OpenLB
Open Library of Bioscience
Advanced Search
Proceedings of the National Academy of Sciences of the United States of America
Aug 12, 2014;111 (32): 11612-7.

Efficient UV-induced charge separation and recombination in an 8-oxoguanine-containing dinucleotide.

Yuyuan Zhang, Jordan Dood, Ashley A Beckstead, Xi-Bo Li, Khiem V Nguyen, Cynthia J Burrows, Roberto Improta, Bern Kohler
Author Information
  1. Yuyuan Zhang: Department of Chemistry and Biochemistry, Montana State University, Bozeman, MT 59717;
  2. Jordan Dood: Department of Chemistry and Biochemistry, Montana State University, Bozeman, MT 59717;
  3. Ashley A Beckstead: Department of Chemistry and Biochemistry, Montana State University, Bozeman, MT 59717;
  4. Xi-Bo Li: Department of Chemistry, University of Utah, Salt Lake City, UT 84112; and.
  5. Khiem V Nguyen: Department of Chemistry, University of Utah, Salt Lake City, UT 84112; and.
  6. Cynthia J Burrows: Department of Chemistry, University of Utah, Salt Lake City, UT 84112; and kohler@chemistry.montana.edu burrows@chem.utah.edu robimp@unina.it.
  7. Roberto Improta: Consiglio Nazionale delle Ricerche, Istituto di Biostrutture e Bioimmagini, 80136 Naples, Italy kohler@chemistry.montana.edu burrows@chem.utah.edu robimp@unina.it.
  8. Bern Kohler: Department of Chemistry and Biochemistry, Montana State University, Bozeman, MT 59717; kohler@chemistry.montana.edu burrows@chem.utah.edu robimp@unina.it.
PMID: 25071180 DOI: 10.1073/pnas.1404411111

Abstract

During the early evolution of life, 8-oxo-7,8-dihydro-2'-deoxyguanosine (O) may have functioned as a proto-flavin capable of repairing cyclobutane pyrimidine dimers in DNA or RNA by photoinduced electron transfer using longer wavelength UVB radiation. To investigate the ability of O to act as an excited-state electron donor, a dinucleotide mimic of the FADH2 cofactor containing O at the 5'-end and 2'-deoxyadenosine at the 3'-end was studied by femtosecond transient absorption spectroscopy in aqueous solution. Following excitation with a UV pulse, a broadband mid-IR pulse probed vibrational modes of ground-state and electronically excited molecules in the double-bond stretching region. Global analysis of time- and frequency-resolved transient absorption data coupled with ab initio quantum mechanical calculations reveal vibrational marker bands of nucleobase radical ions formed by electron transfer from O to 2'-deoxyadenosine. The quantum yield of charge separation is 0.4 at 265 nm, but decreases to 0.1 at 295 nm. Charge recombination occurs in 60 ps before the O radical cation can lose a deuteron to water. Kinetic and thermodynamic considerations strongly suggest that all nucleobases can undergo ultrafast charge separation when π-stacked in DNA or RNA. Interbase charge transfer is proposed to be a major decay pathway for UV excited states of nucleic acids of great importance for photostability as well as photoredox activity.

Keywords

DNA charge transfer states DNA photophysics ab initio calculations photoreactivation time-resolved vibrational spectroscopy

References

Biopolymers. 1970;9(9):1059-77 [PMID: 5449435]
Photochem Photobiol Sci. 2013 Aug;12(8):1527-43 [PMID: 23842735]
J Phys Chem B. 2010 Mar 18;114(10):3660-7 [PMID: 20175506]
Proc Natl Acad Sci U S A. 2014 Mar 25;111(12):4369-74 [PMID: 24616517]
J Am Chem Soc. 2009 Mar 25;131(11):3913-22 [PMID: 19292489]
Nature. 1992 Feb 27;355(6363):796-802 [PMID: 1311417]
J Am Chem Soc. 2014 Apr 30;136(17):6362-72 [PMID: 24735123]
Adv Mater. 2010 Oct 1;22(37):4097-111 [PMID: 20803527]
J Phys Chem B. 2012 Aug 30;116(34):10266-74 [PMID: 22853704]
Science. 1971 Feb 19;171(3972):675-7 [PMID: 5540307]
J Am Chem Soc. 2010 Sep 1;132(34):11834-5 [PMID: 20698570]
Proc Natl Acad Sci U S A. 2008 Jul 29;105(30):10285-90 [PMID: 18647840]
Biochim Biophys Acta. 2004 Jul 9;1657(2-3):82-104 [PMID: 15238266]
Acc Chem Res. 2008 Feb;41(2):157-67 [PMID: 18186612]
Acc Chem Res. 2012 Dec 18;45(12):2151-9 [PMID: 23054469]
Faraday Discuss. 2013;163:173-88; discussion 243-75 [PMID: 24020202]
J Am Chem Soc. 2013 Jul 17;135(28):10290-3 [PMID: 23837540]
J Am Chem Soc. 2007 Feb 21;129(7):2074-81 [PMID: 17256856]
Phys Chem Chem Phys. 2014 Jan 28;16(4):1487-99 [PMID: 24302276]
Nat Mater. 2013 Jan;12(1):66-73 [PMID: 23223125]
J Am Chem Soc. 2003 Aug 27;125(34):10213-8 [PMID: 12926943]
Biophys J. 2004 Sep;87(3):1848-57 [PMID: 15345563]
J Phys Chem A. 2013 Dec 5;117(48):12851-7 [PMID: 24215180]
J Phys Chem A. 2009 Feb 26;113(8):1459-71 [PMID: 19191520]
J Am Chem Soc. 2011 Sep 21;133(37):14586-9 [PMID: 21877686]
J Chem Phys. 2006 Mar 7;124(9):94107 [PMID: 16526845]
J Phys Chem A. 2013 Aug 8;117(31):6771-80 [PMID: 23815368]
J Am Chem Soc. 2008 Oct 1;130(39):13132-9 [PMID: 18767842]
Proc Natl Acad Sci U S A. 2011 Sep 6;108(36):14831-6 [PMID: 21804035]
Science. 2007 Feb 2;315(5812):625-9 [PMID: 17272716]
Chem Rev. 2004 Apr;104(4):1977-2019 [PMID: 15080719]
Angew Chem Int Ed Engl. 2011 Dec 9;50(50):12016-9 [PMID: 22012744]
Proc Natl Acad Sci U S A. 2006 Feb 14;103(7):2150-3 [PMID: 16467159]
Chem Rev. 2005 Aug;105(8):2999-3093 [PMID: 16092826]
Nature. 2005 Aug 25;436(7054):1141-4 [PMID: 16121177]

MeSH Term

Base Pairing
Electron Transport
Guanine
Kinetics
Models, Chemical
Oligonucleotides
Photochemical Processes
Quantum Theory
Spectrophotometry, Atomic
Spectroscopy, Fourier Transform Infrared
Thermodynamics
Ultraviolet Rays

Chemicals

Oligonucleotides
8-hydroxyguanine
Guanine
Journal Article Research Support, Non-U.S. Gov't Research Support, U.S. Gov't, Non-P.H.S.

Word Cloud

Similar Articles

Cited By