STUDIES ON REDOX PROPERTIES OF HETEROPOLY ACIDS (SALTS) AND THEIR DERIVATIVES WITH KEGGIN AND DAWSON STRUCTURES

We have systematically studied redox properties of two series of several dozen heteropoly acids (salts) and their derivatives with vanadium and rare-earth elements with Keggin and Dawson structures, e. g. LnHSiMo_(12), SiMo_(12-n)V_n, M_(1.5)PMo_(12), PMo_(12-n)V_n, PW_(12-n_V_n, Ln(PMo_(11))_2, Sm(XMo_(11))_2 and P_2Mo_(18-n)V_n, etc., and obtained their sequence of oxidation. It was found that there is a linear relationship between the reduction potentials of heteropoly anions and the derivatives of heteropoly anions with rare-earth elements with Keggin structure and nq~2 (n and q are the principal quantum number and charge of the central ion respectively). On the basis of the electrostatic model the regularity of oxidation and reduction was rationalized.     

三苯基锡-2-(1，2-亚乙二硫)亚甲基-3-羰基-5-芳基-4-戊烯酸酯的合成及晶体结构

由2-(1,2-亚乙二硫)亚甲基-3-羰基-5-芳基-4-戊烯酸与三苯基氢氧化锡反应,合成了九个标题化合物3。用X射线衍射法测定了3b的晶体结构。该晶体属三斜晶系,空间群P1,a=0.9074(2)nm,b=1.6809(3)nm,c=2.1834(4)nm,α=77.57(3)ⅲ,β=88.04(3)ⅲ,γ=89.47(3)ⅲ,V=3.2503nm^3,Z=2;R=0.0592。由锡氧原子间距离可推测,该晶体中羧酸根作为双齿配体与锡原子形成了分子内五配位结构。     

穴状稀土杂多化合物的生物活性研究

报道了以「ＴｂＡｓ４Ｗ４０Ｏ１４０」＾２５－及「ＰｒＳｂ９Ｗ２１Ｏ８６」＾１６－为代表的穴状稀土杂多阴离子的体外、体内抗肿瘤活性及体内抗ＲａｕｓｃｈｅｒＭｕＬＶ和ＬＰ－ＢＭ５ＭｕＬＶ病毒活性。以上化合物对Ｈ２２,Ｂ１６,ＨＬ－６０及活体直肠癌、乳腺癌细胞有抑制作用,能减轻荷瘤鼠的瘤重及延长期存活时间及荷病毒鼠的脾重。     

含钆杂多配合物对水氢核的弛豫性能

核磁共振成像(MRI)技术是继CT扫描仪后又一诊断肿瘤的有力工具,已广泛应用于临床.MRI成像时,不同组织间的区别是由于这些组织中水分子的1H核磁弛豫时间的差别引起的.但病变与正常组织的弛豫速率的差别常常达不到诊断的目的,因此诊断时常使用造影剂,其作用是改变体内局部组织中水质子弛豫时间,提高正常与患病部位的成像对比度[1].造影剂的使用要求具有较高的弛豫效率、较高的稳定性,无毒等条件.弛豫效率与化合物中顺磁原子的未成对电子数有关,未成对电子数越多,则配合物的电子自旋磁矩越大,对邻近水质子的弛豫能力越强.因此,研究较多的是…     

Synthesis,Spectroscopic Characterization and Antitumor Activity in vitro of Organometallo Substituted Polyoxotungstates（RM）3P2W15—O59^n—（RM=CpTi,CpZr,C4H7O2Sn or C5H9O2Sn）

Tetrabutylammonium or potassium salts of organometalllic derivatives of lacunary polyanion (RM)3P2W15O59^n-(RM=CpTi,CpZr,C4H7O2Sn or C5H9O2Sn) have been prepared and structurally characterized by elemental analysis,IR,UV-Vis,^1H NMR and^183 W NMR spectroscopies.The title complexes exhibit antitumor activity in vitro.     

Synthesis, Characterization and the Effect of Glucose-lowering of Guanidino Acid Oxovanadium（Ⅳ） Complexes

Two guanidino acid oxovanadium(Ⅳ) complexes have been synthesized. Preliminary tests in vivo have shown that the two title complexes all display lowering glucose activity in vivo to STZ-rats. The effect of glucose-lowering of guanidino acetic acid oxovanadium(Ⅳ) complex in vivo is higher than that of guanidino propanoic acid oxovanadium(Ⅳ) complex.     

钨砷杂多阴离子[KAs4W40O140(M·H2O)2]n-中配位水的取代反应

本文报道了[KAs_4W_(40)O_(140)(M·H_2O_2]~(n-)杂多阴离子中配位水的取代反应.在水溶液中,许多配体,如[Fe(CN)_6]~(4-)、[Fe(CN)_6]~(3-),SO_3~(2-)等都能取代配位水形成具有特征颜色的配离子.在水溶液中不能发生的配体取代配位水的反应,在非极性有机溶剂中却容易发生,这与配位水分子在非极性有机溶剂中易脱去形成配位不饱和态有关.     

镧系元素的双—（9—钨—2—钼磷）杂多酸钾的合成与性质研究

自1971年Peacock等首次合成出以杂多阴离子为配位体的镧系元素的一些杂多配合物[Ln(XW_(11)O_(39))_2]~(n-)(X=P,Si)以来,Zuhairi等又合成出镧的一些其它杂多钨酸盐[La(XW_(11)O_(39))_2]~(n-)(X=B,Si,Ge,P,As)。 为开发新型的镧系元素催化剂,我们系统地研究了镧系元素的杂多钨酸盐和杂多钼酸盐。本文报道有关K_(11)[Ln(PW_9Mo_2O_(39))_2]·nH_2O(Ln=La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Er,Yb)的合成及性质的研究结果。     

双-11钨钛希土三元杂多化合物的合成与性质研究

本文报道了双-11钨钛希土三元杂多化合物K_(13)[Ln(TiW_(11)O_(39))_2]·xH_2O(Ln=La,Ce,Pr,NdSm,Eu,Gd,Tb,Dy,Ho,Er,Yb,Y,Ce(Ⅳ))的合成方法,溶液性质,红外光谱,紫外光谱,X光电子能谱,热分析等的研究结果.     

钨硅铁杂多酸盐的Mossbauer谱研究

首次测定了K_5SiFe(H_2O)W_(11)O_(39)·21H_2O和它的二聚体K_(12)O(SiFeW_(11)O_(39))_2·22H_2O的Mossbauer谱,并结合磁化率、XPS和红外光谱,证实了二聚体中Fe—O—Fe桥键含有d-pπ键,推测其阴离子结构为[SiW_(11)O_(39)FeOFeO_(39)W_(11)Si]~(12-).