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Electron spin resonance, electron spin echo, and electron nuclear double resonance investigations of the photoreduction yield of a series of alkylmethylviologens in dihexadecyl phosphate vesicles: Effect of added cholesterol

Journal Article · · Journal of Physical Chemistry; (United States)
DOI:https://doi.org/10.1021/j100177a099· OSTI ID:7072542
;  [1]
  1. Univ. of Houston, TX (United States)
The initial event in photosynthesis, photoinduced charge separation, takes place in a membrane bound proton/chlorophyll complex - the photosynthetic reaction center. An electron spin resonance (ESR), electron spin echo (ESE), and electron nuclear double resonance (ENDOR) investigation was performed on a series of alkylmethylviolgens which were solubilized in dihexadecyl phosphate (DHP) vesicles and rapidly frozen at 77 K. Photoreduction yields were measured by ESR, while ESE and matrix ENDOR were used to determine the location of the viologen radical in the lipid bilayer with respect to the water interface and the hydrocarbon interior, respectively. The effect of various concentrations on cholesterol on both the photoreduction yield and the location of the viologen probe within the DHP vesicle was measured. The ESE and ENDOR results indicate that the increased lipophilicity of the longer chained viologens effects deeper solubilization into the bilayer. This increased lipophilicity correlates with an enhancement of the photoreduction yield due to a reduced back electron transfer rate. Addition of cholesterol results in a disruption of the integrity of the vesicle interface and some increase in the photoreduction yield. This increase is mostly probably due to a decrease in effective interface charge density of the vesicle as a result of the intercalation of cholesterol molecules into the bilayer.
OSTI ID:
7072542
Journal Information:
Journal of Physical Chemistry; (United States), Journal Name: Journal of Physical Chemistry; (United States) Vol. 95:24; ISSN JPCHAX; ISSN 0022-3654
Country of Publication:
United States
Language:
English