Stabilization of p-Phenylenebis(N-tert-butylaminoxyl) Relative to p-Benzoquinonediimine N,N′-Dioxide

Steric interactions between methoxy and tert -butyl groups are the reason that 2 only exists as p-phenylenebis(N-tert-butylaminoxyl) B . The p-phenylenebis(N-tert-butylaminoxyl) 1 has the p-quinonediimine N,N′-dioxide structure Q in solution as well as in the crystalline state.     

Synthesis of reactive aromatic polyesters having pendant chlorohydrin moieties

A monomer containing a chlorohydrin moiety, propyl chlorohydrin diphenolate (PCHDP), was synthesized. Reactive polyesters having these pendant chlorohydrin moieties were prepared by the interfacial polycondensation of isophthaloyl chloride with PCHDP or with PCHDP and diphenolic acid using phase transfer catalyst. The molar ratio of reactants and the phase ratio of water to organic solvent strongly affect the molecular weight of resulting polymers and polymers with high molecular weight are obtained at the molar ratio of 1.0–1.15 and the phase ratio of 2.0–3.5. Swelling of the growing polymers is dependent on the molar ratio of the reactants and the phase ratio because of the hydrophilic and hydrophobic nature of the pendant chlorhydrin moiety. The resulting polymers are not soluble in any solvent except water in which hydrolysis occurs. Thus so, the structure of polymers was confirmed by ¹³C CP/MAS NMR. © 1996 John Wiley & Sons, Inc.     

Surface roughness assisted 100 kHz femtosecond laser induced nanostructure formation on silicon surface

Spontaneous nanostructure formations on roughened and smooth silicon surface by the femtosecond laser irradiation with the repetition rate of 100 kHz were systematically studied. In addition to the widely accepted so-called coarse ripple, which has the period analogous to the wavelength of the laser beam and aligns perpendicularly to the electric field of the incident laser beam, the ripple which has the period similar to the wavelength of the incident laser beam but aligns parallel to the electric field of the laser beam was observed on the roughened surface for the lower fluence and the higher number of pulse irradiation. Furthermore, the ensemble of dots formed by the enhancement of the local electric field was found on the roughened surface. This structure is preferentially formed around the scratches aligned perpendicularly to the electric field of the laser beam. These novel nanostructures are considered to be peculiar to the femtosecond laser irradiation and open the possibilities for precise control of the spontaneous nanostructure formation by femtosecond laser irradiation.     

Estimation of active conformations of drugs by a new molecular superposing procedure

We have developed a new program, SUPERPOSE, to superpose two molecules based on the physicochemical properties of functional atoms within individual molecules. SUPERPOSE treats a pseudo-molecule consisting of functional atoms instead of a real molecule. Four types of physicochemical properties – hydrophobicity, presence of a hydrogen-bonding donor, presence of a hydrogen-bonding acceptor and presence of a hydrogen-bonding donor/acceptor – were supposed and a score was given to each overlap. When functional atoms with the same physicochemical properties were overlapped, points were added to the score, and when the functional atoms with different physicochemical properties were overlapped, points were subtracted. We applied SUPERPOSE to 12 pairs of 24 enzyme inhibitors and found that the best scored overlay for each inhibitor pair could successfully reproduce the superposition obtained from X-ray crystallography. Next, we applied SUPERPOSE to estimate the active conformations of the thrombin inhibitors MQPA, 4-TAPAP and NAPAP. Superpositions of conformers sampled by the high-temperature molecular dynamics calculation with respect to the three inhibitors were performed, and 13 sets of conformers having the best common overlay to the three inhibitors were selected. One among 13 sets was consistent with the superposition of the active conformations derived from the X-ray crystallography of the thrombin–inhibitor complexes.     

An experimental investigation of the stability of converging cylindrical shock waves in air

An experimental study was made of the stability of converging cylindrical shock waves. The experiments were conducted on annular shock tubes equipped with a double exposure holographic interferometer in the Stoßwellenlabor, RWTH Aachen, and in the Institute of High Speed Mechanics, Tohoku University, Sendai, for shock Mach numbers of 1.1 to 2.1 in air. By comparing these two different shock tube experiments, it is found that in the former facility the mode-three instability is predominant at the center of convergence, whereas the mode-four instability appears in the latter setup. The instabilities are denoted in this way because the shock and the flow field behind it reveal a remarkable triangular and quadrangular symmetry, respectively. It is concluded that the converging cylindrical shock wave is always unstable and sensitive to the structure of the annular shock tube. Usefulness of holographic interferometry to this kind of shock wave research is also demonstrated.To Prof. Dr. sq. techn. Dr.-Ing. e.h. Fritz Schultz-Grunow on the occasion of his 80th birthday     

Enzyme‐catalyzed polymerization of L‐aspartate

Diethyl L ‐aspartate was polymerized by proteinase at a temperature between 4 and 50°C to yield poly(ethyl α,β‐L ‐aspartate). Bulk polymerization of diethyl L ‐aspartate, especially at temperatures between 40 and 50°C, and preferably using alkalophilic proteinase with the addition of a small amount of water gave poly(ethyl L ‐aspartate) as a white powder with a molecular weight of up to 3 600 and having about 88% α‐linkages.