Synthesis,structural characterization and antibacterial activity of diorganotin(Ⅳ) complexes with ONO tridentate Schiff bases containing pyridine ring

Five organotin（IV） complexes,were obtained by reaction of SnR₂Cl₂（R = Ph,Me,Bu） with ONO donor Schiff bases.The synthesized complexes have been investigated by elemental analysis and IR,¹H NMR,and ¹¹⁹Sn NMR spectroscopy.These data show that the Schiff base acts as a tridentate dianionic ligand and coordinates via the imine nitrogen and two oxygen atoms.The Xray crystallography of complex 4 shows a dimeric structure for this molecule.The in vitro antibacterial activities of the Schiff bases and their complexes have been evaluated against Gram-positive（Bacillus subtilis and Staphylococcus aureus） and Gram-negative （Escherichia coli and Pseudomonas aeruginosa） bacteria and compared with the standard antibacterial drugs.     

Novel hybrids of Cu2+ ternary complexes of salicylidene-amino acid Schiff base with phenanthroline（or bipyridine） intercalated in Mg/Al-NO3-layered double hydroxide

Four Cu²⁺ complexes of salicylidene-amino acid Schiff base with 1,10-phenanthroline（Phen） or 2,2’- bipyridine（Bipy） were successfully intercalated in interlayer galleries of Mg/Al-NO₃-layered double hydroxide（LDH） by the swelling-restored method.The hybrids were characterized by elemental analysis,X-ray diffraction,FT-IR spectra,UV-vis DRS,TG-DTA and SEM observation.Good protection of the complexes by LDH in neutral and weak acidic solutions was revealed by UV spectra,cyclic voltammograms and luminescence spectra.     

Syntheses,Spectral Studies and Bioanalyses of Some Triorganotin（IV） Complexes of Cephlaxine

Five novel triorganotin（IV） complexes have been synthesized by refluxing trimethyl, triethyl, tributyl, triphenyl and tribenzyltin chloride with Cephlaxine. These compounds were characterized by spectroscopic （IR, IH, 13C, 119Sn NMR） techniques and elemental analysis. The results obtained through these techniques are in full agreement with the proposed 1：1 stoichiometry. The synthesized compounds were than tested against various microorganisms and fungi. The results of new products obtained showed that the triphenyltin（IV） complex displayed promising activity against all types of bacteria and fungi used while all other compounds showed significant antibacterial and antifungal activity.     

Interaction of Aromatic Hydrocarbons with Sulfuric Acid,Bisulfate and Sulfate Anions

<正>Intermolecular geometries and energies of the dimers formed between simple aromatic hydrocarbons(benzene,toluene and naphthalene)and sulfate species(sulfuric acid, bisulfate and sulfate)were studied by density functional theory.The AH:H_2SO_4 complexes were determined by the OH-πH-bond,with H_2SO_4 acting as the H-bond donor and AHs as the acceptor. However,the AHs:HSO_4~-and AHs:SO_4~(2-)complexes were established by the H-bond,with AHs serving as acid and HSO_4~-or SO_4~(2-)as alkali.The atmospheric implications of those complexes were strongly supported by their considerable binding energies.     

Synthesis and magnetic properties of complexes of a conjugated hyperbranched polymer containing bithiazole rings

A novel conjugated hyperbranched polymer containing bithiazole rings（PBTADB） was synthesized by polycondensation of 1,3,5-benzenetricarboxaldehyde and 2,2’-diamino-4,4’-bithiazole（DABT）.The structure of the hyperbranched polymer was confirmed by FT-IR and ¹H-NMR.PBTADB dissolved in organic polar solvents such as DMSO and NMP.Bithiazole rings were introduced to provide bidentate N-donor sites for binding metal ions.The metal complexes were prepared by chelation of the polymer with Co²⁺ and Sm³⁺.The magnetic behavior of coordination compounds was measured as a function of magnetic field strength（0-4.8×10⁶ A/m） at 5 K and as a function of temperature（5-300 K） at magnetic field strength of 2.4×10⁶ A/m.The magnetic hysteresis loops of PBTADB-Sm³⁺and PBTADB-Co²⁺showed the typical ’S’ shape at 5 K with the Curie-Weiss temperature T_θ=96 K and 41 K respectively.The results show that they exhibit properties of soft ferromagnetic materials.     

Effect of Mn（Ⅱ） and Ce（Ⅳ） Ions on the Oxidation of Lactic Acid by Chromic Acid

The kinetics and mechanism of lactic acid oxidation in the presence of Mn（Ⅱ） and Ce（Ⅳ） ions by chromic acid were studied spectrophotometrically. The oxidation of lactic acid by Cr（Ⅵ） was found to proceed in two measurable steps, both of which gave pyruvic acid as the primary product in the absence of Mn（Ⅱ）.2Cr（Ⅵ）＋2CH3CHOHCOOH→2CH3COCOOH＋Cr（Ⅴ）＋C（Ⅲ） Cr（V）＋CH3CHOHCOOH→Cr（Ⅲ）＋CH3COCOOHThe observed kinetics was explained due to the catalytic and inhibitory effects of Mn（Ⅱ） and Ce（Ⅳ） on the lactic acid oxidation by Cr（Ⅵ）. The reactivity of lactic acid depends upon the experimental conditions. It acts as a two- or three- equivalent reducing agent in the absence or presence of Mn（Ⅱ）. It was examined that Cr（Ⅲ） products resulting from the direct reduction of Cr（Ⅵ） by three-equivalent reducing agents. The oxidation of lactic acid follows the complex order kinetics with respect to [lactic acid]. The activation parameters Eo, △H^#, and AS^# were calculated and discussed.     

Surface-relief-grating formation behavior of two hyperbranched azo polymers

In this work,surface-relief-grating formation behavior was studied by using two hyperbranched azo polymers.The hyperbranched polymers containing pseudo-stilbene type azo chromophores throughout the hyperbranched structure were synthesized by step-growth polycondensation of AB₂ type monomers.The AB₂ monomer,4-（4’-（bis（2-chloroethyl）amino）-phenylazo） benzoic acid（BAA）,was prepared through azo-coupling reaction between N,N’-bis（2-chloroethyl）aniline and 4- aminobenzenic acid.The another AB₂ monomer,4-（4’-（bis（2-chloroethyl）amino）phenylazo）-3-nitro-benzoic acid（BANA）, was prepared through azo-coupling reaction between N,N-bis（2-chloroethyl）aniline and 3-nitro-4-aminobenzcnic acid.The hyperbranched polymers（PBAA and PBANA） were prepared through nucleophilic substitution reaction of BAA and BANA, respectively.The polymers synthesized were characterized by using spectroscopic methods and thermal analysis.The photoinduced dichroism and photo-induced surface-relief-grating（SRG） formation of the hyperbranched polymers were investigated upon irradiation with Ar⁺ laser at 488 nm.PBAA shows typical photoinduced dichroism SRG formation behavior.On the contrary,PBANA does not show the photoresponsive properties.The results indicate that the nitro at the ortho position of azo group of PBANA shows the effect of inhibiting the photoinduced variations.The effect can be attributed to the blockage of the trans-cis isomerization of the azobenzene moieties by the steric hindrance.     

Crystal structures and thermal decomposition kinetics of lanthanide complexes with 3,4,5-trimethoxybenzoic acid and 1,10-phenanthroline

A series of lanthanide complexes with the 3,4,5-trimethoxybenzoic acid(3,4,5-tmoba) and 1,10-phenanthroline(phen),[Ln(3,4,5-tmoba) 3 phen] 2(Ln = Pr(1),Nd(2) and Ho(3)),have been synthesized and characterized by a series of techniques including elemental analysis,IR spectra,X-ray crystallography and TG/DSC-FTIR technology.The three complexes have two kinds of coordination modes,in which the Pr 3+ and Nd 3+ cations are nine-coordinated and the Ho 3+ cation is eight-coordinated.The three-dimensional IR accumulation spectra of gaseous products for complexes 1-3 were analyzed and the gaseous products were identified by the typical IR spectra obtained from the 3D surface graphs.Meanwhile,we obtained the activation energy E of the first steps of complexes 1-3 by the integral isoconversional non-linear(NL-INT) method and discussed the non-isothermal kinetics of complexes 1-3 using the Malek method.Finally,SB(m,n) was defined as the kinetic method of the first-step thermal decomposition.The thermodynamic parameters △G≠,△H≠ and △S≠ of activation at the peak temperature were also calculated.     

Syntheses,Structures and Properties of Three Transition Metal Coordination Polymers Based on Semi-rigid 3-Pyridylnicotinamide and S/N-Containing Dicarboxylate Mixed Ligands

Three new coordination complexes, [Co（L）（ADTZ）]·H2O（1）, [Cd（L）（ADTZ）]·H2O（2） and [Zn（L）（ADTZ）]·H2O（3）[L=3-pyridylnicotinamide, H2ADTZ=2,5-（s-acetic acid）dimercapto-1,3,4-thiadiazole], were synthesized under hydrothermal conditions. These complexes were structurally characterized by single-crystal X-ray diffraction analysis and further characterized by infrared spectroscopy（IR）, powder X-ray diffraction （PXRD） and thermogravimetric analysis（TGA）. Complexes 1-3 exhibit the similar 2D double-layer networks based on 1D [M-L], zigzag chains and 1D [M-ADTZ]2n double-chains with different distances between metal ions and with various conformations of ADTZ anions. In complexes 1 and 3, the 2D sheets are extended into a 3D supramolecular frameworks by hydrogen bonding interactions. The subtle effects of the central metal atoms on the structures of the title coordination polymers were discussed. The electrochemical properties of complex 1 and luminescent properties of complexes 2 and 3 were investigated. In addition, complexes 1-3 exhibit photocatalytic activity for dye methylene blue degradation under UV light and show good stability toward photoca- talysis.     

Studies on Cytochrome c Modified by [PtdienNO_3]Cl

For the first time, [PtdienNO_3]Cl was used as a stable reagent to modify ferricytochrome c and the reaction products were separated and purified with the CM-52 cation exchange chromatography. Five components were obtained, corresponding to the native cytochrome c single-labeled, dual-labeled, and triple-labeled derivatives as shown by the analysis of the molar ratio of the two metal atoms (Pt and Fe). The reduction potentials of these proteins were measured by differential pulse voltammetry. His-33 and Trp-59 were identified by~1HNMR as the binding sites of the platinum complex in the modified cytochrome c derivatives. Trp-59 was a conserved amino acid connected with the heme through hydrogen bond, which had not been modified by other transition metal complexes. The platinummodified cytochrome c derivatives might be valuable in exploring the role of the aromatic amino acids, especially Trp-59, in electron transfer.     

Synthesis and Characterization of New Macrocyclic Cu（Ⅱ） Complexes from Various Diamines, Copper（Ⅱ） Nitrate and 1,4-Bis（2-formylphenoxy）butane

Six new macrocyclic complexes were synthesized by a template reaction of 1,4-bis（2-formylphenoxy）butane with diamines and Cu（NO3）2·3H2O and their structures were proposed on the basis of elemental analysis, FT-IR, UV-Vis, magnetic susceptibility measurements, molar conductivity measurements and mass spectra. The metal to ligand molar ratios of the Cu（Ⅱ） complexes were found to be 1 ： 1. The Cu（Ⅱ） complexes are 1 ： 2 electrolytes as shown by their molar conductivities （∧m） in DMF at 10^-3 mol·L^-1. Due to the existence of free ions the Cu（Ⅱ） complexes are electrically conductive. Their configurations were proposed to be probably distorted octahedral.     

DNA Binding Properties and Cytotoxic Activities of Two Trinuclear Ruthenium（Ⅱ） Polypyridyl Complexes

The interactions between two trinuclear Ru（II） complexes and calf thymus DNA（CT DNA） were studied via absorption spectroscopy, reverse salt titrations, binding stoichiometry, DNA melting experiments, as well as viscosity measurement. The results indicate that complexes 1 and 2 bind to DNA via the interaction of the planar π-delocalized system of the complexes with intrinsic binding constants of 4.18 × 10^5 and 3.85 × 10^6 L/tool, respectively, and non-electrostatic binding free energy makes a predominant contribution to the binding free energy. The in vitro cytotoxic activity of complexes 1 and 2 was evaluated by the MTT[3-（4,5-dimethylthiazol-2-yl）-2,5-diphenyl- 2H-tetrazolium bromide] method. Complex I shows higher anticancer potency than complex 2 against four tumor cell lines. Further mechanism study indicates that complexes 1 and 2 can cause cell cycle arrest in the G2/M phase.     

Determination of Trace Amounts of Vanadium by Kinetic-Catalytic Spectrophotometric Methods

Kinetic-catalytic spectrophotometric methods were proposed for the determination of trace amounts of vanadium element as vanadium（Ⅳ） and/or V（Ⅴ） ions. The vanadium（Ⅳ） as VO^2＋ ion and/or vanadium（Ⅴ） as VO3^- ion showed a catalytic effect on the kinetic reactions between a color reagent such as methylthymol blue （MTB） or SPADNS and bromate in acidic media. The rate of decrease in the absorbance of the reagent MTB at 440 nm or SPADNS at 510 nm was proportional to concentration of V（Ⅳ） and/or V（Ⅴ） ions in the solution. The linear ranges for determination of vanadium were obtained in the range of 1.0-150 and 5.0-100.0 μg/L by the fixed-time and slope methods, respectively, with using MTB as reagent. In the presence of SPADNS as reagent, the calibration curves were made in the amplitude 1.0-200.0 and 5.0-150 μg/L of vanadium ion by the fixed-time and slope methods, respectively. Using fixed-time method, the limits of detection were obtained to be 0.5 and 0.7 μg/L of vanadium in the presence of MTB and SPADNS as reagents, respectively. Detection limits of vanadium by slope method and reagents of SPADNS and MTB were obtained to be 3.5 and 3.8 μg/L of vanadium, respectively. The proposed methods were applied successfully to determination of vanadium in synthetic and real samples.     

One-bath synthesis of hydrophilic molecularly imprinted quantum dots for selective recognition of chlorophenol

A simple one-bath strategy has been developed to synthesize a novel CdTe@SiO₂@MIP（molecularly imprinted and silica-functionalized CdTe quantum dots,MISFQDs）,in which a silica shell was coated on the surface of CdTe quantum dots （CdTe@SiO₂ QDs） and then a polymer for selective recognition of 4-chlorophenol（4-CP） was constructed on the surface of CdTe@SiO₂ QDs using mercaptoacetic acid as stabilizer,3-aminopropyl-trimethoxysilane（APTES） as functional monomers and tetraethoxysilane（TEOS） as crosslink agent.The structures of CdTe@SiO₂@MIP were analyzed by ultraviolet-visible absorption. Fluorescence,FT-IR spectrum and powder X-ray diffraction.The application and characterization of the CdTe@SiO₂@MIP were investigated by experiments.All results indicated that the CdTe@SiO₂@MIP can selectively recognize 4-chlorophenol.     

Synthesis of CdS/SiO2/polymer tri-layer fluorescent nanospheres with functional polymer shells

Tri-layer CdS/SiO₂/polymer hybrid nanospheres were synthesized by distillation precipitation polymerization of either ethyleneglycol dimethacrylate（EGDMA） or EGDMA together with comonomers having different functional groups, such as methacrylic acid,4-vinylpyridine and 2-hydroxyethylmethacrylate,in the presence of 3-（methacryloxy）propyl trimefhoxysilane（MPS）-modified CdS/SiO₂ nanoparticles as seeds in acetonitrile with 2,2’-azobisisobutyronitrile（AIBN） as initiator.In this approach,MPS-modified inorganic seeds were prepared by the modification of CdS/SiO₂ nanoparticles via the self-condensation reaction between the hydroxyl groups of sinaols,in which the CdS/SiO-2 nanoparticles were afforded by a reverse microemulsion technique for the synthesis of CdS core nanoparticles with the subsequent coating of silica layer. The polymer shell-layers encapsulated over the MPS-modified CdS/SiO₂ inorganic seeds via the efficient capture of the monomers and oligomers from the solution with the aid of the vinyl groups incorporated by the MPS modification,in which the polymer shell-thickness and functional groups including carboxyl,pyridyl and hydroxyl,were facilely controlled by the feed of EGDMA as well as the types of comonomers used for the polymerization.These nanospheres were characterized by transmission electron microscopy（TEM）,Fourier-transform infrared spectroscopy（FT-IR）,thermogravimetric analysis （TGA）,fluorescence spectroscopy and zeta potential.     

THERMOCHROMIC EFFECTS OF LEUCO DYES STUDIED IN POLYPROPYLENE

A series of thermochromic polypropylene foils were prepared by embedding various leuco dye-developer-solvent systems in the polymer matrix. Bisphenol A, laurylgallate, ethylgallate and p-hydroxybenzoic acid methyl ester were used as developers, crystal violet lactone and 3,3-bis-（1-n-butyl-2-methyl-3-indolyl）-phthalide as dyes and l-octanoic acid methyl ester as solvent. The molar ratio between the three components of the investigated leuco dye-developer-solvent systems was kept constant. All obtained polypropylene foils exhibit an excellent thermochromic behavior. The foils, prepared by extrusion technology, switch from color to colorless with increasing temperature. The influence of molecular structure of the developer on the intensity of the colored state and the influence of a developer-surfactant complex on the resulting thermochromic properties were investigated. The results are presented and discussed in detail according to a molecular model suggesting that the ring-opening process of the leuco dye is triggered by the formation of dye-developer complexes via H-bondings.     

Synthesis and preliminary biological evaluation of a technetium-99m labeled thymidine analog

The synthesis and labeling of ^99mTc-N³-（N’-[2-sulfanyl-ethylamino）acetyl]-2-aminoethyl-sulfanyl-1-hexanamide}thymidine (^99mTc-NHT) were studied.In the presence of sodium glucoheptonate（GH） and ethylene diamine tetraacetic acid（EDTA）,^99mTc-NHT was obtained by using bisaminoethanethiol（N₂S₂） as a bifunctional coupling agent.The radiochemical purity of the ^99mTc-NHT was over 95%.Biodistribution of ^99mTc-NHT was performed in hepatoma HepA tumor-bearing mice.At 2 h p.i.,the ratios of tumor-to-muscle,tumor-to-bone and tumor-to-blood were 4.41±0.32,2.45±0.24 and 1.51±0.18,respectively.     

Syntheses and structures of tetranuclear Zn（Ⅱ） complexes with in situ generated macrocyclic Schiff base ligands:Applications in Zn2+ sensing

Three novel Zn（II） complexes,[Zn₄L¹Cl₄]-3H₂O（1）,[Zn₄L²Cl₄]-2DMF（2） and[Zn₄L³Cl₄]H₂O（3）,have been synthesized and structurally characterized.In these complexes,interesting 32-membered dodecadentate macrocyclic ligands were generated in situ by ’2 + 2’ type condensation reactions between a tetraamine and various dialdehydes.All the complexes are isostructurally tetranuclear Zn（Ⅱ） complexes,containing endogenous alkoxo and phenoxo bridges.Applications of the macrocyclic ligands as Zn²⁺ sensors have been investigated.Take H₄L¹ for example,it exhibits a 4-fold fluorescence enhancement upon the addition of 2 equiv.of Zn²⁺ in MeOH.     

Capillary Electrophoresis for the Simultaneous Determination of Metals by Using Ethylenediamine Tetraacetic Acid as Complexing Agent and Vancomycin as Complex Selector

A new separation system of capillary electrophoresis for the simultaneous determination of metals by using ethylenediamine tetraacetic acid （EDTA） as complexing agent and employing vancomycin as complex selector was described. The Z-shape cell capillary electrophoresis was used to enhance the sensitivity for the determination of the complexes of Cu（Ⅱ）, Ni（Ⅱ）, Co（Ⅱ） and Fe（Ⅲ） with EDTA. The partial filling method （co-current mode） was used in order to increase the selectivity of the electrophoretic method, meanwhile vancomycin was not present at the detector path during the detection of metal-EDTA complexes. The vancomycin concentration, phosphate concentration and pH of the buffer strongly influenced mobility, resolution and selectivity of the studied analytes. Under the optimal condition, the relative standard deviations （n=5） of the migration time and the peak area were less than 3.14% and 7.35%, respectively. Application of the Z-shape cell capillary electrophoresis method with UV detection and vancomycin loading led to the reliable determination of these metal ions in tap water and the recoveries were 97%-101%. The detection limits based on a signal to noise ratio of 3 ： 1 were found in the range of 2-10 μg·L^-1.     

Chemical Composition of Hydrilla Verticillata （L. f.） Royle in Taihu Lake

Hydrilla verticillata （Linn. f.） Royle is a submerged plant for phytoremediation on Taihu Lake, China. The planted submerged plant should be harvested in every autumn to reduce the nutrition burden of the lake. Five compounds were firstly isolated by column chromatography and purified from the extractions of Hydrilla verticillata （Linn. f.） Royle. 1-（5＇-Hydroxy-4＇-hydroxymethyl-1＇-methyl-1H-pyrrol-2＇-yl）-henicosa-2,12,15-trien-1-one （2） and thymidine （3） were identified by EIMS, 1H NMR, laC NMR and IR spectra. Crystal loliolide （1） and sulfur-gamma （4） were identified by X-ray diffraction. Octadecanedioic acid （5） was also elucidated. Among them, compound 2 is a new natural compound, loliolide （1） and thymidine （3） are known bioactive substances. The results provided basic research data for exploring their application as medical materials.