Hysteresis in the thermally induced phase transition of cellulose ethers.

Functionalized cellulosics have shown promise as naturally derived thermoresponsive gelling agents. However, the dynamics of thermally induced phase transitions of these polymers at the lower critical solution temperature (LCST) are not fully understood. Here, with experiments and theoretical considerations, we address how molecular architecture dictates the mechanisms and dynamics of phase transitions for cellulose ethers. Above the LCST, we show that hydroxypropyl substituents favor the spontaneous formation of liquid droplets, whereas methyl substituents induce fibril formation through diffusive growth. In celluloses which contain both methyl and hydroxypropyl substituents, fibrillation initiates after liquid droplet formation, suppressing the fibril growth to a sub-diffusive rate. Unlike for liquid droplets, the dissolution of fibrils back into the solvated state occurs with significant thermal hysteresis. We tune this hysteresis by altering the content of substituted hydroxypropyl moieties. This work provides a systematic study to decouple competing mechanisms during the phase transition of multi-functionalized macromolecules.

Influence of annealing conditions on the optical and structural properties of spin-coated As(2)S(3) chalcogenide glass thin films.

Spin-coating of chalcogenide glass is a low-cost, scalable method to create optical grade thin films, which are ideal for visible and infrared applications. In this paper, we study the influence of annealing on optical parameters of As(2)S(3) films by examining UV-visible and infrared spectroscopy and correlating the results to changes in the physical properties associated with solvent removal. Evaporation of excess solvent results in a more highly coordinated, denser glass network with higher index and lower absorption. Depending on the annealing temperature and time, index values ranging from n = 2.1 to the bulk value (n = 2.4) can be obtained, enabling a pathway to materials optimization.

Controlling the Surface Chemistry of a Hydrogel for Spatially Defined Cell Adhesion.

A two-step synthesis is described for activating the surface of a fully hydrated hydrogel that is of interest as a possible scaffold for neural regeneration devices. The first step exploits the water content of the hydrogel and the hydrophobicity of the reaction solvent to create a thin oxide layer on the hydrogel surface using a common titanium or zirconium alkoxide. This layer serves as a reactive interface that enables rapid transformation of the hydrophilic, cell-nonadhesive hydrogel into either a highly hydrophobic surface by reaction with an alkylphosphonic acid, or into a cell-adhesive one using a (α,ω-diphosphono)alkane. Physically imprinting a mask ("debossing") into the hydrogel, followed by a two-step surface modification with a phosphonate, allows for patterning its surface to create spatially defined, cell-adhesive regions.