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.

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.

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.

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.

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.

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。

四氯·两个二(2-乙基已基)硫醚合铂(IV)配合物的合成及其分子结构

用萃取法合成了[Pt(DEHS)_2Cl_4],对配合物进行了元素分析,摩尔电导,差热一热重和红外光谱等测试并经X射线单晶结构分析确定了配合物的结构。

L-吡咯烷功能化Zr(IV)金属有机骨架配合物的合成和催化不对称Aldol反应研究

设计合成了L-脯氨甲胺三联苯-4,4’-二甲酸配体(H2L)及其Zr(IV)-金属有机骨架配合物Zr6O4(OH)4(L)6(I),并研究了配合物I催化对硝基苯甲醛和环己酮的不对称羟醛缩合反应,催化反应具有适中的产率(60%)和较低的对映选择性(1.5%),催化产物的dr值为26∶74(anti/syn),以顺式异构体为主.

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.

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.

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。

Encapsulated Fe(IV)Molecular Complex for Photoacoustic Imaging

stable neutral Fe(IV)complex(Fe-HDCL),readily accessible on the g scale,was found to possess high water solubility and good stability(<5%degradation over 4 h upon photoirradiation).Fe-HDCL is green and absorbs light effectively in the visible region(500–800 nm)with aλmax at 650 nm(ɛ=7830 M^(−1)cm^(−1)).Fe-HDCL also exhibits photothermal(PT)behavior comparable to single-wall carbon nanotubes in the solid state.In aqueous solution,high PT conversion(η=72.6%)is achieved,and a strong hyperthermia-based inhibition of cell growth is observed upon subjecting Fe-HDCL to near-infrared 730 nm laser photoirradiation.Initial biological studies in vitro and in vivo confirmed that Fe-HDCL is biocompatible,clears readily,and allows the visual detection of blood vessels.Upon subjecting mice to intravenous injection at low doses(e.g.,50μmol·kg^(−1)),Fe-HDCL also permits the photoacoustic(PA)imaging of kidneys and the evaluation of renal fibrosis in mouse models.In addition,Fe-HDCL allows PA-based imaging of brain tissues,presumably reflecting its ability to pass through the blood-brain barrier.We thus propose that Fe-HDCL has a role to play as PT agent and as a photodiagnostic.

丁基苯酞对原代培养神经元线粒体功能的保护作用

目的：探讨丁基苯酞（butylphthalide,NBP）对原代培养神经元在低糖低氧损伤下的保护作用及线粒体作用机制。方法：采用Hoechst 33342和PI共染的方法,观察NBP对低糖低氧损伤造成神经细胞坏死和凋亡的影响,并用荧光探针标记以及分光光度法检测NBP对神经细胞线粒体膜电位、线粒体膜流动性及线粒体呼吸链复合酶IV活性的影响。结果：NBP（10-6-10-4mol/L）能显著减少低糖低氧引起的神经细胞坏死和凋亡;机制研究表明它能明显改善由损伤引起的神经细胞线粒体膜电位、线粒体膜流动性及线粒体呼吸链复合酶IV活性的降低。结论：NBP对低糖低氧损伤导致的神经细胞坏死和凋亡具有良好的保护作用,而线粒体保护可能是其作用机制之一。

长期运动对老年小鼠骨骼肌线粒体复合物的影响

目的 :研究长期运动训练对老年小鼠骨骼肌线粒体复合物I和复合物Ⅳ活性的影响 ,并探讨其机制。方法 :以C57BL/6J雄性小鼠跑转笼为运动方式 ,通过分光光度法和极谱氧电极法测定线粒体复合物I和复合物Ⅳ的活性。结果 :随着小鼠年龄的增长 ,骨骼肌线粒体复合物I(NADH脱氢酶)活性显著下降 ,复合物IV(细胞色素氧化酶 )活性无明显变化。经过8个月运动训练的小鼠骨骼肌线粒体复合物I及复合物IV活性明显升高 ,显著高于同龄对照鼠甚至高于5月龄鼠。结论 :运动训练在一定程度上致骨骼肌线粒体功能产生适应性变化。

水相法合成双(环戊二烯基)钛氨基酸配合物的研究

以Ｎ－（取代苯基）氨基乙酸及盐与双（环戊二烯基）二氯化钛在水相及有机相反应，得到了五个双（环戊二烯基）钛氨基酸配合物，对配合物进行了熔点、元素分析、ＩＲ及＾１ＨＮＭＲ的表征，确定了它们的结构。这些配合物在空气中稳定。经比较，水相中的合成反应速度快，操作简单，产物较易分离，产率高。

丹参多酚酸盐保护家兔心肌缺血再灌注损伤的机制研究

目的观察丹参多酚酸盐对家兔心肌缺血再灌注损伤的保护机制。方法家兔24只,按随机数字表法分为对照组、模型组、丹参多酚A、B组,采用丝线结扎家兔左冠状动脉前降支30 min后复灌30 min,并反复3次缺血再灌注的方法造模,对照组不造模。造模后丹参多酚A、B两组经耳缘静脉注射丹参多酚酸盐[按2 mg/（kg·d）、4 mg/（kg·d）],模型组注射等量0.9%氯化钠注射液。注射1周后检测家兔心肌线粒体呼吸链酶复合体Ⅰ~Ⅳ的活性;家兔静脉血清高敏C反应蛋白（hs-CRP）、血清肌钙蛋白Ⅰ（c Tn I）、乳酸脱氢酶（LDH）、总超氧化物歧化酶（T-SOD）、肌酸激酶同工酶（CK-MB）、心肌丙二醛（MDA）。结果丹参多酚A、B组Ⅰ~Ⅳ及T-SOD、CK-MB等酶的活性明显提高,hs-CRP、c Tn I、LDH、MDA明显降低,与模型组比较,差异均有统计学意义（P〈0.05）。丹参多酚A、B组组间比较,差异无统计学意义（P〉0.05）。结论丹参多酚酸盐能够相对提高缺血心肌线粒体呼吸链酶复合体Ⅰ~Ⅳ及T-SOD活性,减少氧自由基造成的脂质过化反应,改善缺血心肌能量代谢而实现对缺血再灌注损伤心肌的保护。