Asymmetric reduction of 2-substituted 2-butenolides with reductase from Marchantia polymorpha

A p68 reductase participating in the asymmetric reduction of the C–C double bond of 2-substituted 2-butenolides was isolated from Marchantia polymorpha. The enzyme reduced 2-substituted 2-butenolides to give (R)-butanolides, and the reduction of citraconic anhydride afforded (R)-methylsuccinic anhydride.     

Novel UV‐induced photografting process for preparing poly(tetrafluoroethylene)‐based proton‐conducting membranes

A novel process comprising the UV‐induced photografting of styrene into poly(tetrafluoroethylene) (PTFE) films and subsequent sulfonation has been developed for preparing proton‐conducting membranes. Although under UV irradiation the initial radicals were mainly generated on the surface of the PTFE films by the action of photosensitizers such as xanthone and benzoyl peroxide, the graft chains were readily propagated into the PTFE films. The sulfonation of the grafted films was performed in a chlorosulfonic acid solution. Fourier transform infrared and scanning electron microscopy were used to characterize the grafted and sulfonated membranes. With a view to use in fuel cells, the proton conductivity, water uptake, and mechanical properties of the prepared membranes were measured. Even through the degree of grafting was lower than 10%, the proton conductivity in the thickness direction of the newly prepared membranes could reach a value similar to that of a Nafion membrane. In comparison with γ‐ray radiation grafting, UV‐induced photografting is very simple and safe and is less damaging to the membranes because significant degradation of the PTFE main chains can be avoided. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2624–2637, 2007     

Mechanism of catalytic asymmetric hydrogenation of 2-formyl-1-methylene-1,2,3,4-tetrahydroisoquinoline using Ru(CH3COO)2[(S)-binap]

The mechanism of the asymmetric hydrogenation of 2-acyl-1-alkylidene-1,2,3,4-tetrahydroisoquinolines, the first reported reaction with the Noyori-Takaya Ru(CH₃COO)₂(binap) complex, has been investigated by means of deuterium labeling, kinetics, and NMR analysis. A series of experiments has revealed that (1) a monohydride-unsaturated mechanism operates involving the initial formation of RuH followed by reaction with the enamide substrate, (2) the hydride transfer from RuH to the olefinic double bond is endothermic and reversible, and (3) the rate is determined in the hydrogenolysis step. This view is consistent with that of proposed for the BINAP-Ru catalyzed Kagan reaction.     

Strained silacycle-catalyzed asymmetric Diels-Alder cycloadditions: the first highly enantioselective silicon Lewis acid catalyst

The first highly enantioselective silicon Lewis acid catalyst for an asymmetric organic transformation has been developed. The catalyst derives its activity from the strain induced in the silicon center by virtue of being constrained in a five-membered ring. A simple tridentate ligand has been developed and the derived chlorosilane complex catalyzes the Diels-Alder cycloaddition of methacrolein and cyclopentadiene with 94% ee.     

Method of observation of low density interface states by means of X-ray photoelectron spectroscopy under bias and passivation by cyanide ions

X-ray photoelectron spectroscopy (XPS) measurements under bias can observe low density interface states for metal-oxide-semiconductor (MOS) diodes with low densities. This method can give energy distribution of interface states for ultrathin insulating layers for which electrical measurements cannot be performed due to a high density leakage current. During the XPS measurements, a bias voltage is applied to the rear semiconductor surface with respect to the ∼3 nm-thick front platinum layer connected to the ground, and the bias voltage changes the occupation of interface states. Charges accumulated in the interface states shift semiconductor core levels at the interface, and thus the analysis of the bias-induced shifts of the semiconductor core levels measured as a function of the bias voltage gives energy distribution of interface states. In the case of Si-based MOS diodes, the energy distribution and density of interface states strongly depend on the atomic density of silicon dioxide (SiO₂) layers and the interfacial roughness, respectively. All the observed interface state spectra possess peaked-structures, indicating that they are due to defect states. An interface state peak near the Si midgap is attributable to isolated Si dangling bonds at the interface, while those above and below the midgap to Si dangling bonds interacting weakly with Si or oxygen atoms in the SiO₂ layers. A method of the elimination of interface states and defect states in Si using cyanide solutions has been developed. The cyanide method simply involves the immersion of Si in KCN solutions. Due to the high Si-CN bond energy of ∼4.5 eV, the bonds are not ruptured at 800 °C and upon irradiation. The cyanide treatment results in the improvement of the electrical characteristics of MOS diodes and solar cells.     

Inductively-coupled plasma/atomic emission spectrometry of sulfur with a vacuum scanning spectrometer and its application to the analysis of coal liquefaction catalysts

Inductively-coupled plasma/atomic emission spectrometry with a high-resolution vacuum scanning monochromator is described for the determination of sulfur at 180.734 nm. The behavior of the signal-to-background ratio is investigated as functions of RF power, argon gas flow rate and observation height above the load coil. Under the operating conditions selected, the detection limit is 3 μg l^?1. The Se I 196.090-nm line is chosen as internal standard, because the S/Se line pair exhibited the least change with carrier gas flow rate and acid concentration of solution. Sulfur in NiMo and CoMo/ Al₂O₃ catalysts used for coal liquefaction is determined as S(II) and S(VI) species. The total amount of the species agreed well with the sulfur value obtained by the conventinal combustion method.