多烯席夫碱C=N伸缩频率影响因素的分析。对视紫红质和细菌视紫红质的启示。
Analysis of the factors that influence the C=N stretching frequency of polyene Schiff bases. Implications for bacteriorhodopsin and rhodopsin.
作者信息
Gilson H S, Honig B H, Croteau A, Zarrilli G, Nakanishi K
机构信息
Department of Biochemistry and Molecular Biophysics, Columbia University, New York, New York 10032.
出版信息
Biophys J. 1988 Feb;53(2):261-9. doi: 10.1016/S0006-3495(88)83087-X.
Abstract
In this study quantum mechanical calculations of force constants and normal mode analysis are used to elucidate the factors that influence the C=C and C=N stretching frequencies in polyenes and in protonated Schiff bases. The C=N stretching frequency is found to depend on both the C=N stretching force constant and the C=N-H bending force constant. Due to the contributions of these two modes, the C=N stretching frequency is particularly sensitive to the magnitude of the Schiff base counterion interactions and to the hydrogen bonding environment of the Schiff base nitrogen. Models for chromophore-protein interactions in the retinal binding site and for the photochemical transformations of bacteriorhodopsin and rhodopsin are evaluated in light of these results.
摘要
在本研究中，利用力常数的量子力学计算和简正模式分析来阐明影响多烯和质子化席夫碱中C = C和C = N伸缩频率的因素。发现C = N伸缩频率既取决于C = N伸缩力常数，也取决于C = N - H弯曲力常数。由于这两种模式的贡献，C = N伸缩频率对席夫碱抗衡离子相互作用的大小以及席夫碱氮的氢键环境特别敏感。根据这些结果，对视网膜结合位点中发色团 - 蛋白质相互作用以及细菌视紫红质和视紫红质的光化学转变模型进行了评估。
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