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三种新型醌氰基光酸的超快质子转移。

Ultrafast proton transfer of three novel quinone cyanine photoacids.

机构信息

Raymond and Beverly Sackler Faculty of Exact Sciences, School of Chemistry, Tel Aviv University, Tel Aviv 69978, Israel.

出版信息

J Phys Chem A. 2012 Jul 12;116(27):7353-63. doi: 10.1021/jp304123y. Epub 2012 Jul 2.

Abstract

Steady-state and time-resolved emission techniques were used to study the photoprotolytic properties of three recently synthesized strong quinone cyanine photoacids (QCy7 and its sulfonated derivatives). The rate coefficient of the excited-state proton transfer (ESPT), k(PT), of the three dyes is roughly 1.5 × 10(12) s(-1), a high value that is comparable to the solvation dynamics rate of large polar organic molecules in H(2)O and D(2)O. It is twice as fast as the proton transfer rate between two adjacent water molecules in liquid water. We found that, as expected, two of the sulfonated photoacids geminately recombines with the proton at an elevated rate. The accelerated geminate recombination process of the sulfonated derivatives is different from a simple diffusion process of protons. The ESPT rate coefficient of these molecules is the highest recorded thus far.

摘要

稳态和时间分辨发射技术被用于研究三种最近合成的强醌氰基光酸(QCy7 及其磺化衍生物)的光解性质。三种染料的激发态质子转移(ESPT)速率系数 k(PT)约为 1.5×10(12) s(-1),这是一个很高的值,与 H(2)O 和 D(2)O 中大极性有机分子的溶剂化动力学速率相当。它是液态水中两个相邻水分子之间质子转移速率的两倍。我们发现,正如预期的那样,两种磺化光酸以较高的速率与质子复合。磺化衍生物的加速复合过程不同于质子的简单扩散过程。这些分子的 ESPT 速率系数是迄今为止记录到的最高值。

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