Synthesis and Crystal Structure of a New Copper(II) Complex with 4-Cyanobenzoic Acid

A new Cu（Ⅱ） complex [Cu（4-cba）（1,10-phen）（H2O）2]（NO3） （4-Hcba = 4-cyanobenzoic acid） has been synthesized by solvothermal reaction in an ethanol/water mixed solution at 100 ℃ and structurally characterized by single-crystal X-ray diffraction. Crystallographic data： C20H16CuN4O7, Mr= 487.91, triclinic, space group PI, a = 7.8420（2）, b = 9.1070（2）, c = 15.1140（6） A, a = 76.889（9）, β = 81.332（11）, γ = 74.844（ 11）°, V = 1009.89（5） A^3, Z = 2, Dc = 1.605 g/cm^3, F（000） = 498, μ = 1.134 mm^-1, the final R = 0.0379 and wR = 0.0865 for 2977 observed reflections with 1 〉 2σ（Ⅰ）. The Cu（Ⅱ） atom is coordinated by two terminal water molecules, one chelating 1,10-phen molecule and one monodentate 4-cba ligand to form a slightly distorted square pyramid. The title complex molecules are connected through hydrogen bonds and π-π stacking interactions to generate a 2D layered network. The thermogravimetric analysis of the title complex has also been discussed.

Chlorogenic acid complex(CGA7),standardized extract from green coffee beans exerts anticancer effects against cultured human colon cancer HCT-116 cells

Coffee is commonly consumed beverage in the world and it has been suggested to have beneficial effect.Chlorogenic acids(CGAs)are main ingredient of coffee beans which has been extensively used in nutraceuticals and medicine.Recently,various therapeutic effects of chlorogenic acids have been investigated.However,there are limited studies to investigate its anticancer properties.In the present study,we have used chlorogenic acid complex(CGA7)a decaffeinated water soluble green coffee bean extract to evaluate its cytotoxic effect on human and mouse cancer cell lines by using different approaches.From our results we found CGA7 treatment induces cell death in a dose and time dependent manner in different cancer cell lines.Further,CGA7 induced apoptosis was characterized by DNA fragmentation,PARP-1 cleavage,caspase-9 activation,and down regulation of Bcl-2,an anti-apoptotic protein and up regulation of pro-apoptotic protein BAX.Overall findings indicated that CGA7 complex a potent anticancer molecule found in green coffee beans could be a safe bioactive ingredient for prevention of cancer.

ATR-FTIR and XPS study on the structure of complexes formed upon the adsorption of simple organic acids on aluminum hydroxide

Information on the binding of organic ligands to metal （hydr）oxide surfaces is useful for understanding the adsorption behaviour of natural organic matter on metal （hydr）oxide. In this study, benzoate and salicylate were employed as the model organic ligands and aluminum hydroxide as the metal hydroxide. The attenuated total reflectance Fourier transform infrared （ATR-FTIR） spectra revealed that the ligands benzoate and salicylate do coordinate directly with the surface of hydrous aluminum hydroxide, thereby forming innersphere surface complexes. It is concluded that when the initial pH is acidic or neutral, monodentate and bridging complexes are to be formed between benzoate and aluminum hydroxide while bridging complexes predominate when the initial pH is alkalic. Monodentate and bridging complexes can be formed at pH 5 while precipitate and bridging complexes are formed at pH 7 when salicylate anions are adsorbed on aluminum hydroxide. The X-ray photoelectron （XP） spectra demonstrated the variation of C 1 s binding energy in the salicyate and phenolic groups before and after adsorption. It implied that the benzoate ligands are adsorbed through the complexation between carboxylate moieties and the aluminum hydroxide surface, while both carboxylate group and phenolic group are involved in the complexation reaction when salicylate is adsorbed onto aluminum hydroxide. The information offered by the XPS confirmed the findings obtained with ATR-FTIR.

Study on Copolymerization of Rare Earth-Carboxylic Acid Complex

Complex of rare earth with carboxylic acid was prepared by precipitation and direct method. It was copolymerized with such monomers as acrylic acid and other ones to synthesize ionomer of rare earth and organic polymer with different rare earth contents. Its glass-transition temperature and heat stability were analyzed by TG and DTA. Infra-red detector was used to show its structure. The effect of rare earth complex prepared by different methods on copolymerization and properties of copolymers was also discussed.

Novel Ni/CeO_2-Al_2O_3 composite catalysts synthesized by one-step citric acid complex and their performance in catalytic partial oxidation of methane

A series of novel Ni/CeOe-Al2O3 composite catalysts were synthesized by one-step citric acid complex method, The as-synthesized catalysts were characterized by N2 physical adsorption/desorption, X-ray diffraction （XRD）, Fourier transform infrared （FT-IR） spectroscopy, hydrogen temperature-programmed reduction （Hz-TPR）, X-ray photoelectron spectroscopy （XPS） and thermogravimetry analysis （TGA）. The effects of nickel content, calcination and reaction temperatures, gas hourly space velocity （GHSV） and inert gas dilution of N2 on their performance of catalytic partial oxidation of methane （CPOM） were investigated. Catalytic activity test results show that the highest methane conversion （〉85%）, the best selectivities to carbon monoxide （〉87%） and to hydrogen （〉95%）, the excellent stability and perfect Hz/CO ratio （2.0） can be obtained over Ni/CeO2-Al2O3 with 8 wt% Ni content calcined at 700 ℃ under the reaction condition of 750 ℃, CH4/O2 ratio of 2 ： 1 and gas hourly space velocity of 12000 mL.h-1 .g-1. Characterization results show that the good catalytic performance of this composite catalyst can be contributed to its large specific surface area （~108 m2.g-1）, small crystallite size, easy reducibility and low coking rate.

Solvothermal Syntheses, Crystal Structures, Thermal Stability and Quantum Chemistry of Dinuclear Trialkyltin Complexes Constructed by Camphoric Acid

Two dinuclear organotin complexes C8H14（CO2SnCy3）2（1）（Cy = cyclohexyl group） and C8H14[CO2Sn（CH2CMe2Ph）3]2（2） were synthesized by the reactions of camphoric acid with tricyclohexyltin hydroxide and bis[tri（2-methyl-2-phenyl）propyltin] oxide under solvothermal conditions, and these complexes were characterized by infrared spectra, elemental analyses, and H NMR spectra. The crystal of 1 belongs to the monoclinic system, space group P21/c with a = 1.83478（19）, b = 1.52707（18）, c = 1.9849（2） nm, β = 122.515（7）°, Z = 4, V = 4.6896（9） nm^3, Dc = 1.324 g/cm^3, μ（MoKα） = 1.103 mm^-1, F（000） = 1952, R = 0.0697 and wR = 0.2040. In addition, thermal stability and quantum chemical calculation of 1 were also studied.

Investigation on the syntheses and structures of Y^(Ⅲ) complexes with ami-nopolycarboxylic acids (Ⅳ)

This paper deals with the structure of the Y^iii complex withaminopolycarboxylic acids, synthesis and struc- tural determinationof the complex (NH_4)[Y^III(edta)(H_2O)_3] ·3 H_2O (edta =ethylenediaminetetraacetic acid). The crystal and molecularstructures of the (NH_4)[Y^III(edta)(H_2O)_3] ·3 H_2O complex havebeen determined by single-crystal X-ray structure analysis. Thecrystal of the complex (NH_4)[Y^III(edta)(H_2O)_3] ·3 H_2O belongsto orthorhombic crystal system and fdd2 space group.

Synthesis, Characterization and Fluorescence of Terbium(Ⅲ) Complexes with Phenylglyoxylic Acid and 2,2-Dipyridine, 1,10-Phenanthroline, Triphenyl Phosphine Oxide

Three new complexes TbL3dipy （H2O）2, TbL3phen （H2O） 2 and TbL2 （TPPO） 2NO3 were synthesized （L = phenylglyoxylate ion, dipy = 2, 2-dipyridine, phen = 1,10-phenanthmline, TPPO = Triphenyl phosphine oxide）. Elemental analysis, conductivity, IR spectra, and ^1HNMR spectra studies were performed. IR spectra indicate that the carboxylate ion of phenylglyoxylate is coordinated to the Tb（Ⅲ） ion as an unidentate ligand. In ^1HNMR, the signals of different hydrogens in phenylglyoxylate ion shift upfield. The excitation and emission spectra of the three solid complexes were recorded at morn temperature, in which the optimum excitation wavelengths are, 361.0, 359.0 and 367.0 nm for these three complexes, respectively. Four emission bands due to the ^5D4-^7Fj（j = 6, 5, 4, 3） transitions were observed for TbL3dipy（H2O）2（489.0, 545.0, 584.0, 620.0 nm） and TbL3phen（H2O）2（490.0, 544.0, 583.0, 620.0 nm）. Under the same conditions, only one emission band due to the ^5D4-^7F5 transition was observed for the complex TbL2（TPPO）2NO3. The emission intensity of TbL3dipy（H2O）2 is the strongest among the three complexes.

Synthesis,Crystal Structure and Theoretical Calculations of a Cadmium Complex Containing 3-Hydroxybenzoic Acid and 1,4-Bis(imidazol-1-yl)-butane

A new complex [Cd（hba）2（bib）]n·nH2O（1,Hhba = 3-hydroxybenzoic acid,bib = 1,4-bis（imidazol-1-yl）-butane） has been hydrothermally synthesized and characterized by elemental analysis,IR spectrum,thermogravimetric analysis,fluorescence spectrum,and singlecrystal X-ray diffraction.Yellow crystal crystallizes in the orthorhombic system,space group Pbca with a = 16.220（5）,b = 14.980（5）,c = 20.521（5） ？,V = 4986（3） ？~3,C（24）H（26）CdN4O7,Mr = 594.89,Dc = 1.585 g/cm^3,μ（Mo Kα） = 0.927 mm^（-1）,F（000） = 2416,Z = 8,the final R = 0.0242 and w R = 0.0589 for 4076 observed reflections（I 〉 2s（I））.In 1,the Cd（Ⅱ） ion takes a six-coordination mode,and bib ligand bridges adjacent Cd（Ⅱ） ions to generate 1D zigzag chains; these neighboring chains are connected by O–H···O hydrogen bonding interactions,producing a 2D folded layered structure.Furthermore,by O–H···O hydrogen bonding between layers and layers,a 3D supramolecular architecture is formed.In addition,we analyzed Natural Bond Orbital（NBO） in using the PBE0/LANL2 DZ method built in Gaussian 03 Program.The calculation results indicated obvious covalent interaction between the coordinated atoms and Cd（Ⅱ） ion.

Interaction between uranium and humic acid (Ⅱ): complexation, precipitation and migration behavior of U(Ⅵ) in the presence of humic substances

The complexation, precipitation, and migration behavior of uranium in the presence of humic acid (HA) or fulvic acid (FA) were investigated by cation exchange, ultrafiltration and dynamic experiment, respectively. The results showed that (i) complex equilibrium between the uranium and humic substances was achieved at approximately 72 h, (ii) the coordination number varied from 1:1 to 1:2 ( U(Ⅵ) : humic acid) as pH increased from 3 to 6; and (iii) , while the complex stability constant decreased when temperature increased, but increased with pH value. We found that the precipitation of uranyl could only be observed in presence of HA, and the precipitation was influenced by conditions, such as pH, uranium concentration, temperature, and the HA concentration. The maximum precipitation proportion up to 60% could be achieved in the condition of 40 mg/L HA solution at pH 6. We further observed that the migration behavior of uranium in soil in the presence of humic acid (HA) or fulvic acid (FA) was different from that in the presence of inorganic colloid, and the effect of humic substances (HS) was limited.

Synthesis and spectroscopic characterization of fluorescent solid rare-earth complexes with hydroxamic acids

The complexes RE_2(DHYA)_3 centre dot nH_2O in the title bar were synthesizedthrough some reactions of trivalent rare-earth ions. In the process of synthesis, dihydroxamicacids were taken as ligands while the alcohol was taken as a solvent. The ligands includedadipylhydroxamic acid (ADHA), p-phthalichydroxamic acid (PPHA), oxalohydroxamic acid (OXHA),butadihydroxamic acid (BDHA), o-phthalichydroxamic acid (OPHA), benzoylhydroxamic acid (BHA), etc.Measured at 25 deg C, the molar conductances in various modes are 13.00-21.05 S centre dot cm^2centre dot mol^(-1), which shows that rare-earth complexes are nonelectrolytes and the hydroxaminogroups of the complexes have taken part in bonding. Infrared spectra, ultraviolet spectra, nuclearmagnetic resonance (~1HNMR) spectra, and fluorescence spectra were used to investigate thecomplexes. Experiments have proved that the complexes of En^(3+)and Tb^(3+) with aromatic hydroxamicacids have good fluorescent characteristics.

Crystal Structure and Luminescence Property of Lanthanide Complexes with 2-Fluorobenzoic Acid and 2,2′-Bipyridine

The two compounds of [Ln（2-FBA）3·2,2＇-bpy ]2（2-FBA = 2-fluorobenzoato, 2,2＇-bpy = 2,2＇-bipyridine, Ln = Eu（1 ）, Dy（2）） were synthesized and their structures were determined by X-ray diffraction method. Crystallized complexes 1 and 2 are isomorphous, monoelinie system with P21/n space group. The two complexes are binuclear molecule with an inversion center. The two lanthanide ions are linked by four bridged 2-FBA ligands and each lanthanide ion is further bonded to one chelated bidentate 2-FBA ligand and one 2,2＇-bipyridine molecule. The coordination number of metal ion is eight. The europium complex exhibits strong red fluorescence. ^5D0→^7Fj（j = 1 - 4） transition emission of Eu^3＋ ion was observed.

Thermochemical Study on Coordination Complex of Samarium with Salicylic Acid and 8-Hydroxyquinoline

The coordination complex Sm（C7H5O2）2·（C9H6NO）, synthesized from the reaction of samarium chloride sixhydrate with salicylic acid and 8-hydroxyquinoline, was characterized with IR, elemental analysis, molar conductance, and thermogravimatric analysis. The standard molar enthalpies of solution of [ SmCl3·6H2O （s） ], [ 2C7H6O3 （s） ], [ C9H7NO （ s ） ] and [ Sm （C7H5O3） 2·（ C9H6NO ） （ s ） ] in the calorimetric solvent were determined with the solution-reaction isoperibol calorimeter at 298.15 K to be △sHm^- [ SmCl3·6H2O （s）, 298.15 K ] = - 103.98 ± 0.04 kJ·mol^-1, △sHm^- [2 C7H6O3 （s）, 298.15 K] = 16.35±0.14 kJ·mol^-1,△sHm^-[C9H7NO （s）, 298.15 K] = -6.11±0.08 kJ·mol^-1 and △sHm^-[Sm（C7H5O3）2·（C9H6NO） （s）, 298.15 K] = - 130.08 ± 0.04 kJ·mol^-1, respectively. The enthalpy was determined to be △rHm^- = 89.59 ±0.18 kJ·mol^-1 for the reaction SmCl3·6H2O（s） ＋ 2C7H6O3（s） ＋ C9H7NO（s） = Sm （C7H5O3） 2·（C9H6NO） （ s ） ＋ 3HCl （g） ＋ 6H2O （ l ）. According to the above results and the data given in literature and through Hess＇ law, the standard molar enthalpy of formation of Sin（ C7H5O3 ）2·（C9H7NO）（s） was estimated to be △rHm^- [ Sm （C7H5O3）2·（C9H6NO） （s）, 298.15 K] = - 2055.9 ± 3.03 kJ·mol^-1.

Syntheses and Crystal Structures of Three Ag(Ⅰ) Complexes with Chloro-phenylacetic Acid and Nitrogen Heterocyclic Ligand

Three new coordination polymers {[Ag2（2,4-DCPA）（4,4＂-bipy）2（NO3）].（H20）}, （1）, [Ag（2,4-DCPA）（bpp）], （2） and {[Ag（4-DCPA）（bpp）]＇（H20）}, （3）, were synthesized by evaporation methods using 2,4-dichlorophenylacetic acid （2,4-DCPA）, 4-chlorophenylacetic acid （4-DCPA）, 4,4＂-dipyridyl （4,4＂-bipy）, 1,3-bis（4-pyridyl）propane（bpp） and AgNO3. Compound 1 crystallizes in monoclinic, space group P21/c with a = 10.035（2）, b = 17.796（3）, c = 16.448（2） A, fl = 104.086（2）°, V= 2705.9（2） A3, Dc = 1.893 g/cm-3, C28H23C12NsO6Ag2, Mr = 812.15, F（000） = 1608,μ（MoKot） = 1.615 mm-1, Z = 4, R = 0.0310, wR = 0.0832 for 4357 observed reflections （I 〉 20（/））, and R = 0.0362, wR = 0.0873 for all data. Compound 2 crystallizes in monoclinic, space group P21/c with a = 9.840（2）, b = 24.971（5）, c = 9.3301（2）°, fl = 117.504（2）°, V= 2033.5（7） A3, Dc = 1.666 g/cm3, C2tH19C12N202Ag, Mr = 510.15, F（000） = 1024,/I（MoKa） = 1.273 mml, Z= 4, R = 0.0315 and wR = 0.0680 for 2853 observed reflections （1 〉 20（/）） and R = 0.0454, wR = 0.0736 for all data. Compound 3 crystallizes in monoclinic, space group P21/n with a = 15.472（4）, b = 9.000（2）, c = 16.262（4） A, fl = 112.049（4）°, V = 2099.0（8） A3, Dc = 1.562 g/cm-3, C2H22C1N203Ag, Mr = 493.73, F（000） = 1000, μ（MoKa） = 1.111 mm-1, Z = 4, R = 0.0296, wR = 0.0821 for 3059 observed reflections （I 〉 2δ-（I））, and R = 0.0398, wR = 0.0986 for all data. The complexes were characterized by elemental analysis, FT-IR, thermogravimetrie analysis （TGA） and X-ray single-crystal structure analysis. Fluorescence properties of complex 3 and PXRD of 1 and 2 have been studied. As a result, in complex 1, the Ag（I） ion is surrounded by two nitrogen atoms from two bipy ligands to form an infinite chain, and adjacent Ag-bipy chains produce ＂＇rungs＂ of a ladder by silver ions contact. And in complexes 2 and 3, the two-dimensional ,β-sheet like layers are obtained by Ag……Ag interactions.

A Series of Mononuclear Complexes Constructed from Transition Metals and Amino Acid Derived Ligands: Syntheses, Structures and Photoluminescence

Eight neutral mononuclear complexes constructed from transition metals （M = Co（Ⅱ）, Ni（Ⅱ）, Cu（Ⅱ）, Zn（Ⅱ）, Cd（Ⅱ）） and ligands N-（2-pyridylmethyl）-L-phenylalanine （L-Hpmpa） and N-（2-pyridylmethyl）-L-tyrosine （L-Hpmtyr） have been synthesized by both hydrothermal and conventional room temperature reactions. Four of them have been structurally characterized by single-crystal X-ray diffractions. They are： [Co（L-pmpa）2·2H2O] 1, [Ni（L-pmpa）2·2H2O] 2, [Cu（L-pmpa）2·2H2O] 3 and [Cu（L-pmtyr）2·2H2O] 4. Single-crystal X-ray analysis, IR and elemental analysis revealed that complexes 1, 2 and 3 are isostructural. Powder X-ray diffraction, IR and elemental analysis revealed that complexes 4, 5 （Zn[L-pmtyr]2·2H2O）, 6 （Cd[L-pmtyr]2·2H2O）, 7 （Co[L-pmtyr]2·2H2O） and 8 （Ni[L-pmtyr]2·2H2O） are isostructural. The photoluminescence properties of L-Hpmtyr ligand, compounds 5 and 6 were also investigated.

Syntheses,Crystal Structures,and Magnetic Properties of Cobalt(Ⅱ) Complexes with 1,1-Cyclohexanediacetic Acid

Two new Co（Ⅱ） coordination polymers,{[Co_3（Hchda）_2（chda）_2（bpp）_2（H_2O）_2]}_n 1 and {[Co（chda）（bpe）（H_2O）]·3H_2O}_n 2（H_2chda = 1,1-cyclohexanediacetic acid,bpp = 1,3-bis（4-pyridinyl）propane and bpe = 1,2-bis（4-pyridinyl）ethylene）,were hydrothermally synthesized and then characterized by elemental analysis,IR spectroscopy,thermogravimetric analysis（TGA）,and single-crystal X-ray diffraction.Complex 1 possesses an infinite metal-organic layer based on triply bridged linear trinuclear subunits and complex 2 exhibits a square（4,4） grid layer with dangling lateral arms resulting from eight-membered rings above and below the layer.In addition,magnetic properties of complexes 1 and 2 are also given.

Synthesis and Crystal Structure of a Lanthanum(Ⅲ) Complex with Chelidamic Acid

A new lanthanum complex, （H3O）2[La（C7H3NO5）2（H2O）212.3（H2O） or （HaO）E[La（HChel）2（HEO）E]2.3（H2O） 1 （H3Chel = 4-hydroxypyridine-2,6-dicarboxylic（chelidamic） acid）, has been prepared by the hydrothermal reaction, and its crystal structure was determined based on single-crystal diffraction data. Compound I crystallizes in triclinic, space group Pi with a = 9.6939（19）, b = 10.176（2）, c = 11.502（2）A, α = 111.52（3）, β = 93.74（3）, γ = 103.33（3）°, V = 1013.0（3）A3, Dc = 1.912 g/cm3, Z = 1, Mr = 1166.40, p = 2.188 mm-1, 2（MoKa） = 0.71073 A and F（000） = 574. The final R = 0.0342 and wR = 0.0737 for 4080 observed reflections with I 〉 2σ（I）, and R = 0.0429 and wR = 0.0772 for all data. Compound 1 contains two lanthanum ions, four chelidamic acid ligands, four coordinated water molecules, two hydroniums, and three discrete water molecules. The LaⅢ atom is ten-coordinated by four oxygen and two nitrogen atoms from two tridentate chelating chelidamic acid ligands, two carboxylic oxygen atoms from an adjacent chelidamic acid ligand and two coordinated water molecules, leading to a distorted dodecahedral geometry. A three-dimensional network is formed by H-bonds.

Synthesis and Crystal Structure of a New cis-Dioxovanadium (V) Complex with Pyruvic Acid Isonicotinyl Hydrazone (PAINH)

A new cis-dioxovanadium （V） complex [VO2（C9H8N3O3）]（C5H5N） involving a carboxyl group coordination employing a tridentate Schiff Base derived from pyruvic acid and isonicotinyl hydrazide is reported. This complex crystallizes in triclinic, space group P1^- with a = 7.3522 （12）, b = 7.8376（13）, c = 14.898（2） ,A°, a = 84.010（2）, β = 86.568（2）, γ= 64.586（2）°, V = 771.1（2）A °^3 ,Z = 2, F（000） = 376, Mr = 368.22, D, = 1.586 g/cm^3, g = 0.677 mm ^-1, R = 0.0421 and wR = 0.1253. The vanadium atom of the dioxovanadium （V） is five-coordinated to furnish a distorted trigonal bipyramid geometry.

CRYSTAL STRUCTURE OF BINUCLEAR Y(Ⅲ) COMPLEX WITH p-METHYLBENZOIC ACID, Y_2(p-CH_3C_6H_4COO)_6(C_(12)H_8N_2)_2

Y_2(p-CH_3C_6H_4COO)_6(C_(12)H_8N_2)_2, Mr=1349.08, triclinic, space group P, a=13.00(3), b=19.743(2), c=12.754(3)A, α=97.94(1), β=106.24(2), γ=91.66(1)°, V=3177(1)~3, Z=2, Dc=1.41gcm^(-3), λ(MoKα)=0.71069, μ=18.92 cm^(-1), F(ooo)=1384, T=295K, final R=0.073 for 6504 observed reflections with Ⅰ>36(Ⅰ). There are two nonidentical binuclear molecules with different bridging connection patterns in a cell. One has four bridging carboxyl groups bound two Y(Ⅲ) ions and another only has two. The Y-Y distance is 4.196 for the former and 5.302 for the latter respectively.

Antioxidant activity of bovine serum albumin binding amino acid Schiff-bases metal complexes

Glutamic acid-salicylaldehyde Schiff-base metal complexes are bound into bovine serum albumin （BSA）, which afforded BSA binding Schiff-base metal complexes （BSA-SalGluM, M=Cu, Co, Ni, Zn）. The BSA binding metal complexes were characterized by UV-vis spectra and Native PAGE. It showed that the protein structures of BSA kept after coordinating amino acid Schiff-bases metal complexes. The effect of the antioxidant activity was investigated. The results indicate that the antioxidant capacity of BSA increased more than 10 times after binding Schiff-base metal complexes.