Synthesis,characterization and cytotoxicity of fluorescent organotin complexes of terpyridine derivatives

Five organotin complexes of terpyridine derivatives were synthesized and characterized. The mononuclear Sn（IV） complexes were six-coordinated adopting a distorted octahedral coordination geometry. A brief outline of the fluorescence spectra and the in vitro cytotoxicity of the Sn（IV） complexes have been given.     

New Copper（Ⅱ） and Nickel（Ⅱ） Complexes of 4-Morpholinoacetophenone Thiosemicarbazone： Structural, Electrochemical and Antimicrobial Studies

4-Morpholinoacetophenone thiosemicarbazone, MAPT, and its nickel（Ⅱ） and copper（Ⅱ） complexes have been prepared and characterized by elemental analysis, magnetic susceptibility, spectral methods （FT-IR, ^1H NMR） and cyclic voltammetry. Electrochemical behaviors of the complexes have been studied by cyclic voltammetry in DMF media showing metal centered reduction processes for both of them. The redox properties, nature of the electrode processes and the stability of the complexes were discussed. [Cu（MAPT）2]Cl2 complex shows Cu（Ⅱ）/Cu（Ⅰ） couple and quasi-reversible wave associated with the Cu（Ⅲ）/Cu（Ⅱ） process. The reduction/oxidation potential values depend on the structures of complexes. Also, the antimicrobial activities of these complexes were determined against S. aureus, E. coli and B. subtilis.     

Synthesis and Characterization of Complexes of Copper(II), Nickel(II) and Cobalt(II) with vic-Dioximes Bearing N''-p-Aminobenzoyl Benzaldehyde Hydrazone

Six different arylhydrazone derivatives of p-aminobenzoic hydrazide of vic-dioximes were synthesized by reaction of chloroglyoxime and dichloroglyoxime with N＇-p-aminobenzoyl benzaldehyde, 4-hydroxybenzaldehyde and 4-methoxybenzaldehyde hydrazones, respectively. Metal-ligand （1 ： 2） complexes of vic-dioxime derivatives with Cu（Ⅱ）, Ni（Ⅱ） and Co（Ⅱ） were prepared from corresponding metal acetates. The ligands and their complexes were characterized on the basis of elemental analyses and spectral data. The complexing abilities of these new vic-dioximes toward transition metals of Co（Ⅱ）, Cu（Ⅱ）, Ni（Ⅱ）, Zn（Ⅱ）, Cd（Ⅱ）, Mn（Ⅱ） and Cr（Ⅲ） were determined by solid-liquid extraction studies.     

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.     

Two New Nitronyl Nitroxide Radicals and Their Complexes with M（hfac）2 [M=Co（II）, Ni（ll）, Mn（ll）]： Syntheses,Crystal Structures,and Magnetic Characterizations

Two new nitronyl nitroxides with amido units L1 and L2 were synthesized and characterized. Reactions of L1 and L2 with M（hfac）2 [hfac=hexafluoroacetylacetonate, M=Co（II）, Ni（II）, Mn（II）] afforded five hetero-spin complexes LiCo（hfac）2, LlNi（hfac）2, L2Co（hfac）2, L2Ni（hfac）2 and L2Mn（hfac）2. The crystal structures and magnetic characterizations of L1, L2 and their metal complexes LM（hfac）2 were described and discussed. Crystal structural analysis shows that both the carbonyl oxygen and the nitroxide oxygen are coordinated to the metal ions. Strong antiferromagetic coupling between the nitronyl nitroxides and metal ions were observed for all the five LM（hfac）2 complexes.     

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.     

STRUCTURE AND MORPHOLOGY CHANGES OF HYDROBIOTITES MODIFIED BY CATIONIC SURFACTANTS

In this study, X-ray diffraction （XRD）, Fourier transform infrared spectrometer （FTIR） together with Scanning probe microscopy （SPM） were used to characterize the structure and morphology of the complexes, where the hydrobiotites （Xinfiang） were modified by single-chain surfactants octyltrimethylammonium bromide （OTMA） and octadecyltrimethylammonium bromide （ODTMA）. XRD patterns showed that the structure of complexes was significantly influenced by the surfactant concentration and the alkyl chain length, because obvious changes took place in the basal spacing. Furthermore, according to the XRD results, several arrangements of surfactant molecules within the hydrobiotite interlayer space were deduced. The FTIR spectrum indicated that the surfactant contents in complexes dramatically increased with the alkyl chain length. The SPM micrographs demonstrated that the surfaces of complexes prepared at lower surfactant concentration were relatively flat compared with that prepared at higher concentration, while those with higher surfactant concentration had much steeper surface due to the alkyl chain length. It was concluded that structure and morphology of surfactant/hydrobiotite complexes depend not only on the surfactant concentration, but also strongly on the surfactant species.     

阴离子导向组装：两个具有不同阳离子的多维Ag(I)配合物的晶体结构

Assembly of [Ag（CN）2]^- units with M（Ⅱ）-diamine complex cations [Cu（LN-N）2]^2＋, where LN-N represents L2-diaminopropane （pn） and ethylenediamine （en）, afforded two complexes, [Cu（pn）2][Ag2（CN）4] （1） and [Cu（en）2][Ag3（CN）5] （2）, which were characterized by elemental analysis, IR, UV-Vis and ESR spectra. Single crystal X-ray analyses show that these complexes have 2D and 3D architectures through silver-silver interactions and other weak interactions. The luminescence behaviors of the two complexes were also studied by means of emission spectra.     

Synthesis of Nonionic Oligomeric Manganese（ Ⅱ ） Complexes and Investigation of Their Toxicity and T1 -Relaxation Enhancement

Six nonionic oligomeric manganese （ Ⅱ ） complexes with oligomeric phosphate-polyglycol-EDTA ester ligands were synthesized and characterized. The longitudinal relaxivities of these complexes were measured. One of these complexes, which showed the highest relaxivity, was chosen to be used in the acute toxicity test and the T1-weighted imaging experiment. It has been found that compared to Gd-DTPA, this nonionic oligomeric Mn（ Ⅱ ） complex exhibits no acute toxicity, generates highly enhanced MRI signals and increases the intention time in the rat liver tissue.     

Crystal Structures and Theoretical Calculation of Zn（Ⅱ） and Cu（Ⅱ） Supramolecular Complexes Based on Macrocyclic Triamine Ligand 1,4,7-Triazacyclodecane （tacd）

Two supramolecular complexes [Zn（tacd）2]（C6H8O4）·6H2O（1） and [Cu（tacd）2]Cl2·4H2O（2） were synthesized and characterized by elemental analysis, IR spectra, TGA and single-crystal X-ray diffraction analysis. The crystal structure showed that the metal ions in complexes 1 and 2 had similar coordination circumstance. But for the complex 2, it formed a novel two-dimensional supramolecular network with 12-membered rings and four-membered rings via hydrogen bond interaction. The thermal gravimetric analyses indicated that the two complexes had similar steps of weight-loss. On the basis of experiment, the two complexes were calculated by DFT-B3LYP/6-31G（d） in Gaussian 03. The results of calculation are in good agreement with the experiment.     

The Study on the Stability Constant and Species Distribution of Eu （Ⅲ） and Tb （Ⅲ） Complexes with BDBPH

The stability constants and species distributions of complexes of two lanthanide ions, Eu（Ⅲ） and Tb（Ⅲ）, with a macrocyclic ligand, BDBPH, in 1：1 and 2：lsystem, were determined potentiometrically at 25.0 ℃ and I=0.100 mol L^-l. The two metal ions could form deprotonated mono- or dinuclear complexes with BDBPH after the first two protons of the ligand completely neutralized. At higher pH values, Eu（Ⅲ） could not form hydroxy complexes with BDBPH, while Tb（Ⅲ） could form hydroxy complexes in the type of M2L（OH）, M2L（OH）2, and M2L（OH）3.     

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.     

Zinc Complexes Supported by N,N-Dimethylaniline-arylamido Ligands： Synthesis,Characterization and Catalytic Properties for Ring-opening Polymerization of L-Lactide

The reaction of bidentate N,N-dimethylaniline-arylamido ligands,o-C6H4NMe2（CH2NHAr）（Ar =Ph,1a;2,6-Me2C6H3,1b; 2,6-Et2C6H3,1c; 2,6-ipr2C6H3,1d） with ZnEt2 yields the complexes o-C6H4（NMe2）（CH2NAr）ZnEt （2a-2d）,respectively.All the complexes were characterized by 1H and 13C NMR spectroscopy and elemental analyses.It was found that all the zinc complexes were efficient catalysts for the ring-opening polymerization of L-lactide in the presence of benzyl alcohol with good molecular weight control and narrow polydispersity.     

Studies on PNPP Hydrolysis Catalyzed by Schiff Base Cobalt（Ⅱ） Complexes Containing Benzoaza-15-crown-5

Three novel Schiff base cobalt（Ⅱ） complexes containing benzoaza-15-crown-5, CoL^1, CoL^2 and CoL^3 were synthesized and characterized, and these complexes were used in catalytic hydrolysis of carboxylic ester （PNPP, p-nitrophenyl picolinate） as mimic hydrolytic metalloenzyme. The analysis of specific absorption spectra of the hydrolytic reaction systems indicated that the catalytic hydrolysis involved the key intermediates formed by PNPP with cobalt（Ⅱ） complexes. The CoL^3 bearing the electron withdrawing group shows better catalytic activity due to its stabilization effect on active species MLS^-. The catalytic mechanism of PNPP hydrolysis was also proposed. The kinetic parameter of PNPP catalytic hydrolysis has been calculated and the activation energy for the catalytic hydrolysis is 43.69, 39.76 and 35.44 kJ·mol^-1, respectively.     

Synthesis, luminescence properties and energy transfer of binary and ternary rare earth complexes with aromatic acids and 1,10-phenanthroline

A series of binary and ternary rare earth (Gd, Eu, Tb) complexes with ortho hydroxyl benzoic acid, para aminobenzoic acid, nicotinic acid and 1,10-phenanthroline were synthesized. Phosphorescence spectra and lifetimes of Gd complexes were measured and the lowest triplet state energies of gadolinium binary complexes and the intramolecular energy transfer efficiencies were determined. The luminescence properties and energy transfer process of Eu3+and Tb3+ complexes were discussed.     

Ligand Bridged and Bis-ligand Coordinated Titanium Complexes： Synthesis, Structure and Relevance to Phenylacetylene Hydroanilination Catalysis

Two ligand bridged binuclear titanium complexes Ti2（bppda）3（NMe2）2·3THF （1） and Ti2（bppda）3（NEt2）2·3THF （2） and one bis-ligand coordinated mononuclear complex Ti（bppda）2 （3） （ligand- HEbppda=N,N＇-Bis（2-pyrrylmeth- ylidene）-1,2-phenylenediamine） were synthesized by adjusting the ratio of the starting materials and the reaction speed. The complexes were fully characterized with NMR, elemental analysis and X-ray crystal diffraction. The catalytic activity of the complex 1 to phenylacetylene hydroanilination reaction was also investigated.     

Interactions of ginsenosides with DNA duplexes： A study by electrospray ionization mass spectrometry and UV absorption spectroscopy

The non-covalent complexes of duplexes DNA and 9 ginsenosides（1 aglycone and 8 glycosides） were investigated using electrospray ionization mass spectrometry（ESI-MS） in the gas phase. The results of relative binding affinities in negative ion mode revealed that several factors impact on the duplexbinding properties of ginsenosides. Glycosylations of 20（S）-protopanaxadiol ginsenosides at the position C-20 and 20（S）-protopanaxatriol classification at the position C-6 enhanced the fraction of bound DNA sharply. A rhamnose moiety shows little lower binding intensities than glucose at the same position.Ginsenosides of 20（S）-protopanaxatriol result in subtle higher binding affinities toward the duplex DNA than 20（S）-protopanaxadiol family. However, glycosylation with two sugar moieties does not show a higher binding affinity than with only one moiety. The collision-induced dissociation experimental data demonstrate the gas-phase stability and fragmentation patterns of the ginsenoside/DNA complexes are related to the glycoside number. Positive ion ESI mass spectra of the complexes were also recorded. The result of ESI-MS suggests that hydrogen bonds are the dominate interaction between ginsenosides and DNA. Similar results were obtained in solution-phase by UV spectroscopy, which exhibit a hyperchromism and blue-shift effect when DNA solution was titrated by individual ginsenoside.     

Synthesis,Structural Investigations and Biological Screening of Diorganotin（Ⅳ） Complexes Derived from 5,5-Diethyl Sodium Barbital

Some biologically important tin（Ⅳ） complexes derived from 5,5-diethyl sodium barbital have been synthesized and characterized through various analytical and spectroscopic techniques such as IR, ^1H-, ^13C-NMR and ^119mSn mossbauer. On the basis of these spectroscopic techniques, octahedral geometry has been assigned to all the novel compounds. These complexes, soluble in DMSO and DMF, were screened against a wide range of microorganisms. The results proved that the diphenyltin（Ⅳ） and dibutyltin（Ⅳ） complexes exhibit excellent activity against all types of microorganisms, while the rest of the compounds show significant activity that can be used during the biological study.     

Antituberculosis and cytotoxic activities of triorganotin(Ⅳ) complexes

Five triorganotin（Ⅳ）（1-5） complexes of cinnamic acid.（Z）-2-acetamido-3-phenylacrylic acid,3-methylbut-2-enoic acid,and 2,2-diphenylacetic acid have been synthesized and characterized by ¹H-¹³C-¹¹⁹Sn NMR,UV,and IR.The spectroscopic investigation demonstrated that the carboxylate group acts as a monodentate ligand in triorganotin（IV） compounds.Five triorganotin（Ⅳ） complexes were screened against the log phase culture of Mycobacterium tuberculosis H37Rv by colorimetric method using XTT dye as growth indicator.The MICs were found to be 0.08 and 1.25μg/mL.     

Studies on PNPP Hydrolysis Catalyzed by Schiff Base Cobalt（Ⅱ） Complexes

Two cobalt（Ⅱ） complexes of the Schiff base with morpholino or aza-crown ether pendants, CoL^1 and CoL^2, as mimic hydrolytic metalloenzyme, were used in catalytic hydrolysis of carboxylic ester （PNPP）. The analysis of specific absorption spectra of the hydrolytic reaction systems indicates that key intermediates, made up of PNPP and Co（Ⅱ） complexes, have been formed in reaction processes of the PNPP catalytic hydrolysis. The mechanism of PNPP catalytic hydrolysis has been proposed based on the analytic result of specific absorption spectrum. A kinetic mathematical model, applied to the calculation of the kinetic parameter of PNPP catalytic hydrolysis, has been established based on the mechanism proposed. The acid effect of buffer solution, structural effect of the complexes, and effect of temperature on the rate of PNPP hydrolysis catalyzed by the complexes have been also discussed.