迈向亚硫酸盐氧化酶高氯、低pH形式的建模：氧代钼（V）配合物中赤道氯配体的Ka波段电子自旋回波包络调制
Toward modeling the high chloride, low pH form of sulfite oxidase: Ka-band ESEEM of equatorial chloro ligands in oxomolybdenum(V) complexes.
作者信息
Astashkin Andrei V, Klein Eric L, Enemark John H
机构信息
Department of Chemistry, The University of Arizona, Tucson, AZ 85721, USA.
出版信息
J Inorg Biochem. 2007 Nov;101(11-12):1623-9. doi: 10.1016/j.jinorgbio.2007.05.015. Epub 2007 Jun 12.
Two oxomolybdenum(V) complexes, (dttd)MoOCl and (bdt)MoOCl(2) (where dttd=2,3:8,9-dibenzo-1,4,7,10-tetrathiadecane and bdt=1,2-benzenedithiolate), which contain one or two equatorial chloro ligands, respectively, were studied by electron spin echo envelope modulation (ESEEM) spectroscopy in the microwave K(a)-band (approximately 29GHz). The ESEEM amplitude from the chloro ligands in both compounds is significantly greater than that tentatively attributed to chloride in the vicinity of the oxomolybdenum active site in the high chloride, low-pH (lpH) form of sulfite oxidase (SO). Thus, these ESEEM results rule out equatorial coordination of chloride in the enzyme, although the possibility for a weakly bound chloride in the trans axial position or nearby non-coordinated chloride(s) remains for lpH SO in solution.
通过微波K（a）波段（约29GHz）的电子自旋回波包络调制（ESEEM）光谱研究了两种含氧化钼（V）配合物，即（dttd）MoOCl和[（bdt）MoOCl₂]⁻（其中dttd = 2,3:8,9 - 二苯并 - 1,4,7,10 - 四硫杂环十四烷，bdt = 1,2 - 苯二硫醇盐），它们分别含有一个或两个赤道面氯配体。这两种化合物中氯配体的ESEEM振幅明显大于在高氯、低pH（lpH）形式的亚硫酸盐氧化酶（SO）中，氧钼活性位点附近暂时归因于氯的振幅。因此，这些ESEEM结果排除了酶中氯的赤道配位，尽管对于溶液中的lpH SO，反式轴向位置存在弱结合氯或附近存在非配位氯的可能性仍然存在。
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