Polaronic semiconductor behavior of long-range charge transfer in DNA oligomers in solution: controlling barriers to long-distance radical cation migration in DNA with thymine analogs

2006 ◽  
Vol 131 ◽  
pp. 357-365 ◽  
Author(s):  
Abraham Joy ◽  
Gozde Guler ◽  
Shahadat Ahmed ◽  
Larry W. McLaughlin ◽  
Gary B. Schuster
Keyword(s):  
Charge Transfer ◽  
Long Range ◽  
Radical Cation ◽  
Long Distance ◽  
Dna Oligomers ◽  
Cation Migration ◽  
Semiconductor Behavior ◽  
Charge Transfer In Dna

Effect of positively charged backbone groups on radical cation migration and reaction in duplex DNA

2011 ◽  
Vol 89 (3) ◽  
pp. 326-330 ◽  
Author(s):  
Sriram Kanvah ◽  
Gary B. Schuster
Keyword(s):  
Radical Cation ◽  
Dna Analysis ◽  
Duplex Dna ◽  
Charge Migration ◽  
Electron Hole ◽  
Dna Oligomers ◽  
Phosphodiester Backbone ◽  
Cation Migration ◽  
Covalently Linked ◽  
Positively Charged

A series of DNA oligomers were prepared that contain guanidinium linkages (positively charged) positioned selectively in place of and among the normal negatively charged phosphodiester backbone groups of duplex DNA. One-electron oxidation of these DNA oligomers by UV irradiation of a covalently linked anthraquinone group generates a radical cation (electron “hole”) that migrates by hopping through the DNA and is trapped at reactive sites, GG steps, to form mutated bases that are detected by strand cleavage after subsequent piperidine treatment of the irradiated DNA. Analysis of the strand cleavage pattern reveals that guanidinium substitution in these oligomers does not measurably affect the charge migration rate but it does inhibit reaction at nearby guanines.

Long-Distance Radical Cation Migration through A/T Base Pairs in DNA:  An Experimental Test of Theory

2001 ◽  
Vol 105 (45) ◽  
pp. 11057-11059 ◽  
Author(s):  
Valerie Sartor ◽  
Edna Boone ◽  
Gary B. Schuster
Keyword(s):  
Radical Cation ◽  
Experimental Test ◽  
Base Pairs ◽  
Long Distance ◽  
Cation Migration

One-Electron Oxidation of DNA Oligomers That Lack Guanine:  Reaction and Strand Cleavage at Remote Thymines by Long-Distance Radical Cation Hopping

2006 ◽  
Vol 128 (16) ◽  
pp. 5346-5347 ◽  
Author(s):  
Abraham Joy ◽  
Avik K. Ghosh ◽  
Gary B. Schuster
Keyword(s):  
Radical Cation ◽  
Long Distance ◽  
Dna Oligomers ◽  
Oxidation Of Dna

Long-Distance Radical Cation Migration in Z-Form DNA

2001 ◽  
Vol 123 (27) ◽  
pp. 6696-6697 ◽  
Author(s):  
Ibrahim M. Abdou ◽  
Valerie Sartor ◽  
Huachuan Cao ◽  
Gary B. Schuster
Keyword(s):  
Radical Cation ◽  
Long Distance ◽  
Cation Migration

Long-range Stacking Effects of Nucleobases in Charge Transfer

2020 ◽  
Author(s):  
Zhongwei Li ◽  
Keli Han
Keyword(s):  
Charge Transfer ◽  
Long Range ◽  
Driving Force ◽  
Short Distance ◽  
Squeezing Effect ◽  
Base Pairs ◽  
Long Distance ◽  
Dna Charge Transfer ◽  
Stacking Effect ◽  
Dynamics Simulations

Base-stacked structure is an important feature of DNA molecules. Previous studies on the stacking effect concerning DNA-mediated hole transfer have revealed the influence of neighboring bases on onsite energies. But the neighboring base effect acts only in a short-distance. Besides it, a long-range (longer than three base pairs) stacking effect called squeezing effect in this paper has not yet been reported. Such a squeezing effect causes the bases near the middle of a sequence consisting of same type base pairs have lower onsite energies than the bases near the terminals. We predict it by H ̈uckelanalysis in an unconventional way and confirmed it by semiempirical calculations combinated with molecular dynamics simulations. The results suggest that in order to obtain a reasonable onsite energy map when study charge transfer on DNA, the stacking effects should be considered in a long-distance as possible. The consideration of squeezing effect also provides a new suggestion on the driving force of fluctuation-assisted DNA charge transfer. The method used to calculate the onsite energies in abase stack can be generalized to other π-stacked systems.<br><br>

TOWARD THE MECHANISM OF LONG-RANGE CHARGE TRANSFER IN DNA: THEORIES AND MODELS

2002 ◽  
Vol 01 (01) ◽  
pp. 225-244 ◽  
Author(s):  
YI JING YAN ◽  
HOUYU ZHANG
Keyword(s):  
Charge Transfer ◽  
Green’S Function ◽  
Long Range ◽  
Green's Function ◽  
Theoretical Development ◽  
Base Pairs ◽  
Hole Charge ◽  
Thymine Adenine ◽  
Recent Theoretical Development ◽  
Charge Transfer In Dna

This article reviews our recent theoretical development toward understanding the interplay of electronic structure and dephasing effects on charge transfer/transport through molecular donor-bridge-acceptor systems. Both the generalized scattering matrix and Green's function formalisms for partially incoherent tunneling processes are summarized. Presented is also an exact mapping between the kinetic rate constants and the electric conductances in evaluation of chemical yields of sequential charge transfer in the presence of competing branching reactions. As an important example, the mechanism of long-range charge transfer in DNA in aqueous solution is investigated with a quantum chemistry implementation of the generalized Green's function formalism. A time scale of about 5 ps is found for the partially incoherent tunneling through a thymine/adenine π-stack in DNA. Numerical results further show that while the carrier oxidative charge does hop sequentially over all guanine sites in a DNA duplex, its tunneling over thymine/adenine bridge base pairs deviates substantially from the superexchange regime. Presented are also evidences for the involvement of both intrastrand and interstrand pathways in the ground state hole charge transfer in DNA.

Sign in / Sign up

Export Citation Format

Share Document