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, 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.

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.

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.

Ti(IV)在介孔氧化硅MCM-41中的液相移植

以钛酸丁酯为原料，通过液相移植反应，在介孔氧化硅ＭＣＭ－４１中成功地组装了Ｔｉ（ＩＶ），利用ＸＲＤ、ＴＥＭ、ＥＤＳ、ＦＴ－ＩＲ、Ｎ２吸附－脱附、２９Ｓｉ ＭＡＳ ＮＭＲ等多种实验方法对材料进行了表征，并讨论了液相移植反应的机理．实验表明，通过与介孔材料骨架表面Ｑ３硅原子中的硅醇键（Ｓｉ－ＯＨ）的反应而形成钛－氧－硅（Ｔｉ－Ｏ－Ｓｉ）键，Ｔｉ（ＩＶ）被成功地固定到介孔材料的骨架上面； ９５０～９６０ｃｍ－１红外共振吸收的加强是Ｓｉ－Ｏ－Ｔｉ键形成的标志．

Ti(IV)-石墨烯双助剂协同效应增强钨酸铋光催化性能

助剂修饰是促进光生电子和空穴分离的有效途径。采用新型无定型Ti(IV)空穴助剂与高电子传输率的还原石墨烯(rGO)电子助剂相结合,以水热–浸渍沉积法合成Ti(IV)和rGO共修饰的高效片状钨酸铋(Ti(IV)-r GO/Bi_2WO_6)可见光光催化剂。结果表明,与单独Bi_2WO_6相比,助剂Ti(IV)或r GO修饰的Bi_2WO_6可见光光催化降解甲基橙(MO)性能增强。双助剂共修饰的Bi_2WO_6光催化剂光催化活性更高,当Ti(IV)含量为5wt%时,双助剂共修饰的Bi_2WO_6光催化剂性能最佳,光催化速率常数达2.2×10-2 min-1,是纯Bi_2WO_6的88倍。光催化性能增强主要归因于新型Ti(IV)空穴助剂与r GO电子助剂的协同作用,即Ti(IV)快速转移光生空穴,同时r GO快速传递并转移电子。本文有望为新型助剂修饰光催化材料研究提供新思路。

Regioselective 1,2-Addition of Ti(IV)-enolate to α, β–Unsaturated Compounds

The nucleophilic addition of Ti(IV) enolate derived from methyl aryl ketones to α, β–unsaturated compounds was found to be highly selective to give 1, 2 addition products.

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.

Current Status for Oral Platinum (IV) Anticancer Drug Development

Platinum-based chemotherapeutic drugs such as cisplatin, carboplatin and oxaliplatin are widely applied for the treatment of various types of tumors. However, poor solubility, serious side effects, and more importantly, the intrinsic and acquired resistance limit their clinical applications. These factors motivate scientists to design and synthesize novel and more potent analogues lacking disadvantages of clinical platinum drugs. Platinum (IV) complexes are one of representatives. In this review, we summarized the investigations undertaken into Platinum (IV) antitumor compounds since Rosenberg first noted their antitumor activity. The synthesis method and mechanism of action of Platinum (IV) complexes are outlined, as well as their chemical and pharmacological properties. Recent advances in Platinum (IV) anticancer agents that have been in clinical trials and photoactivatable Platinum (IV) complexes are also summarized, and the purpose here is to provide insight into the requirements for the antitumor activity of Platinum (IV) complexes and a basis for progressing in a new platinum compound.

Study on Preparation and Application of Ti/Si Complex Zeolite

A Ti/Si complex zeolite has been prepared. X-ray diffraction and infrared spectrometry study has shown that two structures, namely the ZSM-5 and MCM-41, exist in the sample. BET tests have revealed that the complex zeolite contains regular mesopores of 2.6 nm. Ultraviolet spectrometry analysis has shown that the Ti species exist in the zeolite skeleton in the form of tetra-coordinate valence. The Ti/Si complex zeolite (TS-1/Ti-MCM-41) has apparently improved catalytic activity with respect to the macromolecular organic compound oxidation as compared to individual components of either Ti or Si containing zeolites (TS- 1 and Ti-MCM-41).

ELECTROCHEMICAL STUDIES OF TITANIUM(IV)IN 1-METHYL-3-ETHYLIMIDAZOLIUM CHLORIDE

A Titanium tetrachloride-1-methyl-3-ethytimidazolium chloride melt has been prepared.The reduction process of Ti(IV)appears to be diffusion controlled in the composition of 0.4:1 mole ralio of TiCl_4-1-methyl-3-ethylimidazolium chloride and the electrochemical behavior of Ti(IV)shows remarkable compositon dependence.

Asymmetric Trimethylsilylcyanation of Benzaldebyde Catalyzed by Novel Ti(Ⅳ)-Chiral Schiff Base Complexes

Benzaldehyde has been trimethylsilylcyanated with a catalyst prepared in situ from titanium tetraisopropoxide and chiral Schiff bases. Cyanohydrin is obtalned in moderate e.e.values

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 Characterization of Oxy-Vanadium （Ⅳ） Complex of 4-（2, 4-dihydroxybenzaldimine） Antipyrine

The reaction of VCl3 with 4-（2, 4-dihydroxybenzaldimine） antipyrine （LH） in a l ： 1 molar ratio results in formation of the general complex of [VOL（CI）OH]. The nature of bonding and stereochemistry of the complex was deduced from the elemental analysis, IR, UV-Vis, 1H and ^13C NMR spectroscopy. This complex has a coordination number five （square pyramidal） as known for many vanadyl complexes. The formation of the vanadyl ion （VO^2＋） and the mode of bonding of the Schiff base through the oxygen of the pyrazol ring and the nitrogen of the azomethine group to the vanadyl ion were established by IR technique.

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.

Fe/Ti/Si复合纳米微粒光催化降解NO_2

采用溶胶 凝胶法制备了Ti/Si和不同浓度Fe3 + 掺杂的Fe/Ti/Si复合纳米粉末 ,并利用XRD、BET、UV vis等技术手段研究了Ti/Si及掺铁形成的Fe/Ti/Si复合微粒的表面结构形态变化 ,以及对污染物NO-2 光催化降解的影响。研究表明 ,Fe/Ti/Si复合微粒的催化活性高于Ti/Si体系 ,并且Fe/Ti/Si[ω(Fe3 + ) =1 .5% ,m(Ti) m(Si) =2 1 ]具有最佳活性 ,样品呈晶化度较低的锐钛矿结构。Fe3 + 掺杂导致晶粒的增大 ,稳定性降低 ,大大提高了半导体的光催化活性 ,有利于对低浓度NO-2 的光催化降解。

络合氢化物Ti-NaAlH_4的制备与储氢特性

采用Ti粉为催化剂前驱体、预处理Al粉和NaH为合成原料,通过机械球磨-加氢方法合成出络合氢化物Ti-NaAlH4,系统研究了球磨保护气氛、球磨时间和氢化加氢压力等制备参数对其储氢性能的影响.结果表明,制备方法对Ti-NaAlH4储氢特性有很大影响.与氩气保护气氛相比,在氢气气氛中球磨制备的复合物具有更高的吸放氢性能.在氢气保护气氛下,随着球磨时间从6h增至24h,复合物的吸氢容量和吸氢速率先增后减,12h时达到最佳值,而复合物的放氢容量和放氢速率则逐渐增高;进一步延长球磨时间会使颗粒发生团聚,从而导致吸氢性能下降.随着氢化加氢压力从7.5MPa升至13.5MPa,复合物的吸氢容量(质量分数)由2.83%逐渐增至4.21%.复合物球磨后出现的Na3AlH6中间氢化物相表明,在氢气下掺Ti球磨对NaH和Al的氢化反应起到很好的促进作用.

CuNi-VTiFe复合型矿化镁铁-超镁铁杂岩体岩相学及岩石地球化学特征:以新疆北部为例

铜镍硫化物矿床和钒钛磁铁矿矿床是镁铁-超镁铁杂岩重要的矿床类型,但二者共生的情况在国内还不多见。新疆北部这类铜镍-钒钛铁复合型矿化岩体较为发育,目前已发现有香山、牛毛泉、土墩南和哈拉达拉等4个岩体属于此类。它们的成岩时代多集中在早二叠世,出露面积在2.8～22km^2,介于通道型铜镍矿化小岩体和大型层状岩体之间,韵律构造发育;岩石组合为超基性-基性-中性岩类,以出现浅色的闪长岩或淡色辉长岩为特点,岩石中金属矿物氧化物(钛铁矿、磁铁矿)和硫化物(黄铁矿、磁黄铁矿、黄铜矿,有时有镍黄铁矿)共存和共生;含矿岩石组合和岩石化学特征与典型铜镍硫化物矿床和钒钛磁铁矿矿床相比,具有重叠和过渡特征;稀土和微量元素特征反映出杂岩体不同岩石类型可能具有相同或相似岩浆来源,是经过强烈分异和演化的产物。新疆北部这类复合型矿化,与北疆地区典型铜镍矿床和典型钒钛磁铁矿矿床,共同构成了新疆北部后碰撞幔源岩浆矿床成矿谱系。