SYNTHESIS OF AMPHIPATHIC PORPHYRINS AND THEIR PHOTOINDUCED ELECTRON TRANSFER REACTIONS AT THE LIPID BILAYER-WATER INTERFACE |
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Authors: | Kuo Chu Hwang David Mauzerall Richard W. Wagner Jonathan S. Lindsey |
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Affiliation: | 1The Rockefeller University, 1230 York Avenue, New York, NY 10021;2Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, PA 15213, USA |
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Abstract: | 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, 105∼ 106 s-1, which is attributed to a near orthogonal orientation between the donor and the acceptor ∼ orbitals. |
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