Catalytic C-h/olefin coupling

The cleavage and addition of ortho C-H bonds in various aromatic compounds such as ketones, esters, imines, imidates, nitrile, and aldehydes to olefins and acetlylenes can be achieved catalytically with the aid of ruthenium catalysts. The reaction is generally highly efficient and useful in synthetic methods. The coordination to the metal center by a heteroatom in directing groups such as carbonyl and imino groups is the key. The reductive elimination to form a C-C bond is the rate-determining step.     

Ammonia assimilation in Klebsiella pneumoniae F-5-2 that can utilize ammonium and nitrate ions simultaneously: purification and characterization of glutamate dehydrogenase and glutamine synthetase

The two ammonia-assimilating enzymes glutamate dehydrogenase (GDH; EC 1.4.1.4) and glutamine synthetase (GS; EC 6.3.1.2) were synthesized steadily during the cell growth of Klebsiella pneumoniae F-5-2 that can utilize NH4+ and NO3- simultaneously under aerobic conditions. The enzymes were purified to homogeneity from cell extracts and characterized. The molecular mass of the purified GDH was 300 kDa with six identical 52-kDa subunits. GDH showed its maximal activity (aminating) at pH 8.0 and was stable between pHs 5.5 and 11.5. The enzyme was NADP-specific and strongly inhibited by Ag+. It catalyzed the amination of 2-ketovalerate, 2-ketoadipate, and 2-ketobutyrate, in addition to 2-ketoglutarate. The purified GS has a molecular mass of 470 kDa with eight identical 60-kDa subunits. GS showed its maximal activity at pH 8.0 and was stable between pHs 6.0 and 7.0. The enzyme was strongly inhibited by Fe3+, Hg2+, and Cu2+.     

Stability tests and stabilization for piecewise linear systems based on poles and zeros of subsystems

This paper provides several stability tests for piecewise linear systems and proposes a method of stabilization for bimodal systems. In particular, we derive an explicit and exact stability test for planar systems, which is given in terms of coefficients of transfer functions of subsystems. Restricting attention to the bimodal and planar case, we show simple stability tests. In addition, we drive a necessary stability condition and a sufficient stability condition for higher-order and bimodal systems. They are given in terms of the eigenvalue loci and the observability of subsystems. All the stability tests provided in this paper are computationally tractable, and our results are applied to the stabilizability problem. We confirm the exactness and effectiveness of our approach by illustrative examples.     

Spontaneous hydrolytic degradability of copolyesters having tetrahydropyran rings in their backbones

Homo- and copolyesters, containing 2,5-linked tetrahydropyran rings in their backbones, were prepared by cationic ring-opening polymerization of bicyclic lactones, 2,6-dioxabicyclo [2.2.2] octan-3-one ( 1 ), and its 4-methoxy-carbonyl and 4-methoxy-carbonyl and 4-benzyloxycarbonyl derivatives ( 3 and 4 ). Copolyesters, having pendant carboxyl groups, were derived from the copolymers containing 4 as one of the comonomers by the catalytic hydrogenolysis of the pendant benzyloxy–carbonyl groups. Copolyesters, containing both 2,5-linked and 2,6-linked tetrahydropyran rings in the main chains, were obtained by the copolymerization of 1 with 6,8-dioxabicyclo [3.2.1] octan-7-one ( 13 ), which is a structural isomer of 1 . Spontaneous hydrolytic degradability of these polyesters was investigated in a phosphate buffer solution (pH 7.5) at 27°C. The degradability of the polyesters markedly depended on the molecular structure: hydrophobic pendant groups retarded the hydrolytic degradation, whereas hydrophilic pendant groups accelerated it. In particular, a small amount of pendant carboxyl groups significantly enhanced the hydrolytic degradability of the copolyesters from 1 . Polyesters, containing 2,6-linked tetrahydropyran rings in their backbones, underwent hydrolytic degradation more readily than those entirely consisting of 2,5-linked tetrahydropyran rings. © 1994 John Wiley & Sons, Inc.     

Far-infrared laser oscillation due to cyclotron emission in p-type germanium

Far-infrared laser oscillation due to cyclotron emission in the light hole band of p-type germanium was observed under crossed electric and magnetic fields. The wavelength is inversely proportional to magnetic fields with a cyclotron mass ofm _c =0.048m _c . Numerical calculations based on Luttinger Hamiltonian show that mixing of wavefunctions between the light and heavy hole bands causes population inversion betweenn=0 andn=1 light-hole Landau levels. It is also shown that non-equidistant energy spacing of light-hole Landau levels is essential to yield net amplification.     

Measurement and correlation of mutual diffusion coefficients for styrene-butadiene rubber(SBR)-n-nonane systems

The mutual diffusion coefficients for styrene-butadiene rubber(SBR)-n-nonane systems were measured using a sorption apparatus with a quartz spring at 100 and 130°C for mass fractions of n-nonane ranging from 0 to 0.16. The mutual diffusion coefficients were correlated with good agreement by the free-volume theory.     

Giant room-temperature magnetoresistance in single-crystal Fe/MgO/Fe magnetic tunnel junctions

The tunnel magnetoresistance (TMR) effect in magnetic tunnel junctions (MTJs) is the key to developing magnetoresistive random-access-memory (MRAM), magnetic sensors and novel programmable logic devices. Conventional MTJs with an amorphous aluminium oxide tunnel barrier, which have been extensively studied for device applications, exhibit a magnetoresistance ratio up to 70% at room temperature. This low magnetoresistance seriously limits the feasibility of spintronics devices. Here, we report a giant MR ratio up to 180% at room temperature in single-crystal Fe/MgO/Fe MTJs. The origin of this enormous TMR effect is coherent spin-polarized tunnelling, where the symmetry of electron wave functions plays an important role. Moreover, we observed that their tunnel magnetoresistance oscillates as a function of tunnel barrier thickness, indicating that coherency of wave functions is conserved across the tunnel barrier. The coherent TMR effect is a key to making spintronic devices with novel quantum-mechanical functions, and to developing gigabit-scale MRAM.     

Three-dimensional expression of adhesion molecules on the superficial synovial intima of LPS-induced arthritis of the mouse knee analyzed by immuno-SEM

Three-dimensional microlocalization of adhesion molecules, i.e. ICAM-1 (intercellular adhesion molecule), VCAM-1 (vascular adhesion molecule), LFA-1 (lymphocyte function-associated antigen), Mac-1 (macrophage differentiation antigen) and VLA-4 (very late activation antigen), expressed on type-A synoviocyte (macrophage-like cell) and type-B synoviocyte (fibroblast-like cell), were detected by immuno-scanning electron microscopy (SEM) to investigate the immunoreactive microenvironment of the superficial synovial intima in lipopolysaccharide (LPS)-induced arthritis of the mouse knee. Type-B synoviocytes extended rich slender processes from the periphery and constructed a cytoplasmic network, to which ICAM-1 was restricted. VCAM-1 was expressed only in the LPS-stimulated group and was relatively limited to the microvilli of type-B synoviocytes. Type-A synoviocytes were located randomly among the network with a smoother surface and expressed Mac-1 and LFA-1, which were counter-receptors for ICAM-1, and VLA-4 for VCAM-1 on the microvilli or lamellipodia. Three-dimensional microlocalization of adhesion molecules suggests that the network constructed by cytoplasmic processes and microvilli of type-B synoviocytes forms the pathway for the migration or the foothold for the fixation of type-A synoviocytes and takes part in forming an immunoreactive environment in the articular cavity.     

Rate of emulsion polymerization of styrene

In emulsion polymerization, the Smith and Ewart theory gives about two or three times the number of polymer particles obtained by experiment. In this paper, a reaction model is proposed which, from the standpoint of reactor design, can give an adequate explanation of the whole course of an emulsion polymerization of monomer highly insoluble in water. Among other things, the generating process of polymer particles is examined in detail. It is demonstrated experimentally that a new parameter proposed here, which represents the degree of difficulty of monomer initiation in micelles, is indispensable in explaining that process. Also confirmed is that monomer initiation takes place more easily in polymer particles than in micelles. According to the new model, the progress of polymerization, i.e., monomer conversion, the number of the polymer particles, and properties of polymer thus produced can be estimated with satisfactory accuracy. Furthermore, approximate equations are derived for easier estimation.