Mechanisms and energetics of free radical initiated disulfide bond cleavage in model peptides and insulin by mass spectrometry† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c5sc01305d Click here for additional data file.
نویسندگان
چکیده
ion from the a-carbon or the b-carbon of a disulfide, followed by b-cleavages yielding C–S or S–S bond scissions. The current mechanistic findings should be generally applicable to other radicaldriven disulfide bond cleavages with different radical species such as the benzyl and methyl pyridyl radicals.
منابع مشابه
Rhodium(i)-catalyzed stereoselective [4+2] cycloaddition of oxetanols with alkynes through C(sp3)–C(sp3) bond cleavage† †Electronic supplementary information (ESI) available. CCDC 1512439 and 1512440. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6sc05246k Click here for additional data file. Click here for additional data file.
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Mechanisms and energetics of free radical initiated disulfide bond cleavage in model peptides and insulin by mass spectrometry.
We investigate the mechanism of disulfide bond cleavage in gaseous peptide and protein ions initiated by a covalently-attached regiospecific acetyl radical using mass spectrometry (MS). Highly selective S-S bond cleavages with some minor C-S bond cleavages are observed by a single step of collisional activation. We show that even multiple disulfide bonds in intact bovine insulin are fragmented ...
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