Dynamics and Efficiency of DNA Hole Transport via Alternating AT versus Poly(A) Sequences

Lewis, Frederick D.; Daublain, Pierre; Cohen, Boiko; Vura‐Weis, Josh; Shafirovich, Vladimir; Wasielewski, Michael R.

doi:10.1021/ja076876o

Cited by 34 publications

(67 citation statements)

References 12 publications

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“…By contrast, for interstrand HT in DNA, Lewis's group reported that the efficiency of interstrand HT in DNA is lower than that of intrastrand HT by a factor of 4, due to the lack of interaction between the HOMOs of A's, based on femtosecond laser flash photolysis studies. 66 We obtained similar results using nanosecond laser flash photolysis in our previous report. 18 Thus, direct measurement of the dynamics of EET in DNA by laser flash photolysis is essential to achieve a quantitative understanding of interstrand EET.…”

Section: Excess Electron Transfer In Dnasupporting

confidence: 89%

Charge transfer dynamics in DNA revealed by time-resolved spectroscopy

Fujitsuka

Majima

2017

Chem. Sci.

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Section: Excess Electron Transfer In Dnasupporting

confidence: 89%

Charge transfer dynamics in DNA revealed by time-resolved spectroscopy

Fujitsuka

Majima

2017

Chem. Sci.

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“…Comparison of rate constants and quantum yields for charge separation in Sa/Sd capped hairpins having alternating AT base sequences vs. poly(A) sequences showed that hole transport is much slower in the alternating sequences [15]. For example, charge separation across an ATAT sequence occurred with lower efficiency than across a longer A 7 sequence.…”

Section: Charge Transport In Homopurine and Alternating Base Sequencesmentioning

confidence: 99%

Dynamics and efficiency of photoinduced charge transport in DNA: Toward the elusive molecular wire

Lewis

Wasielewski

2013

Pure and Applied Chemistry

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Experimental investigations of photoinduced charge transport in synthetic DNA capped hairpins possessing electron acceptor and donor stilbene chromophores at either end have established the mechanism, dynamics, and efficiency of charge transport in DNA. The mechanism for charge transport in repeating A-T base pairs (A-tracts) was found to change from single-step superexchange at short distances to multistep incoherent hole hopping at longer distances. The rate constants for base-to-base hole hopping in longer A-and G-tract sequences are 1.2 × 10 9 s -1 and 4.3 × 10 9 s -1 , respectively, considerably slower than the rate constants associated with molecular wires. Even slower rate constants are observed for alternating or random base sequences such as those encountered in natural DNA. The efficiency of charge separation in capped hairpins with A-tract sequences is also low as a consequence of the competition of hole hopping with charge recombination. Significantly higher efficiencies for charge separation are possible using diblock purine base sequences consisting of two or three adenines followed by a larger number of guanines. The short A-block serves as a molecular rectifier, slowing down charge recombination. More efficient charge separation can also be achieved using non-natural bases or by using the triplet acceptor anthraquinone for hole injection.Keywords: DNA; electron transfer; hole hopping; photochemistry; superexchange.provides a rate constant of 5 × 10 8 s -1 for this process, only slightly slower than the rate constant for A-to-A hole hopping in DNA [12].

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“…Similar to donor-linked hairpin systems, the rate of charge injection into Sd-capped hairpin bridges consisting of only A is several-fold higher than charge injection into bridges containing AT repeats of similar length. 64 The sequence affects the yield of injection as well as the rate, as measured by the transient absorbance of the acceptor cation radical. This sequence dependence was observed in diblock oligomers, where the donor and acceptor were separated by bridges of the type (A·T) n (G·C) m .…”

Section: Dna Ct In Solutionmentioning

confidence: 99%

Solution, surface, and single molecule platforms for the study of DNA-mediated charge transport

Muren

Olmon

Barton

2012

Phys. Chem. Chem. Phys.

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The structural core of DNA, a continuous stack of aromatic heterocycles, the base pairs, which extends down the helical axis, gives rise to the fascinating electronic properties of this molecule that is so critical for life. Our laboratory and others have developed diverse experimental platforms to investigate the capacity of DNA to conduct charge, termed DNA-mediated charge transport (DNA CT). Here, we present an overview of DNA CT experiments in solution, on surfaces, and with single molecules that collectively provide a broad and consistent perspective on the essential characteristics of this chemistry. DNA CT can proceed over long molecular distances but is remarkably sensitive to perturbations in base pair stacking. We discuss how this foundation, built with data from diverse platforms, can be used both to inform a mechanistic description of DNA CT and to inspire the next platforms for its study: living organisms and molecular electronics.

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Dynamics and Efficiency of DNA Hole Transport via Alternating AT versus Poly(A) Sequences

Cited by 34 publications

References 12 publications

Charge transfer dynamics in DNA revealed by time-resolved spectroscopy

Charge transfer dynamics in DNA revealed by time-resolved spectroscopy

Dynamics and efficiency of photoinduced charge transport in DNA: Toward the elusive molecular wire

Solution, surface, and single molecule platforms for the study of DNA-mediated charge transport

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