Hydrogen bonding in redox-modulated molecular recognition. An experimental and theoretical investigation.
Hydrogen bonding in redox-modulated molecular recognition. An experimental and theoretical investigation.
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DOI：
10.1021/ja035228b
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发表时间：
2003-06
影响因子：
15
通讯作者：
M. Gray;A. O. Cuello;G. Cooke;V. Rotello
中科院分区：
文献类型：
--
作者：
M. Gray;A. O. Cuello;G. Cooke;V. Rotello
二氨基三嗪衍生物（DAT）和二氨基吡啶（DAP）两个受体通过三点氢键与电活性萘酰亚胺(N)互补。在n的完全氧化态和自由基阴离子态下，两种受体的结合常数是相同的。然而，与二氨基三嗪相比，二氨基吡啶降低萘酰亚胺的还原电位的程度要大得多，这表明萘酰亚胺在自由基阴离子形式下对二氨基吡啶具有更大的亲和力。这种行为在EPR实验中得到了反映，EPR实验显示，在存在DAT的情况下，N（红色）的超精细耦合模式有很小的偏差，而N（红色）的影响更大。衣冠楚楚的复杂。利用UB3LYP/6-311+G(d,p)//UHF/6-31G(d)杂化体进行计算模拟，得到的理论超细常数与实验结果定量一致。利用这种相关性，我们确定静电和氢键极化率在控制氧化还原调节的分子识别中起关键作用。
Two receptors, a diaminotriazine derivative (DAT) and diamidopyridine (DAP), are complementary to the electroactive naphthalimide (N) through three-point hydrogen bonding. The association constants of the two receptors were evaluated for both the fully oxidized and the radical anion forms of N. In the oxidized state, the two receptors displayed identical binding constants. Diamidopyridine, however, lowers the reduction potential of naphthalimide to a far greater extent than does diaminotriazine, indicating a greater affinity for diamidopyridine by naphthalimide in the radical anion form. This behavior was mirrored by EPR experiments that showed small deviations from the hyperfine coupling pattern of N(red) in the presence of DAT, with greater effects seen for the N(red).DAP complex. Computational simulations using the UB3LYP/6-311+G(d,p)//UHF/6-31G(d) hybrid gave theoretical hyperfine constants in good quantitative agreement with the experimental results. Using this correlation, we determined that electrostatics and hydrogen bond polarizability play key roles in controlling redox-modulated molecular recognition.