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Title: Optical absorption, electron spin resonance, and electron spin echo studies of the photoionization of tetramethylbenzidine in cationic and anionic synthetic vesicles: comparison with analogous micellar systems

Abstract

The photoionization of N,N,N',N'-tetramethylbenzidine (TMB) in dihexadecylphosphate anionic vesicles and in dioctadecyldimethylammonium chloride cationic vesicles has been studied by optical absorption and electron spin resonance in liquid and frozen solutions. The TMB cation has been observed to be stabilized in both types of vesicles. The photoionization efficiency is about twofold greater in the cationic vesicles compared to the anionic vesicles. Shifts in the optical absorption maximum between micellar and vesicle solutions indicate that TMB is in a less polar environment in the vesicle systems. Electron spin echo modulation spectrometry has been used to detect TMB cation-water interactions that are found to be weaker than in previously studied micellar solutions. This is consistent with the optical absorption results and with an asymmetric solubilization site for TMB and TMB/sup +/ within the vesicular structure. A new absorption in the photoionized vesicles is assigned to a nonparamagnetic diamine-diimine charge-transfer complex between two TMB cations in the same vesicle. This complex is not formed in micellar systems. 5 figures.

Authors:
;
Publication Date:
Research Org.:
Univ. of Houston, TX
OSTI Identifier:
5641055
DOE Contract Number:  
AS05-80ER10745
Resource Type:
Journal Article
Resource Relation:
Journal Name: J. Am. Chem. Soc.; (United States); Journal Volume: 105:18
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 14 SOLAR ENERGY; AMINES; ABSORPTION SPECTRA; ACOUSTIC ESR; EXCITATION; RADICALS; MATRIX ISOLATION; ALKANES; AMMONIUM CHLORIDES; AMMONIUM COMPLEXES; ANIONS; AQUEOUS SOLUTIONS; CATIONS; COMPARATIVE EVALUATIONS; EXPERIMENTAL DATA; LOW TEMPERATURE; MATHEMATICAL MODELS; MEDIUM TEMPERATURE; MEMBRANES; MICELLAR SYSTEMS; PHOSPHORIC ACID ESTERS; PHOTOIONIZATION; PHOTOSYNTHESIS; SAMPLE PREPARATION; STRUCTURAL CHEMICAL ANALYSIS; SURFACTANTS; TEMPERATURE DEPENDENCE; ULTRALOW TEMPERATURE; ULTRASONIC WAVES; AMMONIUM COMPOUNDS; AMMONIUM HALIDES; CHARGED PARTICLES; CHEMICAL REACTIONS; CHLORIDES; CHLORINE COMPOUNDS; COMPLEXES; DATA; DISPERSIONS; ELECTRON SPIN RESONANCE; ENERGY-LEVEL TRANSITIONS; ESTERS; HALIDES; HALOGEN COMPOUNDS; HYDROCARBONS; INFORMATION; IONIZATION; IONS; MAGNETIC RESONANCE; MIXTURES; NUMERICAL DATA; ORGANIC COMPOUNDS; ORGANIC PHOSPHORUS COMPOUNDS; PHOTOCHEMICAL REACTIONS; RESONANCE; SOLUTIONS; SOUND WAVES; SPECTRA; SYNTHESIS; 400500* - Photochemistry; 400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987); 400104 - Spectral Procedures- (-1987); 140505 - Solar Energy Conversion- Photochemical, Photobiological, & Thermochemical Conversion- (1980-)

Citation Formats

Li, A.S.W., and Kevan, L. Optical absorption, electron spin resonance, and electron spin echo studies of the photoionization of tetramethylbenzidine in cationic and anionic synthetic vesicles: comparison with analogous micellar systems. United States: N. p., 1983. Web. doi:10.1021/ja00356a008.
Li, A.S.W., & Kevan, L. Optical absorption, electron spin resonance, and electron spin echo studies of the photoionization of tetramethylbenzidine in cationic and anionic synthetic vesicles: comparison with analogous micellar systems. United States. doi:10.1021/ja00356a008.
Li, A.S.W., and Kevan, L. Wed . "Optical absorption, electron spin resonance, and electron spin echo studies of the photoionization of tetramethylbenzidine in cationic and anionic synthetic vesicles: comparison with analogous micellar systems". United States. doi:10.1021/ja00356a008.
@article{osti_5641055,
title = {Optical absorption, electron spin resonance, and electron spin echo studies of the photoionization of tetramethylbenzidine in cationic and anionic synthetic vesicles: comparison with analogous micellar systems},
author = {Li, A.S.W. and Kevan, L.},
abstractNote = {The photoionization of N,N,N',N'-tetramethylbenzidine (TMB) in dihexadecylphosphate anionic vesicles and in dioctadecyldimethylammonium chloride cationic vesicles has been studied by optical absorption and electron spin resonance in liquid and frozen solutions. The TMB cation has been observed to be stabilized in both types of vesicles. The photoionization efficiency is about twofold greater in the cationic vesicles compared to the anionic vesicles. Shifts in the optical absorption maximum between micellar and vesicle solutions indicate that TMB is in a less polar environment in the vesicle systems. Electron spin echo modulation spectrometry has been used to detect TMB cation-water interactions that are found to be weaker than in previously studied micellar solutions. This is consistent with the optical absorption results and with an asymmetric solubilization site for TMB and TMB/sup +/ within the vesicular structure. A new absorption in the photoionized vesicles is assigned to a nonparamagnetic diamine-diimine charge-transfer complex between two TMB cations in the same vesicle. This complex is not formed in micellar systems. 5 figures.},
doi = {10.1021/ja00356a008},
journal = {J. Am. Chem. Soc.; (United States)},
number = ,
volume = 105:18,
place = {United States},
year = {Wed Sep 07 00:00:00 EDT 1983},
month = {Wed Sep 07 00:00:00 EDT 1983}
}