The interactions between four high bioactive diperoxovanadate complexes Kn[OV(O2)2L]mH2O (n = 1~3, m = 1~5, L = oxalate (abbr. oxa), picolinate (abbr. pic), bipyridine (abbr. bipy) and 1,10-phenanthroline (abbr. phen)...The interactions between four high bioactive diperoxovanadate complexes Kn[OV(O2)2L]mH2O (n = 1~3, m = 1~5, L = oxalate (abbr. oxa), picolinate (abbr. pic), bipyridine (abbr. bipy) and 1,10-phenanthroline (abbr. phen); their corresponding complexes abbreviated as bpV(oxa), bpV(pic), bpV(bipy) and bpV(phen), respectively) and imidazole (abbr. imi) in solution were studied by several NMR techniques: multinuclear (1H, 13C and 51V) and variable temperature 51V NMR. Competitive coordination interactions were observed and the order of the interaction strength of the four complexes with imidazole is as follows: bpV(oxa) > bpV(pic) > bpV(bipy) > bpV(phen), which is deeply affected by the identity of the ligands and has the same order as their inhibition effect toward bovine heart phosphotyrosyl protein phosphatase. The species [OV- (O2)2(imi)]- was formed in all cases. Both of the NMR data and equilibrium constants of the interaction systems were reported. The experimental results indicate that the species of bpV(oxa) and [OV(O2)2(imi)]- are six-coordinated, while bpV(pic), bpV(bipy) and bpV(phen) are seven- coordinated in solution. ESI-MS results support the conclusions obtained by NMR.展开更多
The reaction system of diperoxooxalatovanadate {K3[VO(O2)2-(C2O4)]·H2O, bpV(Oxa)} and imidazole was studied in an aqueous solution by 1D multinuclear (1H, 13C and 51V) NMR, 2D NMR diffusion ordered spectroscopy (...The reaction system of diperoxooxalatovanadate {K3[VO(O2)2-(C2O4)]·H2O, bpV(Oxa)} and imidazole was studied in an aqueous solution by 1D multinuclear (1H, 13C and 51V) NMR, 2D NMR diffusion ordered spectroscopy (DOSY), and variable temperature NMR techniques. It was shown that DOSY was a useful tool for the study of a mixture. All of the 1H and 13C NMR signals of the peroxovanadate (V) complexes were assigned. The NMR experimental results indicated that a new complex was formed through the coordination interactions between bpV(Oxa) and imidazole. The newly-formed complex is stable under the experimental condition. Electrospray ioniza-tion mass spectrometry (ESI-MS) provides positive evidence to support the conclusion.展开更多
基金NNSFC (Nos. 10234070 and 10104011) NSF of Fujian Province (No. E0110003) and State Key Laboratory of Structural Chemistry (020058)
文摘The interactions between four high bioactive diperoxovanadate complexes Kn[OV(O2)2L]mH2O (n = 1~3, m = 1~5, L = oxalate (abbr. oxa), picolinate (abbr. pic), bipyridine (abbr. bipy) and 1,10-phenanthroline (abbr. phen); their corresponding complexes abbreviated as bpV(oxa), bpV(pic), bpV(bipy) and bpV(phen), respectively) and imidazole (abbr. imi) in solution were studied by several NMR techniques: multinuclear (1H, 13C and 51V) and variable temperature 51V NMR. Competitive coordination interactions were observed and the order of the interaction strength of the four complexes with imidazole is as follows: bpV(oxa) > bpV(pic) > bpV(bipy) > bpV(phen), which is deeply affected by the identity of the ligands and has the same order as their inhibition effect toward bovine heart phosphotyrosyl protein phosphatase. The species [OV- (O2)2(imi)]- was formed in all cases. Both of the NMR data and equilibrium constants of the interaction systems were reported. The experimental results indicate that the species of bpV(oxa) and [OV(O2)2(imi)]- are six-coordinated, while bpV(pic), bpV(bipy) and bpV(phen) are seven- coordinated in solution. ESI-MS results support the conclusions obtained by NMR.
基金Project supported by the National Natural Science Foundation of China(Nos.Grants 10234070,10104011)and the Naturral Science Foundation of Fujian Province(No.Grant E0110003).
文摘The reaction system of diperoxooxalatovanadate {K3[VO(O2)2-(C2O4)]·H2O, bpV(Oxa)} and imidazole was studied in an aqueous solution by 1D multinuclear (1H, 13C and 51V) NMR, 2D NMR diffusion ordered spectroscopy (DOSY), and variable temperature NMR techniques. It was shown that DOSY was a useful tool for the study of a mixture. All of the 1H and 13C NMR signals of the peroxovanadate (V) complexes were assigned. The NMR experimental results indicated that a new complex was formed through the coordination interactions between bpV(Oxa) and imidazole. The newly-formed complex is stable under the experimental condition. Electrospray ioniza-tion mass spectrometry (ESI-MS) provides positive evidence to support the conclusion.
