VECTORIAL ELECTRON TRANSPORT ACROSS LIPID VESICLE MEMBRANES DRIVEN BY TWO PHOTOREACTIONS. I. ETHYLENEDIAMINETETRAACETIC ACID AS AN ELECTRON DONOR via FLAVIN TRIPLET STATE IN THE INNER COMPARTMENT AND CYTOCHROME c AS AN ELECTRON ACCEPTOR FROM CHLOROPHYLL TRIPLET STATE IN THE OUTER COMPARTMENT

Zhan-Gong Zhao, Gordon Tollin

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

Negatively charged vesicle suspensions containing chlorophyll a (chl) dissolved in the lipid bilayer, flavin mononucleotide (FMN) and/or ethylenediaminetetraacetic acid (EDTA) enclosed in the inner compartment as electron sources and oxidized cytochrome c (cyt c[ox]) in the outer compartment as an electron acceptor have been studied using laser flash photolysis and steady‐state irradiation methods. Cytochrome c initially quenches the chl triplet state (3chl) generating the chlorophyll cation radical (chi+′) in the membrane. Reverse electron transfer from cyt c(red) to chl+. subsequently occurs in a kinetically biphasic reaction, with rate constants of 430 pT 30 and 21.9 pT 1.7 s−1 for the fast and slow phases, respectively. In the absence of FMN, reduction of chl+′ by EDTA in the inner compartment can be observed during steady‐state irradiation but not in a laser flash photolysis experiment. This is due to a low reaction yield, which is probably limited by the repulsive electrostatic interaction between EDTA and the negatively charged membrane. When FMN was enclosed together with EDTA in the inner Compartment, the reaction yield of vectorial electron transfer across the bilayer from EDTA to cyt c(oX) was increased by a factor of six during steadystate white light irradiation. Laser flash photolysis and steady‐state irradiation experiments using red and blue light excitation have demonstrated that the enhancement mechanism involves the formation of fully reduced FMN by blue light‐sensitized photooxidation of EDTA via the flavin triplet state, occumng simultaneously with red lightsensitized electron transfer to cyt c via the chlorophyll triplet state.

Original languageEnglish (US)
Pages (from-to)331-337
Number of pages7
JournalPhotochemistry and Photobiology
Volume57
Issue number2
DOIs
StatePublished - Jan 1 1993

Fingerprint

ethylenediaminetetraacetic acids
cytochromes
chlorophylls
compartments
Chlorophyll
Membrane Lipids
Electron Transport
Cytochromes c
Edetic Acid
atomic energy levels
lipids
Flavin Mononucleotide
Electrons
membranes
Photolysis
Irradiation
flash
photolysis
electron transfer
Lasers

ASJC Scopus subject areas

  • Medicine(all)
  • Biochemistry
  • Physical and Theoretical Chemistry

Cite this

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title = "VECTORIAL ELECTRON TRANSPORT ACROSS LIPID VESICLE MEMBRANES DRIVEN BY TWO PHOTOREACTIONS. I. ETHYLENEDIAMINETETRAACETIC ACID AS AN ELECTRON DONOR via FLAVIN TRIPLET STATE IN THE INNER COMPARTMENT AND CYTOCHROME c AS AN ELECTRON ACCEPTOR FROM CHLOROPHYLL TRIPLET STATE IN THE OUTER COMPARTMENT",
abstract = "Negatively charged vesicle suspensions containing chlorophyll a (chl) dissolved in the lipid bilayer, flavin mononucleotide (FMN) and/or ethylenediaminetetraacetic acid (EDTA) enclosed in the inner compartment as electron sources and oxidized cytochrome c (cyt c[ox]) in the outer compartment as an electron acceptor have been studied using laser flash photolysis and steady‐state irradiation methods. Cytochrome c initially quenches the chl triplet state (3chl) generating the chlorophyll cation radical (chi+′) in the membrane. Reverse electron transfer from cyt c(red) to chl+. subsequently occurs in a kinetically biphasic reaction, with rate constants of 430 pT 30 and 21.9 pT 1.7 s−1 for the fast and slow phases, respectively. In the absence of FMN, reduction of chl+′ by EDTA in the inner compartment can be observed during steady‐state irradiation but not in a laser flash photolysis experiment. This is due to a low reaction yield, which is probably limited by the repulsive electrostatic interaction between EDTA and the negatively charged membrane. When FMN was enclosed together with EDTA in the inner Compartment, the reaction yield of vectorial electron transfer across the bilayer from EDTA to cyt c(oX) was increased by a factor of six during steadystate white light irradiation. Laser flash photolysis and steady‐state irradiation experiments using red and blue light excitation have demonstrated that the enhancement mechanism involves the formation of fully reduced FMN by blue light‐sensitized photooxidation of EDTA via the flavin triplet state, occumng simultaneously with red lightsensitized electron transfer to cyt c via the chlorophyll triplet state.",
author = "Zhan-Gong Zhao and Gordon Tollin",
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AU - Tollin, Gordon

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