Non-Markovian polymer reaction kinetics
Describing the kinetics of polymer reactions, such as the formation of loops and hairpins in nucleic acids or polypeptides, is complicated by the structural dynamics of their chains. Although both intramolecular reactions, such as cyclization, and intermolecular reactions have been studied extensive...
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Published in | Nature chemistry Vol. 4; no. 7; pp. 568 - 573 |
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Main Authors | , , |
Format | Journal Article |
Language | English |
Published |
London
Nature Publishing Group UK
01.07.2012
Nature Publishing Group |
Subjects | |
Online Access | Get full text |
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Summary: | Describing the kinetics of polymer reactions, such as the formation of loops and hairpins in nucleic acids or polypeptides, is complicated by the structural dynamics of their chains. Although both intramolecular reactions, such as cyclization, and intermolecular reactions have been studied extensively, both experimentally and theoretically, there is to date no exact explicit analytical treatment of transport-limited polymer reaction kinetics, even in the case of the simplest (Rouse) model of monomers connected by linear springs. We introduce a new analytical approach to calculate the mean reaction time of polymer reactions that encompasses the non-Markovian dynamics of monomer motion. This requires that the conformational statistics of the polymer at the very instant of reaction be determined, which provides, as a by-product, new information on the reaction path. We show that the typical reactive conformation of the polymer is more extended than the equilibrium conformation, which leads to reaction times significantly shorter than predicted by the existing classical Markovian theory.
Quantifying polymer reaction kinetics requires the non-Markovian dynamics of monomer motion to be taken into account. This difficulty is overcome by explicitly determining the typical reactive conformations of the polymer, which are found to be more extended than equilibrium conformations, leading to reaction times significantly shorter than predicted by existing Markovian theories. |
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Bibliography: | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
ISSN: | 1755-4330 1755-4349 |
DOI: | 10.1038/nchem.1378 |