有机锡二聚体对醛的选择性催化

以Bu2SnO与CF3SO3H(TfOH)直接反应合成了有机锡二聚体[Bu2Sn(OH)(OTf)(H2O)]2, 以[Bu2Sn(OH)(OTf)(H2O)]2为催化剂考察了醛的硅氢化反应. 与传统的路易斯酸催化剂相比, 有机锡二聚体催化剂不仅具有合成简单、贮存容易、使用方便、易于分离、用量少和催化效率高等优点, 而且对醛基的还原催化具有很高的选择性, 且不受分子内和反应体系中其它羰基化合物或可还原基团的影响.     

基于邻香草醛缩2-氨基-4-硝基苯酚的Schiff碱有机锡配合物的合成、晶体结构及生物活性

邻香草醛缩2-氨基4-硝基苯酚(H₂L)分别与二丁基氧化锡、二苄基二氯化锡反应, 合成了二丁基锡Schiff碱配合物(1)和单苄基Schiff碱配合物(2)。配合物经元素分析、¹H NMR、¹³C NMR、IR、UV-Vis表征, 并用X-射线单晶衍射测定了分子结构。研究了配体H₂L及配合物1、2对癌细胞Hela、MCF7、HepG2、Colo205、NCI-H460的抑制活性, 结果表明配合物1对这5种癌细胞的抑制效果优于现有抗癌药物卡铂, 可作为抗癌药物的候选化合物。在Tris缓冲溶液中, 以EB做为荧光探针, 用荧光光谱法研究了配体H₂L及配合物2与鲱鱼精DNA的相互作用, 结果表明配合物与DNA作用主要是由于Schiff碱配体协同效应所致。     

羧酸桥联的四核镧系簇合物的磁热效应和慢磁弛豫

在水热条件下,通过使用羧酸和螯合配体得到了一个系列的四核镧系簇合物,即[Ln₄(mnba)₁₂(tzp)₂(H₂O)₂](Ln=Gd(1),Tb(2),Er(3);Hmnba=间硝基苯甲酸;tzp=2-(1H-1,2,4-三唑-3-基)吡啶))。这3个化合物是同构的,且具有线性的四核簇结构。磁性研究表明,化合物1和3中簇内镧系离子之间是弱铁磁耦合的,但化合物2中铽离子之间是弱的反铁磁相互作用和(或)铽离子激发的斯塔克能级的去布居。化合物1具有较大的磁热效应(-ΔS_m^max=20.6 J·kg^-1·k^-1)。交流磁化率测试表明化合物3展现出频率和温度依赖的虚部信号,这是慢磁弛豫的典型特征,原因是铒离子的强各向异性和铁磁耦合的存在。     

两个有机锡对碘苯甲酸酯的合成、结构、热稳定性和除草活性

在乙醇-苯溶剂中,对碘苯甲酸分别与三苯基氢氧化锡、二丁基氧化锡反应,合成了2个有机锡对碘苯甲酸酯,Ph3Sn(p-IC6H4O2)(1)和{[n-Bu2Sn(p-I-C6H4O2)]2O}2(2)。经IR、1H NMR、元素分析和X射线单晶衍射对配合物进行了表征。配合物1属三斜晶系,空间群为P1,中心锡原子与苯基碳原子、羧基氧原子构成畸型四面体,并且分子间通过氢键和C-I…π共同作用形成二聚体结构;配合物2属单斜晶系,空间群为C2/c,配合物是以Sn2O2构成的平面四元环为中心的二聚体结构,并且分子间通过I…I共同作用形成了一维链状结构。热重分析表明,配合物1和2在230℃以下具有良好的热稳定性。配合物1、2对杂草刺苋(Amaranthus spinosus)、马齿苋(Portulaca oleracea)的抑制活性大于对农作物绿豆的影响,且配合物1的抑制活性高于配合物2的抑制活性,为刺苋、马齿苋除草剂研究提供了一种方法。     

Catalytic Behavior of Mono-N-Protected Amino-Acid Ligands in Ligand-Accelerated C−H Activation by Palladium(II)

Mono-N-protected amino acids (MPAAs) are increasingly common ligands in Pd-catalyzed C−H functionalization reactions. Previous studies have shown how these ligands accelerate catalytic turnover by facilitating the C−H activation step. Here, it is shown that MPAA ligands exhibit a second property commonly associated with ligand-accelerated catalysis: the ability to support catalytic turnover at substoichiometric ligand-to-metal ratios. This catalytic role of the MPAA ligand is characterized in stoichiometric C−H activation and catalytic C−H functionalization reactions. Palladacycle formation with substrates bearing carboxylate and pyridine directing groups exhibit a 50–100-fold increase in rate when only 0.05 equivalents of MPAA are present relative to Pd^II. These and other mechanistic data indicate that facile exchange between MPAAs and anionic ligands coordinated to Pd^II enables a single MPAA to support C−H activation at multiple Pd^II centers.     

Organotin(IV) complexes of NSAID,ibuprofen, X-ray structure of Ph3Sn(IBF), binding and cleavage interaction with DNA and in vitro cytotoxic studies of several organotin complexes of drugs

This study encompasses the synthesis and characterization of organotin(IV) derivatives of non-steroidal anti-inflammatory drug ibuprofen (IBF), viz. [(Me₃Sn)(IBF)] ( 1 ), [(Bu₃Sn)(IBF)] ( 2 ), [Ph₃Sn(IBF)] ( 3 ), {[Me₂Sn(IBF)]₂O}₂ ( 4 ) and [Bu₂Sn(IBF)₂] ( 5 ). The crystal structure of complex 3 , [Ph₃Sn(IBF)], indicates a highly distorted tetrahedral (td) geometry with anisobidentate mode of coordination of the carboxylate group with tin atom, and a similar structure has been proposed for other two triorganotin(IV) derivatives. Moreover, the DFT (density functional theory) calculation and other studies have verified a dimer distannoxane type of structure for complex 4 , {[Me₂Sn(IBF)]₂O}₂. Complex 5 has been found to exhibit a highly distorted octahedral geometry around the tin atom. To investigate the DNA binding profile of the synthesized complexes, viscosity measurement, UV–vis and fluorescence titrations were performed, which revealed an intercalative type of binding with DNA for IBF and complex 5 and external binding in case of the complexes 1 and 2 ; complexes 3 and 4 could not be studied owing to their insufficient solubility in tris buffer. Plasmid DNA fragmentation studies of IBF and complexes 1 , 2 and 5 indicate that they cleaved the pBR322 plasmid potentially. Further, the drugs IBF {2-[4-(2-methylpropyl)phenyl]propanoic acid}, MESNA (sodium 2-mercaptoethane-sulfonate), warfarin [2H-1-benzopyran-2-one,4-hydroxy-3-(3-oxo-1-phenylbutyl)], sulindac (2-{5-fluoro-1-[(4-methanesulfinylphenyl) methylidene]-2-methyl-1H-inden-3-yl}acetic acid) and their corresponding organotin(IV) complexes 1–19 (complexes 6–19 were synthesized/reported previously) were screened in vitro for cytotoxicity against human cancer cell lines viz. DU145 (prostate cancer), HCT-15 (colon adenocarcinoma), Caco-2 (colorectal adenocarcinoma), MCF-7 (mammary cancer), LNCaP (androgen-sensitive prostate adenocarcinoma) and HeLa (cervical cancer), through MTT reduction assay and the cause of cell death was investigated through acridine orange/ethidium bromide staining of cells and DNA fragmentation assay. The probable structure–cytotoxicity relationship is also discussed. The major role of apoptosis along with small necrosis was also validated by flow cytometry assay using annexin V–fluorescein isothiocyanate and propidium iodide analysis.     

以单环有机锡配合物为载体的水杨酸根阴离子选择电极的研究

Two new cyclic pentacoordinative organotin(Ⅳ) complexes, 2,4-dihydroxyacetophenone tribenzyltin(HAPTBT) and 2,4-dihydroxyacetophenone triphenyltin(HAPTPT) were synthesized and used as anion ionophore for PVC membrane electrode. The new electrodes exhibit specificity selectivity for salicylate. The electrode based on HAPTBT as a neutral carrier displays a highly potentiometric response to salicylate and an anti-Hofmeister selectivity sequence in the following order: Sal^- ＞ SCN^- ＞ I^- ＞ NO₂^- ＞ Br^- ＞ Cl^- ＞ ClO₄^- ＞ NO₃^- ＞ SO₄^2-. The electrode has the advantages of fast response, stability and reproducibility, simplicity. The response mechanism is discussed in view of UV spectroscopy technique. The results show that there are close relationship between the potentiometric response characteristics and structure of organotin(Ⅳ) complexes. The electrode was applied to medicine analysis with satisfactory results.     

硅凝胶体系中不同结构羧酸钾对草酸钙结晶的影响

采用扫描电子显微镜(SEM)和X射线衍射(XRD)方法研究了硅凝胶体系中不同种类羧酸钾对草酸钙(CaC₂O₄)晶体生长的调控作用. 加入一元醋酸钾(KOAc)只生成一水草酸钙(COM)晶体; 三元柠檬酸钾(K₃Cit)和四元乙二胺四乙酸二钾(K₂EDTA)可诱导二水草酸钙(COD)形成, 且随着其浓度增加, 对COD的诱导能力增加, 而二元酒石酸钾(K₂Tart)同时诱导了COM, COD和三水草酸钙(COT)生成. 随着结晶温度降低, 多元酸钾可以进一步减小COM晶体的比表面积, 增加COD的百分含量, 但K₂Tart诱导COT的能力减弱. 由于诱导COD和COT晶体形成、减小COM的比表面积均有利于防止草酸钙尿石的形成, 因此, 多元羧酸钾可用于草酸钙结石的预防和治疗.     

Synthesis, Spectroscopic Properties and Crystal Structural Characterization of a Triphenyltin(Ⅳ) Complex with 5-Bromonicotinic Acid

A novel organotin complex [Ph3Sn(C2H5OH)(OCOC5H3NBr)SnPh3(OCOC5H3NBr)]has been synthesized by the reaction of 5-bromonicotinic acid with triphenyltin hydroxide in ethanol and characterized by elemental analysis, IR and 1H NMR. The crystal structure was determined by X-ray single-crystal diffraction. The crystal belongs to the monoclinic system, space group P21/c with a = 15.564(2), b = 24.975(4), c = 12.2973(19) (A), β = 92.224(2)°, Z = 4, V = 4776.5(13) (A)3, Dc = 1.596g/cm3, μ(MoKα) = 2.765 mm-1, F(000) = 2264, R = 0.0385 and wR = 0.0667. In the molecular structure of the title complex, the tin atoms are five-coordinated in a trigonal bipyramidal geometry.