Department of Plant Sciences Research Seminars

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16 February 2012
16:00, Large Lecture Theatre

'The role of mixing entropy in carbohydrate metabolism'

Dr Oliver Ebenhoeh
Institute of Medical Sciences, University of Aberdeen

The vast diversity of carbohydrates is generated by carbohydrate-active enzymes (CAZymes) accepting many different substrates and catalyzing numerous reactions. This promiscuity is in stark contrast to most enzymes active in central metabolism which are highly specific and catalyze exactly one or a very small number of reactions. The multitude of accepted substrates and catalyzed reactions makes CAZymes har d to characterize in classical enzymological terms. Equilibrium constants and Michaelis constants, which were developed for highly specific enzymes, have no straight forward analogon for CAZymes.

We show how statistical thermodynamics can be employed to concisely describe and explain the action of CAZymes, where the mixing entropy of the reactants emerges as an important state variable of metabolic systems. We can thus correctly predict equilibrium distributions and explain their dependence on the initial conditions, which has not been possible with previous approaches. Experimentally verified stochastic simulations confirm the validity of our approach outside equilibrium.

Our proposed interpretation of polydisperse pools as statistical ensembles facilitates a new perspective to understand many enzymatic processes. With a mathematical model of the turnover of the soluble heteroglycan pool, we illustrate how entropy gradients are exploited constructively in vivo to establish a robust buffering and integrating metabolic function. The latter result motivates a novel interpretation of metabolism as an interplay of energy- and entropy-driven processes and hints at a novel evolutionary design principle.

Departmental Research Seminar