Thermodynamics and kinetics of carbon dioxide binding to two stereoisomers of a cobalt(I) macrocycle in aqueous solution
作者:Carol Creutz、Harold A. Schwarz、James F. Wishart、Etsuko Fujita、Norman Sutin
DOI:10.1021/ja00009a022
日期:1991.4
The thermodynamics and kinetics of binding of CO 2 , CO, and H + to N-racemic and N-meso stereoisomers of the cobalt (I) macrocycle CoL + (L=5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene) have been determined in aqueous media with use of the pulseradiolysis technique and transient ultraviolet-visible spectroscopy. N-rac- or N-meso-CoL + was produced by the hydrated electron
CO 2 、CO 和 H + 与钴 (I) 大环 CoL + 的 N-外消旋和 N-内消旋立体异构体结合的热力学和动力学(L=5,7,7,12,14,14-六甲基- 1,4,8,11-四氮杂环十四-4,11-二烯)已在水性介质中使用脉冲辐射分解技术和瞬态紫外-可见光谱法测定。N-rac- 或 N-meso-CoL + 是通过 N-rac- 或 N-meso-CoL 2+ 的水合电子还原产生的,通常添加叔丁醇以清除羟基自由基
Deuterium Substitution in an Electron Spin Resonance Study of Radiation-induced Free Radicals<sup>1a</sup>
作者:Ichiro Miyagawa、Walter Gordy
DOI:10.1021/ja01466a006
日期:1961.3
Effects of deuterium substitution on the electronspinresonance of x- irradiated organic compounds were investigated. The compounds range from carboxylic acids, amino acids and amides to proteins. Substitution of deuterium for the hydrogens of polar groups--hydroxyl, carboxyl, and amino-- showed that the hydrogens of these groups generally do not contribute, or give only a slight contribution, to
研究了氘取代对 x 辐照有机化合物的电子自旋共振的影响。这些化合物的范围从羧酸、氨基酸和酰胺到蛋白质。用氘取代极性基团(羟基、羧基和氨基)的氢表明这些基团的氢通常对共振模式的超精细结构没有贡献,或仅贡献很小的贡献。然而,发现了例外,特别是甲酸和甘氨酸。大多数情况下,与碳键合的氢给出了 esr 图案的超精细结构。在某些情况下,由氘取代提供的附加信息允许对自由基进行相当明确的鉴定。(授权)
Reactivity of Excited Water Molecules in Photochemical Carboxylation
作者:N. GETOFF
DOI:10.1038/211408a0
日期:1966.7
WE have shown that carbon dioxide in aqueous solution can be reduced and converted into simple organic substances under the influence of ultra-violet light1â3. The reduction process is the result of the action of hydrogen atoms produced by the photolysis of water and also of excited molecules of water (H2O*) (refs. 2 and 3): for λ = 184.9 nm the quantum yield for H and OH is Φ = 0.6 (ref. 4).