三种胺羧配合物的113Cd NMR研究

该文对Cd-HEDTA(N-(2-羟基乙基)乙二胺-N',N',N'-三乙酸),Cd-PDTA(1,2丙二胺四乙酸)和Cd-DTPA(二乙三胺五乙酸)的¹¹³Cd NMR谱和自旋晶格弛豫时间T₁,及NOE因子进行了研究.结果表明,Cd-HEDTA和Cd-PDTA结构与Cd-EDTA类似,Cd-PDTA双线归因于其可能的两种异构体.Cd-DTPA大的化学位移表明其具有七配位的五角双锥结构.在这种结构中DTPA可用三个氮原子参加配位.对¹¹³Cd自旋晶格弛豫时间分析表明,Cd-DTPA配合物中质子偶极作用机理的贡献较大,这归因于Cd DTPA有更多的乙酸根亚甲基质子参与偶极作用.     

含有杂环基侧链的新型聚硅氧烷

含有功能性基团的聚硅氧烷的研究一直是有机硅化学中十分活跃的研究领域之一。当含N、S等杂环引入聚硅氧烷链中后，由于杂环基的生理活性、催化活性及光电特性，因而含不同杂环基团的聚硅氧烷（POS）可分别用作催化剂、光电材料、医学材料等。当用作药物载体时，可提高药物的利用率和靶向性，也可降低某些药物的毒性。含环糊精侧基、冠醚侧基的POS亦可应用于气相色谱固定相、相转移催化剂。本文对近年来有关侧链含有吡啶、咪唑等杂环及环糊精基团等功能性侧基的聚硅氧烷结构、合成、及应用作一详细的评述并进行了展望。     

Ge—132对小鼠H22肝癌移植瘤的影响

Ｇｅ－１３２对小鼠Ｈ２２肝癌移植瘤的实验研究证明：１．Ｇｅ－１３２对Ｈ２２肝癌移植瘤有一定的抑制作用，３００ｍｇ／ｋｇ体重剂量抑瘤率达到３６．１９％；２．增强机体的抗氧化作用，抑制脂质的过氧化物水平；３．促进免疫功能，当Ｇｅ－１３２和环磷酰胺联合使用时，可抵抗环磷酰胺的免疫抑制作用，而且并不减弱其抑制瘤作用。     

核磁共振法(NMR)和pH法研究Zn(Ⅱ)与HEDP(1-羟基乙叉-1,1-二膦酸)的配合物

本文用核磁共振法(NMR)和pH法对Zn(Ⅱ)与1-羟基乙叉-1,1-二膦酸(1-hydroxyethylidenel,1-diphosphonic acid,简称HEDP,以H₄L表示)的配合物进行了研究,由于pH<7时溶液中有沉淀生成,故NMR的研究是在溶液pH>7时进行.测定了溶液中不同Zn(Ⅱ)/HEDP摩尔比和pH值时³¹PNMR的化学位移。研究结果表明在pH7.5-11.0范围内生成Zn(Ⅱ)/HEDP=1(摩尔比)组成的配合物,在pH11.8-12.3范围内生成Zn(Ⅱ)/HEDP=2(摩尔比)组成的配合物,分别用pH法和NMR法测定了上述组成配合物的稳定常数.结果如下: logK_[zn(HL)^-] logK_[znL^2-] logK_[zn2L] pH法 4.69 7.51 11.63 NMR法——6.88-7.19 12.44.     

甲基环戊二烯基希土二氯化物Cp′LnCl2·3THF(Ln=Sm-Er,Y)的合成和表征

本文通过无水三氯化希土与等摩尔的甲基环戊二烯基钠(Cp′Na)在四氢呋喃(THF)中反应，合成了八个新的中性甲基环戊二烯基希土二氯化合物Cp′LnCl₂·3THF［Ln=Sm(1), Eu(2), Gd(3), Tb(4), Dy(5), Ho(6), Er(7), Y(8)］，并研究了茂环上甲基取代基对一茂二氯希土配合物分子结构及稳定性的影响。元素分析、红外光谱和质谱鉴定结果表明这八个化合物都是溶剂化的单体结构，其中配合物7的结构还用单晶X射线分析确证。     

C_（60）化学修饰的PNVC材料的UV－VIS谱研究

本实验采用金属有机化学方法成功地将富勒烯分子引入到ＰＮＶＣ侧链形成ＣＢＰ（ＣｈａｒｍＢｒａｃｅｌｅｔＰｏｌｙｍｅｒ）型共聚功能材料，研究了其ＵＶ－ＶＩｓ谱行为。结果表明，Ｃ_（６０）或Ｃ_（６０）／Ｃ_（７０）混合物化学修饰的产物其紫外可见谱明显向长波方向移动，谱峰范围由２８０ｎｍ扩展至８７０ｎｍ。Ｃ_（６０）含量增加，红移程度增大，在可见区域的吸收程度亦增加。产物主要存在５个特征峰，分别位于２１５ｎｍ、２６５ｎｍ、２９８ｎｍ、３３５ｎｍ、３４５ｎｍ处，其中２１５ｎｍ峰为Ｃ_（６０）仅存的特征峰。最后讨论了不同合成条件与产物硝化处理对其ＵＶ－ＶＩＳ谱行为的影响。     

Electrochemical Determination of Ascorbic Acid in Room Temperature Ionic Liquid BPPF6 Modified Carbon Paste Electrode

A room temperature ionic liquid N‐butylpyridinium hexafluorophosphate (BPPF₆) was used as a binder to make an ionic liquid modified carbon paste electrode (IL‐CPE), which showed good characteristics such as simple preparation procedure, fast electrochemical response and good conductivity. The electrochemical oxidation of ascorbic acid (AA) on the new IL‐CPE was carefully studied. The oxidation peak potential of AA on the IL‐CPE appeared at 109 mV (vs. SCE), which was about 338 mV decrease of the overpotential compared to that obtained on the traditional carbon paste electrode (CPE) and the oxidation peak current was increased for about four times. The electrochemical parameters of AA on the IL‐CPE were calculated with the charge transfer coefficient (α) and the electrode reaction rate constant (k_s) as 0.87 and 0.800 s^?1, respectively. Based on the relationship of the oxidation peak current and the concentration of AA a sensitive analytical method was established with cyclic voltammetry. The linear range for AA determination was in the range from 1.0×10^?5 to 3.0×10^?3 mol/L with the linear regression equation as I_p (μA)=?2.52–0.064C (μmol/L) (n=13, γ=0.9942) and the detection limit was calculated as 8.0×10^?6 mol/L (3σ). The proposed method was free of the interferences of coexisting substances such as dopamine (DA) and amino acids etc., and successfully applied to the vitamin C tablets determination.     

Reactivity of organolanthanide and organolithium complexes containing the guanidinate ligands toward isocyanate or carbodiimide: synthesis and crystal structures

The direct reactions of (C5H5)2LnCl with LiN=C(NMe2)2 proceeded at room temperature in THF under pure nitrogen to yield the lanthanocene guanidinate complexes [(C5H5)2Ln(mu-eta1:eta2-N=C(NMe2)2)]2 (Ln = Gd (1), Er (2)). Treatment of phenyl isocyanate with complexes 1 and 2 results in monoinsertion of phenyl isocyanate into the Ln-N(mu-Gua) bond to yield the corresponding insertion products [(C5H5)2Ln(mu-eta1:eta2-OC(N=C(NMe2)2)NPh)]2 (Ln = Gd (3), Er (4)), presenting the first example of unsaturated organic small molecule insertion into the metal-guanidinate ligand bond. Further investigations indicate that N,N'-diisopropylcarbodiimide does not react with complexes 1 and 2 under the same conditions; however, it readily inserts into the lithium-guanidinate ligand bond of LiN=C(NMe2)2. As a synthon of the insertion product Li[(iPrN)2C(N=C(NMe2)2)], its reaction with (C5H5)2LnCl gives the novel organolanthanide complexes containing the guanidinoacetamidinate ligand, (C5H5)2Ln[(iPrN)2C(N=C(NMe2)2)] (Ln = Yb (5), Er (6), Dy (7)). All complexes were characterized by elemental analysis and spectroscopic properties. The structures of complexes 1, 3, 5 and 7 were determined through X-ray single-crystal diffraction analysis.     

(4,4′,4″,4″′-四硝基)·酞菁合钴(Ⅱ)化学修饰电极对抗坏血酸的电催化氧化

合成了一种钴的酞菁配合物,以玻碳为基体、用化学吸附法制备了它的化学修饰电极。用CV法研究了该化学修饰电极对抗坏血酸氧化的电催化作用。结果表明,该化学修饰电极对抗坏血酸的氧化有一定的电催化作用,且电催化活性的稳定性高,抗坏血酸的电催化氧化峰电流和其浓度之间有良好的线性关系。     

Novel Cp2LnX-mediated coupling-cyclization of propargyl bromide: a new construction of the benzene ring skeleton

In the presence of Cp2LnX-HgCl2, the treatment of RC identical to CCH2Br with Mg leads to the formation of benzene derivatives C6H4R2-1,2 (R = H, Ph) in moderate yield, which provides a new method for the construction of the benzene ring skeleton.