Mj. Han et al., RIBOFURANOSE-CONTAINING POLYMERS - SYNTHESIS AND CATALYTIC ACTIVITY FOR THE HYDROLYSIS OF PHOSPHODIESTER AND THE CLEAVAGE OF DNA, Macromolecules, 30(18), 1997, pp. 5408-5415
Two derivatives of 5-deoxy-D-erythro-pent-4-enofuranose (4 and Gland 6
-deoxy-alpha-D-galacto-hex-5-enopyranose (9) were synthesized. Copolym
erization of these monomers with maleic anhydride and subsequent react
ions resulted in (5-deoxy-D-erythro-pent-4-enofuranose)-alt-(maleic ac
id)] (11) and its derivatives, such as dimethyl ester (12), 2,3-O-isop
ropylidene (13), 1-O-methyl (15), and eoxy-alpha-D-galacto-hex-5-enopy
ranose)-alt-maleic acid)](17). Polymers 11, 12, and 15 showed catalyti
c activity for the hydrolysis of phosphodiesters. The rate constant (k
(cat)) for the hydrolysis of ethyl p-nitrophenyl phosphate substrate c
atalyzed by polymer 12 was 9.0 x 10(-1) h(-1) at 50 degrees C, corresp
onding to a rate acceleration of about 10(3) as compared with that of
the uncatalyzed reaction (9.1 x 10(-4) h(-1)). Competitive and noncomp
etitive inhibitions for this catalysis were observed on addition of so
dium acetate (K-I = 5.9 x 10(-4) M) and K2HPO4 (K-I = 2.5 x 10(-4) M),
respectively. The polymers also catalyzed the cleavage of ssDNA of 30
bases and tetradeoxyadenylic acid in Tris buffer (pH 7.4) at ionic st
rength 0.02 (KCl) at 37 degrees C. The catalytic activity of the polym
ers seemed to be attributable to vic-cis-diol groups of furanose rings
on the polymer backbones.