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Charge Photoinjection in Intercalated and Covalently Bound [Re(CO)_(3)(dppz)(py)]^(+)–DNA Constructs Monitored by Time-Resolved Visible and Infrared Spectroscopy

Olmon, Eric D. and Sontz, Pamela A. and Blanco-Rodríguez, Ana-María and Towrie, Michael and Clark, Ian P. and Vlček, Antonín, Jr. and Barton, Jacqueline K. (2011) Charge Photoinjection in Intercalated and Covalently Bound [Re(CO)_(3)(dppz)(py)]^(+)–DNA Constructs Monitored by Time-Resolved Visible and Infrared Spectroscopy. Journal of the American Chemical Society, 133 (34). pp. 13718-13730. ISSN 0002-7863. PMCID PMC3227519. https://resolver.caltech.edu/CaltechAUTHORS:20111115-142739242

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Abstract

The complex [Re(CO)_(3)(dppz)(py′-OR)]+ (dppz = dipyrido[3,2-a:2′,3′-c]phenazine; py′-OR = 4-functionalized pyridine) offers IR sensitivity and can oxidize DNA directly from the excited state, making it a promising probe for the study of DNA-mediated charge transport (CT). The behavior of several covalent and noncovalent Re–DNA constructs was monitored by time-resolved IR (TRIR) and UV/visible spectroscopies, as well as biochemical methods, confirming the long-range oxidation of DNA by the excited complex. Optical excitation of the complex leads to population of MLCT and at least two distinct intraligand states. Experimental observations that are consistent with charge injection from these excited states include similarity between long-time TRIR spectra and the reduced state spectrum observed by spectroelectrochemistry, the appearance of a guanine radical signal in TRIR spectra, and the eventual formation of permanent guanine oxidation products. The majority of reactivity occurs on the ultrafast time scale, although processes dependent on slower conformational motions of DNA, such as the accumulation of oxidative damage at guanine, are also observed. The ability to measure events on such disparate time scales, its superior selectivity in comparison to other spectroscopic techniques, and the ability to simultaneously monitor carbonyl ligand and DNA IR absorption bands make TRIR a valuable tool for the study of CT in DNA.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja205568r DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja205568rPublisherArticle
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC3227519/PubMed CentralArticle
ORCID:
AuthorORCID
Barton, Jacqueline K.0000-0001-9883-1600
Additional Information:© 2011 American Chemical Society. Published In Issue: August 31, 2011; Article ASAP: August 09, 2011; Received: June 15, 2011. We are grateful to the NIH (GM49216) for financial support. E.D.O. also thanks G. E. Keller, N. D. Ford, and J. R. Winkler for assistance with picosecond emission measurements and M. G. Hill for assistance with spectroelectrochemical measurements.
Funders:
Funding AgencyGrant Number
NIHGM49216
Issue or Number:34
PubMed Central ID:PMC3227519
Record Number:CaltechAUTHORS:20111115-142739242
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20111115-142739242
Official Citation:Charge Photoinjection in Intercalated and Covalently Bound [Re(CO)3(dppz)(py)]+–DNA Constructs Monitored by Time-Resolved Visible and Infrared Spectroscopy Eric D. Olmon, Pamela A. Sontz, Ana Maria Blanco-Rodriguez, Michael Towrie, Ian P. Clark, Antonin Vlcek Jr.Jacqueline K. Barton Journal of the American Chemical Society 2011 133 (34), 13718-13730
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:27788
Collection:CaltechAUTHORS
Deposited By: Jason Perez
Deposited On:16 Nov 2011 15:47
Last Modified:03 Oct 2019 03:26

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