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Nitrobenzene "Caged" Compounds as Irreversible Photoreductants: A Rational Approach to Studying Photoinduced Intermolecular Electron-Transfer Reactions in Proteins

DiMagno, Theodore J. and Stowell, Michael H. B. and Chan, Sunney I. (1995) Nitrobenzene "Caged" Compounds as Irreversible Photoreductants: A Rational Approach to Studying Photoinduced Intermolecular Electron-Transfer Reactions in Proteins. Journal of Physical Chemistry, 99 (34). pp. 13038-13047. ISSN 0022-3654. doi:10.1021/j100034a052. https://resolver.caltech.edu/CaltechAUTHORS:20180525-111314381

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Abstract

Nitrobenzene “caged” compounds are well-known for their use in delivering biologically active substrates to a reaction mixture after photoexcitation. We have discovered that they also behave as photoreductants from the triplet state after photoexcitation. To explore the properties of these newly discovered photoreductants, a series of substituted nitrobenzene derivatives have been synthesized. These nitrobenzene derivatives exhibit many desirable characteristics suitable for the physiological photoreduction of different proteins, and examples are shown for the photoreduction of cytochrome c and other heme proteins. The observed rate constant for photoreduction of cytochrome c, k_(obs), ranges from 300 to 36 000 s^(-1) for the various nitrobenzene derivatives. pH and ionic strength experiments are consistent with a bimolecular reaction wherein the photoreductant and the protein form an electrostatic complex prior to electron transfer. A kinetic model for this bimolecular reaction is described and simulations of the experimental data for the photoreductant 4,5-dimethoxy-2-nitrophenylacetic acid (DMNPAA) yield an inherent unimolecular electron-transfer rate constant (ket) of 14 600 s^(-1) for the photoreduction of cytochrome c at pH 6.6.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://dx.doi.org/10.1021/j100034a052DOIArticle
ORCID:
AuthorORCID
Chan, Sunney I.0000-0002-5348-2723
Additional Information:© 1995 American Chemical Society. Received: June 8, 1995. We would like to thank Dr. Jay Winkler for his assistance with the nanosecond transient absorption apparatus in the Beckman Institute Laser Resource Center. This work was supported by grant GM22432 from the National Institute of General Medical Sciences, U. S . Public Health Service. TJD is the recipient of a National Research Service Award from the National Institute of General Medical Sciences (GM 15647).
Funders:
Funding AgencyGrant Number
NIHGM22432
NIH Predoctoral FellowshipGM15647
Other Numbering System:
Other Numbering System NameOther Numbering System ID
Division of Chemistry and Chemical Engineering9014
Issue or Number:34
DOI:10.1021/j100034a052
Record Number:CaltechAUTHORS:20180525-111314381
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20180525-111314381
Official Citation:Nitrobenzene "Caged" Compounds as Irreversible Photoreductants: A Rational Approach to Studying Photoinduced Intermolecular Electron-Transfer Reactions in Proteins Theodore J. DiMagno, Michael H. B. Stowell, and Sunney I. Chan The Journal of Physical Chemistry 1995 99 (34), 13038-13047 DOI: 10.1021/j100034a052
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:86623
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:25 May 2018 19:54
Last Modified:15 Nov 2021 20:40

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