author_facet Sun, K
Mauzerall, D
Sun, K
Mauzerall, D
author Sun, K
Mauzerall, D
spellingShingle Sun, K
Mauzerall, D
Proceedings of the National Academy of Sciences
A simple light-driven transmembrane proton pump.
Multidisciplinary
author_sort sun, k
spelling Sun, K Mauzerall, D 0027-8424 1091-6490 Proceedings of the National Academy of Sciences Multidisciplinary http://dx.doi.org/10.1073/pnas.93.20.10758 <jats:p>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.</jats:p> A simple light-driven transmembrane proton pump. Proceedings of the National Academy of Sciences
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series Proceedings of the National Academy of Sciences
source_id 49
title A simple light-driven transmembrane proton pump.
title_unstemmed A simple light-driven transmembrane proton pump.
title_full A simple light-driven transmembrane proton pump.
title_fullStr A simple light-driven transmembrane proton pump.
title_full_unstemmed A simple light-driven transmembrane proton pump.
title_short A simple light-driven transmembrane proton pump.
title_sort a simple light-driven transmembrane proton pump.
topic Multidisciplinary
url http://dx.doi.org/10.1073/pnas.93.20.10758
publishDate 1996
physical 10758-10762
description <jats:p>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.</jats:p>
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author Sun, K, Mauzerall, D
author_facet Sun, K, Mauzerall, D, Sun, K, Mauzerall, D
author_sort sun, k
container_issue 20
container_start_page 10758
container_title Proceedings of the National Academy of Sciences
container_volume 93
description <jats:p>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.</jats:p>
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id ai-49-aHR0cDovL2R4LmRvaS5vcmcvMTAuMTA3My9wbmFzLjkzLjIwLjEwNzU4
imprint Proceedings of the National Academy of Sciences, 1996
imprint_str_mv Proceedings of the National Academy of Sciences, 1996
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spelling Sun, K Mauzerall, D 0027-8424 1091-6490 Proceedings of the National Academy of Sciences Multidisciplinary http://dx.doi.org/10.1073/pnas.93.20.10758 <jats:p>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.</jats:p> A simple light-driven transmembrane proton pump. Proceedings of the National Academy of Sciences
spellingShingle Sun, K, Mauzerall, D, Proceedings of the National Academy of Sciences, A simple light-driven transmembrane proton pump., Multidisciplinary
title A simple light-driven transmembrane proton pump.
title_full A simple light-driven transmembrane proton pump.
title_fullStr A simple light-driven transmembrane proton pump.
title_full_unstemmed A simple light-driven transmembrane proton pump.
title_short A simple light-driven transmembrane proton pump.
title_sort a simple light-driven transmembrane proton pump.
title_unstemmed A simple light-driven transmembrane proton pump.
topic Multidisciplinary
url http://dx.doi.org/10.1073/pnas.93.20.10758