Synthesis,Crystal Structure and Biological Activities of Novel Di-n-butyl Tin Di-carboxylate

A novel macrocyclic complex 2{[（n-Bu2Sn）4O2-L2]2DMF} was synthesized by the reaction of 4-（1,2- dithioethylene）methylene-3,5-disoxo-1,6-heptadiene-1,7-dis-（o-formy~）-dis-p-phenoxyacetic acid（LH2, compound 1） with di-n-butyltin oxide. Compound 1 and complex 2 were characterized by elemental analysis, FTIR spectroscopy, and ~H NMR spectroscopy. The crystal structure of complex 2 was determined by single crystal X-ray diffraction analysis. There are two crystallographic independent molecules in complex 2, and each molecule structure is centro-symmetric and features a central rhombus cyclic Bu4Sn2O2 unit with two exocyclic Sn atoms linked at the O atoms of the four-membered ring. In molecule A, the four Sn atoms are five-coordinated. However, in molecule B, the four Sn atoms have two different coordination geometries, the endocyclic Sn atoms are five-coordinated and the exocyclic Sn atoms are four-coordinated. The dicarboxylate ligands in molecules A and B bridge exocylic or endocyclic tin atoms, forming two macroheterocycles with 26 atoms. Pilot studies have indicated that complex 2 has good anti- bacterial and antitumour activities.

Syntheses and Crystal Structures of Two Mononuclear Tin(IV) Complexes Derived from Sn(edt)_2(edt = Ethane-1,2-dithiolate)

Two mononuclear tin(IV) complexes, [Sn(pda)2(edt)2] (pda = o-phenylenediamine) (C16H24N4S4Sn, Mr = 519.32) 1 and [Sn(eda)(edt)2] (eda = ethylenediamine) (C6H16N2S4Sn, Mr = 363.14) 2 were synthesized and characterized by X-ray structure analysis. 1 belongs to trigonal, space group P-3c1 with a = b = 20.0280(6), c = 8.7679(5) ? V = 3045.8(2) ?, Z = 6, Dc = 1.699 g/cm3, m = 1.677 mm-1, F(000) = 1572, the final R = 0.0418 and wR = 0.1019 for 1805 independent reflections. 2 crystallizes in monoclinic, space group P21/c with a = 10.911(3), b = 9.783(2), c = 11.831(3) ? b = 100.28(2), V = 1242.6(6) ?, Z = 4, Dc = 1.941 g/cm3, m = 2.690 mm-1, F(000) = 720, the final R = 0.0280 and wR = 0.0627 for 2166 independent reflections. Both Sn4+ ions in these two complexes are six-coordinated with a slightly distorted octahedral configu- ration.

A New Biosensor for Glucose Based on Screen Printed Carbon Electrodes Modified with Tin (IV)-Oxide

Tin (IV) oxide was used as a bulk mediator in carbon paste and carbon ink screen-printed electrodes to improve the better performance of the carbon electrodes for the detection of hydrogen peroxide in comparison with unmodified electrodes. A new glucose biosensor developed from modified carbon paste electrode and coated with glucose oxidase entrapped in Nafion was investigated with a flow injection system. The biosensor could be operated under physiological conditions (pH 7.5, 0.1 M phosphate buffer), with an operating potential of ?200 mV (vs. Ag/AgCl), a flow rate of the carrier of 0.2 mL/min. and an injection volume of 100 μL. The amperometric response of the biosensor showed good linearity up to 200 mg/L with a detection limit (3σ) of 6.8 mg/L. The relative standard deviation for the repeatability of measurements for 100 mg/L glucose was 2.9% (n = 10 measurements) and the corresponding reproducibility was 12% (n = 5 sensors). The effect of all investigated interferences (uric acid, paracetamol, xanthine, hypoxanthine and ascorbic acid) was not fatal and could be eliminated by the use of the standard addition method. The new biosensor was successfully applied to the determination of glucose in human blood plasma.

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.

Stabilization of Nanoscale Tin（IV） Oxide on the Surface of Carbon Nanotubes

Surface of oxidized multiwalled carbon nanotubes was investigated for stabilization of nanosized tin（IV） oxide. The synthesis of nanosized tin（IV） oxide on the surface of carbon nanotubes was carried out with the use of three soft chemical methods： sol-gel, precipitation, and thermal. The synthesized tin（IV） oxide particles on the surface of carbon nanotubes were studied by thermal analysis, X-ray diffraction and electron microscopy. The lattice parameters of tin（IV） oxide on the surface of multiwalled carbon nanotubes were calculated.

Syntheses and Crystal Structures of Two Tin(Ⅳ) Complexes with Aminosilane Bearing Ligand

Aminosilane bearing bulky substituents on nitrogen： LH2 （L = Me2Si（NDipp＇）2, Dipp = 2,6-diisopropylphenyl） was reacted with BuLi in toluene. The resulting bulky chelating dianion Me2Si（NDipp）2 was used to synthesize the unusual spirocyclic heterotriatomic complex [MeESi（NDipp）2]ESn （1） by its reaction with SnCl4 and the bulky heterotriatomic complex Me2Si（NDipp）2SnPh2 （2） with Ph2SnC12. 1 belongs to the monoclinic system, space group P21/n with a = 13.193（2）, b = 20.663（3）, c = 20.403（3）A, β = 99.954（2）°, V = 5478.3（15） A3, C55H85.5N4Si2Sn, Mr = 977.64, Z = 4, Dc. = 1.185 Mg/m3, μ（MoKa） = 0.547 mm-1, F（000） = 2086, S = 1.000, the final R = 0.0614 and wR = 0.1322 for 14446 observed reflections （1 〉 2σ（I）） and R = 0.0797 and wR = 0.1456 for all data. 2 belongs to the triclinic system, space group P1 with a = 10.36（15）, b = 13.204（7）, c = 14.363（7） A, a = 90.214（10）, β = 106.182（7）, y = 109.854（8）°, V = 1764.4（15） A3, C38HsoN2SiSn, M,. = 681.58, Z = 2, Dc = 1.283 Mg/m^3,μ（MoKa） = 0.785 mm-1, F（000） = 712, S = 1.002, the final R = 0.0498 and wR = 0.0955 for 7533 observed reβections （I 〉 2σ（I）） and R = 0.0676 and wR = 0.1018 for all data. In the structure of 1, the tin atom is located in the spirocyclic center of the two fused four-membered SnN2Si rings. The two complexes were characterized by ^1H NMR, elemental analysis, and single-crystal X-ray structural analysis.

Synthesis, Crystal Structure and Quantum Chemistry of Tris[(2-methyl- 2-phenyl)propyl](2,4-dinitro-phenolato)tin

The tris[（2-methyl-2-phenyl）propyl]（2,4-dinitro-phenolato）tin was synthesized by the reaction of bis[tri（2-methyl-2-phenyl）propyltin] oxide with 2,4-dinitrophenol. The compound was characterized by IR, 1H NMR spectra and elemental analysis. The crystal structure has been determined by X-ray diffraction. The crystal belongs to the monoclinic system, space group P21/n with a = 0.9649（0）, b = 1.0087（8）, c = 3.4867（4） nm, β = 90.965（7） , Z = 4, V = 3.3933（7） nm3, Dc = 1.369 Mg·m-3, （MoKa） = 0.796 mm-1, F（000） = 1440, R = 0.0345 and wR = 0.0821. The tin atom has a distorted tetrahedral geometry. The 2D network structure of the complex is formed by hydrogen bonds and π-π effects. The stabilities, orbital energies and composition characteristics of some frontier molecular orbitals of the complexes have been investigated with the aid of G98W software.

五配位阴离子型有机锡化合物[HNR_3][MeCy_2ClSnO_2CCH_2CO_2SnClCy_2Me]的合成及生物活性研究

在有机胺的存在下,MeCy2SnCl与HOOCCH2COOH反应,得到了一系列的五配位阴离子型有机锡化合物,分子结构通式为:[Q][MeCy2ClSnO2CCH2CO2SnClCy2Me](Q=HNR3=H2NEt2(1),HNEt3(2),H2N(i-Pr)2(3)),并通过IR,1H NMR,元素分析对这些化合物进行了表征.测定了[H2N(i-Pr)2]2[MeCy2ClSnO2CCH2CO2SnClCy2Me](3)的晶体结构.结果表明,分子由一个二价阴离子和两个二异丙基胺阳离子组成.锡原子为变形的三角双锥结构,氧原子和氯原子处于竖直轴上.阴阳离子之间通过氢键(N-H…O,N-H…C)相连接,氮原子和氧原子及氮原子和氯原子之间的距离分别为2.798和3.189.测定了化合物的体外抗肿瘤活性和杀菌活性,结果表明该类化合物具有很强的体外抗肿瘤活性和杀菌活性.

透明隔热玻璃涂料的研制

通过掺杂钨,制备了具有常温相转变功能的二氧化钒粉体,采用特殊的研磨工艺,将掺钨二氧化钒粉体和氧化锑锡(ATO)粉体分散成亚纳米或纳米浆料,并将这些浆料直接添加到水性聚氨酯涂料中,从而得到具有一定智能功能的透明隔热保温涂料。该涂料对玻璃附着力好,近红外透过率可调,可广泛用于建筑和汽车玻璃,具有很好的节能效果。

非晶态磷酸锡去除高盐介质中Pb(Ⅱ)研究

利用合成的非晶态磷酸锡作为吸附剂,研究了多种因素(pH、吸附时间、初始浓度、温度、离子强度)对吸附剂吸附水溶液中Pb2+的影响。结果表明,非晶态磷酸锡对Pb2+的吸附量随着pH(3～6)以及吸附时间的增大而增加。用Freundlich、Langmuir模型对等温吸附数据进行处理,Langmuir方程拟合效果最好,20℃时饱和吸附量达到377.36 mg/g。Dubinin-Radushkevich(D-R)模型研究表明,吸附机理属于化学离子交换。反应机理为非晶态磷酸锡中的H+与溶液中的Pb2+发生了离子交换反应。吸附过程的热力学研究表明,非晶态磷酸锡对Pb2+的吸附是一个自发的,吸热的过程,升温有利于吸附。离子强度实验结果表明,高盐强度对非晶态磷酸锡吸附Pb2+有一定的不利影响,但幅度不大,可以用于去除养殖海水中的Pb2+。所吸附的Pb2+可以用HCl解吸,说明非晶态磷酸锡具有重复利用的潜能。

SnCl_4·5H_2O催化合成氯乙酸丁酯

报道了用SnCl4·5H2 O作催化剂合成氯乙酸丁酯 ,最佳合成条件为正丁醇、氯乙酸及催化剂的摩尔比为 2∶1∶0 0 0 5 ,反应时间 2 .5h 该方法酯化率为 97 5 % ,收率为 93 6 % ,反应时间短 ,无腐蚀 。

巯基葡聚糖凝胶分离富集动力学光度法测定痕量锡

基于稀硫酸介质中,痕量锡（Ⅳ）催化溴酸钾氧化偶氮氯膦Ⅲ（CPAⅢ）的褪色反应,建立了测定痕量锡（Ⅳ）的催化动力学光度法。方法检出限为0.25μg·L^-1,线性范围为0.0～8.0μg·L^-1。结合巯基葡聚糖凝胶（MDG）分离富集,用于测定环境水样、人发及岩石样品中痕量锡（Ⅳ）,结果的RSD值均在9.0%以内,回收率在96.0%～103.0%之间。分析了3种岩石标准物质,所得结果与证书值相符。

夹心杂多化合物的合成及晶体结构

PW_9O_(34)^(9-)(简写PW_9)阴离子可以与Sn^(4+)反应生成[Sn_3~Ⅳ(PW_9O_(34))_2]^(6-)杂多化合物.标题化合物经元素分析、红外、极借、^(31)P和^(183)W核磁共振谱、X射线光电子能谱及X射线单晶测定了结构.K_5O_4Na_4H_5[Sn_3(PW_9O_(34))_2]·16H_2O的单晶是单斜晶系,空间群P2_1/n,晶胞参数a=1.3625(3)nm,b=2.3625(5)nm,c=2.9306(6)nm,α=90°,β= 99.67(3)°,γ=90°,V=9.299nm^3,Z=4.它是一种三个Sn^(4+)在两个PW_9单元间的夹心结构.

硅藻土负载无定形磷酸氢锡吸附Pb(Ⅱ)、Cu(Ⅱ)和Zn(Ⅱ)研究

以天然硅藻土为载体,制备了硅藻土负载无定形磷酸氢锡复合材料。利用该材料去除废水中的Pb(Ⅱ)、Cu(Ⅱ)和Zn(Ⅱ),研究了p H值、吸附时间、初始质量浓度对吸附性能的影响,探讨了材料的等温吸附规律,同时考察了材料在模拟海水中的吸附效果及再生能力。结果表明,硅藻土负载无定形磷酸氢锡对Pb(Ⅱ)、Cu(Ⅱ)和Zn(Ⅱ)的吸附量随p H值和吸附时间增大而逐渐增大并趋于平衡。等温吸附数据用Freundlich方程拟合效果最好,25℃时的饱和吸附量分别为27.54 mg/g、19.94 mg/g和16.33 mg/g。复合材料对3种离子的吸附机理均以化学吸附为主,在吸附Pb(Ⅱ)的过程中孔内扩散为速控步骤。高盐度对材料吸附Pb(Ⅱ)、Cu(Ⅱ)和Zn(Ⅱ)有一定的不利影响,但幅度不大,可以用于去除养殖海水中的Pb(Ⅱ)、Cu(Ⅱ)和Zn(Ⅱ)。吸附了重金属离子的复合材料可以用稀HCl再生,具有重复利用的潜能。

单扫示波极谱法连续测定水样中锑和锡

在pH 2.1的H_2SO_4-NaOAc介质中,有微量Se(Ⅳ)存在时,Sb(Ⅱ)或Sn(Ⅳ)—草酸铵—α,α′-联吡啶络合物产生灵敏的络合吸附催化波。锑和锡浓度分别在0.5～200ng·ml^(-1)和0.8～250ng·ml^(-1)范围内与峰高呈线性关系。锑和锡的检出限分别为0.2ng·ml^(-1)和0.4ng·ml^(-1)。方法用于水样中痕量锑、锡的连续测定,结果满意。

无毒增塑剂柠檬酸三丁酯的绿色催化合成

以锡粉和碘代正丁烷为原料合成了氧化二正丁基锡,研究了以氧化二正丁基锡为催化剂合成无毒增塑剂柠檬酸三丁酯（TBC）,考察了催化剂用量、醇酸物质的量比、反应温度等因素对反应结果的影响,对产品进行了表征。实验结果表明,氧化二正丁基锡催化合成柠檬酸三丁酯的最佳条件为：n（正丁醇）∶n（柠檬酸）=4.5∶1,催化剂用量为柠檬酸质量的0.5%,反应温度120~130℃,在最佳反应条件下,柠檬酸三丁酯收率可达98%以上。

四卤化锡混合物中受扩散控制的卤原子交换动力学研究

以1 1 9SnNMR方法研究了四氯化锡和四溴化锡混合物 (1∶1 ,摩尔比 )交换体系在不同条件下的动力学性质 .测定了在不同浓度的氘代氯仿溶液中 5个交换组份的表观纵向弛豫时间 (T1 )及 5个组份相互间的交换速率常数 (k) ,结果表明交换速率常数与表观纵向弛豫速率成正比关系 ;同时 ,根据1 1 9Sn 1DNMR信号的线宽估测了有效横向弛豫时间 (T 2 ) ,并由T1 /T 2 推断在所研究的体系中分子的运动属NMR慢运动极限 .从实验结果可推断在所研究的复杂交换体系中 5个组份间的交换与分子自扩散运动有关 ,即化学交换与交换主体的扩散运动有必然的联系 .

新型离子型有机锡化合物[C_5H_5NH]_2[PhSn(μ~2-SCH_2COO)Cl_3]的合成及晶体结构

在吡啶存在下,PhSnCl_3与HSCH_2COOH反应,得到了六配位阴离子型有机锡化合物[C_5H_5NH]_2[PhSn（μ^2-SCH2COO）Cl3],并通过IR、^1H NMR和元素分析对该化合物进行了表征,测定了晶体结构.结果表明,化合物为八面体结构,阴阳离子之间通过氢键相连接.晶体为单斜晶系,空间群为P21/n,a=0.8817（3）nm,b=0.841 8（3）nm,c=2.886 8（10）nm,β=96.195°,Z=4.

新型液相色谱固定相──单烷基磷酸锡的合成

合成了中间体单烷基磷酸和３种单烷基磷酸盐（十六烷基、十二烷基和辛基磷酸锡）并测定了其组成和结构。

多西他赛与顺铂单药化疗同期放疗治疗非手术食管癌的对照研究

目的比较多西他赛与顺铂单药化疗同期放疗治疗非手术食管癌的疗效及安全性。方法方便收集2011年1月—2013年2月在该院住院治疗的失去手术治疗机会的原发性食管癌患者70例。根据治疗方法分为顺铂组35例和多西他赛组35例。所有患者均接受相同放疗方案,多西他赛组在放疗同期给予多西他赛治疗;顺铂组患者在放疗同期给予顺铂治疗。比较两组的生存期、近期疗效及不良反应发生情况。结果顺铂组生存时间、1年生存率分别为(20.2±3.2)个月、60.0%,多西他赛组分别为(21.0±4.5)个月、57.1%,两组比较差异无统计学意义(P>0.05),多西他赛组的近期有效率为100.0%,明显高于顺铂组的82.9%(P<0.05)。结论多西他赛联合同期放疗对非手术食管癌的有效率较高,毒副作用较轻,值得临床借鉴推广。