Nucleotide recognition and phosphate linkage hydrolysis at a lipid cubic interface.
Mononucleotides, when entrapped within a mono-olein-based cubic Ia3d liquid crystalline phase, have been found to undergo hydrolysis at the sugar-phosphate ester bond in spite of their natural inertness toward hydrolysis. Here, kinetics of the hydrolysis reaction and interactions between the lipid matrix and the mononucleotide adenosine 5'-monophosphate disodium salt (AMP) and its 2'-deoxy derivative (dAMP) are thoroughly investigated in order to shed some light on the mechanism of the nucleotide recognition and phosphate ester hydrolysis. Experiments evidenced that molecular recognition occurs essentially through the sn-2 and the sn-3 alcoholic OH groups of mono-olein. As deduced from the apparent activation energies, the mechanism underlying the hydrolysis reaction is the same for AMP and dAMP. Nevertheless, the reaction proceeds slower for the latter, highlighting a substantial difference in the chemical behavior of the two nucleotides. A model that explains the hydrolysis reaction is presented. Remarkably, the hydrolysis mechanism appears to be highly specific for the Ia3d phase.
Murgia
Sergio
S
Department of Chemical Science, Cagliari University, CNBS and CSGI, ss 554, bivio Sestu, 09042 Monserrato (CA), Italy. murgias@unica.it
Lampis
Sandrina
S
Zucca
Paolo
P
Sanjust
Enrico
E
Monduzzi
Maura
M
D000249:Adenosine Monophosphate / Q000737:chemistry*; D003838:Deoxyadenine Nucleotides / Q000737:chemistry*; D006868:Hydrolysis; D008055:Lipids / Q000737:chemistry*; D010710:Phosphates / Q000737:chemistry*
D003838:Deoxyadenine Nucleotides; D008055:Lipids; D010710:Phosphates; D000249:Adenosine Monophosphate; C012873:2'-deoxy-5'-adenosine monophosphate