Theoretical determination of the vibrational absorption and Raman spectra of 3-methylindole and 3-methylindole radicals
Theoretical determination of the vibrational absorption and Raman spectra of 3-methylindole and 3-methylindole radicals
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DOI：
10.1016/s0301-0104(01)00274-9
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发表时间：
2001-03-15
期刊：
影响因子：
2.3
通讯作者：
Jalkanen, KJ
中科院分区：
文献类型：
--
作者：
Bunte, SW;Jensen, GM;Jalkanen, KJ
我们报告了色氨酸类似物3-甲基吲哚的振动吸收和拉曼光谱的理论计算，使用密度泛函理论、Becke3LYP杂化泛函和TZ/2P基集。这些结果与实验测量的3-甲基吲哚的振动吸收和拉曼光谱进行了比较。目前，色氨酸自由基，无论是中性的还是阳离子的，都被认为参与了细胞色素c过氧化物酶、核糖核苷酸还原酶和DNA光解酶等酶的电子转移。本文还报道了3-甲基吲哚阳离子自由基和3-甲基吲哚中性自由基的理论振动吸收和拉曼光谱。这些预测将为生物系统中中性或阳离子色氨酸自由基的检测提供特定的光谱标记，为电子顺磁共振实验提供可用数据的补充。色氨酸的拉曼光谱已经用于蛋白质构象的研究；对色氨酸自由基种类的理论预测为色氨酸中性或阳离子自由基的检测提供了一种新的工具。(C) 2001年Elsevier Science B.V.出版
We report theoretical calculations of vibrational absorption and Raman spectra for the tryptophan analog 3-methylindole using density functional theory, the Becke3LYP hybrid functional, and the TZ/2P basis set. These results are compared to experimentally measured vibrational absorption and Raman spectra for 3-methylindole. The theoretical calculations represent accurate predictions of the observed vibrational frequencies and intensities, and of the Raman intensities, Currently, tryptophan radicals, either neutral or cationic, are believed to participate in electron transfer in enzymes such as cytochrome c peroxidase, ribonucleotide reductase, and DNA photolyase. In this paper we also report theoretical vibrational absorption and Raman spectra for 3-methylindole cation radical and 3-methylindole neutral radical. These predictions should provide specific spectroscopic markers for the detection of neutral or cationic tryptophan radicals in biological systems, providing a complement to the data available from electron paramagnetic resonance experiments. Raman spectroscopy of tryptophan is already in use in the study of protein conformations; theoretical predictions for the radical species provides a new tool for the detection of neutral or cation radicals of tryptophan in natural systems predisposed to the appropriate experiment. (C) 2001 Published by Elsevier Science B.V.