We analyzed the glassy-state structural relaxation of polymers near surfaces and interfaces by monitoring fluorescence in multilayer films. Relative to that of bulk, the rate of structural relaxation of poly(methyl methacrylate) is reduced by a factor of 2 at a free surface and by a factor of 15 at a silica substrate interface; the latter exhibits a nearly complete arresting of relaxation. The distribution in relaxation rates extends more than 100 nanometers into the film interior, a distance greater than that over which surfaces and interfaces affect the glass transition temperature.

Owing to the improvement of properties including conductivity, toughness and permeability, polymer nanocomposites are slated for applications ranging from membranes to fuel cells. The enhancement of polymer properties by the addition of inorganic nanoparticles is a complex function of interfacial interactions, interfacial area and the distribution of inter-nanofiller distances. The latter two factors depend on nanofiller dispersion, making it difficult to develop a fundamental understanding of their effects on nanocomposite properties. Here, we design model poly(methyl methacrylate)-silica and poly(2-vinyl pyridine)-silica nanocomposites consisting of polymer films confined between silica slides. We compare the dependence of the glass-transition temperature (Tg) and physical ageing on the interlayer distance in model nanocomposites with the dependence of silica nanoparticle content in real nanocomposites. We show that model nanocomposites provide a simple way to gain insight into the effect of interparticle spacing on Tg and to predict the approximate ageing response of real nanocomposites.

Many intracellular membraneless organelles form via phase separation of intrinsically disordered proteins (IDPs) or regions (IDRs). These include the Caenorhabditis elegans protein LAF-1, which forms P granule-like droplets in vitro. However, the role of protein disorder in phase separation and the macromolecular organization within droplets remain elusive. Here, we utilize a novel technique, ultrafast-scanning fluorescence correlation spectroscopy, to measure the molecular interactions and full coexistence curves (binodals), which quantify the protein concentration within LAF-1 droplets. The binodals of LAF-1 and its IDR display a number of unusual features, including 'high concentration' binodal arms that correspond to remarkably dilute droplets. We find that LAF-1 and other in vitro and intracellular droplets are characterized by an effective mesh size of ∼3-8 nm, which determines the size scale at which droplet properties impact molecular diffusion and permeability. These findings reveal how specific IDPs can phase separate to form permeable, low-density (semi-dilute) liquids, whose structural features are likely to strongly impact biological function.

When confined to the nanoscale, the glass transition temperature (T g) of polymer films can deviate substantially from the bulk, i.e., the T g-confinement effect. Due to ease of processing most studies have focused on the thickness-dependent T g of thin films, while few have focused on extending investigations beyond thin films to other geometries. As polymers confined to higher geometrical dimensionalities become the enabling material in technologies ranging from drug delivery to plastic electronics to ultrafiltration, a greater understanding of size effects on the T g is warranted. Here, we investigate the effects of three-dimensional confinement on the T g of polymer nanoparticles under soft and hard confinement and quantitatively compare our results to those of thin films to explore commonalities or differences between the T g-confinement effect for polymers confined to different geometries. Via modulated differential scanning calorimetry, we show that T g decreases with size for polystyrene (PS) nanoparticles suspended in an aqueous solution, in agreement with the corresponding freestanding films. Furthermore, capping of PS nanoparticles with a hard silica shell leads to a size invariant T g. These results suggest that the free surface is a key factor in T g reductions of confined polymer, irrespective of geometry.

We present the synthesis and multifunctional utilization of core-shell Fe3O4 polydopamine nanoparticles (Fe3O4@PDA NPs) to serve as the enabling platform for a range of applications including responsive drug delivery, recyclable catalyst support, and adsorbent. Magnetite Fe3O4 NPs formed in a one-pot process by the hydrothermal approach were coated with a polydopamine shell layer of ~20 nm in thickness. The as prepared Fe3O4@PDA NPs were used for the controlled drug release in a pH-sensitive manner via reversible bonding between catechol and boronic acid groups of PDA and the anticancer drug bortezomib (BTZ), respectively. The facile deposition of Au NPs atop Fe3O4@PDA NPs was achieved by utilizing PDA as both the reducing agent and the coupling agent. The nanocatalysts exhibited high catalytic performance for the reduction of o-nitrophenol. Furthermore, the recovery and reuse of the catalyst was demonstrated 10 times without any detectible loss in activity. Finally, the PDA layers were converted into carbon to obtain Fe3O4@C and used as an adsorbent for the removal of Rhodamine B from an aqueous solution. The synergistic combination of unique features of PDA and magnetic nanoparticles establishes these core-shell NPs as a versatile platform for multiple applications.