Notes on probabilistic radiative transfer

Some further applications are made of Frischs' theorem on the surface values of functions satisfying linear integral equations of transfer. The meaning of the surface values is discussed in terms of random walks.     

An ab initio description of the excited states of the reaction O(3P, 1D) + H2 → OH(2Π, 2Σ+) + H. An attempt to describe several potential energy surfaces with constant accuracy

A new aspects of the role of the solvent mode in the photoinduced electron-transfer process of electron donor and acceptor system in polar solvents has been exploited. Taking into account the important fact that the vibrational frequency of the solvent mode in the initial neutral state of the reactants is considerably smaller than that in the final ionic state, we have derived a new formula for the energy-gap dependence of the electron-transfer rate. In this formulation, the activation energy is greatly reduced and the electron-transfer rate is almost independent of the energy gap over a wide down-hill energy region. This qualitative feature explains the experimental results for the relation between the bimolecular quenching rate constant k_w and the standard free-energy change ΔG° associated with electron transfer in the “anomalous region”.     

An efficient nonisocyanate route to polyurethanes via thiol‐ene self‐addition

A novel and efficient strategy for the synthesis of nonisocyanate polyurethanes has been developed via thiol–ene self‐photopolymerization. An aliphatic thiol–ene carbamate monomer (allyl(2‐mercaptoethyl)carbamate, AMC) was synthesized by a one‐step synthesis procedure, from cysteamine and allyl chloroformate. The urethane group was therefore incorporated directly into the monomer precursor, avoiding the problems associated to toxic isocyanates. AMC was successfully stabilized with the radical inhibitor pyrogallol (1% wt). In addition, the use of phenyl phosphonic acid as coadditive allowed its stabilization for lower concentrations of pyrogallol (0.1% wt). AMC was directly transformed into thermoplastic polyurethane (TPU) through thiol–ene photopolymerization by UV‐irradiation at 365 nm. The obtained TPU presented semi‐crystalline nature and very high thermal stability (T_5% ～325 °C). It was found that high concentrations of pyrogallol decreased the reaction rate and final conversion of photopolymerization. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3017–3025     

NOUVEAUX DÉCONTAMINANTS. ACTION DU MONOPERPHTALATE DE MAGNÉSIUM (MPPM) SUR QUELQUES INSECTICIDES ET TOXIQUES DE GUERRE ORGANOPHOSPHORÉES OU ORGANOSOUFRÉS

Abstract

Magnesium monoperoxyphthalate (MMPP) is a good decontaminant reagent when it is used in alcoholic solvent. Paraoxon (O,O-diethyl O-paranitrophenyl phosphate) but specially VX [O-ethyl S-(2-diiso-propylaminoethyl)] methylphosphonothiolate and HD (2,2′-dichlorodiethyIsulfide) react with MMPP completely in a very short time.

Le monoperphtalate de magnesium (MPPM) est un bon agent de décontamination lorsqu'il est utilisé en milieu alcoolique. Le Paraoxon (O.O-diéthyl O-paranitrophenyl phosphate) mais surtout le VX [O-éthyl S-(diisopropylaminoéthyl-2)] méthylphosphonothiolate et l'ypérite (HD) (dichloro-2.2′diéthyl-sulfure) réagissent de faFon totale avec le MPPM en un temps très court.     

Synthesis of (2-Furyl)Aminomethanephosphonic Acids Derivatives

Abstract

Synthetical aspects of furylaminophosphonic acids are discussed here.     

Bis­[(R)‐1‐phenyl­ethyl isocyanido](5,10,15,20‐tetrakis{2,6‐bis[(S)‐2,2‐di­methyl‐1,3‐dioxolan‐4‐yl­methyl­oxy]­phenyl}­porphyrin)­ruthenium(II) at 110 K

The geometry about the Ru atom in the title compound, [Ru(C₉H₉N)₂(C₉₂H₁₀₈N₄O₂₄)], is approximately tetragonal and the porphyrin ring is nearly planar, while the C—N—R angles [169.3 (3) and 163.9 (3)°] of the isocyanide ligands in the complex are different from the value of 180° expected in the free ligand.     

Spectroscopic characterization of a high-potential lipo-cupredoxin found in Streptomyces coelicolor

For many streptomycetes, a distinct dependence on the "bioavailability" of copper ions for their morphological development has been reported. Analysis of the Streptomyces coelicolor genome reveals a number of gene products encoding for putative copper-binding proteins. One of these appears as an unusual copper-binding protein with a lipoprotein signal sequence and a cupredoxin-like domain harboring a putative Type-1 copper-binding motif. Cloning of this gene from S. coelicolor and subsequent heterologous expression in Escherichia coli has allowed for a thorough spectroscopic interrogation of this putative copper-binding protein. Optical and electron paramagnetic resonance spectroscopies have confirmed the presence of a "classic" Type-1 copper site with the axial ligand to the copper a methionine. Paramagnetic NMR spectroscopy on both the native Cu(II) form and Co(II)-substituted protein has yielded active-site structural information, which on comparison with that of other cupredoxin active sites reveals metal-ligand interactions most similar to the "classic" Type-1 copper site found in the amicyanin family of cupredoxins. Despite this high structural similarity, the Cu(II)/(I) midpoint potential of the S. coelicolor protein is an unprecedented +605 mV vs normal hydrogen electrode at neutral pH (amicyanin approximately +250 mV), with no active-site protonation of the N-terminal His ligand observed. Suggestions for the physiological role/function of this high-potential cupredoxin are discussed.