The activities of the catalytic hydrolysis of phosphate diester (BNPP) [bis(p-nitrophenyl)phosphate diester] and plasmid DNA (pUC 18) by mononuclear macrocyclic polyamine metal complexes have been investigated i...The activities of the catalytic hydrolysis of phosphate diester (BNPP) [bis(p-nitrophenyl)phosphate diester] and plasmid DNA (pUC 18) by mononuclear macrocyclic polyamine metal complexes have been investigated in this paper. The results showed that the highest activity in hydrolysis of BNPP was obtained with le--Zn(II) complex (composed of lipophilic group) as catalyst. The hydrolysis rate enhancement is up to 3.64 × 10^4 fold. These metal complexes could effectively promote the cleavage of plasmid DNA (pUC18) at physiological conditions.展开更多
The cleavage of DNA (pUC18) by lipophilic macrocyclic polyamine Co(II) complex was investigated in metallomicellar system. The results showed that the conversion of plasmid DNA (pUC18) increases with the increase of ...The cleavage of DNA (pUC18) by lipophilic macrocyclic polyamine Co(II) complex was investigated in metallomicellar system. The results showed that the conversion of plasmid DNA (pUC18) increases with the increase of the concentration of complex under physiological conditions.展开更多
The NMR methods (including 1H NMR, vari\| able temperature method and the 2D COSY technique) were employed to study the conformation of 3,13\|dihydroxyl\|1,5,8,11,15,18\|hexaazac yclicami...The NMR methods (including 1H NMR, vari\| able temperature method and the 2D COSY technique) were employed to study the conformation of 3,13\|dihydroxyl\|1,5,8,11,15,18\|hexaazac yclicamine hexahydrobromide in aqueous solution. It was found that the ring is flexible.展开更多
Two new tetraamides bridged calix[4]arenes were synthesized by the condensation reaction of 1,3-bis-chlorocarbonylmethyl p-tert-butylcalix[4]arene with 1,2-bis (2′-amino-2′-methylpropanamido) benzene or 1,2-bis (2′...Two new tetraamides bridged calix[4]arenes were synthesized by the condensation reaction of 1,3-bis-chlorocarbonylmethyl p-tert-butylcalix[4]arene with 1,2-bis (2′-amino-2′-methylpropanamido) benzene or 1,2-bis (2′-amino-2′-methylpropanamido)-4,5-dichloro benzene, respectively. The new compounds were characterized by1H-NMR, MS-FAB, and elemental analysis; macrocyclic polyamine.展开更多
A copper(Ⅱ) complex 1 of a novel macrocyclic polyamine ligand with hydroxylethyl pendant groups, 4,11-bis(hydroxylethyl)-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane (L) has been synthesized and ...A copper(Ⅱ) complex 1 of a novel macrocyclic polyamine ligand with hydroxylethyl pendant groups, 4,11-bis(hydroxylethyl)-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane (L) has been synthesized and characterized. Rate enhancement for hydrolysis of p-nitrophenyl picolinate (PNPP) catalyzed by 1 was studied kinetically under Brij35 micellar condition. For comparision, the catalytic activity of corresponding copper(Ⅱ) complex 2 of non-substituted macrocyclic polyamine ligand, 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraaza-cyclotetradecane (L') toward the hydrolysis of PNPP was also investigated. The results indicate that the macrocyclic polyamine copper(Ⅱ) complex 1 effectively catalyzed the hydrolysis of PNPP, and the pendant ligand hydroxyl group or deprotonated pendant ligand hydroxyl group can act as catalytically active species in the reaction. A ternary Complex kinetic model involving metal ion, ligand and substrate has been proposed, and the results confirmed the reasonability of such kinetic model.展开更多
Two fluorescent anion receptors (1 and 2) based on amide macrocycle were synthesized and corresponding fluorescence quenching induced by anion complexation was observed in different degree. Receptors form 1∶1 complex...Two fluorescent anion receptors (1 and 2) based on amide macrocycle were synthesized and corresponding fluorescence quenching induced by anion complexation was observed in different degree. Receptors form 1∶1 complexes with anions by hydrogen bonding interactions. Receptor 1 bound anions in the order of F->Cl->24HPO->CH3COO->>Br-, I- and receptor 2 showed high selectivity to F- over other anions.展开更多
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 novel cyclic polyamine derivatives bearing double aminoethyl groups have been synthesized. The synthetic intermediate, N-p-toluenesulfonyl-aziridine, was prepared employing an improved procedure.
Macrocyctic tri- and tetra-amines containing a hydroxyl group in the ring have been prepared in moderate yields by a. 1:1 cyclocondensation of 1,3-dichloro-2-propanol with the disodium salt of N-tosylated diethylenetr...Macrocyctic tri- and tetra-amines containing a hydroxyl group in the ring have been prepared in moderate yields by a. 1:1 cyclocondensation of 1,3-dichloro-2-propanol with the disodium salt of N-tosylated diethylenetriamine and triethylenetetraamine. In the case of condensation of 1,3-dichoro-2-propanol with the disodium salt of N-tosylated diethylenetriamine, the 2:2 cyclocondensation product, dihydroxyl macrocyclic hexaamine, was also isolated.展开更多
The mononuclear macrocyclic polyamine metal complexes 5a-5e have been shown to form stable 1:1 complexes with bases and nucleosides. Their binding constants (K) were determined by UV-visible spectrometric titration. T...The mononuclear macrocyclic polyamine metal complexes 5a-5e have been shown to form stable 1:1 complexes with bases and nucleosides. Their binding constants (K) were determined by UV-visible spectrometric titration. The results show that recognition ability of the complexes 5a-5e for uracil, U (Uri-dine), dT (Thymidine) is higher than that for the other bases or nucleosides (such as Cytidine, Guanosine, Adenosine). The metal ion also plays an important role for the recognition ability of complexes.展开更多
Bifunctional molecules containing macrocyclic polyamine [12]aneN3 and carbazol units, 1-4, have been efficiently synthe sized and fully characterized. Through gel electrophoresis, atomic force microscopy, and dynamic ...Bifunctional molecules containing macrocyclic polyamine [12]aneN3 and carbazol units, 1-4, have been efficiently synthe sized and fully characterized. Through gel electrophoresis, atomic force microscopy, and dynamic light scattering experiments, compounds 3 and 4b bearing both [12]aneN3 and carbazol moieties showed effective DNA condensation ability at the concen- tration of 80 jaM. Investigations from EB displacement fluorescence spectra, viscosity titration, and ionic strength effects re vealed that the effective DNA condensation comes from the appropriate combination of carbazol and [12]aneN3 units in the bifunctional molecules, and the DNA condensation process is reversible. The incorporation of triazole units in the molecules clearly reduced the cytotoxicity.展开更多
A new [12]aneN3-based BODIPY sensor I showed highly selective and sensitive recognition of Cu2~ ions through fluorescence quenching effect in aqueous solution. The above copper complex solution can further be used as ...A new [12]aneN3-based BODIPY sensor I showed highly selective and sensitive recognition of Cu2~ ions through fluorescence quenching effect in aqueous solution. The above copper complex solution can further be used as a turn-on fluorescent probe for detecting ADP with high selectivity, and also applied in imaging of living cells.展开更多
基金supported by the Science and Technology Department(No.04JY029-018)Education Department of Sichuan Province(No.2006ZD049).
文摘The activities of the catalytic hydrolysis of phosphate diester (BNPP) [bis(p-nitrophenyl)phosphate diester] and plasmid DNA (pUC 18) by mononuclear macrocyclic polyamine metal complexes have been investigated in this paper. The results showed that the highest activity in hydrolysis of BNPP was obtained with le--Zn(II) complex (composed of lipophilic group) as catalyst. The hydrolysis rate enhancement is up to 3.64 × 10^4 fold. These metal complexes could effectively promote the cleavage of plasmid DNA (pUC18) at physiological conditions.
基金We are thankful to the National Natural Science Foundation of China for financial support (No. 29872027).
文摘The cleavage of DNA (pUC18) by lipophilic macrocyclic polyamine Co(II) complex was investigated in metallomicellar system. The results showed that the conversion of plasmid DNA (pUC18) increases with the increase of the concentration of complex under physiological conditions.
文摘The NMR methods (including 1H NMR, vari\| able temperature method and the 2D COSY technique) were employed to study the conformation of 3,13\|dihydroxyl\|1,5,8,11,15,18\|hexaazac yclicamine hexahydrobromide in aqueous solution. It was found that the ring is flexible.
文摘Two new tetraamides bridged calix[4]arenes were synthesized by the condensation reaction of 1,3-bis-chlorocarbonylmethyl p-tert-butylcalix[4]arene with 1,2-bis (2′-amino-2′-methylpropanamido) benzene or 1,2-bis (2′-amino-2′-methylpropanamido)-4,5-dichloro benzene, respectively. The new compounds were characterized by1H-NMR, MS-FAB, and elemental analysis; macrocyclic polyamine.
基金Project supporter by the National Natural Science Foundation of China (Nos. 20173038, 20107004).
文摘A copper(Ⅱ) complex 1 of a novel macrocyclic polyamine ligand with hydroxylethyl pendant groups, 4,11-bis(hydroxylethyl)-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane (L) has been synthesized and characterized. Rate enhancement for hydrolysis of p-nitrophenyl picolinate (PNPP) catalyzed by 1 was studied kinetically under Brij35 micellar condition. For comparision, the catalytic activity of corresponding copper(Ⅱ) complex 2 of non-substituted macrocyclic polyamine ligand, 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraaza-cyclotetradecane (L') toward the hydrolysis of PNPP was also investigated. The results indicate that the macrocyclic polyamine copper(Ⅱ) complex 1 effectively catalyzed the hydrolysis of PNPP, and the pendant ligand hydroxyl group or deprotonated pendant ligand hydroxyl group can act as catalytically active species in the reaction. A ternary Complex kinetic model involving metal ion, ligand and substrate has been proposed, and the results confirmed the reasonability of such kinetic model.
基金Project supported by the National Natural Science Foundation of China (No. 20372054).
文摘Two fluorescent anion receptors (1 and 2) based on amide macrocycle were synthesized and corresponding fluorescence quenching induced by anion complexation was observed in different degree. Receptors form 1∶1 complexes with anions by hydrogen bonding interactions. Receptor 1 bound anions in the order of F->Cl->24HPO->CH3COO->>Br-, I- and receptor 2 showed high selectivity to F- over other anions.
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 (No. 29502010) supported by the National Natural Science Foundation of China
文摘Two novel cyclic polyamine derivatives bearing double aminoethyl groups have been synthesized. The synthetic intermediate, N-p-toluenesulfonyl-aziridine, was prepared employing an improved procedure.
基金Project (No. 29502010) supported by the National Natural Science Foundation of China
文摘Macrocyctic tri- and tetra-amines containing a hydroxyl group in the ring have been prepared in moderate yields by a. 1:1 cyclocondensation of 1,3-dichloro-2-propanol with the disodium salt of N-tosylated diethylenetriamine and triethylenetetraamine. In the case of condensation of 1,3-dichoro-2-propanol with the disodium salt of N-tosylated diethylenetriamine, the 2:2 cyclocondensation product, dihydroxyl macrocyclic hexaamine, was also isolated.
基金Project supported by the National Natural Science Foundation of China(No.20132020)and Doctoral Foundation from National Educational Committee for Financial support.
文摘The mononuclear macrocyclic polyamine metal complexes 5a-5e have been shown to form stable 1:1 complexes with bases and nucleosides. Their binding constants (K) were determined by UV-visible spectrometric titration. The results show that recognition ability of the complexes 5a-5e for uracil, U (Uri-dine), dT (Thymidine) is higher than that for the other bases or nucleosides (such as Cytidine, Guanosine, Adenosine). The metal ion also plays an important role for the recognition ability of complexes.
基金supported by the Program for New Century Excellent Talents in Universities(NCET-08-0054)the National Natural Science Foundation of China(20972019)
文摘Bifunctional molecules containing macrocyclic polyamine [12]aneN3 and carbazol units, 1-4, have been efficiently synthe sized and fully characterized. Through gel electrophoresis, atomic force microscopy, and dynamic light scattering experiments, compounds 3 and 4b bearing both [12]aneN3 and carbazol moieties showed effective DNA condensation ability at the concen- tration of 80 jaM. Investigations from EB displacement fluorescence spectra, viscosity titration, and ionic strength effects re vealed that the effective DNA condensation comes from the appropriate combination of carbazol and [12]aneN3 units in the bifunctional molecules, and the DNA condensation process is reversible. The incorporation of triazole units in the molecules clearly reduced the cytotoxicity.
基金the financial assistances from the National Natural Science Foundation of China (Nos. 21372032 and 91227109)the Fundamental Research Funds for the Central Universities(2009SC-1)+1 种基金Beijing Municipal Commission of Educationthe Program for Changjiang Scholars and Innovative Research Team in University
文摘A new [12]aneN3-based BODIPY sensor I showed highly selective and sensitive recognition of Cu2~ ions through fluorescence quenching effect in aqueous solution. The above copper complex solution can further be used as a turn-on fluorescent probe for detecting ADP with high selectivity, and also applied in imaging of living cells.