Synthesis of new thermosetting poly(2,6‐dimethyl‐1,4‐phenylene oxide)s containing epoxide pendant groups

A new class of thermosetting poly(2,6‐dimethyl‐1,4‐phenylene oxide)s containing pendant epoxide groups were synthesized and characterized. These new epoxy polymers were prepared through the bromination of poly(2,6‐dimethyl‐1,4‐phenylene oxide) in halogenated aromatic hydrocarbons followed by a Wittig reaction to yield vinyl‐substituted polymer derivatives. The treatment of the vinyl‐substituted polymers with m‐chloroperbenzoic acid led to the formation of epoxidized poly(2,6‐dimethyl‐1,4‐phenylene oxide) with variable pendant ratios, and the structures and properties were studied with nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, and gel permeation chromatography. The ratios of pendant functional groups were tailored for the polymer properties, and the results showed that the glass‐transition temperatures increased as the benzylic protons were replaced by bromo‐, vinyl‐, or epoxide‐functional groups, whereas the thermal stability decreased in comparison with the original polymer. Within a molar fraction of 20–50%, the degree of functionalization had little effect on the glass‐transition temperature; however, it correlated inversely with the thermal stability of each functionalized polymer. The thermal curing behavior of the epoxide‐functionalized polymer was enhanced by the increment of the pendant functionality, which resulted in a significant increase in the glass‐transition temperature as well as the thermal stability after the curing reaction. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5875–5886, 2006     

Synthesis and characterization of 6-O-acyl-2-O-alpha-D-glucopyranosyl-L-ascorbic acids with a branched-acyl chain

We previously reported the chemical synthesis of a series of novel monoacylated vitamin C derivatives, 6-O-acyl-2-O-alpha-D-glucopyranosyl-L-ascorbic acids (6-Acyl-AA-2G) possessing a straight-acyl chain of varying length from C(4) to C(18), as effective skin antioxidants. In this paper, we describe branched type of 6-Acyl-AA-2G derivatives (6-bAcyl-AA-2G) synthesized by use of a 2-branched-chain fatty acid anhydride as an acyl donor. The stability of 6-bAcyl-AA-2G in neutral solution was much higher than that of 6-Acyl-AA-2G, while they were susceptible to enzymatic hydrolysis for exerting vitamin C effect. These branched derivatives as well as 6-Acyl-AA-2G increased the radical scavenging activity against 1, 1-diphenyl-2-picrylhydrazyl and the lipophilicity in octanol/water-partitioning systems with increasing length of their acyl group. In addition, the 6-bAcyl-AA-2G derivative with an acyl chain of C(12), 6-bDode-AA-2G had the excellent solubility to various solvents, suggesting easy handling in cosmetic use. These characteristics of 6-bAcyl-AA-2G may be available for skin care application as an effective antioxidant.     

An Enzyme-Bound Bisubstrate Hybrid Inhibitor of Adenylosuccinate Synthetase

Two relatively weak herbicides, hydantocidin phosphate and hadacidin were linked by a C(3) chain to afford a potent inhibitor (the 2S hybrid is shown) of the enzyme adenylosuccinate synthetase. The crystal structures of the bisubstrate-enzyme complexes were determined.     

Self-consistent density functional calculation of field emission currents from metals

We have developed a fully self-consistent method which is suitable to examine field emission currents, on the basis of the density functional theory. In our method, the nearby counterelectrode is not necessary. By using this method, we have investigated field emission currents from a biased metallic surface represented by the jellium model. We have found that the energy barrier between the jellium and vacuum becomes lower than the Fermi energy under strong electric fields (e.g., 10 V/nm for r(s) = 4 bohr). In this situation, the slope of the Fowler-Nordheim plot becomes flatter than that under a weaker field.     

A synthesis and some reactions of 2-thiocyanato-2-ethylenic carbonyl compounds

A synthesis of 2-thiocyanato-2-ethylenic carbonyl compounds was achieved by the reaction of epoxy ketones with Ph₃P(SCN)₂ (TPPT). Some useful transformations of 2-thiocyanato-2-cyclohexenone to 2,3-disubstituted cyclohexanones and iminothiazolines are described.     

Two-dimensional intrinsic ferromagnetism at nitride-boride interfaces

We predict theoretically novel two-dimensional interface ferromagnetism at AlN/MgB(2)(0001) using first-principles calculations, where the interface is employed as an ordered structure of spin sites instead of point defects. Although N dangling bonds are apparently saturated, interfacial states exhibit spin polarization. Hund's coupling of the two N p(∥) orbitals as well as low density of states at the Fermi energy contribute to strong band ferromagnetism. Furthermore, first-principles electron transport calculations demonstrate that this interfacial spin polarization is responsible for quantum spin transport. The magnetization can be controlled by applied gate bias voltages.     

Dependence of the Schottky barrier on the work function at metal/SiON/SiC(0001) interfaces identified by first-principles calculations

We report investigations based on density functional theory that clarify the dependence of the Schottky barrier height (SBH) on the work function of metals at metal/SiON interfaces formed on the 6H-SiC(0001) surface. We have found that the density of atoms in the Al layer affects neither its work function nor the SBH formed when the layer contacts with the SiON surface. More importantly, the SBH for the B overlayer is lower compared with that for the Al layer, reflecting a difference in the work function of the layers. The present result clearly indicates that Fermi-level pinning does not occur for SiON on SiC(0001), which means that the SBH is controllable for metal/SiON/SiC systems by changing the work function of metals.