Synthesis,Structure and Biological Activities of a Novel Anionic Organotin(Ⅳ)Complex{[(pClC6H4CH2)Sn(H2O)(Cl)2OCOCH(O)CH(O)CO2Sn(H2O)(Cl)2(p-ClC6H4CH2)]·2(HNEt3)}

A novel anionic organotin(Ⅳ) complex {[(pClCHCH)Sn(HO)(Cl)OCOCH(O)CH(O)COSn(HO)(Cl)(p-ClCHCH)]·2(HNEt)}(1) was synthesized by the reaction of di(p-chlorobenzy)tin dichloride with the D-tartaric acid in 2:1 molar in the presence of an organic base triethylamine. The structure was characterized by elemental analysis, IR, TG, XRD and single-crystal X-ray diffraction. It crystallizes in triclinic, P1 space group, with a = 0.7067(1), b = 1.9762(3), c = 2.2383(3) nm, α = 91.544(2)°, β = 90.075(2)°, γ = 90.110(2)°, V = 3.1247(7) nm~3, Z = 3, Dc = 1.621 g/cm~3, m(Mo Kα) = 16.29 cm–1, F(000) = 1530, R = 0.0394, wR = 0.1092,(Δρ)max = 1224 and(Δρ)min = –840 e/nm~3. The stabilities, orbital energies and composition characteristics of some frontier molecular orbitals of 1 have been carefully investigated with quantum chemistry calculation. In addition, the in vitro antitumor activity suggested that 1 had stronger inhibitory activity on H460, MCF7 than on A549.

Synthesis, spectral characterization and biological activities of Organotin(IV) complexes with <i>ortho</i>-vanillin-2-hydrazinopyridine (VHP)

Five new organotin(IV) complexes of ortho-vanillin-2-hydrazinopyridine hydrazone with formula [RnSnCl4–n(VHP)] [R = Me2, n = 2 (2);R = Ph2, n = 2 (3);R= nBu2, n = 2 (4);R = nBu, n = 2 (5) and R = 1, n = 0 (6)] have been synthesized by direct reaction of ortho-vanillin-2-hydrazinopyridine hydrazone [(VHP), (1)], base and organotin(IV) chloride(s) in absolute methanol. The hydrazone ligand [(VHP), (1)] and its organotin(IV) complexes (2-6) have been characterized by UV-Visible, FT-IR and 1H NMR spectral studies. Spectroscopic data suggested that in the complexes (2-4), the ligand (1) acted as a neutral bidentate ligand and is coordinated to the tin(IV) atom via the azomethine nitrogen and pyridyl nitrogen atoms, whereas the ligand (1) acted as a uninegative tridentate ligand and coordinated to the tin(IV) atom through phenolic-O, azomethine-N and pyridyl-N atoms in complexes (5-6). The toxicity of the ligand (1) and its organotin (IV) complexes (2-6) were determined against Artemia salina. Organotin(IV) complexes showed moderate activity against Artemia salina. The ligand (1) and its organotin(IV) complexes (2-6) were also tested against four types of bacteria namely Bacillus cereus, Staphylococcus aureus, Escherichia coli and Enterobacter aerogenes. All organotin(IV) complexes and the free ligand (1) showed better antibacterial activities against bacteria. Among the organotin(IV) complexes (2-6), diphenyltin(IV) complex (3) showed higher activity against the four types of bacteria.

Formation,Structure and In Vitro Antitumour Activity of a Novel Binuclear Organotin Complex

A 1：1 reaction of triphenyltin chloride with potassium N-[（3,5-dibromo-2-hydroxylphenyl）methylene]valinate in benzene led to the formation of a novel mixed organotin dinuclear complex, （HL）SnPh3oPh2SnL [L=2-O-3,5-Br2C6H3CH=NCH（i-Pr）COO], by means of a facile phenyl-tin bond cleavage process. In the complex, there are two distinct types of carboxylate moieties and a trans-O2SnC2N and a trans-O2SnC3 in distorted trigonal bipyramidal geometries were bridged by a carboxylate group. In vitro antitumor activity of the complex against three human tumour cell lines （HeLa, CoLo205 and MCF-7） was found to be much higher than cis-platin used in clinic.

Syntheses, Crystal Structures and Biological Activities of the 2-Oxo-3-phenylpropionic Acid Arylformylhydrazone Dibenzyltin Complexes

Two 2-oxo-3-phenylpropionic acid arylformylhydrazone dibenzyltin(IV)complexes{[C4H3O(O)C=N-N=C(PhCH2)COO](C6H5CH2)2Sn(CH3OH)}2(Ⅰ)and{[t-Bu-C6H4(O)C=N-N=C(PhCH2)COO](C6H5CH2)2Sn(CH3OH)}2(Ⅱ)have been synthesized and characterized by IR,1H,13C and 119Sn NMR spectra,HRMS,and elemental,thermal stability and single-crystal X-ray diffraction analyses.Complex I crystallizes in the triclinic system,space group P1 with a=9.0392(9),b=10.249(1),c=15.5762(15)?,α=98.605(1)°,β=103.765(1)°,γ=104.056(1)°,Z=2,V=1326.3(2)?3,Dc=1.511 Mg·m^–3,m(MoKa)=1.005 mm–1,F(000)=612,R=0.0206 and wR=0.0524.Complex Ⅱ belongs to triclinic system,space group P1,a=11.4643(3),b=11.8885(3),c=13.0362(4)?,α=73.800(1)°,β=71.679(1)°,γ=79.006(1)°,Z=2,V=1609.34(8)?3,Dc=1.381 Mg·m^–3,m(MoKa)=0.833 mm–1,F(000)=688,R=0.0244 and wR=0.0244.In vitro antitumor activities of both complexes were evaluated by MTT against three human cancer cell lines(NCI-H460,HepG2 and MCF7)and human cell lines(HL7702).Both complexes exhibit better antitumor activity.Furthermore,the interaction between both complexes and calf thymus DNA was studied with EB fluorescent probe.

Synthesis and Crystal Structure of a One-dimensional Infinite Chain Organotin Complex [(n-Bu)_3Sn(OCOC_5H_4NO)]_n

A novel organotin complex [（n-Bu）3Sn（OCOC5H4NO）]n has been synthesized and characterized by elemental analysis, IR and ^1H NMR. The crystal structure has been determined by X-ray single-crystal diffraction. The crystal belongs to monoclinic, space group P2 1/c with a = 8.982（2）, b = 17.908（4）, c = 13.219（3） A, β= 96.981（4）°, Z = 4, V= 2110.6（8） A^3, Dc = 1.347 g/cm^3, μ（MoKa） = 12.23 cm^-1, F（000） = 880, R = 0.0497 and wR = 0.1263. In the molecular structure of the title complex, the tin atoms are five-coordinated in a distorted trigonal bipyramidal geometry. A one-dimensional linear polymer is formed through an interaction between the O atoms of pyridine-3-carboxylic acid N-oxide and tin atoms of an adjacent molecule.

Synthesis, Characterization and Antibacterial Activity of Cyclohexyltin Complexes of N-(3,5-Dibromosalicylidene)valine

Three cyclohexyltin complexes of N-（3,5-dibromosalicylidene）valine（H_2L）, Cy_3Sn（HL）（1）, Cy_2SnL（2）, and Cy2 SnL ·Cy_3Sn Cl（3）（Cy = cyclohexyl）, have been synthesized and characterized by elemental analysis, IR, and ~1H and ^（13） C NMR spectra. The crystal structures of 2 and 3 have been determined. Complex 2 belongs to the monoclinic system, space group P21/n with a = 21.250（8）, b = 10.837（4）, c = 23.050（8） ？, b = 93.193（9）°, V = 5300（3） ？~3, Z = 8, D_c = 1.659 g/cm^3, m = 4.004 mm^（-1）, F（000） = 2624, R = 0.0471 and wR = 0.1015. Complex 3 belongs to the monoclinic system, space group P21 with a = 10.3452（10）, b = 18.7665（18）, c = 12.1483（12） ？, b = 103.374（2）°, V = 2294.5（4） ？3, Z = 2, D_c = 1.542 g/cm^3, m = 2.923 mm^（-1）, F（000） = 1072, R = 0.0428 and wR = 0.0936. Complex 2 has a distorted trigonal bipyramidal geometry with the axial locations occupied by one carboxylate oxygen and a phenolic oxygen of the ligand, and 3 reveals that the two tin atoms are joined via the carbonyl atom of the ligand to form a mixed organotin binuclear complex. Bioassay results show that 1 and 2 have good in vitro antibacterial activity against Escherichia coli.

Synthesis of Five-coordinated Anionic Tin(Ⅳ) Complexes and Crystal Structure of [(i-Pr)_2NH_2][PhSn( μ~2-SCH_2COO)_2]

Four new five-coordinated anionic tin(Ⅳ) complexes with a form of [R_ n NH_ 4- n ][PhSn( μ 2-SCH_2COO)_2] were synthesized via the reaction of mercaptoacetic acid with phenyltin trichloride in the presence of different organic bases and characterized by means of IR, 1H NMR and MS spectroscopies. The crystal structure of [( i -Pr)_2NH_2] [PhSn( μ 2-SCH_2COO)_2] was determined by X-ray diffraction. In the crystal structure,the tin atom is five-coordinated and exists in trigonal bipyramid geometry with cell parameters a =1.1766(11) nm, b =1.3144(14) nm, c =1.3336(15) nm,β =90° and Z =4.

Diorganotin Complexes of N-[4-(Diethylamino)salicylidene]-(L)-tryptophane: Syntheses, Structures and Properties

Four chiral diorganotin complexes of N-[4-(diethylamino)salicylidene]-(L)-tryptophane,R2Sn[4-(Et2N)-2-OC6H3CH=NCH(CH2Ind)COO](Ind=3-indolyl;R=Me(1);Et,(2);n-Bu(3);Cy(cyclohexyl)(4)),have been synthesized and characterized by elemental analysis,IR,and 1H and 13C NMR spectra.The crystal structures of 1-CH3OH-CHCl3,2,3-CH3OH and 4-CH3CH2OH have been determined by single-crystal X-ray diffraction.The complexes crystallize in orthorhombic system with P212121 space group,and the tin atoms are in distorted trigonal bipyramidal geometry and form five-and six-membered chelate rings with the chiral ONO tridentate ligand N-[4-(diethylamino)salicylidene]-(L)-tryptophane.In the complexes,the molecules are connected into one-dimensional supramolecular chain by intermolecular N–H…O–H…O=C or N–H…O–C hydrogen bonds.The fluorescence spectrum indicates that the complexes may be explored for potential blue luminescent materials.Bioassay results show that 3 and 4 belong to the efficient cytostatic agents against A549 human tumor cell.

Synthesis, Spectral and Antimicrobial Studies of Bis (Cyclopentadienyl) Titanium (IV) Bis (O,O’-Dialkyl and Alkylenedithiophosphate) Complexes

A new complexes of Cp2Ti[S2P(OR)2]2 (where R = Et, Pr-n, Pr-i, Bu-i and Ph) and Cp2Ti[S2POGO]2 (where G = -CH2CMe2CH2-, -CH2CEt2CH2- and -CMe2CMe2-) were prepared by the dropwise addition of the appropriate O,O’-dialkyl or -alkylenedithiophosphoric acid to biscyclopentadienyl titanium dichloride in 1:2 molar ratio and refluxed in benzene solution. These novel deep red colored complexes were characterized by elemental analyses, molecular weight measurements and spectroscopic techniques (IR., NMR 1H, 13C and 31P NMR). These titanium (IV) dithio complexes have also been screened for their antibacterial activities.

Synthesis and Anion Recognition of a Novel Heterocyclic Organotin Complex

A novel heterocyclic hexacoordinate organotin(Ⅳ) complex, bis(O-vanillin)-semi ethylenediamino dibenzyltin (VEDBT) was synthesized by the reaction of dibenzyltin dichloride with bis(O-vanillin)-semiethyenediamine, its structure has been characterized by spectral methods. The electrodes using VEDBT as a neutral carrier show high selectivity for salicylate anions.

Synthesis, spectral, 3D molecular modeling and antibacterial studies of dibutyltin (IV) Schiff base complexes derived from substituted isatin and amino acids

New dibutyltin(IV) complexes of Schiff base derived from 5-chloroindoline-2,3-dione, indoline- 2,3-dione with amino acids (tryptophan, alanine and valine) were synthesized and characterized by elemental analysis, IR, electronic spectra, conductance measurements, and biological activity. The analytical data showed that the Schiff base ligand acts as bidentate towards metal ions via the azomethine nitrogen and carboxylate oxygen by a stoichiometric reaction of M:L (1:2) to form metal complexes. NMR (1H, 13C and 119Sn) spectral data of the ligands and metal complex agree with proposed structures. The conductivity values between 14 - 27 ohm-1cm2mol-1 in DMF imply the presence of non-electrolyte species. 3D molecular modeling and analysis of bond lengths and bond angles have also been conducted for a representative compound, [Bu2Sn(L2)2], to substantiate the proposed structures. Antibacterial results indicate that the metal complexes are more active than the free ligands.

Adsorption and reduction of platinum(Ⅳ) chloride complex ions on activated carbon

The adsorption kinetics of platinum（IV） chloride complex ions on the activated carbon Norit GF40 was investigated. Experiments were carried out at different initial concentrations of Pt（IV） chloride complex ions, temperature, rate of mixing and pH. It was found that the value of activation energy of the studied process is equal to 19.7 kJ/mol. From the ICP MS analysis it was confirmed that platinum ions （Pt（IV） and Pt（II）） are removed from the solution due to the adsorption and are further reduced to the metallic state. Such mechanism was confirmed by XPS analysis which showed that on the carbon surface three forms of platinum species, i.e. Pt（0）, Pt（II） and Pt（IV）, exist. The presence of platinum in the solution at different oxidation states was also confirmed spectrophotometrically by identification of their characteristic absorption bands. The metallic form of Pt present on the surface of activated carbon was observed in the form of small spherical islands with the diameter not exceeding 500 nm. Those islands consist of smaller, flake-shape particles with a thickness of about 35 nm.

Spectrophotometric Investigation of Complex Formation of Ge（IV） with Bis（2,3,4-Trigidroksifenilazo） Benzidine in the Presence of Cationic Surfactants Active Substances

It is investigated the interaction of Ge（IV） with bis（2,3,4-trigodroksifenolazo） benzidine （R） in the presence of KSAS （cationic surface active substances）-CPCl （cetylpyridinium chloride）, CPBr （cetylpyridinium bromide） and CTMABr （cetyltrimethylammonium bromide）. It is studied the effect pH, time on the formation of ternary complexes. It is determinated of molar absorption coefficients and stability constants of germanium. Binary （Ge-R） and triple （Ge-R-CPCI, Ge-R-CPBr, Ge-R-CTMaBr） complex form at pH 4 and pH 1, respectively. The composition proportion of binar system is 1：2 and the composition proportion triple complex is 1：1：2. The concentration interval of germanium which obeying beer low in the Ge-R 0.12-2.92 mkq/mL, in the Ge-R-CPCI is 0.04-1.46 mkq/mL, in the Ge-R-CPBr is 0.00-1.00 mkq/mL and in the Ge-R-CTMaBr is 0.00-1.00 mkq/mL. Molar absorbtivities of complexes are 45,000, 57,000, 59,000 and 60,000, respectively. The effect of interfering ions and masking agents has been learned. Stability constants of complexes have been determined： lgKl = 7.21 ＋ 0.06 （Ge-R）,＇ lgK1 = 12.08 _＋ 0.05 （Ge-R-CPCI）, lgK1 = 12.12 ＋ 0.07 （Ge-R-CPBr） and lgK1 = 12.85 ＋ 0.06 （Ge-R-CTMaBr）. It is developed highly selective method of photometric determination of trace amounts of Ge（IV） in petroleum coke.

New Square-Pyramidal Oxovanadium (IV) Complexes Derived from Polydentate Ligand (L1)

New series of oxovanadium (IV) complexes isolated from 2,4,6-tris-(2-pyridyl)-1,3,5-triazine (L1) are incorporated and portrayed using spectroscopic (IR, UV-Vis, ESR, mass spectrometric), magnetic moment, thermal and cyclic voltammetry measurements. The results demonstrate that L1 acts in various styles of chelation with [V3O3(L1)(SO4)3(EtOH)1/2(H2O)3/2] 1), [VO(L1)(2,4-pentadionate)]·Cl·4HCl 2), [V2O2(L1)(SO4)2(EtOH)5/2] 3), [V2O2(L1)(SO4)2(EtOH)3/2(H2O)1/2] 4), [VO(L1)SO4 (H2O)3/2]·2.5H2O 5) and [V2O2(L1)(SO4)2(H2O)]·H2O 6). The values of magnetic moments and spectral studies suggest a square-pyramidal geometry around the V (IV) ion for all complexes. The molar conductance values suggest that the complexes are non-electrolyte, except the [VO(L1) (2,4-pentadionate)] Cl·4HCl. Molecular modeling calculates the bond length, bond angle, chemical reactivity, energy components (Kcal/mol) and binding energy (Kcal/mol) for the isolated complexes. The in vitro antibacterial studies of these complexes screened against pathogenic bacteria prove them as growth inhibiting agents. Antitumor activity is carried out in vitro on human mammary gland (breast) MCF-7 and cervical cancer cell-HeLa has shown that [VO(L1)SO4(H2O)3/2]·2.5 H2O and [VO(L1)(2,4-pentadionate)] Cl·4HCl complexes display the highest powerful activity between all of the investigated complexes.

Synthesis and Crystal Structure of a Novel Mercapto-organotin Complex: [Et_3NH] [Ph_2SnCl(μ~2-SCH_2COO^-)]

A novel complex [Et3NH] [Ph2SnCl(μ2- SCH2COO-)] has been unexpectedly obtained by the reaction of Ph3SnCl and HSCH2COOH in 2:1 molar ratio in the presence of organic base Et3N. Possible dephenylation mechanism was illustrated. The X-ray diffraction study has shown that the title complex consists of cation moiety [Et3NH] and anion moiety [Ph2SnCl(μ2 - SCH2COO)] with tin(IV) in a trigonal bipyramidal coordination geometry.

Study on the Tin （IV） Complex of 4,5-benzo-1,2-dithiole-3-thione with IR, Analysis Centesimal, and Theatrically

A tin （IV） complex with 4,5-benzo-1,2-dithiol-3-thione （C7H4S3） （A）, [SnCI4 （C7H4S3）2] （B） was synthesized. The structure of the obtained complex （B） was characterized by Infrared Spectroscopy （IR）, analysis centesimal composition, and theoretical study. The complex （B） has an octahedral structure, where a tin in the center takes an octahedral geometry and is coordinated by four atoms of chlorine and two thiocarbonyl sulfur atom （C=S） of the ligand.

Crystal Structure of A Novel Ionic Organotin Complex:{[Ph_(2)Sn]_(2)[2,6-(O_(2)C)_(2)C_(5)H_(3)N]_(3)H_(2)O}^(2-)[HNEt_(3)]_(2)^(+)

A novel ionic organotin complex{[Ph_(2)Sn]_(2)[2,6-(O_(2)C)_(2)]C_(5)H_(3)N}_(3)H_(2)O}^(2-)[HNEt_(3)]^(2+)has been unexpectedly obtained by the reaction of Ph_(3)SnCl and 2,6-pyridine dicarboxylic acid in 1:1 molar ratio in the presence of organic base Et_(3)N.Possible dephenylation mechanism was illustrated.The X-ray diffraction study has shown that the title complex consists of cation moiety[HNEt_(3)]^(+)and anion moiety{[Ph_(2)Sn]_(2)[2,6-(O_(2)C_(2))C_(5)H_(3)N]_(3)H_(2)O}^(2-)with tin(IV)in a pengonal bipyramidal coordination geometry.

Se(IV)在北山花岗岩上的吸附

采用批式法研究了粉碎的甘肃北山花岗岩样品(BS03, 600 m)对Se(IV)的吸附作用. 实验结果表明: 在pH 3-7范围内, Se(IV)的吸附分配比(Kd)基本不随pH变化; 当pH > 7时, Se(IV)在北山花岗岩上的Kd随pH的增大而减小. Se(IV)在北山花岗岩上的吸附不随离子强度变化. 北山地下水条件下的Ca2+(4.10×10-3 mo·lL-1)和SO42- (3.17×10-3 mo·lL-1)对Se(IV)的吸附没有影响. 此外, Se(IV)/Eu(III)/北山花岗岩三元吸附体系的实验结果表明, Se(IV) (1.46×10-5 mo·lL-1)和Eu(III) (3.33×10-6 mo·lL-1)在北山花岗岩上的吸附作用相互之间没有表观影响. 通过假定HSeO3-在广义的吸附位点≡SOH上发生了生成≡SHSeO3和≡SSeO3-的两个表面配位反应, 定量解释了Se(IV)的吸附实验结果.

单核四价锰配合物Mn^(IV)(salae)_2的合成和晶体结构

目的合成高价锰配合物并研究其晶体结构。方法席夫碱配体H2salae(水杨醛缩乙醇胺)与Mn(OAc)3.2H2O在甲醇-水混合溶剂中反应,溶液静置,溶剂挥发后得到单晶。结果配合物MnIV(salae)2的单晶属六方晶系,空间群R-3,晶胞参数:a=1.7907(1)nm,b=1.7907(1)nm,c=2.8162(3)nm,α=90°,β=90°,γ=120°,V=7.8201(1)nm3,Z=18,Mr=381.28,Dc=1.457 g/cm3。结论MnIV由两个席夫碱配体进行配位,每个配体提供两个氧原子和一个氮原子。中心锰IV处于八面体的配位环境中。不同单元的分子由分子间C—H…O氢键和C—H…π弱相互作用连接在一起,形成三维结构。

具有抗肿瘤免疫治疗作用的铂类药物研究进展

经典铂类药物是一类潜在的免疫调节剂,通过诱导免疫原性细胞死亡(ICD)来参与肿瘤免疫调节。因而可将铂类药物分子与免疫治疗药物分子或其药效团进行拼合或融合,提高协同抗肿瘤疗效。铂(Ⅱ)药物是临床化疗最常见药物,由于其副作用和耐药性等缺点,使其临床应用受限。铂(Ⅳ)配合物具有动力学惰性和优于铂(Ⅱ)配合物的药理作用机制受到广泛关注和研究。本文旨在总结近年来发表的具有免疫调节功能的抗肿瘤铂配合物,通过化疗协同免疫疗法提高抗肿瘤疗效,为具有免疫功能的铂类药物的进一步研发和未来临床应用提供依据。