Kinetics and thermodynamics of Markov chain copolymerization
Dienstag, 25. November 2014 14:30 Uhr;
Sprecher: Pierre Gaspard; Center for Nonlinear Phenomena and Complex Systems, Université Libre de Bruxelles
At the molecular scale, the growth of a single copolymer is stochastic and proceeds by successive random attachments or detachments of monomers continuously supplied by the surrounding solution. Remarkably, the kinetics of Bernoulli and first-order chain copolymerization can be exactly solved in the presence of both attachment and detachment processes. This allows us to establish the thermodynamics of copolymerization, predicting the existence of a regime where copolymers can grow in an adverse free-energy landscape thanks to the entropic effect of disorder in their sequence of monomeric units. This disorder is characterized in terms of quantities from information theory. This is also the case for copolymerization with a template, in which case the thermodynamic entropy production involves the mutual information between the template and the growing copy. A further prediction is that the ceiling temperature, where the growth speed is vanishing, depends not only on the average enthalpy and entropy of copolymerization but also on the Shannon disorder in the sequence grown near equilibrium. References:  D. Andrieux and P. Gaspard, Nonequilibrium generation of information in copolymerization processes, Proc. Natl. Acad. Sci. USA 105, 9516 (2008).  D. Andrieux and P. Gaspard, Molecular information processing in nonequilibrium copolymerizations, J. Chem. Phys. 130, 014901 (2009).  P. Gaspard and D. Andrieux, Kinetics and thermodynamics of first-order Markov chain copolymerization, J. Chem. Phys. 141, 044908 (2014).
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