Two long-chain multidentate ligands: 2,9-di-(n-2',5',8'-triazanonyl)-1,10-phenanthroline (L^1) and 2,9-di- (n-4',7',10'-triazaundecyl)-1,10-phenanthroline (L^2) were synthesized. The hydrolytic kinetics of 2-hydroxypropyl p-nitrophenyl phosphate (HPNP) catalyzed by the complexes of L^1 or L^2 with La(Ⅲ) or Gd(Ⅲ) have been studied in aqueous solution at (298.2±0.1) K, I=0.10 mol·dm^-3 KNO3 in pH 7.5-9.1, respectively, finding that the catalytic effect of GdL^1 was the best among the four complexes for hydrolysis of HPNP. Its kLnLH-1, kLnLand pKa are 0.047 mol^-1·L·s^-1, 0.000074 mol^-1·L·s^-1 and 8.90, respectively. This paper expounded the studied result with the structure of the ligands and the properties of the metal ions, and deduced the catalysis mechanism.
A simple colorimetric acetate ion receptor based on 3-methoxysalicylaldehyde-4'-nitrophenyl-hydrazone was synthesized in an ethanol solution through one step,and characterized by 1H NMR and elemental analyses.Its anion-binding ability was examined by UV-Vis absorption spectroscopy in DMSO(dimethyl sulfoxide).The result shows that the compound has a high affinity for and a high selectivity toward acetate ions,and also an advantage of 'naked-eye' recognition of color changing from yellow to purple.
Two multidentate ligands 2,9-di[6'-(2″-hydroxyl-3″-methoxyphenyl)-n-2',5'-diazahexyl]-1,10-phenanthroline(LA)and 2,9-di(6'-α-phenol-n-2',5'-diazahexyl)-1,10-phenanthroline(LB)were synthesized and fully characterized.Protonation of the ligands and the stability of the complexes of the ligands with divalent metal ions were investigated.The trinuclear metal complexes [Cu(Ⅱ)and Zn(Ⅱ)] of the ligands were studied,as catalysts,for the transphosphorylation of the RNA-model substrate 2-hydroxypropyl-p-nitrophenyl phosphate(HPNP).The second-order rate constants of HPNP-hydrolysis catalyzed by M3L and M3LH-1 were obtained,which indicated that Zn3LBH-1 was the most efficient catalyst among them.The proposed mechanisms included the activation of the substrate via binding to the metal ions and intramolecular nucleophilic attack by the deprotonated C2-hydroxyl of HPNP.