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• W2094804945 startingPage "13991" @default.
• W2094804945 abstract "Two-dimensional infrared (2D IR) spectroscopy was used to study the carbonyl vibrational modes of guanine and cytosine bases in A- and B-form DNA. Located between 1600 and 1700 cm(-1), these modes are often used to monitor DNA secondary structure with traditional infrared spectroscopies such as FTIR, but traditional spectroscopies lack the necessary observables to unravel the coupling mechanisms that make these modes sensitive to secondary structure. By using 2D IR spectroscopy and electronic structure calculations on d(G(5)C(5)) and d(GC)(8) model nucleic acids, we find that hydrogen-bonded guanine/cytosine base pairs are primarily electrostatically coupled and that the coupling between these modes can be modeled with a transition dipole density approach. In comparison, electrostatics is insufficient to model stacked bases because of cooperative charge-sharing effects, but the coupling can be accurately calculated using a finite difference method. We find that the coupling is very strong for both hydrogen-bonded and stacked base geometries, creating vibrational modes that extend both across the base pairs and along the lengths of the helices. Our results provide a physical basis for understanding how strong coupling gives rise to the empirically established relationship between infrared spectroscopy and DNA/RNA secondary structure." @default.
• W2094804945 created "2016-06-24" @default.
• W2094804945 creator A5022637430 @default.
• W2094804945 creator A5090981806 @default.
• W2094804945 date "2006-06-22" @default.
• W2094804945 modified "2023-10-01" @default.
• W2094804945 title "DNA Vibrational Coupling Revealed with Two-Dimensional Infrared Spectroscopy: Insight into Why Vibrational Spectroscopy Is Sensitive to DNA Structure" @default.
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• W2094804945 doi "https://doi.org/10.1021/jp062597w" @default.
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• W2094804945 hasPublicationYear "2006" @default.
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