The Topology of Polymer Brushes Determines Their Nanoscale Hydration.

Time-of-flight neutron reflectometry (ToF-NR) performed under different relative humidity conditions demonstrates that polymer brushes constituted by hydrophilic, cyclic macromolecules exhibit a more compact conformation with lower roughness as compared to linear brush analogues, due to the absence of dangling chain ends extending at the polymer-vapor interface. In addition, cyclic brushes feature a larger swelling ratio and an increased solvent uptake with respect to their linear counterparts as a consequence of the increased interchain steric repulsions. It is proposed that differences in swelling ratios between linear and cyclic brushes come from differences in osmotic pressure experienced by each brush topology. These differences stem from entropic constraints. The findings suggest that to correlate the equilibrium swelling ratios at different relative humidity for different topologies a new form of the Flory-like expression for equilibrium thicknesses of grafted brushes is needed.

Monitoring the Swelling Behavior of PEDOT:PSS Electrodes under High Humidity Conditions.

Polymer electrodes made of poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) are used in many applications but are also sensitive to humidity. We study humidity-induced changes of PEDOT:PSS electrodes as monitored with in situ time-of-flight neutron reflectivity (TOF-NR) measurements under high humidity conditions. The influence of the solvent additive Zonyl and a post-treatment of PEDOT:PSS films with ethylene glycol (EG) serving as electrodes are analyzed with respect to the swelling ratio and water uptake. Depending on the applied PEDOT:PSS treatment, PEDOT and PSS enrichment layers are clearly identified with TOF-NR at the substrate-polymer and polymer-air interface, respectively. The additive Zonyl reduces the water uptake and limits film swelling. EG post-treatment further increases hydrophobicity and thereby water incorporation into the PEDOT:PSS film is strongly suppressed. The characteristic time constants and effective interaction parameters extracted from the kinetic NR data show that additive and post-treatment reduce the sensitivity of the PEDOT:PSS electrodes to humidity.

Enzymatic Catalysis at Nanoscale: Enzyme-Coated Nanoparticles as Colloidal Biocatalysts for Polymerization Reactions.

Enzyme-catalyzed controlled radical polymerization represents a powerful approach for the polymerization of a wide variety of water-soluble monomers. However, in such an enzyme-based polymerization system, the macromolecular catalyst (i.e., enzyme) has to be separated from the polymer product. Here, we present a compelling approach for the separation of the two macromolecular species, by taking the catalyst out of the molecular domain and locating it in the colloidal domain, ensuring quasi-homogeneous catalysis as well as easy separation of precious biocatalysts. We report on gold nanoparticles coated with horseradish peroxidase that can catalyze the polymerization of various monomers (e.g., N-isopropylacrylamide), yielding thermoresponsive polymers. Strikingly, these biocatalyst-coated nanoparticles can be recovered completely and reused in more than three independent polymerization cycles, without significant loss of their catalytic activity.