紫外光诱导氧合型肌红蛋白氧化反应及机理

引用本文: 曹洪玉, 高凌星, 唐乾, 苏晋红, 郑学仿. 紫外光诱导氧合型肌红蛋白氧化反应及机理[J]. 物理化学学报, 2016, 32(4): 872-878. doi: 10.3866/PKU.WHXB201601046 shu

Citation: CAO Hong-Yu, GAO Ling-Xing, TANG Qian, SU Jin-Hong, ZHENG Xue-Fang. Mechanism of Oxymyoglobin Oxidation Reaction Induced by Ultraviolet Light[J]. Acta Physico-Chimica Sinica, 2016, 32(4): 872-878. doi: 10.3866/PKU.WHXB201601046 shu

紫外光诱导氧合型肌红蛋白氧化反应及机理

1.
1. 大连大学生命科学与技术学院, 辽宁大连 116622;
2.
2. 大连大学环境与化学工程学院, 辽宁大连 116622;
3.
3. 大连大学, 辽宁省生物有机化学重点实验室, 辽宁大连 116622

通讯作者: 郑学仿

基金项目:
国家自然科学基金(21571025, 21271036) (21571025, 21271036)

辽宁省教育厅科学技术研究项目(L2013470, L2013471)资助 (L2013470, L2013471)

摘要: 肌红蛋白通常在无光条件下可进行输氧、储氧等重要功能,实验中我们发现紫外光照射可促进氧合肌红蛋白(MbO₂)的氧化反应,证实其在光照时部分生理功能会发生变化。紫外-可见(UV-Vis)吸收光谱数据显示,光照射时MbO₂的Soret 带最大吸收波长蓝移、Q吸收带544 和580 nm处还原峰强度下降,说明紫外光光照促进O₂解离,MbFe(Ⅱ)可被氧化至MbFe(Ⅲ)。四种波长光对光照氧化的影响程度为254 nm > 280 nm >430 nm > 409 nm;通入CO气体时氧合肌红蛋白较难发生光照氧化反应,即Fe的第六配位强度影响反应程度;溶液中的H⁺或OH^-对光照氧化反应有促进作用;254、280 nm波长光照射时,苯丙氨酸(Phe)、酪氨酸(Tyr)、色氨酸(Trp)三种游离氨基酸均促进光照氧化反应的进行,而409、430 nm波长光照射时三种游离氨基酸对光照氧化反应的影响较小。以上数据表明体内光诱导MbO₂氧化反应过程中蛋白质内的Fe(Ⅱ)能否被光照激发形成未成对电子处于激发态是O₂离去和二价铁被氧化的关键。

关键词:

English

Mechanism of Oxymyoglobin Oxidation Reaction Induced by Ultraviolet Light

1.
1. College of Life Science and Biotechnology, Dalian University, Dalian 116622, Liaoning Province, P. R. China;
2.
2. College of Environmental and Chemical Engineering, Dalian University, Dalian 116622, Liaoning Province, P. R. China;
3.
3. Liaoning Key Laboratory of Bio-Organic Chemistry, Dalian University, Dalian 116622, Liaoning Province, P. R. China

Corresponding author: 郑学仿

Received Date: 09 November 2015
Available Online: 04 January 2016
Fund Project:
国家自然科学基金(21571025, 21271036)

辽宁省教育厅科学技术研究项目(L2013470, L2013471)资助

Abstract: Myoglobin (Mb) achieves its biological functions such as oxygen transfer and storage in the dark. In this research, we found that UV light irradiation could promote oxidation of ferroporphyrin, which significantly affected the physiological function of oxymyoglobin (MbO₂). The blue shift of the Soret band and decreased intensities of Q-band reduction peaks at 544 and 580 nm observed in UV-Vis absorption spectra revealed that UV light could promote O₂ dissociation, and consequently MbFe(Ⅱ) was oxidized to MbFe(Ⅲ). The effect sequence of wavelength on the strength of this photo-oxidation was 254 nm > 280 nm > 430 nm > 409 nm. CO could inhibit the photo-oxidation process, indicating that the strength of the sixth coordination bond of Fe with a gas molecule influences the degree of photo-oxidation. The H⁺ and OH^- in the solution could also promote the photo-oxidation process. Irradiated by 254 and 280 nm light, free amino acids phenylalanine (Phe), tyrosine (Tyr), and tryptophan (Trp) promoted the light oxidation reaction. Meanwhile, irradiation with 409 and 430 nm light had less influence on the UV-light-induced oxidation reaction under the same conditions. The results illustrated that in photo-induced oxidation of MbO₂, the formation of an excited state of Fe(Ⅱ) with unpaired electrons upon irradiation is crucial process for O₂ dissociation and Fe(Ⅱ) oxidation.

Key words:

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

紫外光诱导氧合型肌红蛋白氧化反应及机理

通讯作者: 郑学仿

English

Mechanism of Oxymyoglobin Oxidation Reaction Induced by Ultraviolet Light

Corresponding author: 郑学仿

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

紫外光诱导氧合型肌红蛋白氧化反应及机理

通讯作者: 郑学仿

English

Mechanism of Oxymyoglobin Oxidation Reaction Induced by Ultraviolet Light

Corresponding author: 郑学仿

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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