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 21,279 document(s) hit in 31,850,051 MEDLINE articles (0.00 seconds)

Several metal complexes [(FeII(DPAH)2 (DPAH2 = 2,6-dicarboxyl pyridine), FeII(PA)2 (PAH = picolinic acid), FeII(bpy)2(2+), FeII(OPPh3)4(2+), (Cl8TPP)FeIIIX (X = Cl, OH, SCH2Ph) [Cl8TPP = tetrakis (2,6-dichlorophenyl)porphyrin], (TPP) FeIIICl (TPP = tetraphenylporphyrin), and CuI(tpy)2+ (typ = 2,2'-6,2"-terpyridine)] in combination with one of several reductants [DH2; PhNHNHPh (mimic of dihydroflavin), PhNHNH2, ascorbic acid (H2asc), and PhCH2SH (model ligand for cysteine residue)] catalytically activate O2 (1 atm) for the hydroxylation of saturated hydrocarbons (e.g. c-C6H12-->c-C6H11OH). This chemistry closely parallels that of cytochrome P-450 proteins, and both appear to involve a Fenton-like reactive intermediate), [LxFeOOH(DH)]. With cyclohexane as the substrate the dominant product is its ketone (as well as significant amounts of its hydroperoxide). 1,4-Cyclohexadiene (with two double-allylic carbon centers) undergoes dehydrogenation to give benzene, but also yields substantial amounts of phenol via ketonization of an allylic carbon. The 1:1 FeII(bpy)2(2+)/(PhNHNH2 or H2asc), FeII(PA)2/H2asc, and (Cl8TPP)FeIIICl/PhNHNH2 combinations initiate the autoxidation of 1,4-cyclohexadiene with turnover numbers (moles of product per mole of reductant) from 71 to 26, respectively (alpha-tocophenol reduces the turnover numbers by 20-80%). With respect to aerobic biology, the present results indicate that dysfunctional transition metals (degradation products of metalloproteins) in combination with biological reductants activate O2 for reaction with organic substrates. The level of activation is similar to that for Fenton reagents and cytochrome P-450 hydroxylases. Hence, dysfunctional transition metals, reductants, and O2 are a hazardous combination within a biological matrix.
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PMID:Iron(II)/reductant(DH2)-induced activation of dioxygen for the hydroxylation and ketonization of hydrocarbons; mimics for the cytochrome P-450 hydroxylase/reductase system. 778 1

The infrared absorption spectra of the carbonyl stretching vibrations of 2-acetylthiophene (AcTh) have been investigated in cyclo-hexane/alcohol mixtures (C6(12/C2H5OH; (6H12/n-C4H9OH; C6H12/i-C3H7OH and C6H12/t-C5H11OH). Five types of carbonyl stretching vibration bands for AcTh are found with the change of the mole fraction of the aprotic solvent C6H12 (x(C6H12)) in binary solvent mixtures. The dependencies of the frequencies of carbonyl stretching vibrations (nu(C=O)) on x(C6H12) allow a distinction and assignment of all species resulting from the solvent-solute interactions. Linear correlations between the nu(C=O) of each species and x(C6H12) are found. The influence on the transformation of some species caused by the self association of alcohols is discussed.
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PMID:Infrared study on solvent-solute interactions of 2-acetylthiophene in binary mixtures. 1467 May 4

The infrared spectroscopy studies of the C3 and C20 carbonyl stretching vibrations (upsilon(C=O)) of progesterone in CHCl3/cyclo-C6H12 binary solvent systems were undertaken to investigate the solute-solvent interactions. With the mole fraction of CHC13 in the binary solvent mixtures increase, three types of C3 and C20 carbonyl stretching vibration band of progesterone are observed, respectively. The assignments of upsilon(C=O) of progesterone are discussed in detail. In the CHCl3-rich binary solvent systems or pure CHCl3 solvent, two kinds of solute-solvent hydrogen bonding interactions coexist for C20 C=O. Comparisons are drawn for the solvent sensitivities of upsilon(C=O) for acetophenone and 5alpha-androstan-3,17-dione, respectively.
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PMID:Solvent effects on infrared spectra of progesterone in CHCl3/cyclo-C6H12 binary solvent systems. 1705 77

Electronic absorption and emission spectra of 10-bis(phenylethynyl)anthracene (PEA) and coumarin 153 (C153) are measured as functions of composition along the bubble-point curve at 25 degrees C in CO2-expanded cyclohexane (c-C6H12), acetonitrile (CH3CN), and methanol (CH3OH). The nonlinear dependence of the spectral frequencies on composition suggests substantial preferential solvation of both solutes by the liquid components of these mixtures. Estimates of enrichment factors (local mole fraction of a component divided by its bulk value) based on the assumption that spectral shifts are linearly related to local composition are quite large (approximately 10) in the cases of the C153/CH3CN + CO2 and C153/CH3OH + CO2 systems at high xCO2. Computer simulations of anthracene, the chromophore of PEA, and C153 in these three CO2-expanded liquids are used to clarify the relationship between local composition and spectral shift. A semiempirical model consisting of additive electrostatic and dispersive interactions is able to capture the main features observed experimentally in all six solute/solvent combinations. The simulations show that the commonly used assumption of a linear relation between spectral shifts and local compositions grossly exaggerates the extent of preferential solvation in these mixtures. The collective nature of electrostatic solvation and the composition dependence of the solute's coordination number are shown to be responsible for the breakdown of this assumption.
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PMID:Solvation and solvatochromism in CO2-expanded liquids. 2. Experiment-simulation comparisons of preferential solvation in three prototypical mixtures. 1738 63