Haibin Chu

Synthesis, characterization and enhanced luminescence of terbium complexes with 2-pyrazinecarboxylic acid and butanedioic acid by inert-fluorescent lanthanide ions

Ten solid terbium complexes with 2-pyrazinecarboxylic acid (Hpyca) and butanedioic acid (BDAH) were synthesized via coprecipitation method and characterized by elemental, EDTA titration, inductively coupled plasma (ICP), thermogravimetry-differential scanning calorimetry (TG-DSC) and infrared (IR) analyses. The results showed that the complexes had the compositions of Tb(pyca)(BDA)·2H2O, Tb0.5Y0.5(pyca)(BDA)·2H2O, Tb0.5La0.5(pyca)(BDA)·3H2O, Tb0.5Gd0.5(pyca)(BDA)·2H2O, Tb0.7Y0.3(pyca)(BDA)·3H2O, Tb0.7La0.3(pyca)(BDA)·0.5H2O, Tb0.7Gd0.3(pyca)(BDA)·H2O, Tb0.6Y0.4(pyca)(BDA)·2.5H2O, Tb0.6La0.4 (pyca)(BDA)·2.5H2O and Tb0.6Gd0.4(pyca)(BDA)·3H2O. IR spectra indicated that the rare earth ions coordinated with the carboxylic oxygen atoms of Hpyca and BDAH. Luminescence spectra showed that the doped La3+, Y3+ or Gd3+ ions did not affect the luminescence emission peak positions, but remarkably increased the luminescent intensities of terbium complexes. Furthermore, the doped lanthanide complexes showed longer luminescence lifetimes and higher quantum yields than pure terbium complex. The enhanced luminescence efficiencies of Tb3+ ions in the doped complexes might result from the antenna effect of the two carboxylate ligands as well as the decrease of the self-quench of the Tb3+ ions induced by the doped lanthanide ions.

Fluorescence enhancement of Tb 3+ complexes by adding silica-coated silver nanoparticles

Six kinds of terbium ternary complexes with halo-benzoic acids were synthesized. Their compositions were determined by C, H elemental analyzer and EDTA titration. The infrared spectra, ultraviolet absorption spectra, and fluorescence spectra were also measured to identify the complexes. Elemental analysis showed that the compositions of these complexes were Tb(p-BrBA)3·H2O, Tb(p-ClBA)3·2H2O, Tb(p-FBA)3·H2O, Tb(o-FBA)3·2H2O, Tb(o-ClBA)3·H2O, and Tb(o-BrBA)3·H2O, respectively. The monodispersed Ag@SiO2 core-shell nanoparticles with silica thicknesses of 10, 15, and 25 nm were successfully prepared and characterized by transmission-electron microscopy. Fluorescence intensities of the complexes were detected before and after Ag@SiO2 core-shell nanoparticles were added; the enhancement times were related to the silica-shell thickness. The fluorescence enhancement times were largest when the thickness of the silica shell was 25 nm. The mechanism may be attributed to the localized surface-plasmon resonance. Furthermore, the enhancement effect of terbium fluoro-benzoate complexes was the strongest in these complexes. This result may be attributed to the hydrogen bond between the hydroxyl on the surface of the silica shell and the fluorine atom.

Fluorescent studies on the interaction of DNA and ternary lanthanide complexes with cinnamic acid‐phenanthroline and antibacterial activities testing

Twelve lanthanide complexes with cinnamate (cin(-) ) and 1,10-phenanthroline (phen) were synthesized and characterized. Their compositions were assumed to be RE(cin)3 phen (RE(3+)  = La(3+) , Pr(3+) , Nd(3+) , Sm(3+) , Eu(3+) , Gd(3+) , Tb(3+) , Dy(3+) , Ho(3+) , Tm(3+) , Yb(3+) , Lu(3+) ). The interaction mode between the complexes and DNA was investigated by fluorescence quenching experiment. The results indicated the complexes could bind to DNA and the main binding mode is intercalative binding. The fluorescence quenching constants of the complexes increased from La(cin)3 phen to Lu(cin)3 phen. Additionally, the antibacterial activity testing showed that the complexes exhibited excellent antibacterial ability against Escherichia coli, and the changes of antibacterial ability are in agreement with that of the fluorescence quenching constants.

Synthesis, characterization and luminescent properties of europium complexes with 2,4,6-tris-(2-pyridyl)-s-triazine as highly efficient sensitizers

Using 2,4,6-tris-(2-pyridyl)-s-triazine (TPTZ) as a neutral ligand, and p-hydroxybenzoic acid, terephthalic acid and nitrate as anion ligands, five novel europium complexes have been synthesized. These complexes were characterized using elemental analysis, rare earth coordination titrations, UV/vis absorption spectroscopy and infrared spectroscopy. Luminescence spectra, luminescence lifetime and quantum efficiency were investigated and the mechanism discussed in depth. The results show that the complexes have excellent emission intensities, long emission lifetimes and high quantum efficiencies. The superior luminescent properties of the complexes may be because the triplet energy level of the ligands matches well with the lowest excitation state energy level of Eu(3+). Moreover, changing the ratio of the ligands and metal ions leads to different luminescent properties. Among the complexes, Eu2(TPTZ)2(C8H4O4)(NO3)4(C2H5OH)·H2O shows the strongest luminescence intensity, longest emission lifetime and highest quantum efficiency.

Synthesis, crystal structure and fluorescence properties of terbium complexes with phenoxyacetic acid and 2,4,6‐tris‐(2‐pyridyl)‐s–triazine

Two complexes of Tb(3+), Gd(3+) /Tb(3+) and one heteronuclear crystal Gd(3+)/Tb(3+) with phenoxyacetic acid (HPOA) and 2,4,6-tris-(2-pyridyl)-s-triazine (TPTZ) have been synthesized. Elemental analysis, rare earth coordination titration, inductively coupled plasma atomic emission spectrometry (ICP-AES) and thermogravimetric analysis-differential scanning calorimetry (TG-DSC) analysis show that the two complexes are Tb2 (POA)6 (TPTZ)2 · 6H2O and TbGd(POA)6 (TPTZ)2 · 6H2O, respectively. The crystal structure of TbGd(POA)6 (TPTZ)2 · 2CH3OH was determined using single-crystal X-ray diffraction. The monocrystal belongs to the triclinic system with the P-1 space group. In particular, each metal ion is coordinately bonded to three nitrogen atoms of one TPTZ and seven oxygen atoms of three phenoxyacetic ions. Furthermore, there exist two coordinate forms between C6H5OCH2COO(-) and the metal ions in the crystal. One is a chelating bidentate, the other is chelating and bridge coordinating. Fluorescence determination shows that the two complexes possess strong fluorescence emissions. Furthermore, the fluorescence intensity of the Gd(3+)/Tb(3+) complex is much stronger than that of the undoped complex, which may result from a decrease in the concentration quench of Tb(3+) ions, and intramolecular energy transfer from the ligands coordinated with Gd(3+) ions to Tb(3+) ions.