Synthesis of amphipathic porphyrins and their photoinduced electron transfer reactions at the lipid bilayer-water interface.
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.
Hwang
K C
KC
Rockefeller University, New York, NY 10021.
Mauzerall
D
D
Wagner
R W
RW
Lindsey
J S
JS
D004563:Electrochemistry; D004579:Electron Transport; D008051:Lipid Bilayers / Q000737:chemistry; D010777:Photochemistry; D011166:Porphyrins / Q000138:chemical synthesis* / Q000737:chemistry / Q000528:radiation effects*; D014867:Water / Q000737:chemistry
D008051:Lipid Bilayers; D011166:Porphyrins; D014867:Water