The selenite radical, SeO3-, has been found to selectively produce the cytosyl radical upon one-electron oxidation of duplex DNA. This is at first a surprising result as SeO3- can only oxidize guanine of the DNA bases, implying that the transiently formed guanyl radical cation must transpose into the neutral cytosyl radical with loss of a proton. Back oxidation to produce the neutral guanyl radical, in competition with another fixation reaction, is observed.
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http://dx.doi.org/10.1021/ja0658416 | DOI Listing |
J Am Chem Soc
March 2022
Department of Chemistry, University of Texas at Austin, Austin, Texas 78712, United States.
The biosynthesis of blasticidin S has drawn attention due to the participation of the radical -adenosyl methionine (SAM) enzyme BlsE. The original assignment of BlsE as a radical-mediated, redox-neutral decarboxylase is unusual because this reaction appears to serve no biosynthetic purpose and would need to be reversed by a subsequent carboxylation step. Furthermore, with the exception of BlsE, all other radical SAM decarboxylases reported to date are oxidative in nature.
View Article and Find Full Text PDFChembiochem
July 2012
State Key Laboratory of Microbial Metabolism, and School of Life Sciences & Biotechnology Shanghai Jiao Tong University, 1954 Huashan Road, Shanghai, 200030, China.
Mildiomycin (MIL) is a peptidyl-nucleoside antibiotic produced by Streptoverticillum remofaciens ZJU5119 that exhibits strong inhibitory activity against powdery mildew. The entire MIL biosynthesis gene cluster was cloned and expressed in Streptomyces lividans 1326. Systematic gene disruptions narrowed down the cluster to 16 functional ORFs and identified the boundaries of the gene cluster.
View Article and Find Full Text PDFJ Am Chem Soc
December 2006
Department of Chemistry, The University of Auckland, Auckland 1, New Zealand.
The selenite radical, SeO3-, has been found to selectively produce the cytosyl radical upon one-electron oxidation of duplex DNA. This is at first a surprising result as SeO3- can only oxidize guanine of the DNA bases, implying that the transiently formed guanyl radical cation must transpose into the neutral cytosyl radical with loss of a proton. Back oxidation to produce the neutral guanyl radical, in competition with another fixation reaction, is observed.
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