[Co(Ⅱ)(H2O)6](C4H4O4)·2C6H12N4·4H2O修饰电极电化学催化谷胱苷肽研究

利用气相沉积法研制了基于TiO2凝胶固定化[Co(H2O)6](C4H4O4).2C6H12N4.4H2O(CoL)修饰电极。研究了该修饰电极对谷胱苷肽(GSH)的催化活性,发现在pH 7.5,0.1 mol/L NaAc-HAc的缓冲溶液中,CoL对电氧化GSH浓度之间有较好的线性关系.线性范围为2×10-6~1×10-4mol/L,检测下限为8×10-7mol/L,相对标准偏差为2.0%(cGSH=5×10-6mol/L,n=6)。应用该法测定生物样品中谷胱苷肽的含量并与紫外分光光度法进行对照,结果一致。     

配合物[Co(phendione)(SO4)(H2O)]5H2O非等温热分解动力学

以热重-差热法(TG-DTG)为手段,研究配合物[Co(phendione)(SO4)(H2O)]·5H2O非等温热分解过程动力学.结果表明,标题配合物第一阶段热分解为相界控制反应(三维)机理,表观活化能为59.85KJ·mol-1,指前因子InA为16.36,反应速率方程为dα/dt=Ae-E(1-α)<2/3>.第...     

A tetranuclear oxomolybdenum(V) complex with bridging squarate ligands, [MoV4O8(OH)2(H2O)2(C4O4)2]2−

The new tetranuclear polyoxomolybdate(V) ion [Mo^V₄O₈(OH)₂(H₂O)₂(C₄O₄)₂]²⁻ has been obtained in one step by the reaction of sodium molybdate, hydrazine and squaric acid in water and crystallized as a potassium salt. The structure has been solved by single-crystal X-ray diffraction showing the location of the hydroxo and water molecule ligands.     

(NH4)2C2O4·H2O和NH4HC2O4·0.5H2O 单晶的培养研究

利用六次甲基四胺缓慢水解产生的NH3和草酸反应,扩散法培养出(NH4)2C2O4·H2O和NH4HC2O4·0.5H2O两种单晶.     

三维超分子化合物[Zn(C6H4O2N)2·(H2O)4]n的水热合成及晶体结构

用2-羧基吡啶和六水合氯化锌反应制备了一种新的三维氢键超分子配合物,经X-射线衍射分析确定了单晶结构。该晶体属单斜晶系,P2(1)/n空间群,晶胞参数为:a=9.836(2),b=5.2256(10),c=14.611(3),Mr=381.64,β=90.01(3)°,V=751.0(3)3,Z=2,Dc=1.688Mg.m-3,F(000)=392,μ=1.680mm-1,R=0.0258,wR=0.0612。共收集2159个衍射数据,其中1273个为独立衍射点(Rint=0.0332),可观测点数1139个(I>2σ(I))。结果表明,在组成该超分子体系的基本结构单元[Zn(C6H4O2N)2.(H2O)4]中,Zn(Ⅱ)离子形成六配位的畸变的八面体构型,配合物单元之间通过氢键OH…O相互连接,形成了无限延伸的具有网状结构的三维超分子体系。     

超分子化合物Mn(HPDA)(H2O)4(ClO4)的研究

以吡啶二酸作为配体,合成了分子间形成弱相互作用的锰配合物,即通过氢键连接成了超分子体系并具有新颖的梯状、格子状的三维结构.以元素分析、X-射线单晶衍射、红外光谱、紫外光谱、室温及低温ESR谱对化合物进行了表征.     

配合物Pd(C4H2O4)(C4H8N2)0.5的合成及对苯酚的氧化羰基化的催化活性

A novel complex Pd(C4H2O4)(C4H8N2)0.5 has been synthesized by solvent thermal synthesis and used as a heterogeneous catalyst for direct synthesis of diphenyl carbonate (DPC) by oxidative carbonylation of phenol. In the reaction system of Pd(C4H2O4)(C4H8N2)0.5/Cu(OAc)2/ tetrabutylammonium bromide/ hydroquinone/ 4A molecular sieves, the effect of reaction temperature, time and CO pressure on catalytic activity were investigated, and the results revealed that the catalyst could catalyze oxidative carbonylation of phenol effectively. Under suitable reaction conditions of T=90℃, t=4h, p(O2)=0.3 MPa, p(CO)=3.9 MPa and CH2Cl2 as solvent, the turnover number (TON) of diphenyl carbonate can reach about 13.50 (mol-DPC/mol-Pd), which is higher than the TON for pure PdCl2 under the same reaction conditions.     

CaC2O4—H2C2O4—H2O体系相平衡研究

测量了25 C时CaC_2O_4-H_2C_2O_4-H_2O三元系的固液平衡数据,实验数据用Pitzer模型进行了关联。     

Synthesis,structure and properties of a new copper (II) complex, [Cu2(4,4′-bpy)5(H2O)4](ClO4)4(4,4′-bpy)(DMF)2(H2O)2

A new copper (II) complex with formula [Cu₂(4,4′-bpy)₅(H₂O)₄](ClO₄)₄(4,4′-bpy)(DMF)₂(H₂O)₂ has been synthesized by reaction of 4,4′-bpyridine (4,4′-bpy) with Cu(ClO₄)₂. While strong hydrogen bonds play central roles in the formation of the 3D structure, the combined influence of the weak interactions such as C–H?O bonds, anion?π and C–H?π interactions are also evident in the structure. The preliminary investigation on the thermal property of the complex is presented.     

The first ladder-like lanthanide double chain complex [Tm(NTA)(H2O)2]·2H2O (H3NTA=nitrilotriacetic acid)

The title complex has been synthesized in aqueous solution and its crystal structure was determined by X-ray diffraction. It consists of a one-dimensional ladder-like chain. One carboxyl group bridges the adjacent Tm ions giving rise to the edge of the ladder, a second one links the Tm ions from the neighboring edge in zigzag form to act as the rung of the ladder, and a third one monodentately coordinates with Tm to serve as the pendant of the ladder. Each Tm ion is eight coordinated by one nitrogen atom, five oxygen atoms from three NTA molecules and two oxygen atoms from H₂O.     

Suppressing fire hazard of poly(vinyl alcohol) based on (NH4)2[VO(HPO4)]2(C2O4)·5H2O with layered structure

Two-dimensional layered ammonium vanadium oxalate-phosphates (AVOPh) with the structural formula of (NH₄)₂[VO(HPO₄)]₂(C₂O₄)·5H₂O are synthesized though a hydro-thermal method, which is dispersed into poly(vinyl alcohol) (PVA) matrix to prepare PVA/AVOPh composites. The results of thermal analysis indicate that AVOPh and PVA have similar decomposition temperature from 280 to 500°C, which is critical for choosing flame retardant. The incorporation of AVOPh significantly improves the thermal stability and flame retardancy of PVA/AVOPh composites that the T_5% value of PVA/2 wt% AVOPh composites is up to 215°C, and the residue of PVA/8 wt% AVOPh composites is enhanced to 16.9%, while those of pure PVA are only 178°C and 2.4%. PVA/4 wt% AVOPh composites can pass V-0 level, and its limiting oxygen index value is up to 32.0%. Furthermore, the peak heat release rate (PHRR) and total heat release (THR) of PVA/AVOPh composites are obviously decreased, which reduced by 43.4% and 43.8% with the addition of 4 wt% AVOPh, compared with those of pure PVA. The excellent thermal stability and flame retardancy are mainly attributed to the uniform dispersion and barrier effect of 2D layered AVOPh, the release of crystal water, ammonia and phosphorus free radicals and the two-phase flame retardant catalytic mechanism of vanadium and phosphorus.     

Surface immobilisation of the sandwich type Na14[Fe4(Ox)4(H2O)2(SbW9O33)2]·60H2O polyoxometalate

A functionalised Fe-substituted Keggin Na₁₄[Fe₄(C₂O₄)₄(H₂O)₂(SbW₉O₃₃)₂]·60H₂O type POM termed “Fe₄Ox₄” has been successfully immobilised onto carbon electrode surfaces through the employment of conducting polypyrrole films and the layer-by-layer (LBL) technique. For the POM doped polypyrrole films the redox systems associated with the POM's tungsten-oxo framework was not apparent upon redox cycling, however a reversible redox couple associated with the Fe^III/II redox system was clearly seen within the pH range 2–7. Organised multilayer assemblies were constructed by the employment of the layer by layer (LBL) technique through alternating anionic Fe₄Ox₄ layers and cationic Ru^II metallodendrimers with poly(diallyldimethylammonium chloride) (PDDA) employed as an initial base layer. Stable redox couples associated with both the Fe^III/II and tungsten-oxo framework, for the Fe₄Ox₄ POM, and the Ru^III/II for the metallodendrimer, were clearly observed upon layer construction and redox switching within the pH domain of 2–7. The resulting multilayer assembly showed good stability towards redox cycling. Further investigations into the multilayer assembly were undertaken by determining it is charge transfer resistance using AC-impedance voltammetry. The layer also showed catalytic ability towards the reduction of H₂O₂ at pH 6.5.