桂皮酸-8-羟基喹啉稀土配合物的合成、表征及与牛血清白蛋白的作用

合成了以桂皮酸、8-羟基喹啉为配体,以镱、铕为中心离子的稀土配合物,采用元素分析、摩尔电导、红外光谱、紫外光谱和荧光光谱法进行表征,并采用紫外光谱和荧光光谱研究了配合物与牛血清白蛋白(BSA)的相互作用。结果表明,随着配合物浓度的增加,BSA紫外光谱表现出明显的增色效应,配合物可有规律地猝灭BSA的荧光。     

Synthesis,characterization and fluorescence spectra of mononuclear Zn(II), Cd(II) and Hg(II) complexes with 1,10-phenanthroline-5,6-dione ligand

The mononuclear complexes of Zn(II), Cd(II) and Hg(II), [Zn(phen-dione)Cl₂], [Cd(phen-dione)Cl₂] and [Hg(phen-dione)Cl₂], where phen-dione?=?1,10-phenanthroline-5,6-dione, have been synthesized and characterized by elemental analysis and IR, ¹H?NMR and electronic absorption spectroscopies. The ν(C=O) of coordinated phen-dione ligands in these complexes shows that the phen-dione is not coordinated to metal ion from its C=O sites. Electronic spectra of the complexes show two absorption bands for intraligand transitions. These absorption bands show dependence on the dielectric constant of solvents. These complexes exhibit an intense fluorescence band around 545?nm in DMSO when the excitation wavelengths are 200?nm at room temperature.     

Synthesis and spectroscopic characterization of new heteroleptic ruthenium(II) complexes incorporating 2-(2′-pyridyl)quinoxaline and 4-carboxy-2-(2′-pyridyl)quinoline

Starting from cis-[Ru(dcbpyH₂)₂Cl₂] (1), two new heteroleptic ruthenium(II) complexes, [Ru(dcbpyH₂)₂(L¹)](NO₃)₂ (L^1?=?2-(2′-pyridyl)quinoxaline (2), and [Ru(dcbpyH₂)₂(L²)](NO₃)₂ (L^2?=?4-carboxy-2-(2′-pyridyl)quinoline (4); dcbpyH_2?=?2,2′-bipyridine-4,4′-dicarboxylic acid), were synthesized and spectroscopically characterized. During the preparation of 2 and 4, the homoleptic [Ru(dcbpyH₂)₃]Cl₂ complex (3) was isolated as a side product. Characterization includes IR and Raman spectroscopy, UV-Vis, multinuclear NMR spectroscopy, elemental, and ESI-mass spectrometric analyses.     

Synthesis,spectral and biological investigations of 5(2′-hydroxyphenyl)-3-(4-substituted-phenyl) pyrazolinates of cobalt(II) and their addition complexes with N,P donor ligands

5(2′-Hydroxyphenyl)-3-(4-substituted-phenyl)pyrazolinates of cobalt(II) of the type (C₁₅H₁₂N₂OX)₂Co [here substituted group X is–H,–Cl,–CH₃ or–OCH₃] have been synthesized by reaction of anhydrous cobalt(II)chloride with the sodium salt of the pyrazolines in 1 : 2 molar ratio. Their addition complexes with N and P donor ligands [2, 2′-bipyridine, 1, 10-phenanthroline and triphenylphosphine] were prepared in 1 : 1 molar ratio. The newly synthesized complexes were characterized by elemental analyses, molecular weight measurement, magnetic susceptibility, IR, electronic, ³¹P NMR and FAB mass spectra. All complexes are amorphous as determined by XRD. Tetrahedral geometry around cobalt(II) has been suggested, confirming the presence of two pyrazoline bidentate ligands, cobalt(II)5- (2′-hydroxyphenyl)-3-(4-substituted-phenyl)pyrazolinates. Upon ligand addition, pyrazoline changes to monodentate. The bidentate and monodentate behavior of pyrazoline ligands was confirmed by IR spectral data. The metal complexes and their adducts exhibit good antibacterial and antifungal activity, better than the pyrazolines.     

Synthesis,spectroscopic, antimicrobial and anti-inflammatory studies of 5(2′-hydroxyphenyl)-3-(4-x-phenyl)pyrazolinates of copper(II) and their addition complexes with donor ligands

Complexes of copper(II) with 5(2′-hydroxyphenyl)-3-(4-x-phenyl)pyrazolines, (C₁₅H₁₂N₂OX)₂Cu [X =–H,–Cl,–CH₃,–OCH₃] have been synthesized with their addition complexes with 2,2′-bipyridine, 1,10-phenanthroline and triphenylphosphine. The complexes were characterized by elemental analyses, molecular weight measurement, magnetic, conductivity measurement, IR, electronic, ³¹P NMR, ESR and FAB mass spectra. The complexes were examined for crystalline/amorphous nature through XRD. Square-planar geometry around copper(II) is suggested with two bidentate pyrazoline ligands. In the additional complexes pyrazoline is monodentate. The bidentate and monodentate behavior of pyrazoline ligands was confirmed by IR and ³¹P NMR spectral data. All complexes were tested for in vitro antibacterial and antifungal activity and exhibit very good antibacterial and antifungal activity; coordination has a pronounced effect on the microbial activities. The brine shrimp bioassay was also carried out to study their in vitro cytotoxic properties. All complexes and adducts displayed potent cytotoxic activity against Artemia salina. Anti-inflammatory activity was also carried out by the carrageenan induced rat paw edema test. The complexes and adducts were found to have higher anti-inflammatory activity.     

Hydrothermal synthesis and crystal structure of a metal–organic compound with unique pseudo-hexagonal water channels: [CuII(phen)(sal)]·0.5H2O (phen=1,10-phenanthroline,sal=salicylic acid)

This article presents a metal–organic compound [Cu^II(phen)(sal)]?·?0.5H₂O (1) with intriguing structural motif of 3D hexagonal water channels. Furthermore, IR, element analysis, and TGA were employed to characterize it. The TG-DTA showed that this structure is stable to 300°C. Compound 1 belongs to the hexagonal system, space group R-3, a?=?33.337(5)?Å, b?=?33.337(5)?Å, c?=?9.4599(19)?Å, γ?=?120°, V?=?9105(3)?ų, Z?=?18.     

Synthesis and luminescence of polymeric metal complexes based on 1,10-phenanthroline and 8-hydroxyquinoline

A ligand containing different coordination groups, 5-([1,10]phenanthroline-[4,5-f]imidazo-2-yl)-8-hydroxyquinoline (PhenI8Q) has been synthesized and two corresponding polymeric metal complexes Cu(II) (1) and Zn(II) (2) were prepared by coordination polymerization of the ligand with copper(II) and zinc(II) halides, respectively. The ligand was characterized by ¹H-NMR, ¹³C-NMR, and Fourier transform-infrared (FT-IR) and its corresponding polymeric metal complexes 1 and 2 were characterized by FT-IR, UV-Vis, elemental analysis, thermal gravimetric analysis, and conductivity measurements. The absorption spectra and luminescence of the ligand, 1, and 2 were investigated by UV-Vis and fluorescence spectroscopy at room temperature. Compared with the ligand, the fluorescence spectra of the polymeric metal complexes exhibit blue shifts in dimethyl sulfoxide (DMSO) solution and bathochromic shifts in the solid state. Complexes 1 and 2 emit blue light with emission maximum (λ _{f max}) at 449 and 431 nm in DMSO solution and at 485 and 484 nm in the solid state, respectively.     

Synthesis,structure and electrochemical behavior of an organic-inorganic hybrid compound based on Dawson-type polyoxometalates

An organic-inorganic hybrid compound constructed from Wells-Dawson polyanion clusters and metal-organic complex subunits, [Cu(phen)₃][Cu(phen)₂Cu(phen)₂(P₂W₁₈O₆₂)]·2H₂O (1) has been prepared hydrothermally and characterized by elemental analysis, IR, UV, cyclic voltammetry (CV) and single-crystal X-ray diffraction. Crystal structural analysis indicates that two terminal oxygen atoms of the Wells-Dawson polyanion located in the “belt” site coordinate with Cu²⁺. Three Cu ions have different coordination environments: Cu1 and Cu2 are five-coordinate, while Cu3 is six-coordinate. The bisupporting polyoxoanions [Cu(phen)₂Cu(phen)₂(P₂W₁₈O₆₂)]^2? are polymerized into a 1D chain by hydrogen bonding interactions, then the chains are stacked into a two-dimensional structure via offset, face-to-face, π ··· π stacking interactions. CV reveals that 1 exhibits three chemically-reversible processes.     

基于表面富Cd2+的硫化镉量子点荧光增强测定半胱氨酸

采用一步法可控合成了表面富Cd2+的水溶性荧光硫化镉量子点,并成功用于半胱氨酸测定.通过控制镉-硫前驱体合适比例,使合成的量子点表面富含Cd2+,它们能与半胱氨酸分子中巯基结合引起体系量子点荧光增强,由此实现半胱氨酸的选择性定量分析检测.在pH=2.87的B-R缓冲体系中,测定半胱氨酸的线性区间分别为0.01～5.0 μmol/L和5.0～100 μmol/L;检出限(3σ)为3.3 nmol/L,且其它氨基酸干扰小,可应用于混合氨基酸合成样品、复方氨基酸注射液和人血清实际样品中半胱氨酸的检测.     

助剂对Co/Al2O3催化剂浆态床费托合成反应性能影响

考察了ZrO₂、Ru或Pt助剂对Co/Al₂O₃催化剂结构及浆态床费托合成反应性能的影响。实验结果表明,添加ZrO₂助剂可阻止或降低难还原铝酸钴的形成、促进催化剂的还原、提高Co/Al₂O₃催化剂对费托合成反应的催化活性、降低甲烷选择性并提高C₅₊烃选择性。H₂-TPR表征结果表明,少量Ru或Pt助剂均能降低Co-ZrO₂/Al₂O₃催化剂中钴物种还原温度(Co₃O₄→CoO和CoO→Co⁰),提高催化剂的还原度,催化剂呈现出良好的CO加氢反应活性。此外,催化剂组分间浸渍次序对费托合成反应性能有重要影响,载体γ-Al₂O₃先浸渍Zr组分,可有效抑制难还原化合物形成;Co、Ru组分共浸渍加强了Co和Ru组分密切接触程度,更利于钴物种的还原;Co、Pt组分依次浸渍更利于活性组分的均匀分布,催化剂具有最佳的费托合成反应性能。