The reaction of oxyhemoglobin with nitric oxide: EPR evidence for an iron(III)-nitrate intermediate

The reaction of oxyhemoglobin with nitric oxide: EPR evidence for an iron(III)-nitrate intermediate
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氧合血红蛋白与一氧化氮的反应:硝酸铁 (III) 中间体的 EPR 证据

DOI:
10.1016/j.ica.2015.07.037
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发表时间:
2015
影响因子:
2.8
通讯作者:
Silaghi-Dumitrescu R
Silaghi-Dumitrescu R
中科院分区:
化学3区
文献类型:
--
作者:
Silaghi-Dumitrescu R

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氧合血红蛋白与一氧化氮的反应已知在体内发生,具有直接的医学和病理生理学相关性。该机制被认为涉及一种瞬时铁(III)-过氧亚硝酸盐中间体,它的形成将是限速的,它的衰变将产生铁(III)-水/铁(III)-羟基血红蛋白。本文报道了氧合血红蛋白与一氧化氮反应的快速冻冷EPR (RFQ-EPR)光谱数据;没有直接证据表明存在铁(III)-过氧亚硝酸盐中间体。这些发现与理论考虑是一致的,根据这种中间物确实形成,但太短而无法检测。相反,在RFQ-EPR实验中检测到铁(III)低自旋和高自旋瞬态物质,这可以解释为硝酸盐与高铁血红蛋白的相互作用。
The reaction of oxyhemoglobin with nitric oxide is known to occurin vivo, with direct medical and pathophysiological relevance. The mechanism has been proposed to involve a transient iron(III)-peroxynitrite intermediate, the formation of which would be rate-limiting and the decay of which would yield iron(III)-aqua/iron(III)-hydroxo hemoglobin. Reported here are rapid-freeze-quench EPR (RFQ-EPR) spectroscopy data on the reaction of oxyhemoglobin with nitric oxide; no direct evidence is seen for an iron(III)-peroxynitrite intermediate. These findings are consistent with theoretical considerations according to which such an intermediate does form but is too short-lived to be detectable. Instead, iron(III) low-spin and high-spin transient species are detected in the RFQ-EPR experiments, which can be explained as arising from interactions of nitrate with methemoglobin.
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