组氨酸钴氧合反应的电喷雾串联质谱

高等学校化学学报 ›› 2011, Vol. 32 ›› Issue (7): 1483.

组氨酸钴氧合反应的电喷雾串联质谱

符继红, 李俊芳, 付佩, 岳凡, 张旭龙, 王吉德

新疆大学化学化工学院, 乌鲁木齐 830046

收稿日期:2010-10-04 修回日期:2011-03-12 出版日期:2011-07-10 发布日期:2011-06-02
通讯作者: 王吉德 E-mail:awangjd@xju.edu.cn
基金资助:
国家自然科学基金(批准号: 20961010, 20762009)和教育部高等学校博士学科点专项科研基金(批准号: 20096501110001)资助.

Oxygenation Reaction of Histidine Cobalt Complex by Electrospray Tandem Mass Spectrometry

FU Ji-Hong, LI Jun-Fang, FU Pei, YUE Fan, ZHANG Xu-Long, WANG Ji-De*

College of Chemistry and Chemical Engineering, Xinjiang University, Urumqi 830046, China

Received:2010-10-04 Revised:2011-03-12 Online:2011-07-10 Published:2011-06-02
Contact: WANG Ji-De E-mail:awangjd@xju.edu.cn
Supported by:
国家自然科学基金(批准号: 20961010, 20762009)和教育部高等学校博士学科点专项科研基金(批准号: 20096501110001)资助.

摘要/Abstract

摘要： 组氨酸合钴配合物是重要的氧载体模型化合物，对揭示氧载体的可逆吸氧机理的研究有着重要的作用。本文以组氨酸合钴吸氧初和吸氧中期两个阶段为研究体系，采用电喷雾多级串联质谱技术对组氨酸合钴氧载体的质谱裂解规律进行了研究。在其质谱裂解图谱中发现了氧合配合物碎片峰，将该氧合配合物碎片峰进一步裂解，可得到失去中性氧分子的子离子碎片峰，从而对其氧合形式进行了确认，根据所得质谱数据对组氨酸合钴氧合产物的结构、裂解规律及氧气的存在形态给出合理的推论。结果表明，吸氧过程是一个动态的变化过程，组氨酸合钴配合物吸氧初和吸氧24h后，分子氧均以超氧型形式存在，但其型态经历了从双核超氧桥联配合物到双核双桥联超氧羟基配合物的转变。对此过程的研究一直缺乏直接测定方法未被完全确定。本文采用电喷雾多级串联质谱技术对此氧合反应的机理进行了探讨，并初步确立电喷雾质谱（ESI-MS）可做为研究氧合反应和表征氧合配合物的有效技术手段。

关键词: 组氨酸, 钴, 电喷雾串联质谱, 氧合反应, 氧载体

Abstract: Histidine-cobalt compex is a known model compound of oxygen carriers. The investigation of its oxygenation is of great significance in revealing the oxygenation mechanism of reversibly absorbing oxygen. In this paper, a new method was proposed to directly investigate the oxygenation reaction of histidine-cobalt compex by electrospray tandem mass spectrometry. The fragment ions of the oxygenated complexes were found from both aqueous samples of histidine-cobalt compex separately adsorbing oxygen at early 10-20 minutes and continuously adsorbing oxygen for 24 hours. The fragment ions of the oxygenated complexes were confirmed by its sub-fragment ion which just lost a neutral fragment of dioxygen by further fragmentating. Based on these results, the structure, mechanism and the form of dioxygen existed in the complex were deduced. The results showed that the absorption process is a dynamic process, and the structure of the complex could be changed from dinuclear superoxo-bridged complex to dinuclear superoxo-hydroxo dibridge complex according to the progress of oxygenation time. ESI-MS method can be an effective technique of researching the oxygenation reaction and characterizing oxygenated complexes

Key words: Histidine, Cobalt, ESI-MS/MS, Oxygenation, Oxygen carrier

中图分类号:

O657.6

TrendMD:

符继红李俊芳付佩岳凡张旭龙王吉德. 组氨酸钴氧合反应的电喷雾串联质谱. 高等学校化学学报, 2011, 32(7): 1483.

FU Ji-Hong, LI Jun-Fang, FU Pei, YUE Fan, ZHANG Xu-Long, WANG Ji-De*. Oxygenation Reaction of Histidine Cobalt Complex by Electrospray Tandem Mass Spectrometry. Chem. J. Chinese Universities, 2011, 32(7): 1483.

参考文献

[1] Wang, J. D., Collange, E., Aymes, D.. J. Bull. Soc. Chim. Fr. [J], 1994, 131:37-44 [2] Simplicio J., Wilkins R. G.. J. Am. Chem. Soc. [J], 1967, 89:6092 [3] Wang J. D., Martell A. E., Reibenspies J. H.. Inorg. Chim. Acta. [J], 2002, 328:53-60 [4] Feng Y., Liu G., Tian X. M., Wang J. D.. Acta Crystallogr. C. [J], 2007, C63:598-600 [5] Wang W., Feng S., Li Y. N., et al.. J. Chromatogr. A. [J], 2008, 1193:142-145 [6] Yoshihito H., Takayuki K., Hideki S., et al.. J. Am. Chem. Soc. [J], 1995, 117:11220-11229 [7] YUE Fan(岳凡), WANG Ji-De(王吉德), ZHANG Yi(张翼), et al.. Chinese J. Inorg. Chem. (无机化学学报)[J], 2002, 18(5):489-492 [8] WANG Ji-De(王吉德), WANG Yao(王瑶), ZHANG Yi(张翼), et al.. Chinese J. Appl. Chem. (应用化学)[J], 1998, 15(2):97-99 [9] YUE Fan(岳凡), WANG Ji-De(王吉德), CUI Yong(崔勇), et al.. Chem. Rese. Appl. (化学研究与应用) [J], 2000, 12(6):632-634 [10] LIAO Ming(廖明), YANG Shu-Xun(仰蜀薰). Chinese J. Anal. Chem. (分析化学) [J], 1983, 11(3):207 [11] Busch’st D. H., Alcockt N. W.. Chem. Rev. [J], 1994, 94:585-623 [12] Whitehouse C. M., Dreyer R. N., Yamashita M., et al.. Anal. Chem. [J], 1985, 57:675-679 [13] WU Wei(吴巍)，ZHOU Yi-Han(周奕含)，LIU Zhi-Qiang(刘志强)，et al.. Chinese J. Anal. Chem. (分析化学) [J], 2005, 33(5):683-686 [14] SU Qiang(苏强)，LIU Qing-fei(刘清飞)，LIANG Qiong-lin(梁琼麟) ，et al.. Chem. J. Chinese Universities(高等学校化学学报)[J]，2007，28(8):1486-1488 [15] YAN Li(颜莉), ZHAO Ji-Shou(赵吉寿), LI Wen-Hui(李文辉). Journal of Yunnan University of the Nationalities (云南民族学院学报) [J], 2000, 9(1):29-33 [16] QU Chen-Ling(渠琛玲)，ZHANG Han-Qi(张寒琦)，ZHANG Hua-Rong(张华蓉)，et al.. Chem. J. Chinese Universities(高等学校化学学报)[J]，2008，29(9):1721-1726