Synthesis of N,N,N-4,4＂-Di-（4-methylphenyl）-2,2＇：6＇,2＂- terpyridine-N,N,N-tris（isothiocyanato） Ruthenium（Ⅱ） and Application to Colorimetric Hg^2＋ Sensor

A terpyridine derivative DPTP [di-（4-methylphenyl）-2,2＇：6＇,2＂-terpyridine] was conveniently synthesized from 2-bromopyridine via halogen-dance reaction, Kharash coupling and Stille coupling reaction. Then its corresponding ruthenium complex Ru-DPTP [N,N,N-4,4＇＇-di-（4-methy,phenyl）-2,2＇：6＇,2＂-terpyridine-N,N,N-tris（is,-thi,cyanat,）- ruthenium（H） ammonium] was obtained and fully characterized by IR, UV-Vis, ESI MS and elemental analysis. The MLCT absorption band of Ru-DPTP was blue-shifted from 570 to 500 nm upon addition of Hg^2＋. Among a series of surveyed metal ions, the complex showed a unique recognition to Hg^2＋, indicating that it can be used as a selective colorimetric sensor for Hg^2＋.     

Polyethylenimine （PEI）-g-comb-poly（ethylene glycol）-transferrin（Ⅰ）： Tumor-targeted Vector for Gene Delivery In.vitro

The work described the synthesis and evaluation of PEI-g-comb-PEG-transferrin as a potential system for gene therapy in vitro. The MW of PEG was 10KDa, and PEI was 2KDa. Its structure was identified by NMR, FT-IR and TGA spectroscopy. MTT assay found that at concentration up to 4000 n mol/L of the polymer, cell viability was over 85%. The bio-character of polymer/DNA complex was characterized by agarose gel electrophoresis, ethidium bromide exclusion and zeta-potential assay. The polymer could retardate DNA at N/P ratio 3.0-3.5 （mol/mol）. The particle size of the polymer/DNA complex was less than 300 nm. Transfection efficiency of the complex was studied in COS7 and NT2 cell lines.     

Synthesis and Structural Characterization of Manganese Carbonyl Incorporated Polyoxomolybdate （n-Bu4N）2 [Mo6O16（OCH3）2 {HOCH2C（CH2O）3}2 {Mn（CO）3}2]

The polyoxoanion incorporated {Mn（CO）3^＋} complex, （n-Bu4N）2[Mo6O16（OCH3）2{HOCH2C（CH2O）3}2·{Mn（CO）3}2]（1）, has been synthesized by the reaction of （n-Bu4N）4[Mo8O26] with Mn（CO）5Br in methanol, in the presence of C（CH2OH）4. The complex 1 has been characterized by IR, UV-Vis, X-ray single crystal diffraction, and TG. Crystal data for the complex 1：C25H48MnMo3NO16 （1）, Triclinic Pi, a=0.9405（3） nm, b=1.3351（4） nm, c=1.5455（4） nm, α=103.206（5）°, β=102.165（5）°, γ=100.784（5）°, V=1.7896（9） nm^3, Z=2, R1=0.0703, wR2= 0.1495. The structure analysis of complex 1 shows that the complex consists of two tetrabutylammonium cations and a polyoxomolybdate anion that incorporates two fac-Mn（CO）3^＋ units. The anion of complex 1 can be considered as the dimer of two rhomb-like anions by sharing of two comers.     

Synthesis,DNA-binding,and Photocleavage of 2,3-Di-2-pyridylquinoxaline-silver（I） Complex

A new dinuclear complex, [Ag（L）（CH3CN）]2（ClO4）2·2H2O（L=2,3-di-2-pyridylquinoxaline）, was prepared and characterized by elemental analyses, IR spectroscopy, and single-crystal X-ray diffraction analyses. The interaction of the complex with calf thymus DNA（CT-DNA） was investigated by absorption, fluorescence spectroscopies, and viscosity measurement. The results suggested that the complex was bound to DNA via an intercalative mode. The intrinsic binding constant value Kb was found to be approximately 1.48×10^3 L·mol^-1. Moreover, the Ag（I） complex could cleave the plasmid pUC19 DNA from the supercoiled Form Ⅰto the nicked FormⅡ under irradiation at 365 nm.     

Synthesis,Structure and Norbornene Polymerization Activity of a Novel Palladium（ II ） Complex with N,N＇-bis（2-benzoyl-3-oxobutane）-trans-l,2- diaminocyclohexane Ligand

The title complex N,N＇-bis（2-benzoyl-3-oxobutane）-trans-l,2-diaminocyclo- hexane-palladium （C28H28N2PdO4） has been synthesized by the reaction of N,N＇-bis（2- benzoyl-3-oxobutane）-trans-l,2-diamino-cyclohexane with PdCI2, and characterized by ele- mental analysis, IR spectrum, WAXD and TG. The spatial structures of the complex have been confirmed by single-crystal X-ray diffraction analysis. The compound crystallizes in the monoclinic system, space group C2/c with a = 29.763（6）, b = 10.320（2）, c = 18.921（4） A, fl = 102.75（3）°, V = 5668（2） A3, C28H28N2PdO4·CH3OH, Mr = 594.97, Z = 8, Dc = 1.394 g/cm3, μ（MoKa） = 0.694 mm-1, F（000） = 2448, T= 293（2） K, R = 0.0572 and wR = 0.1347 （I〉 2σ（I））. The compound was investigated for the catalytic behavior towards norbornene （NB） vinyl addition polymerization. And the palladium complex showed excellent catalytic activity up to 9.97x 106g of PNB （mol of Pd）-1 h-1 with high monomer conversion using methylaluminoxane （MAO） as a cocatalyst.     

手性配合物Λ, Δ-[Ru(phen)2hpip]2+的两种结构对含G:T错配DNA识别的分子力学研究

In this work, the recognition of DNA including G：T mismatched pairs by the two different structures of [Ru（phen）2hpip]^2＋ was firstly studied with molecular modeling respectively. The results revealed that all of the four chiral isomers of the two structures could recognize the mismatched DNA from the minor groove orientation especially and the interaction was enantioselective and sitespecific. The two left isomers were more preferential than the right ones. Especially, the structure Ⅱ which had much lower energy after interacting with DNA was the advantaged structure. Detailed energy analysis indicated that the steric interaction in the process of the complex inserting base stack determined the recognition results and the electrostatic interaction made an effect to some extent.     

Coumarin Modified Rhodamine Derivative： Fluorescent Chemosensor Selectively Recognizing Al^3＋ and Ca^2＋

A fluorescent probe with a coumarin moiety bound to rhodamine 6G hydrazide（l） was synthesized. Its sensing behavior toward various metal ions was investigated with fluorescence methods. Compound I displays different fluorescence emission responses to Al^3＋ and Ca^2＋ at the same excitation wavelength in the visible light region, while no changes occur after the addition of other metal ions. The binding ratios of the complexs of 1-Al^3＋ and 1-Ca^2＋ are both 2：1 according to the Job plot and high resolution mass spectrometer（HRMS） experiments. Moreover, emission spectrum of 1-Ca^2＋ complex and absorption spectrum of the rbodamine dyes overlap largely. When Al^3＋ was added to the 1-Ca2＋ system, calcium in complex 1-Ca2＋ can be displaced by Al^3＋, resulting in the output of another ratiometric sensing signal, which demonstrates that the 1-Ca^2＋ complex can be served as a new and effective fluorescence resonance energy transfer（FRET） donor for rhodamine derivatives.     

Crystal structure and DNA binding studies of a cobalt(Ⅱ) complex containing mixed-ligands of 1,10-phenathroline and glycollic acid

A cobalt（11） complex containing mixed-ligands of 1,10-phenathroline（phen） and glycollic acid（GA）.|Co（GA）₂（phen）| was synthesized and its structure was characterized by X-ray diffraction.The interaction of the complex with DNA was investigated by electronic absorption spectra and electrochemical methods.Electronic absorption spectrum experiments showed that after interaction with DNA.the characteristic absorption peaks of |Co（GA）₂（phen）| underwent hypochromic effect as well as redshift. Also,the binding strength of 3.8×10⁴L/mol was estimated by titration method.Electrochemical assays revealed that the redox peak currents of the complex decreased obviously accompanied by a positive shift of the formal potential after association with DNA.All these results revealed that the synthesized cobalt complex bound with DNA via an intercalation mode.     

The Reaction of Molybdenum with 2,3-Dihydroxynaphthalene

[H2N（CH2）3NH312[MoO2（C10H6O2）2] （1） was synthesized by the 2,3-dihydroxynaphthalene in the mixed solvent of CH3OH, CH3CN reaction of （n-Bu4N）4[Mo8O26] with and 1,3-propanediarnine. （C5HllN2）2- [HeN（CH2）3NH2][MoO2（CloH6O2）2] （2） was obtained by the reaction of Na2MoO4.2H20 with 2,3-dihydroxynaphthalene in the same solvent above. Both of the complexes possess complex anion [Mo（VI）O2（OC10H6O）2]^2- which shows pseudo-octahedrally coordinated fashion, while the counterions are two protonated 1,3-propanediamine in complex 1 and （CsH11N2）^＋ in complex 2. （C5H11N2）＋ is the byproduct of reaction 2, which results from combination of acetonitrile with 1,3-propanediamine. Packing diagrams of the two complexes are also different. There is anti-parallel-aligned-double-meso-bilayer unit in complex 1. However there are four chiral anions arranged in anticlockwise orientation in complex 2.     

Synthesis and Magnetic Properties of Polyamide Complex Containing Bithiazole Moieties

A new polyamide containing bithiazole moieties （PTA） was synthesized by the polycondensation of 2, 2＇-diamino-4, 4＇-bithiazole （DABT） and oxalyl chloride. The polymer complex was prepared from PTA and NdC13 in DMSO. They were characterized through IR and elemental analysis. The preliminary magnetic properties of the complex PTA-Nd^3＋ was investigated, it was found that the material is a ferromagnet at low temperature.     

Synthesis,Characterization, and DNA Binding Properties of Dinuclear Copper（Ⅱ） Complex [Cu2（TATP）2（L-Leu）2（CIO4）2]2·2H2O

A dinuclear copper（Ⅱ） complex[Cu2（TATP）2（L-Leu）2（CIO4）2]2·2H2Owas synthesized and characterized, where, TATP=1,4,8,9-tetraazatriphenylene, and L-Leu=L-leucinate. The complex was crystallized in the triclinic space group P1, with two independent molecules in a unit cell. Two Cu（Ⅱ） ions in each complex [Cu2（TATP）2（L-Leu）2（CIO4）2] molecule were found to be in different coordination geometries, i.e., Cu2 or Cu4 of a distorted square-pyramidal geometry coordinated with two nitrogens of TATP, the amino nitrogen and one carboxylate oxygen of L-Leu and one oxygen of perchlorate, and Cul or Cu3 with an octahedral geometry coordinated with the above stated similar coordinated atoms, and another carboxylate oxygen of L-Leu coordinating to Cu2 or Cu4. The complex can interact with CT-DNA by an intercalative mode and cleave pBR322 DNA in the presence of ascorbate.     

Synthesis and Crystal Structure of a Complex of Melamine with Benzoic Acid

A new complex of melamine（MA） with benzoic acid（HBA） was prepared, affording [（HMA＋）（BA-）]-2H2O. Each HBA molecule is deprotonated and one triazine nitrogen atom of MA is protonated. The adjacent HMA＋ cations are related via an inverse center to form ribbons with a pair of N--H…N hydrogen bonds. COO- groups of BA- anions are hydrogen bonded to alternate sides of the （HMA＋）∞ ribbons to generate indention ID tapes, which are extended into a 3D structure via N--H…O- and N--H…OW hydrogen bonds and π-π stacking interactions. Predominant patterns of the hydrogen bond present in the complex are anion/water and amino/water tape structures. The hydrogen-bonding patterns consist of alternate 6, 10-membered rings sharing two edges. Infrared（IR） spectroscopy conforms that proton transfer has taken place in the complex.     

Crystal Structure and Ethylene Oligomerization Catalytic Activity of {2-Carbethoxy-6-[1-[（2,6-diethylphenyl）imino]ethyl]pyridine}CoCl2

The unsymmetric precursor ethyl 6-acetylpyridine-2-carboxylate （4） was synthesized from 2,6-dimethylpyridine （1）. On the basis of this precursor, a new mono（imino）pyridine ligand （5） and the corresponding Co（Ⅱ） complex {2-carbethoxy-6-[1-[（2,6-diethylphenyl）imino]ethyl]pyridine}CoCl2 （6） were prepared. The crystal structure of complex indicates that the 2-carbethoxy-6-iminopyridine is coordinated to the cobalt as a tridentate ligand using [N, N, O] atoms, and the coordination geometry of the central cobalt is a distorted trigonal bipyramid, with the pyridyl nitrogen atom and the two chlorine atoms forming the equatorial plane. Being applied to the ethylene oligomedzation, this cobalt complex shows catalytic activity of 1.820× 10^4 g/mol-Cooh at 101325 Pa of ethylene at 15.5℃ for 1 h, when 1000 equiv, of methylaluminoxane （MAO） is employed as the cocatalyst.     

Studies on the Interaction of Dinitratobis（phen） Cadmium Complex with DNA

DNA-binding properties of the dinitratobis（phen） cadmium complex [Cd（phen）2（NO3）2] （where phen = 1,10-phenanthroline） have been investigated with absorption titration, fluorescence spectroscopy, viscosity measurement, molecular modeling and density functional theory （DFT） calculations. The results indictate DNA-binding mode of the complex to be weak groove binding rather than partial intercalative interaction expected of the extended planar aromatic phen ring. In addition, the DNA cleavage study was carried out by gel electrophoresis experiment. The results showed that the complex both hardly cleaves pBR322 DNA in the absence and present ascorbate. So it is suggested that the formation of cadmium complex can decrease cadmium toxicity to some extents.     

Interference study on the free calcium in the human peripheral lymphocyte by acrylamide

The role of acrylamide on the human peripheral lymphocytes was studied by laser scanning confocal microscopy technique and fluo-3. The calibration value of the apparent dissociation constant （Kd） of the fluo-3-Ca^2＋ complex was obtained as 4.83 × 10^-7 moi/L. Acrylamide （〈54 μg/mL） evoked a rise in free intracellular calcium concentration [Ca^2＋]i, in a dosedependent manner. Acrylamide induced the increase of [Ca^2＋]i was discussed in detail.     

Studies on the Interaction of Cobalt Mixed-Ligand Coordination Compound Containing Tetrapyrido [3,2-a:2′,3′-c:3″, 2″-h:2■,3■-j] phenazine with DNA

A new monometallic complex [Co(phen)_2tpphz]~(3+) (where tpphz is tetrapyrido [3,2-a:2′,3′-c:3″,2″-h:2′″,3′″-j] phenazine) was synthesized by the reaction of 5, 6-diamino-1,10-phenanthroline with [Co(phen)_2(phendione)]~(3+). It was characterized by elemental analysis, molar conductivity, IR, ~1H NMR, ultraviolet and fluorescence spectroscopy. The interaction of the complex with DNA was also investigated. The complex shows the absorption hypochromicity, fluorescence enhancement, the specific viscosity increased when bound to calf thymus DNA. The cyclic voltammetry (CV) measurement showed a change in peak current with the addition of DNA. All the results provide the support for the intercalative binding mode of the mononuclear complex.     

Synthesis and Crystal Structure of a Cu^2＋ Supramolecular Complex [Na2Cu（BTA）2（H2O）8]·H2O with a Three-dimensional Network Structure

A three-dimensional Cu^2＋ supramolecular complex [Na2Cu（BTA）2（H2O）8]·H2O 1 （H2BTA = bistetrazolylamine） was synthesized by reacting the aqueous solution of CuSO4·5H2O and H2BTA under stirring. The crystal structure of 1 was determined by single-crystal X-ray diffraction. The result indicates that 1 crystallizes in triclinic, space group P1, with a = 7.0518（2）, b = 12.2692（2）, c = 13.8583（3） A, α = 115.7260（10）,β = 93.2440（10）, γ = 98.3610（10）°, Mr = 573.90, V= 1059.01（4） A^3, Z = 2, De= 1.800 g·cm^-3,μ（MoKα） = 1.155 mm^-l, F（000） = 586.0, S = 1.074, the final R = 0.0273 and wR = 0.0744 for 4334 observed reflections with I 〉 2σ（I）. The Cu^2＋ ion is five-coordinated with a N4O1 donor set with r = 0.153 according to the method of Addison et al. And the Na^＋ ions form an infinite main chain through bridging O atoms from coordinated water molecules. In 1, a three-dimensional supratnolecular network is formed by O-H….O, O-H…N, N-H…O and N-H…N hydrogen bonds.     

EFFECT OF N,N,N’,N’-TETRAALKYL TEREPHTHALAMIDE ON NON-ISOTHERMAL CRYSTALLIZATION KINETICS OF POLYPROPYLENE

The effect of N,N,N＇,N＇-tetraalkyl terephthalamide （TATA） on the non-isothermal crystallization and melting characteristics ofpolypropylene （PP） was studied. The addition of TATA can lead to the formation ofβ-crystal PP. With the increase in TATA concentration the degree of crystallinity for β-crystal PP increased significantly, and that for a-crystal PP decreased, which indicated that TATA effectively induced the formation of β-crystal PP. WAXD also revealed the existence of β-crystal PP after the introduction of TATA into PP. PP containing TATA crystallized at a temperature range of 5-10℃ higher than that of pure PP, and the half-crystallization time （t1/2） and Avrami exponent （n） of PP at the same cooling rate were decreased by the addition of TATA, indicating that TATA influenced the crystallization rate and crystallization growth mode of PP. The rate constant of crystallization of PP containing TATA （Zc） was larger than that of pure PP, which further indicated that the crystallization of PP was accelerated by the addition of TATA.     

Highly Selective Salicylate Membrane Electrode Based on N,N＇- （Aminoethyl）ethylenediamide Bis（2-salicylideneimine） Binuclear Copper（Ⅱ） Complex as Neutral Carrier

A new ion selective electrode for salicylate based on N,N＇-（aminoethyl）ethylenediamide bis（2-salicylideneimine） binuclear copper（Ⅱ） complex [Cu（Ⅱ）2-AEBS] as an ionophore was developed. The electrode has a linear range from 1.0 × 10^-1 to 5.0 ×10^-7 mol·L^- 1 with a near-Nemstian slope of （ - 55 ±1 ） mV/decade and a detection limit of 2.0 × 10-7 mol·L^-1 in phosphorate buffer solution of pH 5.0 at 25 ℃. It shows good selectivity for Sal^- and displays anti-Hofmeister selectivity sequence： Sal^-〉SCN^-〉 ClO4^- 〉I^-〉 NO2^- 〉Br^-〉 NO3^- 〉Cl^-〉 SO3^2- 〉 SO4^2- The proposed sensor based on binuclear copper（Ⅱ）complex has a fast response time of 5-10 s and can be used for at least 2 months without any major deviation. The response mechanism is discussed in view of the alternating current （AC） impedance technique and the UV-vis spectroscopy technique. The effect of the electrode membrane compositions and the experimental conditions were studied. The electrode has been successfully used for the determination of salicylate ion in drug pharmaceutical preparations.     

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.