Hu J, Griffin R G, Herzfeld J
Department of Chemistry, Brandeis University, Waltham, MA 02254-9110.
Proc Natl Acad Sci U S A. 1994 Sep 13;91(19):8880-4. doi: 10.1073/pnas.91.19.8880.
UV-visible and solid-state NMR studies of a series of 6-s-trans protonated Schiff bases of retinal with aniline show that the bathochromic shift induced by weakening the imine counterion is significantly greater in the 6-s-trans conformation than in the 6-s-cis conformation. Based on the observed magnitude of this coupling between the electronic effects of 6-s isomerization and imine counterion strength in the model compounds, the large opsin shift and unusual chemical shifts in light-adapted bacteriorhodopsin can be fully explained. These phenomena therefore do not require a negative point charge or polarizability effects in the chromophore binding pocket. The results are consistent with an effective center-to-center distance between the Schiff base and its counterion of about 4 A in light-adapted bacteriorhodopsin.
对一系列视网膜与苯胺形成的6-s-反式质子化席夫碱进行的紫外可见光谱和固态核磁共振研究表明,在6-s-反式构象中,因亚胺抗衡离子减弱而引起的红移比在6-s-顺式构象中显著更大。基于在模型化合物中观察到的6-s异构化的电子效应与亚胺抗衡离子强度之间这种耦合的大小,光适应型细菌视紫红质中较大的视蛋白位移和异常的化学位移可以得到充分解释。因此,这些现象不需要发色团结合口袋中存在负点电荷或极化率效应。结果与光适应型细菌视紫红质中席夫碱与其抗衡离子之间约4埃的有效中心距一致。