous Carbon–Vanadium Oxide Films by Resol-Assisted, Triblock Copolymer-Templated Cooperative Self-Assembly

Unlike other crystalline metal oxides amenable to templating by the combined assemblies of soft and hard chemistries (CASH) method, vanadium oxide nanostructures templated by poly­(ethylene oxide-<i>b</i>-1,4-butadiene-<i>b</i>-ethylene oxide) (OBO) triblock copolymers are not preserved upon high temperature calcination in argon. Triconstituent cooperative assembly of a phenolic resin oligomer (resol) and an OBO triblock in a VOCl₃ precursor solution enhances the carbon yield and can prevent breakout crystallization of the vanadia during calcination. However, the calcination environment significantly influences the observed mesoporous morphology in these composite thin films. Use of an argon atmosphere in this processing protocol leads to nearly complete loss of carbon–vanadium oxide thin film mesostructure, due to carbothermal reduction of vanadium oxide. This reduction mechanism also explains why the CASH method is not more generally successful for the fabrication of ordered mesoporous vanadia. Carbonization under a nitrogen atmosphere at temperatures up to 800 °C instead enables formation of a block copolymer-templated mesoporous structure, which apparently stems from the formation of a minor fraction of a stabilizing vanadium oxynitride. Thus, judicious selection of the inert gas for template removal is critical for the synthesis of well-defined, mesoporous vanadia–carbon composite films. This resol-assisted assembly method may generally apply to the fabrication of other mesoporous materials, wherein inorganic framework crystallization is problematic due to kinetically competitive carbothermal reduction processes

Hierarchical Electrospun and Cooperatively Assembled Nanoporous Ni/NiO/MnO_<i>x</i>/Carbon Nanofiber Composites for Lithium Ion Battery Anodes

A facile method to fabricate hierarchically structured fiber composites is described based on the electrospinning of a dope containing nickel and manganese nitrate salts, citric acid, phenolic resin, and an amphiphilic block copolymer. Carbonization of these fiber mats at 800 °C generates metallic Ni-encapsulated NiO/MnO_<i>x</i>/carbon composite fibers with average BET surface area (150 m²/g) almost 3 times higher than those reported for nonporous metal oxide nanofibers. The average diameter (∼900 nm) of these fiber composites is nearly invariant of chemical composition and can be easily tuned by the dope concentration and electrospinning conditions. The metallic Ni nanoparticle encapsulation of NiO/MnO_<i>x</i>/C fibers leads to enhanced electrical conductivity of the fibers, while the block copolymers template an internal nanoporous morphology and the carbon in these composite fibers helps to accommodate volumetric changes during charging. These attributes can lead to lithium ion battery anodes with decent rate performance and long-term cycle stability, but performance strongly depends on the composition of the composite fibers. The composite fibers produced from a dope where the metal nitrate is 66% Ni generates the anode that exhibits the highest reversible specific capacity at high rate for any composition, even when including the mass of the nonactive carbon and Ni⁰ in the calculation of the capacity. On the basis of the active oxides alone, near-theoretical capacity and excellent cycling stability are achieved for this composition. These cooperatively assembled hierarchical composites provide a platform for fundamentally assessing compositional dependencies for electrochemical performance. Moreover, this electrospinning strategy is readily scalable for the fabrication of a wide variety of nanoporous transition metal oxide fibers

Operando Grazing Incidence Small-Angle X‑ray Scattering/X-ray Diffraction of Model Ordered Mesoporous Lithium-Ion Battery Anodes

Emergent lithium-ion (Li⁺) batteries commonly rely on nanostructuring of the active electrode materials to decrease the Li⁺ ion diffusion path length and to accommodate the strains associated with the insertion and de-insertion of Li⁺, but in many cases these nanostructures evolve during electrochemical charging–discharging. This change in the nanostructure can adversely impact performance, and challenges remain regarding how to control these changes from the perspective of morphological design. In order to address these questions, operando grazing-incidence small-angle X-ray scattering and X-ray diffraction (GISAXS/GIXD) were used to assess the structural evolution of a family of model ordered mesoporous NiCo₂O₄ anode films during battery operation. The pore dimensions were systematically varied and appear to impact the stability of the ordered nanostructure during the cycling. For the anodes with small mesopores (≈9 nm), the ordered nanostructure collapses during the first two charge–discharge cycles, as determined from GISAXS. This collapse is accompanied by irreversible Li-ion insertion within the oxide framework, determined from GIXD and irreversible capacity loss. Conversely, anodes with larger ordered mesopores (17–28 nm) mostly maintained their nanostructure through the first two cycles with reversible Li-ion insertion. During the second cycle, there was a small additional deformation of the mesostructure. This preservation of the ordered structure lead to significant improvement in capacity retention during these first two cycles; however, a gradual loss in the ordered nanostructure from continuing deformation of the ordered structure during additional charge–discharge cycles leads to capacity decay in battery performance. These multiscale operando measurements provide insight into how changes at the atomic scale (lithium insertion and de-insertion) are translated to the nanostructure during battery operation. Moreover, small changes in the nanostructure can build up to significant morphological transformations that adversely impact battery performance through multiple charge–discharge cycles