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.
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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). | ||||||
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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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