具有生物活性钼钨仿生配合物与ATP作用的NMR研究

An NMR Study on the Interaction between ATP and Biologically Active Molybdenum and Tungsten Bionic Complexes

在常温下合成了以邻苯二酚为配体,分别以乙二胺、1,2-丙二胺、1,3-丙二胺为抗衡离子的7种手性钼钨八面体配合物(NH2CH2CH2NH3)3[Mo(V)O2(OC6H4O)2](1),(NH2CH2CH2NH3)2[W(VI)O2(OC6H4O)2](2),(NH2CH2CH2NH3)2.5[Mo(V)0.5W(VI)0.5O2(O2C6H4)]2](3),(NH3CH2CHNH2CH3)3[Mo(V)O2(OC6H4O)2](4),(NH3CH2CHNH2CH3)2[W(VI)O2(OC6H4O)2](5),(NH3CH2CHNH2CH3)2.5[Mo(V)0.5W(VI)0.5O2(OC6H4O)2](6),(NH3CH2CH2CH3NH2)2.5[Mo(V)0.5W(VI)0.5O2(OC6H4O)2](7),并在生理条件下对其与ATP的相互作用进行了液体NMR研究,发现标题配合物的中心金属离子在纯D2O溶剂中大多数以+5价形式存在,W(VI)被还原为W(V),但与ATP混合后又转化为+6价,配合物原有的顺磁性特征完全消失.研究还发现ATP可以促进中心离子与原配体发生解离.

Seven molybdenum and tungsten octahedral complexes,with benzene-1,2-diol as a ligand and ethylenediamine 1,2-diaminopropane and 1,3-diaminopropane as counterions,respectively,were synthesized under normal temperature.The interactions between adenosine-triphosphate（ATP） and these compounds：（NH2CH2CH2NH3）3 [Mo（V）O2（OC6H4O）2]（1）,（NH2CH2CH2NH3）2 [W（VI）O2（OC6H4O）2]（2）,（NH2CH2 CH2NH3）2.5 [Mo（V）0.5W（VI）0.5O2（O2C6H4）]2]（3）,（NH3CH2CHNH2CH3）3 [Mo（V）O2（OC6H4O）2]（4）,（NH3CH2CHNH2CH3）2 [W（VI）O2（OC6H4O）2]（5）,（NH3CH2CHNH2CH3）2.5 [Mo（V）0.5W（VI）0.5O2（OC6H4O）2]（6） and（NH3CH2CH2 CH3NH2）2.5 [Mo（V）0.5W（VI）0.5O2（OC6H4O）2]（7） were studied by LC-NMR.The results showed that the valence of the center ions were ＋5 when the complexes were dissolved in D2O and the reduction of W（VI） to W（V） occurs.W（V） could be oxidized again when ATP solution was mixed with the original solution and hydrolysis of benzene-1,2-diol ligand took place.