Hwang K C, Mauzerall D, Wagner R W, Lindsey J S
Rockefeller University, New York, NY 10021.
Photochem Photobiol. 1994 Feb;59(2):145-51. doi: 10.1111/j.1751-1097.1994.tb05014.x.
A one flask synthesis of cis-substituted amphipathic porphyrins is reported. These porphyrins were used to study electrostatic effects on photoinduced electron transfer across the lipid bilayer-water interface. A neutral porphyrin undergoes only dynamic interfacial electron transfer reactions irrespective of charge of the acceptor, although ionic strength effects indicate a negative charge on the porphyrin donor species. A dianionic porphyrin forms an interfacial static complex with a dicationic electron acceptor, methyl viologen, at low ionic strength. The electron transfer rate within the complex is slow, 10(5) approximately 10(6) s-1, which is attributed to a near orthogonal orientation between the donor and the acceptor pi orbitals.
报道了一种顺式取代两亲性卟啉的单瓶合成方法。这些卟啉被用于研究静电作用对光诱导电子穿过脂质双层-水界面转移的影响。一种中性卟啉仅发生动态界面电子转移反应，而与受体电荷无关，尽管离子强度效应表明卟啉供体物种上带有负电荷。一种二价阴离子卟啉在低离子强度下与二价阳离子电子受体甲基紫精形成界面静态复合物。复合物内的电子转移速率较慢，约为10⁵至10⁶ s⁻¹，这归因于供体和受体π轨道之间近乎正交的取向。
