Topic
Hydrogen atom abstraction
About: Hydrogen atom abstraction is a research topic. Over the lifetime, 7059 publications have been published within this topic receiving 151781 citations.
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53 citations
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TL;DR: In this article, the photochemistry of 2-(3-benzoylphenyl)propionic acid (Ketoprofen) has been studied in the β-cyclodextrin cavity by stationary and time-resolved (picosecond and nanosecond) spectroscopic techniques.
Abstract: The photochemistry of 2-(3-benzoylphenyl)propionic acid (Ketoprofen) has been studied in the β-cyclodextrin cavity by stationary and time-resolved (picosecond and nanosecond) spectroscopic techniques. Conformational calculations of the inclusion complex were performed. Induced circular dichroism was measured and theoretically interpreted. Photodecarboxylation was found to occur with lower quantum yield than in aqueous medium. An additional photoreaction was evidenced. A mechanism in which the lowest triplet state of the Ketoprofen–β-cyclodextrin inclusion complex undergoes both intramolecular electron transfer and hydrogen abstraction is proposed. Adducts of reduced ketoprofen with β-cyclodextrin are the likely photoproducts of the additional reaction channel.
53 citations
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TL;DR: Kinetic measurements were possible through a specifically designed competition system measuring the reaction of thiyl radicals with either the C-H bonds of the carbohydrates or the C(alpha)-H bond of cysteine under conditions where the extent of other competitive reactions of the thIyl radicals were minimized.
53 citations
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TL;DR: In this paper, the authors studied three possible modes of reaction between dioxygen and dihydrogen molecules at the ground triplet state and excited singlet state of O2.
Abstract: Calculations at the (14,10)CASSCF/6-31G** and the MR-(S)DCI/cc-pVTZ levels are employed to answer the title question by studying three possible modes of reaction between dioxygen and dihydrogen molecules at the ground triplet state and excited singlet state of O2. These reaction modes, which are analogous to well-established mechanisms for oxidants such as transition metal oxene cations and mono-oxygenase enzymes, are the following: (i) the concerted addition, (ii) the oxene-insertion, and (iii) the hydrogen abstraction followed by hydrogen rebound. The “rebound” mechanism is found to be the most preferable of the three mechanisms. However, the barrier of the H-abstraction step is substantial both for the triplet and the singlet states of O2, and the process is highly endothermic (>30 kcal/mol) and is unlikely to proceed at ambient conditions. The calculations revealed also that the lowest singlet state of O2 has very high barriers for reaction and therefore cannot mediate a facile oxidation of H2 in con...
53 citations
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TL;DR: The chemistry of DNA cleavage by esperamicins A 1, C, D, and E (ep A, C-E) has been examined in this article, where high-resolution gel electrophoresis reveals that esp A, a known single-strand cleaver, affords fragmentation products consistent with exclusive 5'-hydrogen abstraction.
Abstract: The chemistry of DNA cleavage by the esperamicins A 1 , C, D, and E (ep A, C-E) has been examined. High-resolution gel electrophoresis reveals that esp A, a known single-strand cleaver, affords fragmentation products consistent with exclusive 5'-hydrogen abstraction. In contrast, ep C-E, analogs that produce significant double-strand cleavage, generate fragmentation products consistent with both 5'- and 4'-hydrogen abstraction
53 citations