Exchangeable proton ENDOR as a probe of the redox-active iron center in activated bleomycin and ferric bleomycin

Activated bleomycin (ABLM) is a drug-Fe(iii)-hydroperoxide complex kinetically competent in DNA attack (via H4' abstraction). This intermediate is relatively stable, but its spontaneous conversion to ferric bleomycin (Fe(iii)·BLM) is poorly characterized because no observable intermediate produ...

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Bibliographic Details
Published in:Dalton transactions : an international journal of inorganic chemistry 2017-10, Vol.46 (39), p.13263-13272
Main Authors: Burger, Richard M, Grigoryants, Vladimir M, Scholes, Charles P
Format: Article
Language:English
Subjects:
Bleomycin - analogs & derivatives
Bleomycin - chemistry
Electron Spin Resonance Spectroscopy
Iron - chemistry
Oxidation-Reduction
Photolysis
Protons
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Summary:Activated bleomycin (ABLM) is a drug-Fe(iii)-hydroperoxide complex kinetically competent in DNA attack (via H4' abstraction). This intermediate is relatively stable, but its spontaneous conversion to ferric bleomycin (Fe(iii)·BLM) is poorly characterized because no observable intermediate product accumulates. The Fe(iii)·BLM formed cryophotolytically from ABLM and kept at 77 K was remarkably similar by EPR and ENDOR criteria to Fe(iii)·BLM formed from Fe(iii) + BLM solution. The notable ENDOR criteria were the ENDOR frequencies and features of orientation-selected, strongly hyperfine-coupled, exchangeable protons associated with the environs of the iron within
ISSN:1477-9226
1477-9234
DOI:10.1039/c7dt01354j