A simple light-driven transmembrane proton pump.
Light-induced lipophilic porphyrin/aqueous acceptor charge separation across a single lipid-water interface can pump protons across the lipid bilayer when the hydrophobic weak acids, carbonylcyanide m-chlorophenylhydrazone and its p-trifluoromethoxyphenyl analogue, are present. These compounds act as proton carriers across lipid bilayers. In their symmetric presence across the bilayer, the positive currents and voltages produced by the photogeneration of porphyrin cations are replaced by larger negative currents and voltages. The maximum negative current and voltage occur at the pH of maximum dark conductance. The reversed larger current and voltage show a positive ionic charge transport in the same direction as the electron transfer. This transport can form an ion concentration gradient. The movement of protons is verified by an unusual D2O isotope effect that increases the negative ionic current by 2- to 3-fold. These effects suggest that an interfacial pK shift of the weak acid caused by the local electric field of photoformed porphyrin cations/acceptor anions functions as the driving force. The estimated pumping efficiency is 10-30%. Time-resolved results show that proton pumping across the bilayer occurs on the millisecond time scale, similar to that of biological pumps. This light-driven proteinless pump offers a simple model for a prebiological energy transducer.
Sun
K
K
Rockefeller University, New York, NY 10021, USA.
Mauzerall
D
D
D000143:Acids / Q000737:chemistry; D001693:Biological Transport, Active; D004553:Electric Conductivity; D006863:Hydrogen-Ion Concentration; D008027:Light; D008564:Membrane Potentials; D008567:Membranes, Artificial; D008956:Models, Chemical; D010713:Phosphatidylcholines / Q000737:chemistry; D010777:Photochemistry; D011166:Porphyrins / Q000737:chemistry
D000143:Acids; D008567:Membranes, Artificial; D010713:Phosphatidylcholines; D011166:Porphyrins