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Chemical reactivity within a smectic B liquid crystalline phase: A model of enzyme catalysis?
Authors:B Samori  S Masiero  G R Luckhurst  S K Heeks  B A Timimi  P Mariani
Abstract:The rearrangement of allyl p-dimethylaminobenzenesulphonate (ASE) to form a zwitterionic product has already been recognized as an effective probe for the study of reactivity within the smectic B phase 4, 5, 19]. We have used deuterium NMR, linear dichroism and X-ray diffraction techniques to investigate the phase diagram of the ASE-OS35 reaction system. The partitioning of the reactant molecules between coexisting smectic, nematic and/or isotropic phases and the structural organization of the smectic catalytic host at different temperatures and reactant guest concentrations have been characterized. On the basis of these measurements, a model of ASE reactivity in smectic solvents has been developed. The reaction takes place provided that coexisting isotropic or nematic phases are present to act as a reservoir for the ASE reactant molecules prior to their entering the smectic phase; they then react and leave the smectic phase as a zwitterionic product. The analogy between this model of reactivity within smectic phases and the Michaelis-Menten enzyme processes is discussed. This relationship opens up the intriguing possibility of designing new experiments with which to investigate further liquid crystalline models of enzyme catalysis.
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