Synthesis and ~(183)W NMR Characterization of α-K_7GaW_(11)(TiO_2)O_(39)·11H_2O Heteropolyanion

In recent years, the research of peroxy polyoxometalates (POMs) has attracted increasing attention because of the two reasons. First, peroxy POMs are more active as oxygenation catalysts in some oxygen transfer reactions1~5. Second, recent research from our group and others has established that peroxy POMs are more active antiviral agents and less toxic both in vitro and in vivo than the parent metal-free POMs6. In order to entirely understand the properties and activities of peroxy POMs…     

Keggin型铁取代杂多阴离子PW_(11)O_(39)Fe(Ⅲ)(H_2O)~(4-)光催化降解硝基苯

以Keggin型铁取代杂多阴离子PW11O39Fe(Ⅲ)(H2O)4-[PW11Fe(Ⅲ)(H2O)]代替传统光芬顿方法中的Fe3+作为光催化剂,构成一个新颖的光催化体系并用于水体生物难降解有机污染物硝基苯(NB)的降解.详细研究了在紫外光照射和H2O2存在下,PW11Fe(Ⅲ)(H2O)对NB降解的均相光催化作用.考察了NB初始浓度、溶液pH、H2O2和PW11Fe(Ⅲ)(H2O)浓度对光催化降解反应速率的影响.实验结果表明,1.0mmol·L-1PW11Fe(Ⅲ)(H2O)+5.0mmol·L-1H2O2+1.0mmol·L-1NB的中性溶液在300W汞灯照射下反应120min,NB的降解率达93%,总有机碳(TOC)去除约31%,显示了该新颖体系对NB光催化降解的高效性和优越性.     

PW_(11)O_(39)Co(Ⅱ)(H_2O)~(5-)的均相及异相体系可见光催化性能研究

以模型污染物罗丹明B(RhB)的光降解为探针,评估了Keggin型钴取代杂多阴离子PW11O39Co髤(H2O)5-(PW11Co)及其异相体系PW11Co/D301R的可见光催化活性,提出了光催化反应的机理,同时考察了催化剂用量、溶液酸度以及溶液中PW11Co和RhB的相互作用对RhB可见光催化降解速率的影响。实验结果表明,PW11Co均相体系及其异相体系PW11Co/D301R对RhB的可见光降解均有较高的光催化活性,但PW11Co/D301R的光催化活性更高。导致RhB降解的主要是羟基自由基。与PW11Co均相体系相比,在PW11Co/D301R异相体系中由于PW11Co与RhB的配位作用大为减弱,同时D301R对RhB具有富集作用,因而大大提高了RhB的光催化降解速率。     

K_3H_3[As_2W_(21)O_(69)(H_2O)]·19H_2O的合成及晶体结构(英文)

利用二缺位K14[As2W19O67]·nH2O前驱体在酸性条件下的结构转变得到了饱和的砷钨酸盐K3H3[As2W21O69(H2O)]·19H2O(1),借助傅立叶变换红外光谱和X射线单晶衍射对其结构进行了表征.结果表明,化合物1的多阴离子骨架由两个相同的三缺位[α-AsW9O33]9-片段通过三个W=O基团连接而成.值得提及的是,在化合物1的阴离子骨架中心空腔中存在一个游离的水分子.     

包含银的Keggin型锗钼酸盐[NH_4]_2[Ag(H_2O)(H_2PDCA)]_2[α-GeMo_(12)O_(40)]·12H_2O（英文）

利用常规水溶液方法合成了一种有机-无机杂化的包含银的Keggin型锗钼酸盐[NH_4]_2[Ag(H_2O)(H_2PDCA)]_2[α-GeMo_(12)O_(40)]·12H_2O(1),并通过元素分析、红外光谱和单晶X射线衍射等对其进行了表征.X射线晶体学研究表明化合物1的分子结构由1个典型的Keggin结构[α-GeMo12O40]~(4-)聚阴离子、2个[Ag(H_2O)(H_2PDCA)]~+配离子、2个NH+4离子和12个结晶水分子构成.值得注意的是在[α-GeMo_(12)O_(40)]~(4-)单元中,锗原子呈现出立方体几何配位构型,这归结于与锗原子相连的每个氧原子都无序地排列在两个位置.有趣的是,每个[α-GeMo_(12)O_(40)]~(4-)多阴离子通过4个[Ag(H_2O)(H_2PDCA)]~+桥配离子与4个[α-GeMo_(12)O_(40)]~(4-)多阴离子相连构筑了二维层状结构.此外,我们还在室温下研究了化合物1的电化学性质.     

K_8[Zn(H_2O)MnW_(11)O_(39)]/PANI/TiO_2复合材料的制备及光催化性能

采用直接合成法制备K_8[Zn(H_2O)Mn W_(11)O_(39)],以(NH_4)_2S_2O_8为氧化剂,通过化学氧化法将聚苯胺包覆在纳米Ti O_2颗粒表面制得PANI/Ti O_2,然后运用静电自组装法将K_8[Zn(H_2O)Mn W_(11)O_(39)]与PANI/Ti O_2复合成K_8[Zn(H_2O)Mn W_(11)O_(39)]/PANI/Ti O_2复合材料。运用IR、UV、XRD、XPS、SEM、N2吸附-脱附等分析方法对K_8[Zn(H_2O)Mn W_(11)O_(39)]/PANI/Ti O_2进行表征。利用K_8[Zn(H_2O)Mn W_(11)O_(39)]/PANI/Ti O_2为催化剂,研究其对孔雀石绿溶液的光催化降解性能。结果表明:紫外光照射下,孔雀石绿p H为2,浓度为20 mg/L,催化剂为10 mg时,脱色率可达93.66%。     

新型仲钨酸盐-B化合物[Na_2(H_2O)_(10)][Cu_4(H_2O)_(12)(H_2W_(12)O_(42))]·15H_2O体外抗肿瘤活性研究

对化合物[Na_2(H_2O)_(10)][Cu_4(H_2O)_(12)(H_2W_(12)O_(42))]·15H_2O(简称Na_2Cu_4W_(12))进行了体外抗肿瘤活性研究.应用四甲基偶氮唑盐(3-[4,5-dimethylthiazo-2-y]-2,5-diphenyltetrazolium bromide,MTT)比色法分析Na_2Cu_4W_(12)对人肝癌细胞(Hep G2)、人神经母细胞瘤细胞(SHY5Y)增殖抑制活性.采用光学显微镜观察肿瘤细胞的凋亡形态变化,用流式细胞术分析细胞周期和细胞凋亡,计算各期细胞比例及细胞凋亡率.结果表明,Na_2Cu_4W_(12)对Hep G2和SHY5Y 2种肿瘤细胞增殖半数抑制浓度IC_(50)值分别为5.3和10.2μmol·L~(-1),且呈剂量依赖性.光学显微镜下处理组细胞出现皱缩、变圆、缩小等形态变化,不同浓度Na_2Cu_4W_(12)处理12h早期凋亡细胞所占的百分比显著增加且呈剂量依赖性.综上所述,Na_2Cu_4W_(12)能够抑制胞瘤细胞增殖,诱导细胞凋亡.     

Synthesis and Crystal Structure of Na_(10)[LaSiW_(11)O_(39)(H_2O)_4]_2·22H_2O

1 INTRODUCTION The pseudoliquid character of heteropoly compounds as catalysts is determined by their crystallographic properties. Study on the crystal structures of the heteropoly compounds could provide interesting information to enrich heteropoly acid and catalytic chemistry[1]. In the past, Zhuo Ying-Li抯 group has synthesized the carbamidine salts of 1:1 LnL(Ln=lanthanide, L=[SiW11O39]n－)[2], and Pope抯 group has reported that -SiW11O39 units are connected by lanthanide catio…     

Crystal Structure of the 1:2 Stoichiometric Nd: [α-SiW_(11)O_(39)]~(8-): K_5Na_5H_3[Nd(α-SiW_(11)O_(39))_2]·6H_2O

Single-crystal X-ray structural analysis of K5Na5H3[Nd(α-SiW11O39)2]·6H2O (triclinic, space group P1, a = 13.7738(10), b = 19.722(2), c = 20.6647(15) , α = 111.0090(10), β = 105.1740(10), γ = 98.6870(10)o, Z = 2, V = 4867.2(8), Mr = 5914.40, Dc = 4.026, μ = 26.754 mm-1, F(000) = 5076, R = 0.0750 and wR = 0.2077) reveals that two [α-SiW11O39]8- moieties are connected through one Nd atom which is in a square antiprismatic coordination environment by eight oxygen atoms from two [α-SiW11O391]8- moieties. The Nd(Ⅲ ) ion is substituted for a [WO]4+ unit in the "cap" region of the tungsten-oxygen framework of the parent Keggin ion. Disordered Na+ cations and water molecules reside outside these channels, leaving empty pores with an intersecting slot (13 × 10 ).     

H_3PW_(12)O_(40)催化水相介质中苯并恶嗪和喹唑啉合成（英文）

A heteropolyacid efficiently catalyzed the cyclocondensation reaction of 2‐aminobenzamide and salicylamide with aldehydes and ketones to afford good yields of benzoxazine and quinazoline ring systems in an aqueous medium. The method gives clean reactions, has simple workup procedure, and uses environment friendly conditions.     

十一钼硅钴杂多蓝H_8[SiMo_(11)Co(H_2O)O_(39)]·20H_2O的合成与晶体结构

采用电解法制备了未见文献报道的杂多蓝H8[SiMo11Co（H2O）O39]·20H2O，通过X-射线衍射测定了其晶体结构，该晶体属单斜晶系，空间群P21；。晶胞参数全矩阵最小二乘法修正至中心原子Si与4个氧形成四面体结构，配原子M（M＝11／12Mo＋1／12Co）与O形成12个MO6八面体结构3个MO6共边形成4个M3O13三金属簇，4个三金属簇与SiO4四面体共角相连形成阴离子结构。     

Preparation and Characterization of Heteropoly-complex K_11[La(GaW_11O_39H_2)_2]· xH_2O

Heteropoly complexes K11[Ln(CaW 11O39H2)21 · x H2O(Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy ) have been prepared and analysed. Some properties such as thermal behavior, IK and UV spectra, X-ray powder diffraction, magnetic susceptibility and X-ray photoelectron spectrum have been investigated.     

CRYSTAL STRUCTURE OF K_7H_6[Nd(GeMo_(11)O_(39))_2]·27H_2O

<正> K7H6[Nd(GeMo11O39)2]·27H2O, Mr = 4413.8, crystallizes in monoclinic, space group P21/n with a = 17. 095(4), b = 26. 895(3), c = 21. 214(5) (?); β=103. 11(2)°;V = 9499. 4(3)(?)3; F(000) = 8808; Z = 4; Dc = 3. 05g/cm3; μ(MoKα) = 43. 7cm-1 and λ=0. 71069(?). A total of 8644 reflections with I≥3σ(I) were used in the structure analysis. The final R value is 0. 090, Rw value is 0. 091. The atom Nd is situated between two tetradentate heteropoly (GeMo11O39)8- ligands to form the anion [Nd(GeMo11O39)2]13-. Nd is surrounded by eight oxygen atoms at average distances of 2. 446 (?), forming a square antiprism.     

Non-Isothermal Decomposion Kinetics of Supermolecule Compound [Eu(C_(10)H_9N_2O_4)(C_(10)H_8N_2O_4)(H_2O)_3]_2·phen·4H_2O

Europium(Ⅲ) compound with 2-oxopropionic acid salicyloyl hydrazone (C_(10)H_(10)N_2O_4,H_3L) and 1,10-phenan-throline (C_(12)H_8N_2,phen) has been prepared.A yellow prismatic crystal of the compound was obtained,and themolecule crystallized in the triclinic space group P-1.There are two 9-coordinated complex molecules in everystructure unit,where every Eu atom is coordinated by three water molecules and two tridentate C_(10)H_(10)N_2O_4 ligands,forming two stable pentacycles.The coordination polyhedron around Eu~(3+) was described as a single cap squareantiprism.In the crystal cell,there are one free 1,10-phenanthroline and four water molecules.The thermaldecomposition of the compound and its kinetics were studied by non-isothermal thermogravimetry.The Kissinger'smethod and Ozawa's method were used to calculate the activation energy value of the first-step decomposition.Thestages of the decompositions were identified by TG-DTG-DSC curve.The non-isothermal kinetic data were ana-lyzed by means of integral and differential methods.The possible reaction mechanism and the kinetic equationswere investigated by comparing the kinetic parameters.     

Syntheses and Structures of Two New Coordination Polymers:[Cu(C_(14)H_9O_4)(C_(14)H_(10)O_4)(C_(12)H_(12)N_2)_2] and [Ag(C_(14)H_9O_4)(C_(13)H_(14)N_2)]·0.5H_2O

1 INTRODUCTION Supramolecular approaches to self-assembly of infinite molecular solids with novel structural topo- logies attract considerable attention for their po- tential applications as functional materials and their fascinating architectures[1]. In…     

Syntheses and Crystal Structures of [Na(H_2O)](C_(17)H_(13)O_6SO_3)·2H_2O and [Ni(H_2O)_6](C_(17)H_(13)O_6SO_3)_2·4H_2O

Introduction Flavonoids exist widely in edible plants, and have pharmacological activity. They played a major role in the successful medical treatments at ancient times, and their uses have been persevered up to now.1-3 Flavonoid sulfates were found in a large number of plant species. They occupy an important position in the field of natu-ral products chemistry since they provide structures consisted of organic and inorganic components. The pharmacological assay revealed that flavonoid sulfat…     

[Cu（en）_2]_2[Cu（en）_2（H_2O）][PW_（11.5）Cu_（0.5）O_（40）]·OH·3H_2O的水热合成及结构表征

利用水热合成法制备了基于Keggin结构阴离子的1D链状化合物[Cu（en）2]2[Cu（en）2（H2O）][PW11.5Cu0.5O40].OH.3H2O,并经红外、紫外和X射线单晶衍射等手段进行了表征.标题化合物属于单斜晶系,P21/c空间群,晶胞参数：a=1.266 25（10）,b=2.145 45（19）,c=2.455 95（18）nm,β=114.919（3）,V=6.050 9（8）nm3,Z=4,R1=0.068 1,wR2=0.146 8.     

[Eu(C_(10)H_9N_2O_4)(C_(10)H_8N_2O_4)(H_2O)_3]·0.5bipy·3H_2O配合物的合成、晶体结构及荧光性质

在水-乙醇混合体系中,以2-羰基丙酸水杨酰腙(C_(10)H_(10)N_2O_4)、2,2-联吡啶(C_(10)H_8N_2,简写bipy)与Eu(NO_3)_3·4H_2O反应,首次培养出黄色单晶[Eu(C_(10)H_9N_2O_4)(C_(10)H_8N_2O_4)(H_2O)_3]·0.5bipy·3H_2O.该晶体属三斜晶系,空间群为P-1,晶胞参数a=0.93392(16)nm,b=1.3100(2)nm,c=1.3895(2)nm,α=97.205(3)°,β=105.411(2)°,γ=106.364(2)°,V=15.35(2)nm~3,Z=2,μ=2.118mm~(-1),Dc=1.686Mg/m~3,F(000)=786,R=0.0116,wR=0.0507,GOF=0.995.晶体测试结果表明,该单晶结构为铕的9配位配合物,两个2-羰基丙酸水杨酰腙分别以负一价和负二价酮式和三个水分子同时参与配位;每个2-羰基丙酸水杨酰腙中的羧基氧、酰胺基中的羰基氧和C=N中的氮与Eu~(3+)配位,形成两个共边的稳定五元环,另三个配位原子则分别来自三个水分子中的氧原子,该配合物在空间呈扭曲的单帽四方反棱柱,而在不对称单位中还有游离的一个2,2-联吡啶分子和三个水分子,这些游离分子与配位分子之间存在大量分子内和分子间氢键,整个分子在空间呈三维网状结构.发光性能测试表明该配合物具有很好的荧光性质.     

H_2O-DMF混合溶剂中[Co(N_3)(NH_3)_5]~(2 )与[Fe(H_2O)_6]~(2 )间电子转移反应

研究了H_2O-DMF馄合溶剂中[Co(N_3)(NH_3)_5]~(2 )被Fe(Ⅱ)还原的反应速度变化规律后,证实:当DMF的摩尔分数X_(DMF)<0.3时,表观速度常数K_(aDD)随着X_(DMF)增大而增大;X_(DMF)>0.3时,K_(app)随着X_(DMF)增大而减小;K_(aDD)与[H~ ]有良好线性关系。 H_2O-DMF混合溶剂中所测定的吸收光谱显示出:近紫外区溶液的吸光度随X_(DMF)增大而增大,它反映出Fe(Ⅱ)的配位圈中配体H_2O分子被DMF分子逐渐置换而形成混合配体配合物的过程。 还观察到,在H_2O-DMF混合溶剂中,Fe(Ⅱ)的电极电势与X_(DMF)的依存性:随X_(DMF)增加,Fe(Ⅱ)的电极电势下降,但X_(DMF)>0.3后,Fe(Ⅱ)的电极电势几乎为一定值。 因此,反应速度的变化,可归因于Fe(Ⅱ)配位圈中水分子的被置换和Fe(Ⅱ)电极电势的变化上。     

H_3PW_(12)O_(40)掺杂TiO_2介孔材料的制备及光催化性能

以P123为模板剂,采用溶胶-凝胶的溶剂热合成方法制备了H3PW12O40掺杂TiO2介孔材料H3PW12O40/TiO2.利用紫外可见漫反射吸收光谱(UV-vis/DRS)、X射线粉末衍射(XRD)、N2吸附和透射电子显微镜(TEM)手段对所制备的材料进行结构表征,罗丹明B(RB)为模型污染物评价其光催化性能.结果表明,所制备的介孔材料具有锐钛矿与板钛矿复合的晶型结构、大的BET比表面积和孔径均匀分布的介孔结构.光催化实验表明,H3PW12O40/TiO2可将罗丹明B完全矿化.