Redox-mediated carbon monoxide release from a manganese carbonyl—implications for physiological CO delivery by CO releasing moieties

The dynamics of hydrogen peroxide reactions with metal carbonyls have received little attention. Given reports that therapeutic levels of carbon monoxide are released in hypoxic tumour cells upon manganese carbonyls reactions with endogenous H2O2, it is critical to assess the underlying CO release m...

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Autores principales:	Jacob A. Barrett, Zhi Li, John V. Garcia, Emily Wein, Dongyun Zheng, Camden Hunt, Loc Ngo, Lior Sepunaru, Alexei V. Iretskii, Peter C. Ford
Formato:	article
Lenguaje:	EN
Publicado:	The Royal Society 2021
Materias:	hydrogen peroxide manganese carbonyl CO releasing moiety redox reaction Science Q
Acceso en línea:	https://doaj.org/article/20bbbbaa1aad4ed79fd1ab8821fc0649
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spelling	oai:doaj.org-article:20bbbbaa1aad4ed79fd1ab8821fc06492021-11-23T06:17:50ZRedox-mediated carbon monoxide release from a manganese carbonyl—implications for physiological CO delivery by CO releasing moieties10.1098/rsos.2110222054-5703https://doaj.org/article/20bbbbaa1aad4ed79fd1ab8821fc06492021-11-01T00:00:00Zhttps://royalsocietypublishing.org/doi/10.1098/rsos.211022https://doaj.org/toc/2054-5703The dynamics of hydrogen peroxide reactions with metal carbonyls have received little attention. Given reports that therapeutic levels of carbon monoxide are released in hypoxic tumour cells upon manganese carbonyls reactions with endogenous H2O2, it is critical to assess the underlying CO release mechanism(s). In this context, a quantitative mechanistic investigation of the H2O2 oxidation of the water-soluble model complex fac-[Mn(CO)3(Br)(bpCO2)]2–, (A, bpCO22– = 2,2′-bipyridine-4,4′-dicarboxylate dianion) was undertaken under physiologically relevant conditions. Characterizing such pathways is essential to evaluating the viability of redox-mediated CO release as an anti-cancer strategy. The present experimental studies demonstrate that approximately 2.5 equivalents of CO are released upon H2O2 oxidation of A via pH-dependent kinetics that are first-order both in [A] and in [H2O2]. Density functional calculations were used to evaluate the key intermediates in the proposed reaction mechanisms. These pathways are discussed in terms of their relevance to physiological CO delivery by carbon monoxide releasing moieties.Jacob A. BarrettZhi LiJohn V. GarciaEmily WeinDongyun ZhengCamden HuntLoc NgoLior SepunaruAlexei V. IretskiiPeter C. FordThe Royal Societyarticlehydrogen peroxidemanganese carbonylCO releasing moietyredox reactionScienceQENRoyal Society Open Science, Vol 8, Iss 11 (2021)
institution	DOAJ
collection	DOAJ
language	EN
topic	hydrogen peroxide manganese carbonyl CO releasing moiety redox reaction Science Q
spellingShingle	hydrogen peroxide manganese carbonyl CO releasing moiety redox reaction Science Q Jacob A. Barrett Zhi Li John V. Garcia Emily Wein Dongyun Zheng Camden Hunt Loc Ngo Lior Sepunaru Alexei V. Iretskii Peter C. Ford Redox-mediated carbon monoxide release from a manganese carbonyl—implications for physiological CO delivery by CO releasing moieties
description	The dynamics of hydrogen peroxide reactions with metal carbonyls have received little attention. Given reports that therapeutic levels of carbon monoxide are released in hypoxic tumour cells upon manganese carbonyls reactions with endogenous H2O2, it is critical to assess the underlying CO release mechanism(s). In this context, a quantitative mechanistic investigation of the H2O2 oxidation of the water-soluble model complex fac-[Mn(CO)3(Br)(bpCO2)]2–, (A, bpCO22– = 2,2′-bipyridine-4,4′-dicarboxylate dianion) was undertaken under physiologically relevant conditions. Characterizing such pathways is essential to evaluating the viability of redox-mediated CO release as an anti-cancer strategy. The present experimental studies demonstrate that approximately 2.5 equivalents of CO are released upon H2O2 oxidation of A via pH-dependent kinetics that are first-order both in [A] and in [H2O2]. Density functional calculations were used to evaluate the key intermediates in the proposed reaction mechanisms. These pathways are discussed in terms of their relevance to physiological CO delivery by carbon monoxide releasing moieties.
format	article
author	Jacob A. Barrett Zhi Li John V. Garcia Emily Wein Dongyun Zheng Camden Hunt Loc Ngo Lior Sepunaru Alexei V. Iretskii Peter C. Ford
author_facet	Jacob A. Barrett Zhi Li John V. Garcia Emily Wein Dongyun Zheng Camden Hunt Loc Ngo Lior Sepunaru Alexei V. Iretskii Peter C. Ford
author_sort	Jacob A. Barrett
title	Redox-mediated carbon monoxide release from a manganese carbonyl—implications for physiological CO delivery by CO releasing moieties
title_short	Redox-mediated carbon monoxide release from a manganese carbonyl—implications for physiological CO delivery by CO releasing moieties
title_full	Redox-mediated carbon monoxide release from a manganese carbonyl—implications for physiological CO delivery by CO releasing moieties
title_fullStr	Redox-mediated carbon monoxide release from a manganese carbonyl—implications for physiological CO delivery by CO releasing moieties
title_full_unstemmed	Redox-mediated carbon monoxide release from a manganese carbonyl—implications for physiological CO delivery by CO releasing moieties
title_sort	redox-mediated carbon monoxide release from a manganese carbonyl—implications for physiological co delivery by co releasing moieties
publisher	The Royal Society
publishDate	2021
url	https://doaj.org/article/20bbbbaa1aad4ed79fd1ab8821fc0649
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Redox-mediated carbon monoxide release from a manganese carbonyl—implications for physiological CO delivery by CO releasing moieties

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