Hydrogen-deuterium exchange of the carbon-bound C(8)-H protons of the inosine residues in tetrakis(inosine)platinum(ii) chloride, S, with Pt binding at N(7), was studied in aqueous buffer solutions at 60 degrees C by (1)H NMR spectroscopy. The kinetics at all four C(8) sites as a function of pD of the D(2)O/OD(-) medium was measured through the disappearance of the C(8)-H signal, which yielded the
在60°C的
水溶液缓冲液中研究了四(
肌苷)
铂(ii)
氯化物S中
肌苷残基的碳结合C(8)-H质子的氢
氘交换,S,Pt结合在N(7)上。 (1)H NMR光谱分析。通过C(8)-H信号的消失来测量D(2)O / OD(-)
培养基中所有四个C(8)位点的动力学,其作为pD的函数,这产生了伪一阶交换速率常数,k(obs)。k(obs)与[OD(-)]的曲线表明,曲率使人联想到饱和型动力学,并且表明N(1)-H位竞争性去质子化。相反,类似的N(1)-甲基化的顺式双(
1-甲基肌苷)二
氨合
铂(ii)
氯化物导致线性k(obs)与[OD(-)]图。该图显示出良好的线性度(R(2)= 0.99),这与线性自由能关系(LFER)相符。该LFER的较大的负斜率值(-2.3)反映了电子密度从电离N(1)经由Pt和/或空间穿过到其余C(8)-H位置的高灵敏度传输。就我们所知,这是通过调节单个分子中的结构产生LFER的