Effect of Mg2+ cations on the dynamics and efficiency of hole transport in DNA

Arun Kalliat Thazhathveetil; Anton Trifonov; Michael R. Wasielewski; Frederick D. Lewis

doi:10.1021/jp502974s

Effect of Mg²⁺ cations on the dynamics and efficiency of hole transport in DNA

Arun Kalliat Thazhathveetil, Anton Trifonov, Michael R. Wasielewski, Frederick D. Lewis^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

3 Scopus citations

Abstract

The effect of Mg²⁺ cations on the electronic spectra and dynamics and efficiency of hole transport has been determined by means of femtosecond time-resolved transient absorption spectroscopy for DNA hairpins possessing stilbene electron acceptor and donor chromophores. The results are compared with those obtained previously for the same hairpins in the presence of Na⁺ cations and for one hairpin with no added salt. Quantum yields and rate constants for charge separation are smaller in the presence of Mg²⁺ than Na⁺, the largest differences being observed for the hairpins with the largest number of base pairs. Slower charge separation is attributed to minor groove binding by Mg²⁺, which results in a stiffer duplex structure rather than a change in ground state geometry. Reduction in the Na⁺ concentration has little effect on either the dynamics or efficiency of hole transport.

Original language	English (US)
Pages (from-to)	10359-10363
Number of pages	5
Journal	Journal of Physical Chemistry A
Volume	118
Issue number	45
DOIs	https://doi.org/10.1021/jp502974s
State	Published - Nov 13 2014

ASJC Scopus subject areas

Physical and Theoretical Chemistry

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title = "Effect of Mg2+ cations on the dynamics and efficiency of hole transport in DNA",

abstract = "The effect of Mg2+ cations on the electronic spectra and dynamics and efficiency of hole transport has been determined by means of femtosecond time-resolved transient absorption spectroscopy for DNA hairpins possessing stilbene electron acceptor and donor chromophores. The results are compared with those obtained previously for the same hairpins in the presence of Na+ cations and for one hairpin with no added salt. Quantum yields and rate constants for charge separation are smaller in the presence of Mg2+ than Na+, the largest differences being observed for the hairpins with the largest number of base pairs. Slower charge separation is attributed to minor groove binding by Mg2+, which results in a stiffer duplex structure rather than a change in ground state geometry. Reduction in the Na+ concentration has little effect on either the dynamics or efficiency of hole transport.",

author = "Thazhathveetil, {Arun Kalliat} and Anton Trifonov and Wasielewski, {Michael R.} and Lewis, {Frederick D.}",

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T1 - Effect of Mg2+ cations on the dynamics and efficiency of hole transport in DNA

AU - Thazhathveetil, Arun Kalliat

AU - Trifonov, Anton

AU - Wasielewski, Michael R.

AU - Lewis, Frederick D.

PY - 2014/11/13

Y1 - 2014/11/13

N2 - The effect of Mg2+ cations on the electronic spectra and dynamics and efficiency of hole transport has been determined by means of femtosecond time-resolved transient absorption spectroscopy for DNA hairpins possessing stilbene electron acceptor and donor chromophores. The results are compared with those obtained previously for the same hairpins in the presence of Na+ cations and for one hairpin with no added salt. Quantum yields and rate constants for charge separation are smaller in the presence of Mg2+ than Na+, the largest differences being observed for the hairpins with the largest number of base pairs. Slower charge separation is attributed to minor groove binding by Mg2+, which results in a stiffer duplex structure rather than a change in ground state geometry. Reduction in the Na+ concentration has little effect on either the dynamics or efficiency of hole transport.

AB - The effect of Mg2+ cations on the electronic spectra and dynamics and efficiency of hole transport has been determined by means of femtosecond time-resolved transient absorption spectroscopy for DNA hairpins possessing stilbene electron acceptor and donor chromophores. The results are compared with those obtained previously for the same hairpins in the presence of Na+ cations and for one hairpin with no added salt. Quantum yields and rate constants for charge separation are smaller in the presence of Mg2+ than Na+, the largest differences being observed for the hairpins with the largest number of base pairs. Slower charge separation is attributed to minor groove binding by Mg2+, which results in a stiffer duplex structure rather than a change in ground state geometry. Reduction in the Na+ concentration has little effect on either the dynamics or efficiency of hole transport.

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Effect of Mg²⁺ cations on the dynamics and efficiency of hole transport in DNA

Abstract

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