金刚烷胺邻香兰素Schiff碱稀土配合物的合成、表征及抗菌活性研究

The new solid complexes [LnL₂(NO₃)₂]NO₃ (L=C₁₈H₂₃NO₂, N-2-hydroxy-3-methoxy-benzaldehyde-1-aminoadamanantane, Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y) of rare earth nitrates with Schiff base derived from o-vanillin and adamantaneamine have been synthesized in non-aqueous system and characterized by elemental analysis, molar conductance, infrared spectra, ¹H NMR spectra, thermal analysis. The coordination modes of the bonding in these complexes were discussed and the possible structure were proposed. Every central Ln(Ⅲ) ion in the complexes coordinates with both two Schiff base ligands via four oxygen atoms of the phenol hydroxy groups and methoxy groups and two nitrates via their four oxygen atoms. Their coordination numbers are eight. In addition, the antibacterial activity of the Schiff base ligand and the complexes were studied.     

Anderson结构稀土钼铬多金属氧酸盐的合成与表征

A new kind of Anderson-type chromium-molybdates containing the rare earth elements are synthesized， which have the general molecular formula of (NH₄)₆[CrMo₅Ln(OH₂)₂O₂₄H₆]·xH₂O (Ln=La，Ce，Pr，Nd，Sm，Gd and Yb). The components of these heteropoly complexes are determined by chemical elemental analysis， ICP and TG-DTA. And IR， UV， ESR，XPS and ¹H NMR are also applied to characterize the complexes as well. The results indicate that the structures of these complexes are Anderson B type and the rare earth elements are in the inner sphere of the heteropoly salts. The thermal stabilities of these complexes studied by TG-DTA show that the range of pyrolysis temperature is between 490℃ and 500℃.     

噻吩甲酰基吡唑啉酮缩氨基酸稀土配合物的合成、表征及生物活性

A new amino-acid Schiff base, 1-phenyl-3-methyl-4-(2-thenoyl) pyrazolone-5-β-alanine (HL) and its ten rare earth complexes have been synthesized. On the basis of elemental analysis and molar conductance, the general formula of the complexes, [REL₂NO₃]·nH₂O (RE=La, Nd, Eu, Tb, Y, n=2; RE= Pr, Sm, n=1; RE= Dy, Er, Yb, n=3), is given. They were characterized by IR, UV-visible, ¹H NMR, ¹³C NMR and fluorescence. The results show that the rare earth ions exhibit coordination of eight in the complexes.The antibacterial experiments indicate that they have high antibacterial activities against S. Aureus, B. Subtillis, E. Coli, E. Carotovora and C. Flaccumfaciens.     

三种1,10-邻菲咯啉-铜(Ⅱ)-L-氨基酸配合物与DNA的相互作用

The Interaction of three complexes [Cu(phen)(Gly)(H₂O)]·ClO₄·2.5H₂O (1), [Cu(phen)(L-Val)(H₂O)]·ClO₄ (2) and [Cu(phen)(L-Ile)(H₂O)]·ClO₄ (3) (phen=1,10-phenanthroline, Gly=glycinate, L-Val=L-valinate, L-Ile=L-isoleucinate) with DNA have been investigated by electronic absorption spectroscopy, ethidium bromide(EB) fluorescence spectroscopy, viscosity and gel electrophoresis measurements. The intensity of maximal absorption peaks from absorption spectra are weakened with dropping DNA into the complexes. The emission intensity of EB-DNA systems in fluorescence spectroscopy have descended 50%, when the data of C_Cu / C_DNA is 30～40. Moreover, the viscosity of DNA increase and then decrease with the increasing of complexes. All of the results indicate that the interaction of complexes with DNA are partial intercalation, and the result of agarose gel electrophoresis show that the complexes can cleave pBR322 DNA in the present of H₂O₂ / vitamin C.     

6′，6″-二吡啶基-2，2′：4′，4″：2″，2′′′-四联吡啶稀土配合物的合成、表征及荧光性质研究(英)

Two series of solid complexes of rare earth nitrates and picrates with the “back-to-back” terpyridine, 6′,6″-bis(2-pyridyl)-2,2′:4′,4″:2″,2′′′-quaterpyridine (L) have been synthesized. These complexes have been characterized by elemental analysis, conductivity measurements, thermal analysis and IR spectroscopy. At the same time, the luminescent properties of the Eu(Ⅲ) and Tb(Ⅲ) complexes were also studied.     

N，N，N′，N′-四丁基丙二酰胺从硝酸盐介质中萃取铈(Ⅲ)

Study on the extraction and separation of rare earth with new extractants is important in the rare earth chemistry and nuclear reprocessing. In this work， the extraction of Ce(Ⅲ) with N，N，N′，N′-tetrabutylmalonamide (TBMA) in toluene from nitrate media has been investigated. The effect of the concentration of nitric acid， TBMA and salt-ing-out agent (LiNO₃) and also the temperature on the distribution ratios was examined. The stoichiometries of the extracted complexes were determined to be Ce(NO₃)₃·3TBMA and Ce(NO₃)₃·4TBMA， respectively. The ap-parent extraction constants and the enthalpy of the extraction were calculated based on the extraction data， which are logK_ex1=3.97， logK_ex2=4.75 and Δ_rH_m^?=-31.25kJ·mol^-1， respectively. The IR spectra of the loaded organic phase supported the suggested extraction mechanism.     

Sm(Ⅲ)(MTB)2配合物与DNA作用的光谱法研究

The interaction between Sm(Ⅲ)(MTB)₂ complex and Herring Sperm DNA has been studied by UV-Vis spectral, Fluorescence spectral in buffer solution of Tris-HCl (pH=7.25) using Neutral Red (NR) as a probe. The intercalation and electrostatic manner are confirmed to be the two major modes for interaction between Sm(Ⅲ)(MTB)₂ complex and Herring Sperm DNA. The balance constant of Sm(Ⅲ)(MTB)₂ rare earth metal complex and Herring Sperm DNA is K=4.10 × 10⁴ L·mol^-1. The results indicate that biological functions of Herring Sperm DNA are changed to a certain extend due to the interaction between Sm(Ⅲ)(MTB)₂ rare earth metal complex and Herring Sperm DNA.     

4-(3-吲哚基)-3-丁烯-2-酮苯甲酰腙Schiff碱过渡金属配合物的合成、表征及生物活性研究

A Schiff base ligand 4-[indol-3-yl]-but-3-en-2-one benzoyl hydrazone (HL), and its four transition metal complexes (ML₂，M=Cu(Ⅱ), Ni(Ⅱ), Zn(Ⅱ) and Co(Ⅱ)) have been prepared and characterized by means of elemental analysis, EI-MS, molar conductivity, IR, UV-Vis and ¹H NMR. The results showed that HL as a bidentate ligand coordinated with transition metal ions to form four-coordination complexes. The antibacterial activity was studied by using the filter scraps diffusion method, and the results indicated that the ligand and the complexes had a low bacteriostatic activity against S. Aureu, P. Aeruginosa and E. Coli. The low in vitro antitumor activity of the title complexes was also observed by using MTT method against KB, A2780, Bel7402 and HELF.     

水杨醛缩2-氨基-4-苯基噻唑及其配合物的合成与仿酶催化活性研究

The new containing Surfur Schiff base Salicylaldelye-2-amino-4-Phenylthiazole(SAPTZ) and its Cu(Ⅱ)、Zn(Ⅱ)、Ni(Ⅱ) and Co(Ⅱ) compelexes were synthesized. The structures of the complexes were characterized by elemental analysis, IR and UV-vis. The peroxidase-like activity of the complexes for the oxidation of Vc with H₂O₂ was determined.     

三元稀土配合物RE(NTA)2AA的合成、共聚反应性及荧光性能研究

Four new ternary rare earth complexes RE(NTA)₂AA (RE=Sm³⁺， Eu³⁺， Tb³⁺， Dy³⁺) have been synthesized by the reaction of rare earth chloride(RECl₃·6H₂O) with Acrylic Acid (HAA) and 4，4，4-trifluoro-1-(3-pyridyl)-1，3-butanedione(NTA) in alcohol. The copolymerization of the complexes RE(NTA)₂AA (RE=Sm³⁺， Eu³⁺) with methyl methacrylate (MMA) has been studied by 2， 2-azobis-isobutyronitrile as an initiator. Influence of adding Eu(Ⅲ) and 2，2′-bipyridine(bipy) into copolymer Eu(NTA)₂AA-co-MMA on fluorescence property of the Eu copolymer was investigated. The compositions of the complexes and copolymer were characterized by means of elemental analysis and FTIR. The heat decomposing behaviors of the complexes were determined by TG-DTA. The glass transition temperature and molecular weight were obtained by DSC and GPC. The results of fluorescence properties show that the Eu， Sm complexes and Eu copolymer can efficiently emit fluorescence， but the Tb and Dy complexes only emit the fluorescence of β-diketone ligand.     

草酸根桥联Cr(Ⅲ)-Ni(Ⅱ)配合物的合成和磁性

Two new heteropolynuclear metal complexes ［Ni(phen)₂］₃［Cr(ox)₃］₂·8H₂O(1) and ［Ni(bipy)₂］₂［Cr(ox)₃］NO₃·4H₂O(2)(phen=1,10-phenanthroline, ox=oxalato, bipy=2,2-bipyridine) have been synthesized and characterized by elemental analyses, IR, TG-DTA and diffuse reflectance UV-VIS spectra. The temperature dependence of the magnetic susceptibilities of the complexes have been studied over the range 73.6～300K. The results show that ferromagnetic spin exchange interaction exist between Cr(Ⅲ) and Ni(Ⅱ) in the complex (1). The magnetic property of the complex(2) abides Curie law.     

掺镍型层状LixNiyMn1-yO2正极材料的合成与电性能研究

A kind of cathode material of layered Li_xNi_yMn_1-yO₂ characterized with the O2 type has been synthesized by a simple method. Its precursor Na_xNi_yMn_1-yO₂ has been prepared from manganese dioxide， nickel hydroxide and sodium carbonate at high temperature in air and quickly cooled in cold water， then it has been exchanged by the melted LiNO₃ at 300～400℃ in air. The effects of calcine-temperature for the precursors and its compositions (the content of Na and Ni) on the electrochemical properties of the material Li_xNi_yMn_1-yO₂ have been investingated by XRD and electrochemical tests. The results show that the sample Li_0.7Ni_0.3Mn_0.7O₂， has the best electrochemical properties which shows only one charge-discharge potential stage of 2.8～3.0V and has a high specific capacity over 180mAh·g^-1 cycled between 2.0～4.20V. A significant structure transformation to the spinal-type phase has not been found in the charge-discharge cycling and the discharge specific capacity around 165mAh·g^-1 has re-mained after the 20th cyclings for the material.     

锌(Ⅱ)-氨基酸水杨醛席夫碱-α-氨基酸三元配合物的稳定性

The stability constants of binary complexes of Zn(Ⅱ)-α-amino acid and ternary complexes of Zn(Ⅱ)-N-Salicylideneaminio acid (ligand A)-α-amino acid(ligand B) at (25±0.1)℃ and in the presence of 0.1 mol·L^-1 KNO₃ have been determined by pH method. The α-amino acid(Aa) used were Glycine(Gly), L-Serine(Ser), L-Leucine(Leu), L-Proline(Pro) and L-Phenylalanine(Phe). It was found that the linear free energy relationship (LFER) exists nicely between the following parameter pairs logβ₁₀₂ and pK^B₂, logβ₁₁₁ and pK^B₂, and logβ₁₁₁ and pK^A₂. The ΔlgK was used to characterize the stability of ternary complexes related to the stability of parent binary complexes. The hydrophobic interaction between ligands in the ternary complexes was studied.     

Yb(Cl4)3·3H2O-18C6-C2H5OH体系(25℃)的相化学研究及固态配合物的合成与性质

The solubilities of Yb(ClO₄)₃·3H₂O-18C6-C₂H₅OH ternary system at 25 were invstigated by a semimicro method for study of phase equilibrium.and the refractive indexes of saturated solutions were determined.The behavior of water in this system during the equilibrium was examined.The results indicate that there are two kinds of complexes formed in the system, their chemical compositions are: Yb(ClO₄)₃·18C6·3H₂O·2C₂H₅OH (I) and Yb(ClO₄)₃ 18C6·3H₂O·C₂H₅OH.Both are incongruently soluble in EtOH.The influences of rare earth ions and salt anions on formation of complexes were discussed.The two solid complexes have been prepared, and their composihons and properties have been investigated by chemical analysis, IR, DTG and DSC.According to the DSC, the enthalpies of some steps during the decomposition have been obtained for complexes (Ⅲ)and (Ⅳ).     

(R)-1，1′-联萘手性单元通过溶胶凝胶法合成杂化硅干凝胶(英)

Precursor molecule (R)-6,6′-bis(triethoxysilylethen-2-yl)-2,2′-di(methoxyethoxymethyloxy)-1,1′-binaphthyl (R-2) was synthesized by Pd-catalyzed Heck reaction of (R)-6,6′-dibromo-2,2′-di(methoxyethoxymethyloxy)-1,1′-binaphthyl (R-1) intermediate with vinyltriethoxysilane. The hydrolysis and polycondensation of the precursor R-2 produced the corresponding xerogel. Both precursor and xerogel were analysed by NMR, FTIR, UV, CD spectra, fluorescent spectroscopy, polarimetry and elemental analysis. The precursor and xerogel can emit strong blue fluorescence and are expected to have a potential application in the separation of chiral molecules as fluorescent sensor. The precursor exhibits strong Cotton effect in its circular dichroism (CD) spectrum indicating a highly rigid structure.     

Zn(Ⅱ)、Ni(Ⅱ)与5-氯水杨醛缩乙二胺Schiff碱单、双核配合物的合成及其对O2-的催化歧化作用

A Series of mono and di-nuclear Zn(Ⅱ)、Ni(Ⅱ) complexes with 5-chlorosalicylaldehyde -ethylenediamine Schiff base have been synthesized.Theirs compositions and structures were characterized by the elemental analysis.UV.IR spectra and ¹H NMR.The Dismutation to O₂^- free radical has also been investigated.     

银(Ⅰ)、锌(Ⅱ)与2，2′-(2-氨基-苯氧基)乙醚配合物的合成及晶体结构

The compound 2,2′-(2-amino-phenoxy)-ether[L] was synthesized from the reaction of diethylene glycol with tosyl chloride. AgClO₄ and ZnCl₂ each react with L to give two complexes [Ag₂L₂(H₂O)(ClO₄)₂] (1) and [ZnLCl₂]_n (2) respectively, and characterized by FTIR and single crystal X-ray diffraction. The results of structural analysis indicated that both complexes crystallize in the monoclinic system with space group P2₁/c. 1 is a dinuclear complex, and 2 forming 1D zigzag chain by Zn(Ⅱ) linking adjacent ligands in turn. When viewed from the top of the chain, the structure of 2 shows the unidimensional tube. CCDC: 748592, 1; 748594, 2.     

1,10-邻菲咯啉-铜(Ⅱ)-L-蛋氨酸配合物的合成、表征及其分子结构

The complex [Cu(L-met)(phen)(H₂O)]NO₃·H₂O has been synthesized and investigated by elemental analysis, molar conductivity, spectroscopic and X-ray diffraction methods, where phen=1,10-phenanthroline and L-met=L-methioninate group. The complex crystallized in the monoclinic space group P2₁ with a=12.053(2)?, b=6.886(1)?, c=13.385(3)?, β=113.59(3)°, V=1018.1(3)?³, Z=2,D_c=1.598g·cm^-3, μ=1.223mm^-1, F(000)=506, R₁=0.0306, and wR₂=0.0742. The copper(Ⅱ) atom is ligated in a distorted square-pyramidal geometry by two nitrogen atoms of one phen and the amino nitrogen atom , one carboxylate oxygen atom of L-met in the base plane, and an aqua at the apical position. A one-dimensional chain configuration formed by the hydrogen-bonding and weak Cu-O (the uncoordinated carboxyl oxygen atom) coordination interactions be-tween neighboring [Cu(L-met)(phen)(H₂O)]⁺ cations. CCDC: 183368.     

合成大比表面γ-Mo2N的新方法

The production of high specific surface area γ-Mo₂N (up to 165 m²·g^-1, passivated) by temperature programmed reaction of MoO₃ with mixtures of N₂ and H₂ was reported. The synthetic condition of high surface area γ-Mo₂N (usually, S_BET>100 m²·g^-1) were quite difficult and the amount of starting material MoO₃ in each batch was much less than 0.5 gram. However, some synthetic conditions had been greatly improved in our experiments. The crystalline phase and specific surface area had been characterized by XRD and BET. The XRD gave some information for reaction mechanism.     

RE(Et2dtc)3(phen)(RE=La，Pr，Nd，Sm)的恒容燃烧能测定(英)

Four ternary solid complexes were synthesized with sodium diethyldithiocarbamate (NaEt₂dtc)(b), 1,10-phenanthroline (o-phen) (c) and hydrated lanthanide chlorides in absolute ethanol by an improved reported method. The complexes were identified as the general formula of RE(Et₂dtc)₃(phen) (RE=La, Pr, Nd, Sm) by chemical and elemental analyses. IR spectra of the complexes showed that the RE³⁺ was coordinated with sulfur atoms of NaEt₂dtc and nitrogen atoms of o-phen. The constant-volume combustion energies of complexes, Δ_cU, were determined by a precise rotating-bomb calorimeter at 298.15 K. The standard enthalpies of combustion, Δ_cH_m^?, and standard enthalpies of formation, Δ_fH_m^?, were calculated for these complexes, respectively.