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Supramolecular Polymer/Surfactant Complexes as Catalysts for Phosphate Transfer Reactions
journal contribution
posted on 2017-02-10, 00:00 authored by Adriana
P. Gerola, Eduardo H. Wanderlind, Yasmin S. Gomes, Luciano A. Giusti, Luis García-Río, René A. Nome, Anthony J. Kirby, Haidi D. Fiedler, Faruk NomeDesigning
artificial enzymes with tailored molecular interactions
between the substrate and active site is of major intellectual and
practical significance. We report the improved catalytic efficiency
of a supramolecular polymer/surfactant complex comprised of PAIM–, a poly(acrylic acid) derivative with imidazole groups
attached to the polymer by amide bonds, and the cationic surfactant
cetyltrimethylammonium bromide (CTAB). Supramolecular complex formation,
at concentrations below the respective CMC values, provides convenient
hydrophobic pockets for the reactants close to the multiple catalytic
centers, where imidazole and carboxylate groups act as nucleophiles
for the degradation of a model phosphate triester, delivering the
highly efficient performance of the supramolecular catalysts. Catalytic
effects are on the order of thousands for nucleophilic catalysis and
are higher by 2 orders of magnitude for the supramolecular polymer/surfactant
complex at pH 9. The reported supramolecular catalytic complexes allow
important changes in polarity and, given the presence of functional
groups common to a variety of hydrolytic enzymes, could be of general
applicability in such reactions.