Abstract
Vesicles prepared with synthetic amphiphiles constitute useful microreactors, where reaction rates can be delicately controlled. Here we review our work on quantitative analysis of reaction rates in vesicles and show that reaction at several vesicular sites can be probed and controlled. Vesicles prepared with dialkyldimethylammonium halides, (DODA)X, can accelerate bimolecular reactions by more than a million fold. Quantitative analysis of the vesicular effect on ester thiolysis, using a pseudophase ion exchange formalism, suggests that the rate increase is primarily due to reagent concentration in the bilayer and interfacial effects on ion distribution, as well as contributions from enhanced nucleophile reactivity. Vesicle-containing solutions exhibit a variety of potential reaction sites: the inner and outer surfaces, bilayer and internal aqueous compartment. Site dissection and reagent distribution has been accomplished, in several cases. For this purpose we have prepared vesicles of various sizes, determined some of their physical properties and developed theoretical and experimental tools for probing vesicular sites. The reactivity of OH− in the internal compartment is identical to that in bulk solution. Moreover, the reaction rates of OH− at the inner and outer vesicular interface are also comparable. However, since OH− permeation through the bilayer can limit reaction rate, the relative inner/outer rate ratios can be controlled by changing the composition of the external and/or internal medium.
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Chaimovich, H., Cuccovia, I.M. (1997). Quantitative analysis of reagent distribution and reaction rates in vesicles. In: Texter, J. (eds) Amphiphiles at Interfaces. Progress in Colloid & Polymer Science, vol 103. Steinkopff. https://doi.org/10.1007/3-798-51084-9_8
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DOI: https://doi.org/10.1007/3-798-51084-9_8
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