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THE EFFECTS OF WATER SOLVATION OF DOUBLE PROTON TRANSFER REACTIONS

机译:双质子转移反应水溶剂的影响

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Femtosecond pump-probe studies are presented on water-solvated 7-azaindole dimers formed in a molecular beam. The 7-azaindole dimer has been studied for many years as a model system for the exploration of excited state proton transfer reactions in DNA. It has been demonstrated that the 7-azaindole dimer forms two conformational isomers in the gas phase, one that undergoes proton transfer, and one which does not. Contrary to steady state experiments, our dynamics studies reveal that the nonreactive isomer is actually induced to undergo a double proton transfer reaction when clustered with water. Reactive behavior has been seen with as little as one and as many as nine water molecules clustered along with the dimer. Moreover, in contrast to previous suggestions, we show that the addition of water to the reactive dimer does not prevent the occurrence of the proton transfer reaction.
机译:Femtosecond泵探针研究显示在分子束中形成的水​​溶化7-唑底二聚体上。已经研究了7-唑底二聚体多年作为探索DNA中激发态质子转移反应的模型系统。已经证明,7-唑底二聚体在气相中形成两个构象异构体,其中经历质子转移,并且其中一个不存在。与稳态实验相反,我们的动力学研究表明,当与水聚集时,实际上诱导非反应性异构体进行双质子转移反应。与二聚体一起聚集的九个水分子很少看到反应性行为。此外,与先前的建议相反,我们表明向反应性二聚体加入水不会阻止质子转移反应的发生。

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