在合成和表征了 4种具有较强生物活性双过氧钒配合物K3 [VO(O2 ) 2 (ox) ]·2H2 O ,Na[VO(O2 ) 2 (bipy) ]·5H2 O ,K[VO(O2 ) 2 (phen) ]·3H2 O和K2 [VO(O2 ) 2 (pic) ]·2H2 O [分别缩写为pV(ox) ,pV(bipy) ,pV(phen)和pV(pic) ,其中ox为草酸根 ,bipy为 2 ,2′ 联吡啶 ,phen为邻菲咯啉 ,pic为 2 羧酸吡啶负离子 ]的基础上 ,利用多种NMR技术和电喷雾质谱 (ESI MS)研究了这 4种含有机配体双过氧钒配合物与组氨酸 (His)在溶液中的相互作用以及反应物浓度、时间、pH等对相互作用体系的影响 .51VNMR跟踪监测的结果表明 :双过氧钒配合物pV(ox)和pV(pic)与His在中性水溶液中存在强配位相互作用 ,而pV(bipy)和pV(phen)与His在中性水溶液中无明显作用 .我们还利用谱学方法确定了pV(ox)和His相互作用后所生成产物是pV(ox)分别与His咪唑基上的 3 N和 1 N配位的一对异构体.
In order to explore the structure2activity relationship and molecular mechanism of the specific
recognition between peroxovanadium (pV) complexes bearing organic ligands and the target enzymes of tyrosine
phosphatase , several NMR techniques and ESI2MS were used to study the interactions of four pV complexes
{pV(ox) , pV ( bipy) , pV (phen) and pV (pic) , where pV = [VO (O2 ) 2L ] n - , in which L = oxalic acid
dianion (ox) , bipyridine (bipy) , 1 ,102phenanthroline (phen) , and pyridine222carboxylic acid (pic) } towards
histidine. Strong coordination interactions between imidazole of histidine and vanadium of pV(ox) or pV(pic)
were observed in neutral solution , while there are not obvious interactions between histidine and pV(bipy) or
pV(phen) . All 13C and 1H NMR signals of 1∶1 stoichiometric mixture of pV(ox) and histidine were assigned.
Spectroscopic studies demonstrated that new complexes in the mixture of pV(ox) and histidine are a pair of
isomers in which the vanadium in pV(ox) binding to the 32N and 12N of the imidazole ring. Moreover , the
results of effective factors on the interaction system indicated that the new isomers were stable under the
condition of physiological pH and the structure2activity relationship of these pV complexes may be relevant to
their specific recognition towards histidine residues in tyrosine phosphatase.国家自然科学基金 (Nos.2 0 172 0 42 ,2 9832 0 2 0 )资助项
