Journal ArticleDOI
Effect of Structural Dynamics on Charge Transfer in DNA Hairpins
Ferdinand C. Grozema,Ferdinand C. Grozema,Stefano Tonzani,Yuri A. Berlin,George C. Schatz,Laurens D. A. Siebbeles,Mark A. Ratner +6 more
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TLDR
It is concluded both that the relatively strong distance dependence for short bridges is mostly due to this electrostatic interaction and that structural fluctuations play a critical role in the charge transfer, especially for longer bridge lengths.Abstract:
We present a theoretical study of the positive charge transfer in stilbene-linked DNA hairpins containing only AT base pairs using a tight-binding model that includes a description of structural fluctuations. The parameters are the charge transfer integral between neighboring units and the site energies. Fluctuations in these parameters were studied by a combination of molecular dynamics simulations of the structural dynamics and density functional theory calculations of charge transfer integrals and orbital energies. The fluctuations in both parameters were found to be substantial and to occur on subpicosecond time scales. Tight-binding calculations of the dynamics of charge transfer show that for short DNA hairpins (<4 base pairs) the charge moves by a single-step superexchange mechanism with a relatively strong distance dependence. For longer hairpins, a crossover to a fluctuation-assisted incoherent mechanism was found. Analysis of the charge distribution during the charge transfer process indicates that for longer bridges substantial charge density builds up on the bridge, but this charge density is mostly confined to the adenine next to the hole donor. This is caused by the electrostatic interaction between the hole on the AT bridge and the negative charge on the hole donor. We conclude both that the relatively strong distance dependence for short bridges is mostly due to this electrostatic interaction and that structural fluctuations play a critical role in the charge transfer, especially for longer bridge lengths.read more
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疟原虫var基因转换速率变化导致抗原变异[英]/Paul H, Robert P, Christodoulou Z, et al//Proc Natl Acad Sci U S A
TL;DR: PfPMP1)与感染红细胞、树突状组胞以及胎盘的单个或多个受体作用,在黏附及免疫逃避中起关键的作�ly.
Journal ArticleDOI
Mechanisms for DNA Charge Transport
TL;DR: Some of the critical characteristics of DNA charge transport chemistry are reviewed, taking examples from a range of systems, and consider these characteristics in the context of their mechanistic implications.
Journal ArticleDOI
Hyperuniform states of matter
TL;DR: Hyperuniform states of matter are correlated systems that are characterized by an anomalous suppression of long-wavelength (i.e., large-length-scale) density fluctuations compared to those found in garden-variety disordered systems, such as ordinary fluids and amorphous solids as mentioned in this paper.
Journal ArticleDOI
Hyperuniform States of Matte
TL;DR: Hyperuniform states of matter are correlated systems that are characterized by an anomalous suppression of long-wavelength (i.e., large-length-scale) density fluctuations compared to those found in garden-variety disordered systems, such as ordinary fluids and amorphous solids.
Journal ArticleDOI
Electronic couplings for molecular charge transfer: benchmarking CDFT, FODFT, and FODFTB against high-level ab initio calculations.
TL;DR: In this paper, the authors introduced a database (HAB11) of electronic coupling matrix elements (Hab) for electron transfer in 11 π-conjugated organic homo-dimer cations.
References
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疟原虫var基因转换速率变化导致抗原变异[英]/Paul H, Robert P, Christodoulou Z, et al//Proc Natl Acad Sci U S A
TL;DR: PfPMP1)与感染红细胞、树突状组胞以及胎盘的单个或多个受体作用,在黏附及免疫逃避中起关键的作�ly.
Journal ArticleDOI
Chemistry with ADF
G. te Velde,F.M. Bickelhaupt,Evert Jan Baerends,C. Fonseca Guerra,S. J. A. van Gisbergen,J.G. Snijders,T. Ziegler +6 more
TL;DR: The “Activation‐strain TS interaction” (ATS) model of chemical reactivity is reviewed as a conceptual framework for understanding how activation barriers of various types of reaction mechanisms arise and how they may be controlled, for example, in organic chemistry or homogeneous catalysis.
Journal ArticleDOI
Application of the multimolecule and multiconformational RESP methodology to biopolymers: Charge derivation for DNA, RNA, and proteins
TL;DR: The combined use of multiple molecules, multiple conformations, multiple Lagrangian constraints, and RESP fitting is shown to be a powerful approach to deriving electrostatic charges for biopolymers.
Journal ArticleDOI
Photoinduced Electron Transfer in Solution: Exciplex and Radical Ion Pair Formation Free Enthalpies and their Solvent Dependence
Journal ArticleDOI
Long-range photoinduced electron transfer through a DNA helix
Catherine J. Murphy,Michelle R. Arkin,Yonchu Jenkins,Naresh D. Ghatlia,Stefan H. Bossmann,Nicholas J. Turro,Jacqueline K. Barton +6 more
TL;DR: The stacked aromatic heterocycles of the DNA duplex therefore serve as an efficient medium for coupling electron donors and acceptors over very long distances.