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Mechanistic Probes (mechanistic + probe)
Selected AbstractsNovel Model Sulfur Compounds as Mechanistic Probes for Enzymatic and Biomimetic OxidationsEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 1 2005Alicia B. Peñéñory Abstract To test for the intermediacy of sulfide radical cations in biomimetic and enzymatic oxidations, the sulfides PhSCH3 (1a), PhSCH2Ph (1b), PhSCHPh2 (1c), PhSCPh3 (1d), CH3SCHPh2 (2), PhSCH2CH=CH2 (3), PhSCH2CH=CHPh (4) and CH3SCH2CH=CHPh (5) were studied, and their results were compared to those obtained for the corresponding chemical electron transfer (CET) and photoinduced electron transfer (PET) oxidations. The radical cations generated from 3,5 by CET in the presence of cerium(IV) ammonium nitrate (CAN) yielded only fragmentation products from the alkyl cations and the thiyl radicals (RS·), whereas 2·+ afforded both fragmentation and mainly ,-deprotonation products. Photochemical treatment of the sulfides 1a and 1b with C(NO2)4 gave only the corresponding sulfoxides, while fragmentation was the main pathway for the photoreactions of 1c, 2 and 5, and for 1d only this latter process was observed. These results support our selection of the sulfides RSCHPh2, RSCH2CH=CHPh (R = Me, Ph) and PhSCPh3 as models for the biomimetic and enzymatic studies. As evidenced by the sulfoxides and sulfones detected as unique products both in protic and in aprotic solvents, it is proposed that the mechanism of the biomimetic sulfoxidations of sulfides 1c and 2,5 by TPPFeIIICl is direct oxygen transfer. Three enzymes , Coprinus cinereus peroxidase (CiP), horseradish peroxidase (HRP) and chloroperoxidase (CPO) , were studied in the oxidation of sulfides 1a, 2, 4 and 5. The use of a racemic alkyl hydroperoxide in the CiP enzymatic oxidation of sulfides 5 and 2 yielded the corresponding sulfoxides (23 and 29%) and the aldehyde or benzophenone (5%), respectively. These results suggest the involvement of an ET process for the CiP-catalysed oxidation. Fragmentation products were observed in the enzymatic oxidation of sulfide 4 with HRP, which confirms the previously proposed ET mechanism. On the other hand, the CPO-enzymatic oxidation of sulfide 5 yielded only the corresponding sulfoxide, as would be expected for a direct oxygen-transfer or oxene mechanism. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] , -Fluoro Thiafatty Acids: New Mechanistic Probes of Desaturase-Mediated ReactionsHELVETICA CHIMICA ACTA, Issue 11 2003Derek A series of 18-fluoro thiastearates were prepared and incubated with a yeast ,9-desaturating system. The relative efficiency of desaturase-mediated sulfoxidation was monitored via19F-NMR analysis of the sulfoxide products, and a strong preference for oxo transfer to the S-atom occupying the 9-position was confirmed. The oxidation profile obtained in this manner matched that of analogous experiments with non-fluorinated substrates. These results form the basis of a versatile 19F-NMR-based method for mapping the position of the putative diiron oxidant relative to substrate, and has potential application to the study of membrane-bound desaturases in vitro. [source] Preparation and Analysis of Oligonucleotides Containing the C4,-Oxidized Abasic Site and Related Mechanistic Probes.CHEMINFORM, Issue 3 2006Jaeseung Kim No abstract is available for this article. [source] Biomedical applications of 7Li NMRNMR IN BIOMEDICINE, Issue 2 2005Richard A. Komoroski Abstract The biomedical applications of 7Li MRS and MRI have been progressing slowly. The interest derives primarily from the clinical use of Li to treat bipolar disorder. One area of concern is the nature of ionic transport and binding, so as to elucidate the mechanism(s) of therapeutic action and toxicity. Another is the development of a non-invasive, in vivo analytical tool to measure brain Li concentration and environment in humans, both as an adjunct to treatment and as a mechanistic probe. Here we review the most recent progress toward these goals. Copyright © 2005 John Wiley & Sons, Ltd. [source] | ||||||||||