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Title: Reversible Redox-Based Optical Sensing of Parts per Million Levels of Nitrosyl Cation in Organic Solvents by Osmium Chromophore-Based Monolayers

Abstract

Exposure of an osmium(II)-based monolayer on glass to organic solvents containing 0.36-116 ppm of NOBF{sub 4} results in one-electron transfer from the covalently immobilized complexes to the inorganic analyte with concurrent optical changes. The NO{sup +} induced oxidation of the monolayer can be detected optically with an off-the-self-UV/vis spectrophotometer (260-800 nm). The redox-based NO{sup +} detection and quantification system can be reset with water within {approx}20 s for at least 40 times. The reaction of the monolayer with a THF solution containing 5 ppm of NOBF{sub 4} follows pseudo first-order kinetics in the monolayer with {Delta}G{sup {double_dagger}}{sub 298K} = 21.5 {+-} 0.7 kcal/mol, {Delta}H{sup {double_dagger}} = 9.5 {+-} 0.3 kcal/mol, and {Delta}S{sup {double_dagger}} = -40.6 {+-} 1.1 eu. The monolayer structure and properties have been resolved by electrochemical measurements and synchrotron X-ray reflectivity measurements in combination with density functional theory calculations (B3LYP/SDD level of theory).

Authors:
; ; ; ;
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL) National Synchrotron Light Source
Sponsoring Org.:
Doe - Office Of Science
OSTI Identifier:
930378
Report Number(s):
BNL-81100-2008-JA
Journal ID: ISSN 1932-7447; TRN: US0901378
DOE Contract Number:  
DE-AC02-98CH10886
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Physical Chemistry C; Journal Volume: 111
Country of Publication:
United States
Language:
English
Subject:
43 PARTICLE ACCELERATORS; CATIONS; DETECTION; FUNCTIONALS; GLASS; KINETICS; ORGANIC SOLVENTS; OSMIUM; OXIDATION; REFLECTIVITY; SPECTROPHOTOMETERS; SYNCHROTRON RADIATION; WATER; national synchrotron light source

Citation Formats

Gupta,T., Cohen, R., Evmenenko, G., Dutta, P., and van der Boom, M. Reversible Redox-Based Optical Sensing of Parts per Million Levels of Nitrosyl Cation in Organic Solvents by Osmium Chromophore-Based Monolayers. United States: N. p., 2007. Web. doi:10.1021/jp066853g.
Gupta,T., Cohen, R., Evmenenko, G., Dutta, P., & van der Boom, M. Reversible Redox-Based Optical Sensing of Parts per Million Levels of Nitrosyl Cation in Organic Solvents by Osmium Chromophore-Based Monolayers. United States. doi:10.1021/jp066853g.
Gupta,T., Cohen, R., Evmenenko, G., Dutta, P., and van der Boom, M. Mon . "Reversible Redox-Based Optical Sensing of Parts per Million Levels of Nitrosyl Cation in Organic Solvents by Osmium Chromophore-Based Monolayers". United States. doi:10.1021/jp066853g.
@article{osti_930378,
title = {Reversible Redox-Based Optical Sensing of Parts per Million Levels of Nitrosyl Cation in Organic Solvents by Osmium Chromophore-Based Monolayers},
author = {Gupta,T. and Cohen, R. and Evmenenko, G. and Dutta, P. and van der Boom, M.},
abstractNote = {Exposure of an osmium(II)-based monolayer on glass to organic solvents containing 0.36-116 ppm of NOBF{sub 4} results in one-electron transfer from the covalently immobilized complexes to the inorganic analyte with concurrent optical changes. The NO{sup +} induced oxidation of the monolayer can be detected optically with an off-the-self-UV/vis spectrophotometer (260-800 nm). The redox-based NO{sup +} detection and quantification system can be reset with water within {approx}20 s for at least 40 times. The reaction of the monolayer with a THF solution containing 5 ppm of NOBF{sub 4} follows pseudo first-order kinetics in the monolayer with {Delta}G{sup {double_dagger}}{sub 298K} = 21.5 {+-} 0.7 kcal/mol, {Delta}H{sup {double_dagger}} = 9.5 {+-} 0.3 kcal/mol, and {Delta}S{sup {double_dagger}} = -40.6 {+-} 1.1 eu. The monolayer structure and properties have been resolved by electrochemical measurements and synchrotron X-ray reflectivity measurements in combination with density functional theory calculations (B3LYP/SDD level of theory).},
doi = {10.1021/jp066853g},
journal = {Journal of Physical Chemistry C},
number = ,
volume = 111,
place = {United States},
year = {Mon Jan 01 00:00:00 EST 2007},
month = {Mon Jan 01 00:00:00 EST 2007}
}