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1,2-萘醌与腺嘌呤在二元水-乙腈溶液中的光化学反应。

Photochemical Reaction Between 1,2-Naphthoquinone and Adenine in Binary Water-Acetonitrile Solutions.

机构信息

Hefei National Laboratory for Physical Sciences at the Microscale, Department of Chemical Physics, University of Science and Technology of China, Hefei, Anhui, China.

Synergetic Innovation Center of Quantum Information & Quantum Physics, University of Science and Technology of China, Hefei, Anhui, China.

出版信息

Photochem Photobiol. 2018 Jan;94(1):61-68. doi: 10.1111/php.12808. Epub 2017 Sep 8.

Abstract

The photochemical reaction between 1,2-naphthoquinone (NQ) and adenine was investigated using nanosecond time-resolved laser flash photolysis. With photolysis at 355 nm, the lowest triplet state T of NQ was produced via intersystem crossing from its singlet excited state. The triplet-triplet absorption of the state contributes three bands of transient spectra at 374, 596 and 650 nm, respectively, in pure acetonitrile and binary water-acetonitrile solutions. In the presence of adenine, the observation of A· (at 363 nm) and NQ+H· radical (at 343 and 485 nm) indicates a multistep mechanism of electron transfer process followed by a proton transfer between NQ* and adenine. By fitting with the Stern-Volmer relationship, the quenching rate constant k of NQ* by adenine in binary water-acetonitrile solutions (4/1, volume ratio, v/v) is determined as 1.66 × 10  m  s . Additionally, no spectral evidence confirms the existence of electron transfer between NQ* with thymine, cytosine and uracil.

摘要

使用纳秒时间分辨激光闪光光解技术研究了 1,2-萘醌(NQ)与腺嘌呤之间的光化学反应。在 355nm 的光解下,NQ 的最低三重态 T 通过系间窜越从其单重激发态产生。该状态的三重态-三重态吸收在纯乙腈和二元水-乙腈溶液中分别贡献三个瞬态光谱带,分别在 374、596 和 650nm 处。在腺嘌呤存在下,观察到 A·(在 363nm 处)和 NQ+H·自由基(在 343 和 485nm 处)表明电子转移过程后是 NQ和腺嘌呤之间的质子转移的多步骤机制。通过与 Stern-Volmer 关系拟合,确定了在二元水-乙腈溶液(4/1,体积比,v/v)中 NQ被腺嘌呤猝灭的速率常数 k 为 1.66×10 m s 。此外,没有光谱证据证实 NQ*与胸腺嘧啶、胞嘧啶和尿嘧啶之间存在电子转移。

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