Poly(propylene imine) dendrimer complexes of Cu(II), Zn(II), and Co(III) as catalysts of hydrolysis of p-nitrophenyl diphenyl phosphate

Poly(propylene imine) dendrimers having 8, 32, and 64 primary amine end gro ups form diamino Cu(II), diamino Zn(II), and tetramino Co(III) complexes th at are identified spectrophotometrically and titrimetrically. The dendrimer -metal ion complexes catalyze the hydrolysis of p-nitrophenyl diphenyl phos phate in zwitterionic buffer solutions at pH less than or equal to 8.1 with relative activities Cu(II) > Zn(II) > Co(III). The rates of hydrolysis are faster with sodium perchlorate than with sodium chloride to control ionic strength. In sodium perchlorate solutions with Cu(II) the rates increase wi th increasing size of the dendrimer. In sodium chloride solutions with Cu(I I) the rates decrease with increasing size of the dendrimer. Rate constants in buffered sodium chloride solutions of dendrimers and 1.0mM Cu(II) are 1 .3-6.3 times faster than in the absence of Cu(II). The fastest hydrolyses o ccurred at a dendrimer primary amine to Cu(II) ratio NH2/Cu less than or eq ual to 2. At NH2/Cu = 4 and with the 1,4,7,10-tetraazacyclodecane complex o f Cu(II) hydrolysis rates were much slower. (C) 1999 John Wiley & Sons, Inc .