组氨酸钴氧合配合物二聚体形态的电喷雾串联质谱验证研究  

Confirmation of Dinuclear Oxygenated Cobalt-Histidine Complex by Electrospray Tandem Mass Spectrometry

作　　者：付佩[1] 符继红[1] 李俊芳[1] 岳凡[1] 张旭龙[1] 王吉德[1] 

机构地区：[1]新疆大学化学化工学院,乌鲁木齐830046

出　　处：《无机化学学报》2012年第7期1360-1364,共5页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.20961010;21162027);教育部高校博士学位点专项科研基金(No.20096501110001)资助项目

摘　　要：电喷雾质谱(ESI-MS)是一种软电离质谱技术,已在配合物的结构和机理的研究中显示了重要的作用。本文根据组氨酸钴(CoL2)(L=组氨酸)对分子氧活性很高,极易生成双核氧合配合物(CoL2-O2-CoL2)的特点,采用ESI-MS方法研究了组氨酸钴氧合物(CoL2-O2-CoL2)和组氨酸配合物ML2(M=Cu、Zn)。结果发现,质谱图中在相应于双核氧合配合物的高质荷比端(m/z>ML2),CoL2出现质谱峰,而组氨酸配合物ML2(M=Cu、Zn)在质谱图中高质荷比端没有出现质谱峰,只有配合物ML2的相关峰;这个结果证明了文献报道中的双核氧合配合物(CoL2-O2-CoL2)的存在,根据所得质谱结果,初步研究了组氨酸钴双核氧合配合物和ML2配合物的裂解规律。结果表明,可根据质谱数据中有无二聚体形态,做出Co配合物有无吸氧性能的初步判断,因此电喷雾质谱(ESI-MS)可做为研究Co配合物氧合反应和表征Co氧合配合物的有效分析手段。ESI-MS is a kind of soft ionization mass spectrometric technique; it has proved to be a very important technique in the investigations on structures and mechanisms of complexes. In this paper a comparison study was conducted on the oxygenated cobalt complex of histidine （L） and copper/zinc complex of histidine in oxygen atmosphere since according to literatures among histidine complexes only histidine cobalt complex has a very high affinity to dioxygen and easily form a dinuclear oxygenated complexes （CoL2-O2-CoL2）. The ESI-MS results showed that in mass spectrum, the fragment ions corresponding to the dinuclear oxygenated species in higher m/z range （m/z〉ML2） were observed for CoL2 while for CuL2 and ZnL2 only fragment ions corresponding to ML2 were observed. Theses results confirmed the dinuclear oxygenated complexes （CoL2-O2-CoL2） existed in the Cola complex reported in literature. The possible fragmentation mechanism of CoL2 was proposed. Results from this study proved that ESI-MS could be used as a method to estimate preliminarily if a Co（Ⅱ） complex have the ability of uptaking dioxygen or not, and it could be used as an effective technique to research the oxygenation and characterize oxygenated Co（Ⅱ） complexes.

关 键 词：电喷雾串联质谱 氧载体 组氨酸 钴配合物 二聚体氧合配合物 

分 类 号：O614.812[理学—无机化学] O629.71[理学—化学]