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Updated: Jun 17, 2026

CD Spectroscopy to Study DNA-Protein Interactions
Published on: February 10, 2022
Negative dissociation energy phenomenon of metastable H-bonds as revealed in triplex DNA hole migration
Jun Wang1, Lixiang Sun, Yuxiang Bu
1The Center for Modeling and Simulation Chemistry, Institute of Theoretical Chemistry, Shandong University, Jinan, 250100, P.R. China.
Abstract:
Ab initio calculations reveal an unknown energetic phenomenon for H-bonds in the hole-trapping triplex C(p)*GC motif observed experimentally in hole migration which can explain the lower but really available oxidization possibility in C(p)*GC site. Hole trapping can considerably destabilize the C(p)*GC unit and lead to an unexpected barrier-hindered channel with a negative dissociation energy. This channel is governed by a balance between electrostatic repulsion and H-bonding attraction in the two associated moieties and different attenuations of two opposite interactions with respect to the H-bond distance. This C(p)*GC unit can be viewed as a high-energy node in a DNA wire which modulates migration of a hole into or through it via its unusual energetics. It provides useful information for understanding of an unknown type of the complicated intermolecular interactions, a novel type of "high-energy" bond, and can be applied further to interpret the hidden transport properties and the energy conversion/transfer mechanisms in the related fields.
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