The internal structure of nanometric microgels in water has been studied as a function of temperature, crosslinker content, and level of deuteration. Small-angle neutron scattering from poly(N isopropylmethacrylamide) (pNIPMAM, volume phase transition ≈ 44 °C) microgel particles of radius well below 100 nm in D2O has been measured. The intensities have been analyzed with a combination of polymer chain scattering and form-free radial monomer volume fraction profiles defined over spherical shells, taking polydispersity in size of the particles determined by AFM into account. A reverse Monte Carlo optimization using a limited number of parameters was developed to obtain smoothly decaying profiles in agreement with the experimentally scattered intensities. Result are compared to the swelling curve of microgel particles in the temperature range from 15 to 55 °C obtained from photon correlation spectroscopy (PCS). In addition to hydrodynamic radii measured by PCS, our analysis provides direct information about internal water content and gradients, the strongly varying steepness of the density profile at the particle-water interface, the total spatial extension of the particles, and the visibility of chains. The model has also been applied to a variation of the crosslinker content, N,N′ methylenebisacrylamide (BIS), from 5 to 15 mol%, providing insight in the impact of chain architecture and crosslinking on water uptake and on the definition of the polymer-water interface. The model can easily be generalized to arbitrary monomer contents and types, in particular mixtures of hydrogenated and deuterated species, paving the way to detailed studies of monomer distributions inside more complex microgels, in particular core-shell particles.

Red blood cells under shear flow present a specific swinging motion superimposed to a fluid-like tanktreading motion. Swinging is hypothesized to originate from periodic storage of shear energy in the cell membrane. Here we designed giant unilamellar vesicles with two lipid phases separated by a contact line, which swing and tanktread like red cells. We propose a model that quantitatively fits our data, finds the value of the contact-line tension and shows that swinging is due to the storage of elastic energy associated with the periodic modulation of the contact-line length during tanktreading.

The addition of nanoparticles to a polymermatrix is a well-known process to improve the mechanicalproperties of polymers. Many studies of mechanical reinforcementin polymer nanocomposites (PNCs) focus on rubberymatrices; however, much less effort concentrates on thefactors controlling the mechanical performance of thetechnologically important glassy PNCs. This paper presentsa study of the effect of the polymer molecular weight (MW)on the overall mechanical properties of glassy PNCs withattractive interaction by using Brillouin light scattering. Wefound that the mechanical moduli (bulk and shear) have anonmonotonic dependence on MW that cannot be predictedby simple rule of mixtures. The moduli increase with increasing MW up to 100 kg/mol followed by a drop at higher MW. Wedemonstrate that the change in the mechanical properties of PNCs can be associated with the properties of the interfacialpolymer layer. The latter depend on the interfacial chain packing and stretching, as well as polymer bridging,which vary differently with the MW of the polymer. These competing contributions lead to the observed nonmonotonicvariations of the glassy PNC moduli with MW. Our work provides a simple, cost-effective, and efficient way to control themechanical properties of glassy PNCs by tuning the polymer chain length. Our finding can be beneficial for the rational designof PNCs with desired mechanical performance.

The possibility to impart surface properties to any polymeric substrate using a fast, reproducible, and industrially friendly procedure, without the need for surface pretreatment, is highly sought after. This is in particular true in the frame of antibacterial surfaces to hinder the threat of biofilm formation. In this study, the potential of aryl‐azide polymers for photofunctionalization and the importance of the polymer structure for an efficient grafting are demonstrated. The strategy is illustrated with a UV‐reactive hydrophilic poly(2‐oxazoline) based copolymer, which can be photografted onto any polymer substrate that contains carbon–hydrogen bonds to introduce antifouling properties. Through detailed characterization it is demonstrated that the controlled spatial distribution of the UV‐reactive aryl‐azide moieties within the poly(2‐oxazline) structure, in the form of pseudogradient copolymers, ensures higher grafting efficacy than other copolymer structures including block copolymers. Furthermore, it is found that the photografting results in a covalently bound layer, which is thermally stable and causes a significant antiadherence effect and biofilm reduction against Escherichia coli and Staphylococcus epidermidis strains while remaining noncytotoxic against mouse fibroblasts.

Surface-inactive, highly hydrophilic particles are utilized to effectively and reversibly stabilize oil-in-water emulsions. This is a result of attractive van der Waals forces between particles and oil droplets in water, which are sufficient to trap the particles in close proximity to oil–water interfaces when repulsive forces between particles and oil droplets are suppressed. The emulsifying efficiency of the highly hydrophilic particles is determined by van der Waals attraction between particle monolayer shells and oil droplets enclosed therein and is inversely proportional to the particle size, while their stabilizing efficiency is determined by van der Waals attraction between single particles and oil droplets, which is proportional to the particle size. This differentiation in mechanism between emulsification and stabilization will significantly advance our knowledge of emulsions, thus enabling better control and design of emulsion-based technologies in practice.