ESR Study of a Nitroxide Radical in Sol-Gel Glasses

A spin probe TEMPOL (4-hydroxy-2,2,6,6-tetramethylpiperidinyl-1-oxy) was dissolved in a tetraethyl orthosilicate sol-gel reaction system and measured by electron spin resonance spectroscopy at 295 K. The nitrogen hyperfine coupling constant was from 1.64–1.66 mT in the sol-gel solutions. The values were sensitive to the ethanol-to-water ratio of the solutions. The hyperfine coupling constant in the xerogels was 1.70 mT, which was almost the same as that in water, indicating that the probe molecules were trapped in silica pores with water adsorbed on the silica surfaces. The motion of TEMPOL in the xerogels was considerably slower than in the sol-gel solutions. The local viscosity estimated was from 70–90 cP. The ESR spectra of TEMPOL were altered during the sol-gel process, indicating that adsorbed water on the silicas surfaces has an important role for trapping organic molecules in sol-gel glasses.     

Strong lateral growth and crystallization via two-dimensional allotropic transformation of semi-metal Bi film

Two-dimensional (2D) nano-objects, such as metallic nanofilms are the most fundamental building blocks for nanoelectronics devices. However, the fabrication of highly ordered nanofilms has been difficult because of well known Stranski-Krastanov growth, which results in rough growth front and high density grains. Here we report on the unusual high-quality film growth of Bi on a Si surface with atomic-level surface/interface smoothness and high film crystallinity. The formation of a newly discovered 2D allotrope was clarified to initiate its strong 2D growth. Above several-monolayer thickness, the 2D allotrope transforms into a single-crystalline film with bulk-like layered structure. Our study unveils the atomistic growth process of nano-sized Bi, and the obtained knowledge here will be generally applicable for the fabrication of various nano-devices using this intriguing material that shows rich thermal, magnetic, electronic properties in nanometer scale.     

Pulsed NMR study of the curing process of epoxy resin

To analyze a curing process of epoxy resin in terms of molecular motion, we adapted a pulsed NMR method. Three kinds of (1)H spin-spin relaxation times (T(2L) (long), T(2S) (short) and T(2M) (intermediate)) were estimated from observed solid echo train signals as the curing process proceeded. A short T(2S) value below 20 micros suggests the existence of a motion-restricted chain, that is, cured elements of resin, and its fraction, P(S), sigmoidally increased with the curing time. On the other hand, the fraction of T(2L), P(L), decreased with the reaction time reciprocally against P(S), suggesting the disappearance of highly mobile molecules raised from pre-cured resin. The spin-lattice relaxation time, T(1), was also measured to check another aspect of molecular motion in the process. T(1) of the mixed epoxy resin and curing agent gradually increased just after mixing both of them. This corresponds to an increment of a less-mobile fraction, of which the correction time is more than 10(-6) s, and also means that the occurrence of a network structure whose mobility is strongly restricted by chemically bonded bridges between the epoxy resin and curing agent. The time courses of these parameters coincided with those of IR peaks pertinent to the curing reaction. Therefore, pulsed NMR is a useful tool to monitor the hardening process of epoxy resin in real time non-distractively in terms of the molecular motion of protons.     

Effects of Microcrystalline Cellulose on Suspension Stability of Cocoa Beverage

The rheological properties and particle size distributions of cocoa beverage as well as aggregate structures of solid particles were studied to elucidate the effects of microcrystalline cellulose (MCC) on suspension stability of solid particles in cocoa beverage. Fluidity curve, dynamic viscoelasticity, particle size distribution, and SEM observation were made for beverage samples containing 0.1–0.5 wt% MCC and 11 model samples with various combinations of six ingredients. This revealed that cocoa and MCC particles are highly cohered into an aggregate and the aggregated particles further interact weakly with the milk component, leading to stabilization of the whole system of cocoa beverage.     

One-dimensional plasmon in an atomic-scale metal wire

We have measured one-dimensional (1D) plasmons in an atom wire array on the Si(557)-Au surface by inelastic scattering of a highly collimated slow electron beam. The angular dependence of the excitation energy clearly indicates the strong 1D confinement and free propagation of the plasma wave along the wire. The observed plasmon dispersion is explained very well by a quantum-mechanical scheme which takes into account dynamic exchange-correlation effects, interwire interactions, and spin-orbit splitting of the 1D bands. Although the qualitative feature of the plasmon dispersion is reminiscent of that of a high-density free-electron gas, we detected the substantial influence of electron correlation due to strong 1D confinement.     

Spin-lattice relaxation behaviour of water in cellulose materials in relation to the tablet forming ability of microcrystalline cellulose particles

Medical tablet forming ability of microcrystalline cellulose (MCC) was investigated in relation to the mobility of water molecules in MCC particles. For this purpose, the spin-lattice relaxation time T1 of water in the system was measured by 1H-NMR. Over a wide range of water contents (0.02 H2O/cellulose (g/g) 1.79), two different T1 (T1,l and T1,s) values were observed for water in each MCC sample. Below the equilibrium water content, water having these two different T1 values exchange with each other in an MCC particle reaching an equilibrium state within a given time scale (equilibrium constant K). The T1,l, T1,s and K values for water in MCC, estimated at the equilibrium water content, showed fairly good correlations with the hardness of the tablets made by the MCC samples. Sample with a shorter T1, or larger K tended to have a stronger tablet forming ability. In the spin-spin relaxation time T2 measurements for protons in an MCC/D2O system, two T2 components originating from the glassy cellulose solid (T2,G) and the swelling region (T2,l) were observed. It was found that the mole fraction xL of protons with T2,L in the system exhibits a clear linear correlation with K. From these results, a structural model for the distribution of water in MCC particles was propoed by taking the surface of each microfibril and the disordered region within the microfibril into consideration