Membraneless Ionic Liquid Droplet Nanoprobe for Oxygen Sensing and Gas Phase Scanning Electrochemical Microscopy.

A novel membraneless oxygen sensing nanoprobe was developed based on a hanging drop ionic liquid electrochemical cell. An ultrasmall (<500 nm) working electrode and small volume electrochemical cell allowed for an impressively low detection limit of ∼13 ppm and a response time less than 100 ms, which is unusually fast for an electrochemical gas sensor. The oxygen sensor was stable for hours of operation and, owing to the membraneless design, was easily regenerable when fouled. The pulled capillary form factor of the nanoprobe was found compatible with scanning probe techniques, the demonstration of which was made by application as a tip electrode in gas phase scanning electrochemical microscopy (SECM). In the SECM experiments, the oxygen nanoprobe exhibited micrometer scale spatial resolution with ease. This unique probe design developed here may potentially be engineered into versatile sensors for various volatile molecules other than oxygen, such as those pertinent to hazard analysis and biomedical diagnosis.

Carbon-free high-performance cathode for solid-state Li-O2 battery.

The development of a cathode for solid-state lithium-oxygen batteries has been hindered in practice by a low capacity and limited cycle life despite their potential for high energy density. Here, a previously unexplored strategy is proposed wherein the cathode delivers a specific capacity of 200 milliampere hour per gram over 665 discharge/charge cycles, while existing cathodes achieve only ~50 milliampere hour per gram and ~100 cycles. A highly conductive ruthenium-based composite is designed as a carbon-free cathode by first-principles calculations to avoid the degradation associated with carbonaceous materials, implying an improvement in stability during the electrochemical cycling. In addition, water vapor is added into the main oxygen gas as an additive to change the discharge product from growth-restricted lithium peroxide to easily grown lithium hydroxide, resulting in a notable increase in capacity. Thus, the proposed strategy is effective for developing reversible solid-state lithium-oxygen batteries with high energy density.

Solvent evaporation induced liquid crystalline phase in poly(3-hexylthiophene).

We report on the evolution of the chain orientation of a representative π-conjugated polymer, poly(3-hexylthiophene) (P3HT), during the solution-casting process, as monitored using polarized Raman spectroscopy. These measurements point to the formation of a liquid-crystalline phase of P3HT solutions within a specific time period during solvent evaporation, which leads to a conducting channel. These conclusions are based on the angular dependence of polarized Raman scattering peaks, the anisotropy in the fluorescence background signal, analysis of the scattering-peak shape, and direct observations of the three-phase contact line in an optical microscope under crossed polarizers. These results shed new light on the evolution of chain alignment and thus materials nanostructure, specifically in solution-processed P3HT and more generally in π-conjugated systems. They may further enable the design of improved materials and processes for this important class of polymers.

Viscoelastic and mechanical behavior of recombinant protein elastomers.

Recombinant DNA synthesis was employed to produce elastin-mimetic protein triblock copolymers containing chemically distinct midblocks. These materials displayed a broad range of mechanical and viscoelastic responses ranging from plastic to elastic when examined as hydrated gels and films. These properties could be related in a predictable fashion to polymer block size and structure. While these materials could be easily processed into films and gels, electrospinning proved a feasible strategy for creating protein fibers. All told, the range of properties exhibited by this new class of protein triblock copolymer in combination with their easy processability suggests potential utility in a variety of soft prosthetic and tissue engineering applications.

Control of anchoring of nematic fluids at polymer surfaces created by in situ photopolymerization.

In situ photopolymerization of alkyl acrylate monomers in the presence of a nematic fluid provides a cellular matrix of liquid crystalline droplets in which the chemical structure of the encapsulating polymer exerts control over the alignment (anchoring) of the liquid crystalline molecules. Control is obtained by variation of the alkyl side chains and through copolymerization of two dissimilar monofunctional acrylates. For example, among a series of poly(methylheptyl acrylate)s, the 1-methylheptyl analogue prefers planar anchoring of a nematic (TL205) over the temperature range studied. However, the polymers of other methylheptyl side chains display a homeotropic-to-planar anchoring thermal transition temperature similar to that of the n-heptyl analogue. Copolymerization of two monofunctional acrylates with opposing tendencies of aligning liquid crystal leads to tunability of anchoring behavior over a wide temperature range. The broad anchoring transitions we observed provide a way of achieving highly tilted anchoring.

A novel enzymatic technique for limiting drug mobility in a hydrogel matrix.

An oral colon specific drug delivery platform has been developed to facilitate targetted release of therapeutic proteins as well as small molecule drugs. A simple enzymatic procedure is used to modify the molecular architecture of a lightly chemically crosslinked galactomannan hydrogel as well as a model drug-galactomannan oligomer conjugate, fluoroisocynate (FITC) tagged guar oligomer, to entrap the model drug. The enzyme-modified hydrogel retains the drug until it reaches the colonic environment where bacteria secrete enzymes (namely beta-mannanase) to degrade the gel and release the drug molecule. Laser scanning confocal microscopy combined with fluorescence recovery after photobleaching is used to quantify the diffusion of the drug conjugate. The diffusion coefficient of solutes in the lightly crosslinked galactomannan hydrogel is approximately equal to the diffusion coefficient in the guar solution for simple diffusional drug loading. After drug loading, alpha-galactosidase treatment generates additional physical crosslinks in the hydrogel matrix as well as between the drug-oligomer conjugate and the hydrogel, which reduces diffusion of the drug-oligomer conjugate significantly. Degradation of the hydrogel by beta-mannanase results in a slow and controlled rate of FITC-guar oligomer diffusion, which generates an extended release profile for the model drug.

Microscopic observations and simulations of Bloch walls in nematic thin films.

We study Bloch wall defects formed by quenching nematic thin films from planar anchoring to homeotropic anchoring through a temperature-driven anchoring transition. The director profiles of the walls are directly visualized using fluorescence confocal polarizing microscopy, and shown to agree well with the simulation based on the Frank elasticity theory. A pure twist wall exists if the ratio of sample thickness to surface extrapolation length p is smaller than or close to 1; while a diffuse Bloch wall is obtained if p is much greater than 1.

Control of the anchoring behavior of polymer-dispersed liquid crystals: effect of branching in the side chains of polyacrylates.

A temperature-driven anchoring transition in a polymer/nematic fluid composite that is far from the bulk nematic-isotropic transition temperature is reported. A series of poly(methylheptyl acrylates) were studied to probe the subtle effects of the side chain structure of the polymer on control of the anchoring. A polymer-dispersed liquid crystal film made from TL205 and 1-methylheptyl acrylate shows only planar anchoring over the temperature range studied, while the films made from TL205 and each of the other methylheptyl acrylates or n-heptyl acrylate show the homeotropic-to-planar anchoring transition at temperatures between 70 and 78 degrees C. An interfacial model is proposed in which the different conformation of the side chains is suggested as the cause for the dramatic difference in the observed anchoring behavior.

Permanent bubble arrays from a cross-linked poly(para-phenyleneethynylene): picoliter holes without microfabrication.

An azide-substituted poly(para-phenyleneethynylene) (PPE) 4 was prepared by the Heck-Cassar-Sonogashira-Hagihara method. Thin films of 4 form self-assembled bubble arrays from carbon disulfide solution utilizing the breath figure method. The as-formed porous films of 4 are soluble in common solvents, and the air bubbles are interconnected. Upon heating to 300 degrees C, 4 cross-links and the thin film turn into insoluble matrix with isolated bubbles. The cross-linking process has transformed the bubble arrays of 4 into insoluble picoliter beakers or picoliter vials, whose diameters are approximately 3.0 and 1.5 mum at the top and bottom, respectively.