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1.
Rate constants have been measured by pulse radiolysis for the reactions of the carbonate radical, CO3·?, with a number of organic and inorganic reactants as a function of temperature, generally over the range 5 to 80°C. The reactants include the substitution-inert cyano complexes of FeII, MoIV, and WIV, the simple inorganic anions SO32?, ClO2?, NO2?, I?, and SCN?, several phenolates, ascorbate, tryptophan, cysteine, cystine, methionine, triethylamine, and allyl alcohol. The measured rate constants ranged from less than 105 to 3 × 109 M?1 s?1, the activation energies ranged from ?11.4 to 18.8 kJ mol?1, and the pre-exponential factors ranged from log A = 6.4 to 10.7. The activation energies for the metal complexes and inorganic anions generally decrease with increasing driving force for the reaction, as expected for an outer sphere electron transfer. For highly exothermic reactions, however, the activation energy appears to increase, probably reflecting the temperature dependence of diffusion. For many of the organic reactants, the activation energies were low and independent of driving force, suggesting that the oxidation is via an inner sphere mechanism. 相似文献
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Electrospray ionization mass spectrometry is used to detect both the cations (C+) and the anions (A–) of ionic liquids (CA). In this study, the ionic liquids are diluted with aqueous methanol before injection. In addition to the main peaks of the parent ions, fragmentation products are observed upon increasing the cone voltage, whereas aggregates of the parent ion with one or more ionic liquid molecules (e.g., C(CA)n+, A(CA)n–) are observed upon decreasing the cone voltage. The ions of several ionic liquids in a mixture are also detected and the ratios of their concentrations estimated. A method is developed to determine quantitatively the concentration of an ionic liquid in solution by using the cation and anion of another ionic liquid as internal standards. By using this method, the solubilities in water at room temperature (22±1 °C) of three typical hydrophobic ionic liquids have been determined: 0.70±0.08 g L–1 for methyltributylammonium bis(trifluoromethylsulfonyl)imide (MeBu3NNTf2), 6.0±0.5 g L–1 for butylmethylpyrrolidinium bis(trifluoromethylsulfonyl)imide (BuMePyrNTf2), and 18.6±0.7 g L–1 for 1-butyl-3-methylimidazolium hexafluorophosphate (BMIPF6). 相似文献
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Batinić-Haberle I Spasojević I Stevens RD Hambright P Neta P Okado-Matsumoto A Fridovich I 《Dalton transactions (Cambridge, England : 2003)》2004,(11):1696-1702
Three new Mn(III) porphyrin catalysts of O2.-dismutation (superoxide dismutase mimics), bearing ether oxygen atoms within their side chains, were synthesized and characterized: Mn(III) 5,10,15,20-tetrakis[N-(2-methoxyethyl)pyridinium-2-yl]porphyrin (MnTMOE-2-PyP(5+)), Mn(III)5,10,15,20-tetrakis[N-methyl-N'-(2-methoxyethyl)imidazolium-2-yl]porphyrin (MnTM,MOE-2-ImP(5+)) and Mn(III) 5,10,15,20-tetrakis[N,N'-di(2-methoxyethyl)imidazolium-2-yl]porphyrin (MnTDMOE-2-ImP(5+)). Their catalytic rate constants for O2.-dismutation (disproportionation) and the related metal-centered redox potentials vs. NHE are: log k(cat)= 8.04 (E(1/2)=+251 mV) for MnTMOE-2-PyP(5+), log k(cat)= 7.98 (E(1/2)=+356 mV) for MnTM,MOE-2-ImP(5+) and log k(cat)= 7.59 (E(1/2)=+365 mV) for MnTDMOE-2-ImP(5+). The new porphyrins were compared to the previously described SOD mimics Mn(III) 5,10,15,20-tetrakis(N-ethylpyridinium-2-yl)porphyrin (MnTE-2-PyP(5+)), Mn(III) 5,10,15,20-tetrakis(N-n-butylpyridinium-2-yl)porphyrin (MnTnBu-2-PyP(5+)) and Mn(III) 5,10,15,20-tetrakis(N,N'-diethylimidazolium-2-yl)porphyrin (MnTDE-2-ImP(5+)). MnTMOE-2-PyP(5+) has side chains of the same length and the same E(1/2), as MnTnBu-2-PyP(5+)(k(cat)= 7.25, E(1/2)=+ 254 mV), yet it is 6-fold more potent a catalyst of O2.-dismutation , presumably due to the presence of the ether oxygen. The log k(cat)vs. E(1/2) relationship for all Mn porphyrin-based SOD mimics thus far studied is discussed. None of the new compounds were toxic to Escherichia coli in the concentration range studied (up to 30 microM), and protected SOD-deficient E. coli in a concentration-dependent manner. At 3 microM levels, the MnTDMOE-2-ImP(5+), bearing an oxygen atom within each of the eight side chains, was the most effective and offered much higher protection than MnTE-2-PyP(5+), while MnTDE-2-ImP(5+) was of very low efficacy. 相似文献
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Neta Shefer 《Tetrahedron letters》2007,48(46):8178-8181
Thiols and disulfides are oxidized to the corresponding sulfonic and sulfinic acids using HOF·CH3CN. This oxidation is suitable for a variety of thiols and disulfides and proceeds under mild conditions, in short reaction times and with high yields. 相似文献
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Spectrophotometric pulse radiolysis experiments with cis- and trans-stilbene (Sc and St) in 2-propanol show that both isomers react with the solvated electron with a rate constant of 4.5 × 109 M?1 s?1. The absorption spectra of the two anion radicals have maxima at 496 and 486 nm, respectively. The absorbances at 400–550 nm disappear exponentially corresponding to a pseudo first order protonation of the anion radicals. The rate constants for the protonation of the cis isomer is 6.4 × 105 and of the trans isomer 0.7 × 105 s?1. In mixtures of cis- and trans-stilbene the electron transfer has a forward rate constant of 9 × 107 M?1 s?1 while the back reaction has a rate constant of 2.15 × 107 M?1 s?1. An equilibrium constant K = 4.2 is calculated. 相似文献
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The convergence of a finite element scheme approximating a nonlinear system of integro-differential equations is proven. This system arises in mathematical modeling of the process of a magnetic field penetrating into a substance. Properties of existence, uniqueness and asymptotic behavior of the solutions are briefly described. The decay of the numerical solution is compared with both the theoretical and finite difference results. 相似文献
9.
Russian Physics Journal - Results of calculation of the transmission function for ensembles of ice crystals typical of crystal clouds are presented as functions of the wave numbers. Considering... 相似文献
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