The first example of cyclodextrin dimer appending a macrocyclic polyamine spacer on the primary faces was synthesized via two approaches: 1, a direct reaction of 1,7-bis(2′-aminoethyl)-4,10-dimethyl-1,4,7,10-tetraaza...The first example of cyclodextrin dimer appending a macrocyclic polyamine spacer on the primary faces was synthesized via two approaches: 1, a direct reaction of 1,7-bis(2′-aminoethyl)-4,10-dimethyl-1,4,7,10-tetraazacyclododecane (1) with an excess of 6-deoxy-6-O-tosyl-β-cyclodextrin; 2, a condensation of 1 with two equivalents of 6-deoxy-6-formyl-β-cyclodextrin, which wan followed by a reduction with NaBH4.展开更多
Two imidazolium-bridged cyclodextrin dimers 3a and 3b were prepared by reacting 6-deoxy-6-N-imidazolyl-β-CD (2) with bis(bromomethyl) benzene. The catalytic properties of 2, 3a and 3b in the hydrolytic cleavage of p-...Two imidazolium-bridged cyclodextrin dimers 3a and 3b were prepared by reacting 6-deoxy-6-N-imidazolyl-β-CD (2) with bis(bromomethyl) benzene. The catalytic properties of 2, 3a and 3b in the hydrolytic cleavage of p-nitrophenyl alkanoates, in the form of acetate (PNPA), butanoate (PNPB), hexanoate (WH) and octanoate ( PNPO), were examined. CD dimers showed middling rate enhancements around neutrality. Catalytic rate constants ( kc) in the presence of 3a or 3b did not vary much with chain length of esters. In contrast, dissociation constants (Kd) and selectivity factors (kc/Kd) for “long-chain” esters were much smaller and significantly larger than those for “short-chain” ones respectively, indicating CD dimers 3a and 3b have good dimensional recognition ability and substrate selectivity in the hydrolytic cleavage of p-nitrophenyl alkanoate. Their kinetic consequences are briefly interpreted.展开更多
基金We gratefully acknowledge the support of this work from Zhaoqing University and the financial support of Nature Science Foundation of the Guangxi province(9912001).
基金Project (29502010) supported by the National Natural Science Foundation of China
文摘The first example of cyclodextrin dimer appending a macrocyclic polyamine spacer on the primary faces was synthesized via two approaches: 1, a direct reaction of 1,7-bis(2′-aminoethyl)-4,10-dimethyl-1,4,7,10-tetraazacyclododecane (1) with an excess of 6-deoxy-6-O-tosyl-β-cyclodextrin; 2, a condensation of 1 with two equivalents of 6-deoxy-6-formyl-β-cyclodextrin, which wan followed by a reduction with NaBH4.
基金Project supported by the National Natural Science Foundation of China (No. 29632004 and 29772023)the State Education Commission (No. 380)the Research Program of Sichuan University.
文摘Two imidazolium-bridged cyclodextrin dimers 3a and 3b were prepared by reacting 6-deoxy-6-N-imidazolyl-β-CD (2) with bis(bromomethyl) benzene. The catalytic properties of 2, 3a and 3b in the hydrolytic cleavage of p-nitrophenyl alkanoates, in the form of acetate (PNPA), butanoate (PNPB), hexanoate (WH) and octanoate ( PNPO), were examined. CD dimers showed middling rate enhancements around neutrality. Catalytic rate constants ( kc) in the presence of 3a or 3b did not vary much with chain length of esters. In contrast, dissociation constants (Kd) and selectivity factors (kc/Kd) for “long-chain” esters were much smaller and significantly larger than those for “short-chain” ones respectively, indicating CD dimers 3a and 3b have good dimensional recognition ability and substrate selectivity in the hydrolytic cleavage of p-nitrophenyl alkanoate. Their kinetic consequences are briefly interpreted.
