Synthesis,Crystal Structure and Interaction with DNA of a Novel Chromium(Ⅲ) Complex Containing Salicylaldehyde Semicarbazone

The novel chromium（Ⅲ） complex with salicylaldehyde semicarbazone was synthesized and characterized by IR spectra and single-crystal X-ray diffraction analysis. The crystal belongs to the orthorhombic system, space group Pbca with a = 8.9849（13）, b = 12.0475（16）, c = 34.522（5）A, V = 3736.9（9）A3, Z = 8, C16H18C1CrN6O5, Mr= 461.81, De= 1.642 g/cm^3, F（000） = 1896,A（MoKα） = 0.799 mm^-1, the final R = 0.0370 and wR = 0.0827 for 2908 observed reflections with I 〉 2σ（I）. The interaction between the chromium（Ⅲ） complex with calf thymus DNA （Ct-DNA） has been investigated by absorption spectroscopy, fluorescence spectroscopy and viscosity measurements. The results indicated that the complex was bonded to Ct-DNA through a non-classical intercalative mode.

Synthesis and Kinetic Study on the Chromium（Ⅲ） Complex [Cr（ASA）（en）2]Cl·2H2O

In order to explore the transfer mechanism of chromium（Ⅲ） in mammals, a novel complex [Cr（ASA）（en）2]Cl·2H2O, bis（ethylenediamine-κ2 N,N′）（4-aminosalicylic acid-κ^2 O,O′） chromium（Ⅲ） monochloride dihydrate was synthesized （4-aminosalicylic acid=H2ASA, ethylenediamine=en）. The crystal structure belongs to orthorhombic system with the space group P212121 by means of X-ray diffraction. The characteristic for transfer of Cr^3＋ from the compound to the low-molecular-mass chelator EDTA and the iron-binding protein apoovotransferrin （apoOTf） was followed by UV-visible （UV-Vis） and fluorescence spectra in 0.01 mol·L^-1 Hepes at pH 7.4. The second order rate constants were calculated. Those spectra in conjunction were used to obtain more accurate information about the interaction of chromium complex with apoOTf. The experimental results indicate that Cr^3＋ can be transferred from the complex to apoOTf with the retention of the 4-aminosalicylic acid acting as a synergistic anion.

Impact of Cr(Ⅲ)complexation with organic acid on its adsorption in silts and fine sands

Trivalent chromium(Cr(Ⅲ))can form stable soluble complexes with organic components,altering its adsorption properties in the water-soil environment.This increases the risk of Cr(Ⅲ)migrating to deeper soils and transforming into toxic Cr(VI)due to the presence of manganese oxides in sediments.In this study,Citric Acid(CA)was selected as a representative organic ligand to prepare and characterize Cr(III)-CA complexes.The characteristics,mechanisms and environmental factors influencing the adsorption of Cr(Ⅲ)-CA on porous media(silts and fine sands)were investigated in the study.The results show that Cr(Ⅲ)coordinates with CA at a 1:1 molar ratio,forming stable and soluble Cr(Ⅲ)-CA complexes.Compared to Cr(III)ions,the equilibrium adsorption capacity of Cr(Ⅲ)-CA is an order of magnitude lower in silts and fine sands.The adsorption of Cr(Ⅲ)-CA in silts and fine sands is dominated by chemical adsorption of monolayers,following the pseudo-second-order kinetic equation and the Langmuir isotherm adsorption model.Varying contents of clay minerals and iron-aluminum oxides prove to be the main causes of differences in adsorption capacity of Cr(Ⅲ)-CA in silts and fine sands.Changes in solution pH affect the adsorption rate and capacity of Cr(Ⅲ)-CA by altering its ionic form.The adsorption process is irreversible and only minimally influenced by ionic strength,suggesting that inner-sphere complexation serves as the dominant Cr(Ⅲ)-CA adsorption mechanism.

Oligomannuronate-Chromium (Ⅲ) Complex Ameliorates Insulin Resistance in C57BL/KsJ-db/db Mice

Diabetes mellitus is the most common metabolic disease and its prevalence is increasing in many countries year by year.More than 90% of diabetes patients are type 2 diabetes,which is caused by insulin resistance and beta-cell dysfunction.In this paper,the oligomannuronate-chromium(III)complex(OM2)was prepared and its effect and mechanism on attenuating insulin resistance in diabetic C57BL/KsJ-db/db mice were studied.The results indicated that oral intake of OM2(50 mg kg-1d-1)for 42 d decreased blood glucose and lipid concentration,which was associated with the reduced serum insulin concentration and insulin resistance.According to western blot assay,OM2 could activate AMPK pathway to regulate glycogen synthesis,gluconeogenesis and lipid metabolism in the liver,and attenuate the hyperglycemic symptom in db/db mice.The effects of OM2 on attenuating insulin resistance were com-parable to that of the established antidiabetic drug metformin,and OM2 showed less adverse effect than metformin in vivo.Based on the effectiveness and low toxicity,OM2 may potentially be used for prevention and treatment of type 2 diabetes mellitus.

A Defective Linear Pentachromium Complex for the Enhanced Catalysis of the Cycloaddition of CO2 with Propylene Oxide

Based on the ligand（2,7-bis（α-pyrimidylamino）-1,8-naphthyridine（H2 bpmany））, a linear pentachromium complex [Cr5（μ5-bpmany）4Cl2]PF6（1, μ5-bpmany = 2,7-bis（a-pyrimidylamino）-1,8-naphthyridine） was synthesized. The crystal structure of compound 1 has been characterized by X-ray crystallography. Interestingly, one metal atom in the center is missing in this linear chain, leading to the defective pentachromium metal string structure which is similar with the reported complex [Cr5（μ5-dpznda）4Cl2]（2, dpznda = N^2,N^7-di（pyrazin-2-yl）-1,8-naphthyridine-2,7-diamine）. The central Cr（Ⅲ） ion of 1 is eight-coordinated and is also rare in the chromium complex. The reaction of carbon dioxide with propylene oxide that generates propylene carbonate（PC） when catalyzed by [Cr5（μ5-bpmany）4Cl2]PF6 was investigated. Different reaction conditions including temperature and pressure were studied to optimize the reaction conditions.

含氮杂环卡宾配体的半三明治铱(Ⅲ)配合物的合成及抗肿瘤转移作用

铱(Ⅲ)抗肿瘤配合物[(η^(5)-C_(5)MeC_(6)H_(4)C_(6)H_(5))Ir(C∧C)Cl]PF_(6)能够选择性杀伤、抑制肿瘤细胞,但其内在的作用机制尚不完全明确.采用细胞划痕法、迁移及侵袭等实验考察了金属铱(Ⅲ)配合物对A549细胞的抗转移能力,采用免疫组织化学法和蛋白印迹法分析NEDD9、β-catenin表达水平.研究结果显示:金属铱(Ⅲ)配合物对A549细胞有明显的抗转移作用,可能通过作用于NEDD9降低肺癌细胞的增殖和转移.同时该金属配合物也可通过诱发β-catenin蛋白的表达,增加细胞膜表面粘性,降低A549细胞的转移能力.

Complexation separation for vanadium and chromium by dithiocarbamate and its application in treatment of chromium-vanadium-bearing slag

A novel method for the separation and reclamation of vanadium and chromium from acidic solution was proposed. The principle for the separation is based on selective complexation. In specific, V(V) can be complexated by dithiocarbamate to form VO(R1R2NCS2)3 precipitate, leaving Cr(Ⅲ) remained in the acidic solution. Then the reclamation of V and Cr from VO(R1R2NCS2)3 precipitate and Cr(Ⅲ)-bearing solution can be reached by decomplexation and neutralization, respectively. The kinetics of the complexation reaction was studied. In addition, the precipitation ratio of vanadium reached 97% and the loss of chromium was less than 4% after process optimization. The complexing agent could be regenerated with a high ratio of 99.5%. The method was successfully applied to treating chromium-vanadium-bearing slag produced in conventional vanadium production industry. Vanadium and chromium could be extracted from the slag in the form of calcium vanadate and Cr2O3 product with a purity of over 98%.

Thermal Decomposition Kinetics and Mechanism of Tb(Ⅲ) m-Methylbenzoate Complex with 1,10-Phenanthroline in Static Air Atmosphere

The thermal behavior of [Tb_2( m -MBA)_6(phen)_2](H_2O)_2( m -MBA=C_8H_7O_2, methoxybenzoate; phen=C_ 12 H_8N_2, 1,10-phenanthroline) in static air atmosphere was investigated by means of TG-DTG and DTA methods. The thermal decomposition of the title compound takes place mainly in two steps. The intermediate and the residue for each decomposition were identified by the TG curve. By the kinetic method of processing thermal analysis data put forward by Malek et al ., it is defined that the kinetics model for the first-step thermal decomposition is SB( m,n ).

Synthesis of Eu(Ⅲ) and Tb(Ⅲ) Complexes with New Aryl Amide Type Tetrapodal Ligand and Their Luminescence Properties

A new aryl amide type tetrapodal ligand L (1, 1, 1, 1 tetrakis-{[(2 benzylaminoformyl) phenoxyl]methyl}methane) and its europium and terbium nitrate complexes were synthesized. The luminescence properties of these complexes were also studied.

Synthesis,Fluorescence and Magnetic Properties of a New Europium(Ⅲ)Complex Eu(C14H9O3)2(C12H8N2)2(NO3)

A new europium(III)complex Eu(CHO)(CHN)(NO)has been synthesized with 2-benzoylbenzoic acid and 1,10-phenanthroline as ligands.Crystal data for the complex are as follows:monoclinic,space group P2/c,a=9.6733(6),b=22.9521(14),c=19.7701(12)?,β=94.9800(10)o,V=4372.8(5)?~3,D=1.557 g/cm~3,Z=4,μ(Mo Kα)=1.501 mm,F(000)=2064,the final R=0.0214 and w R=0.0510.The Eu(III)ion is coordinated by ten atoms to give a bicapped square antiprism coordination geometry.The complex shows two intense fluorescence emission bands arising from the transitions of Eu:~5D→~7F(594 nm)and ~5D→~7F(618 nm).In addition,its XT decreases from 1.29767 cm~3?mol?K at 300 K to 0.01531 cm~3?mol?K at 2 K.

Intercalation Assembly, Characterization and Luminescent Properties of Novel Supramolecular Composite Materials, Tb(Ⅲ) Complex with Tetrapodal Ligand-Montmorillonite

Two kinds of Tb（ Ⅲ ） complexes with tetrapodal ligand, [TbL（NO3）]^3＋ and [TbL]^3＋ （L： 1,1, 1＇, 1＇-tera （ 2-pyridinecarboxylester ）-di （ trimethylpropane）） were intercalated into the interlayer space of montmorillonite （MT） by ion exchange and coordination reaction of L with the Tb^3＋ ion existing in the interlayer space of Tb-MT respectively. The obtained luminescent supramolecular composite materials, [ TbL （NO3） ]^2＋-MT and [TbL]^3＋-MT were characterized by elemental analysis, XRD, FT-IR, UV-vis and thermal analysis. At the same time, the luminescent properties of the materials were also studied. The results show that the intercalated materials with regular layered structure, good thermal stability and the interlayer spacing （d001） approximates to the size of the complex ions which are located in the interlayer space of MT in the form of a monolayer.

Investigation on Molecular and Crystal Structures of Metal Complexes with Aminopolycarboxylic Acids——Synthesis and Structure of K[In~Ⅲ(EDTA)(H_2O)]·2H_2O

The title complex was synthesised and its molecular and crystal structures were determined by single crystal X ray reflection structure analysis. The crystal data are as follows: K[In Ⅲ(EDTA)(H 2O)]·2H 2O (EDTA=ethylene diamine N, N, N′, N′ tetraacetate), Monoclinic, C c space group, a=0.9096(2) nm,b=1.1996(2) nm, c =1.5144(3) nm, β =99.40(3)°, V =1.6302(6) 3, Z =3, D c=1.498 g·cm -3 , μ =1.325 mm -1 , F (000)=726, R =0.0320 and R W=0.0903 for 2315 observed independent reflections. The complex anion [In Ⅲ(EDTA)(H 2O)] - has a seven coordinate pseudo pentagonal bipyramidal (PB D 5h ) structure, in which the EDTA serves as a hexadentate ligand with two N atoms and four O atoms and one water molecule (H 2O) directly coordinated to the central metal ion In Ⅲ as a seventh ligand. 〓〓

Synthesis and Characterization of Some Lanthanide(Ⅲ) Complexes with 4-[N-(2-methoxybenzylimine)formyl]-2, 3-dimethyl-1-phenyl-3-pyazolin-5-one

A series of seven novel lanthanide（Ⅲ ） nitrato complexes with 4-[ N-（2-methoxybenzylimine）formyl] 1-2, 3- dimethyl-1-phenyl-3-pyazolin-5-one （2mbfa）, were synthesized. These complexes were characterized by elemental analysis, molecular mass determination, conductance and magnetic moment measurements, IR, UV-visible, and ^13CNMR spectral studies, In these complexes, the Schiff base, 2mbfa, acts as neutral bidentate ligand by utilizing the carbonyl oxygen and azomethine nitrogen as donor sites. All the three nitrate ions are also coordinated unidentately with 7 coordination for the lanthanide（Ⅲ） ions with a tentative monocapped octahedral geometry for the complexes. All the seven lanthanide（Ⅲ） complexes have a general formula, [ Ln（2mbfa）：（NO3）3 ].

Crystal Structure and Fluorescent Study of a Binuclear Europium(Ⅲ) Complex

A novel binuclear Eu（Ⅲ） complex [Eu2（dpa dioxide）2（NO3）4（bpdioxide）-（EtOH）] （dpa dioxide = di-2-pyridylamine N,N＇-dioxide, bpdioxide = 2,2＇-bipyridine N,N＇-dioxide） has been synthesized and it exhibits strong and sharp fluorescent emission at 614 nm under UV radiation of 245 nm at room temperature. X-ray structural determination indicates two independent Eu（Ⅲ） ions in the structure with different EuO8N and EuOgN environments. The compound crystallizes in the triclinic system, space group P1, with a = 10.8089（7）, b = 11.4670（8）, c = 17.1440（12） A, α = 92.834（2）, β = 93.854（3）, γ = 95.433（2）°, Z = 2, Dc = 1.876 g/cm3, V= 2107.3（2） A3, F（000） = 1168.0, the final R = 0.032 and wR = 0.086 for 6331 observed reflections with I 〉 2σ（I）.

Syntheses and Magnetic Properties of Cu（Ⅱ）－RE（Ⅲ） Heterobinuclear Complexes with N，N′－Bis（3－carboxyisalicylidene）－trimethylenediamine

ine heterobinuclear complexes of Cu (Ⅱ)-RE (Ⅲ) with N, N′-bis-(3-car-boxylsalicylidene ) trimetliylenediamine (TS) were syntliesized and characterized bymeans of elemental analyses, molar conductivity, thermogravimetry,IR and elec-tronic spectra. The measurements of variable-temperature magnetic susceptibilitysliow that there exists only a very weak antiferromagnetic spin exchange interactionbetween the ions of Cut(Ⅱ) and RE(Ⅲ) in CuRETSCI . 3H_2O.

Synthesis and Fluorescent, Magnetic and Thermal Stability Properties of a New Europium（Ⅲ） Complex Eu2(C15H11O3)6(C12H8N2)2

A new europium（Ⅲ） complex Eu2(C15H11O3)6(C12H8N2)2 has been synthesized with 2-（4-Methylbenzoyl）benzoic acid and 1,10-phenanthroline as ligands. Crystal data for the complex are as follows: monoclinic, space group P21/n, a = 15.1238（5）, b = 13.5928（4）, c = 22.9840（7） ?, β = 104.132（3）o, V = 4582.0（2） ?3, Dc = 1.522 g/cm3, Z = 4, μ（Mo Kα） = 1.433 mm-1, F（000） = 2128, the final R = 0.0447 and wR = 0.0826. The Eu（Ⅲ） ion is coordinated by eight atoms to give a distorted square antiprism coordination geometry. The complex shows two intense fluorescence emission bands arising from the transitions of Eu3+: 5 D0 → 7 F1（594 nm） and 5 D0 → 7 F2（617 nm）. The complex is an antiferromagnetism system in the range of 150～300 K. Also reported in the paper is the thermal stability property of the title complex.

Synthesis, Crystal Structure and Fluorescence Properties of a Terbium(Ⅲ) Complex with Biphenyl-2,3,3’,5’-tetracarboxylic Acid

A new terbium complex based on biphenyl-2,3,3’,5’-tetracarboxylic acid（H4bptc） has been synthesized, {[Tb（Hbptc）（H2O）4]×H2O}n（1）. Its structure was determined by single-crystal X-ray diffraction analysis and further characterized by elemental analysis, IR spectra and TG analyses. Title complex crystallizes in monoclinic, space group P21/n with a = 14.090（2）, b = 8.0824（13）, c = 15.5591（17） ?, V = 1775.4（5） ?3, Mr = 576.22, Dc = 2.156 g/cm3, μ（Mo Kα） = 4.059 mm-1, F（000） = 1128, Z = 4, the final R = 0.027 and w R = 0.0726 for 3296 observed reflections（I > 2σ（I））. Complex 1 exhibits a 2 D layer structure, and such layers are further united together into a three-dimensional supramolecular structure through π···π interaction and intricate hydrogen bonding. The fluorescence excitation and emission spectroscopy of 1 showed that H4 bptc is a kind of highly efficient sensitizer for terbium（Ⅲ） ion. The title complex also displays efficient ligand sensitized luminescence in the visible region with long lifetime of 2.02 ms in the solid state.

Hydrothermal Syntheses and Crystal Structures of Three Lanthanide(Ⅲ)Complexes Based on Carboxyl Derivatives of 1,10-Phenanthroline

Three lanthanide（III） complexes [Ln（4-NCP）（1,4-BDC）]n·xn H2O（Ln = Pr（1）, Sm（2）, Nd（3）. 4-HNCP = 2-（4-carboxyphenyl）imidazo（4,5-f）（1,10）phenanthroline, 1,4-H2 BDC = benzene-1,4-dicarboxylic acid） have been hydrothermally synthesized and characterized via elemental analysis, infrared spectrometry and single-crystal X-ray diffraction. Structural analyses revealed that complexes 1~3 possess similar porous three-dimensional frameworks with the point symbol {4^（12）·6~3}. Meanwhile, complexes 1~3 exhibit excellent thermal stabilities and complex 2 exhibits characteristic luminescent property.

Synthesis and Crystal Structure of a Binuclear Gadolinium（Ⅲ） Complex Bridged by Cucurbit[6]uril

A new cucurbit[6]uril bridsed binuclear complex {[Gd（H2O）6]2[Q6（H2O）]}C16·4H2O, where Q6 represents cucurbit[6]uril, has been synthesized and characterized by X-ray diffraction. The crystal structure shows that the complex has an extended cucurbit[6]uril-bridged structure consisting of two gadolinium（Ⅲ） ions, in which each gadolinium（Ⅲ） ion is coordinated with two neighboring carbonylic oxygen atoms of Q6 and six oxygen atoms of water molecules that leans toward one side of the portal. One disordered guest water molecule resides in the Q6 molecule cavity and occupies two different positions. Hydrogen bonds assemble the complcx to threedimensional supramolecular structure.