Tritopic Bis-Urea Receptors for Anion and Ion-Pair Recognition.

This work reports on the synthesis and characterization of three tritopic receptors and their binding properties toward various anions, as their tetrabutylammonium salts, and three alkali metal-acetate salts by UV-vis, fluorescence, H, Li, Na, and K NMR in MeCN/dimethyl sulfoxide (DMSO) 9:1 (v/v). Molecular recognition studies showed that the receptors have good affinity for oxyanions. Furthermore, these compounds are capable of ion-pair recognition of the alkali metal-acetate salts studied through a cooperative mechanism.

Electrophilic assistance to the cleavage of an RNA model phopshodiester via specific and general base-catalyzed mechanisms.

Kinetics of transesterification of the RNA model substrate 2-hydroxypropyl 4-nitrophenyl phosphate promoted by Mg(2+) and Ca(2+), the most common biological metals acting as cofactors for nuclease enzymes and ribozymes, as well as by Co(NH(3))(6)(3+), Co(en)(3)(3+), Li(+), and Na(+) cations, often employed as mechanistic probes, was studied in 80% v/v (50 mol %) aqueous DMSO, a medium that allows one to discriminate easily specific base (OH(-)-catalyzed) and general base (buffer-catalyzed) reaction paths. All cations assist the specific base reaction, but only Mg(2+) and Na(+) assist the general base reaction. For Mg(2+)-assisted reactions, the solvent deuterium isotope effects are 1.