二茂铁亚胺环钯化合物－－一种新型芳基氯化汞偶联催化剂

发现在催化量二茂铁亚胺环钯化合物催化下，芳基氯化汞可在湿和条件下偶联 ，以中等或高的收率生成联芳烃。对于铑盐不能催化偶联的邻位取代苯基氯化汞和 α－基氯化汞，在此体系中亦可发生偶联。以HMPA为溶剂，在x = 0.025（摩尔分 数）化合物1或2催化下与2.0当量氯化锂存在时，得到最好的催化效果。     

Synthesis, Crystal Structure, UV-vis and EPR Studies of（ NH3CH2CH2NH2 ） 2.5 [ Mo0.5^（V）W0.5^（VI）O2 （ OC6H4O ） 2]

Cis-dioxo-metal complex ( NH3CH2CH2NH2 ) 2.5 [ Mo0.5^(V)W0.5^(VI)O2 ( OC6H4O ) 2] 1 was obtained by the reaction of tetra-butyl ammonium hexamolybdotungstate with 1, 2-dihydroxybenzene in the mixed solvent of CH3OH, CH3CN and ethylenediamine,and characterized by X-ray diffraction, UV-vis and EPR analysis. Compared with its analogous complexes (NH3CH2CH2NH2)3[Mo^(V)O2(OC6H40)2] 2 and (NH3CH2CH2NH2)2[W^(VI)O2(OC6H4O)2] 3, the results show that tungsten(VI) is less active in redox than molybdenum (VI) and that the change of the valence induced by substitution of W(VI) for Mo(V) in EMO2(OC6H40)2]n- does not influence the coordination geometry of the complex anion in which the metal center exhibits distorted octahedral coordination with cis-dioxo catechol. The responses to EPR of complexes 1 and 2 are active but complex 3 is silent,and the UV-vis spectra exhibited by the three complexes are obvious different because of the different electronic configuration between the central Mo(V) and W(VI) ions in the complexes.It is noteworthy that complexes 1 and 2 have the similar EPR signal to flavoenzyme, suggesting that the three complexes have the same coordination geometry feature with the co-factor of flavoenzyme.     

一维棒状ZnO的制备及电化学嵌锂性能研究

目前,商业化锂离子电池一般采用石墨作为负极材料,因其电位与金属锂电极的电位很接近,所以当电池反复循环和过充时,石墨表面易析出金属锂,会因形成枝晶而短路。在温度过高时还容易引起热失控。同时,锂离子电池的容量在很大程度上取决于负极的锂嵌入量,而且石墨材料容量相对较低     

铈离子引发N-对甲苯基丙烯酰胺类聚合物膜上丙烯酰胺接枝共聚合的研究

合成了NTAAM,NTMAAM,NPMAAM功能单体,发现这类功能单体与铈离子组成的体系能引发丙烯酰胺聚合,带有这类功能单体的聚合物和共聚物铸成的膜,能用铈离子引发丙烯酰胺接枝共聚合。这可从反应后的膜比基膜有较大的吸水率、与水有较小的接触角,也可从扫描电子显微镜观察到表面上有凸起图象的高分子链,以及从膜表面的X射线光电子能谱所证实。同时研究了共聚物膜的组成、反应条件对接枝共聚合的影响。     

Structure of Palladium( Ⅱ ) Complex with 2-Hydroxy-propane 1, 3-diamine-N,N,N'''' N'''',-tetraacetic Acid

The reaction of PdCl2 in water with 2-hydroxypropane-1, 3-diaminetetraacetic acid (HPDTA) gave the complex Pd (C11H16N2O9)·1. 5H2O, which was characterized by elemental analysis, IR, NMR and single-crystal X-ray diffraction. The spectroscopic and X-ray diffraction data show that Pd ( Ⅱ ) is coordinated by two nitrogen atoms and two car-boxylic oxygen atoms. The complex crystallizes in monoclinic space group Pc with a = 1. 1240(2), b=1. 1183(2), c=1. 2597(3) nm, β=96. 33(2)°V=1. 5737(6) nm3, Z = 4, R= 0.038. The structure contains two crystallographically independent molecules which have slightly different orientations and are connected by hydrogen bonds.     

硫杂蒽酮类稀土配合物的合成、表征及与DNA的作用(I)

合成了新的O-(硫杂蒽酮-[2]-基)-氧乙酸及其稀土配合物. 通过元素分析, IR, ¹H NMR, UV, DTA-TG和¹³C NMR谱对其结构进行了表征. 研究表明: 配体羧羰基脱质子后与金属离子配位, 2位氧原子也与金属离子配位, 配合物中含有一定量的配位水, 配合物为非电解质类型. 同时, 研究了O-(硫杂蒽酮-[2]-基)-氧乙酸稀土配合物对质粒DNA的切割作用. 结果表明: 铕的配合物对DNA的切割较明显, 且当配合物浓度增加时, 质粒DNA的超螺旋构型逐渐减少, 而缺刻、开环型构型逐渐增多. 在相同条件下, Eu(III)离子对质粒pBR322DNA几乎没有切割作用; 配体O-(硫杂蒽酮-[2]-基)-氧乙酸对质粒pBR322DNA也有切割作用, 但配合物EuL₃对质粒pBR322DNA的切割作用明显强于配体, 表明稀土离子Eu(III)与配体生成配合物后有较好的协同切割作用.     

CrOx/ SBA-15介孔催化剂上丙烷在二氧化碳气氛中脱氢反应的研究

The structure and catalytic properties based on Chromium Oxide supported on mesoporous SBA-15 for oxidative dehydrogenation of propane by CO₂ have been studied by using X-ray diffraction (XRD), ultraviolet-visible diffuse reflectance spectra (UV-Vis DRS), electron spin resonance (ESR), X-ray photoelectron spectroscopy (XPS) and propane pulsing experiments in the absence of gas-phase O₂. It has been shown that propane conversion and propene yield increase with Cr loadings. The propane conversion and propene yield on CrO_x(Cr: 10wt%)/SBA-15 catalyst for oxidative dehydrogenation of propane by CO₂ at 550 ℃ reach 24.8% and 21.8%, respectively .The results of ESR, UV-Vis DRS and propane pulsing experiments indicate that Cr^Ⅲ in the CrO_x/ SBA-15 catalyst is the main active species in oxidative dehydrogenation of propane by CO₂ and Cr^Ⅵ, Cr^Ⅴ is inactive in dehydrogenation.     

加速溶剂萃取同步净化-同位素内标-气相色谱-高分辨质谱测定水产品中32种多氯联苯

建立了加速溶剂萃取同步净化-同位素内标-气相色谱-高分辨质谱同时测定水产品中32种多氯联苯含量的方法。通过在加速溶剂萃取仪中加入2 g无水硫酸钠、1 g弗罗里硅土、50 g中性氧化铝作为吸附剂实现同步净化的效果，萃取溶剂为二氯甲烷-正己烷（1:1，v/v），萃取温度为100℃，循环2次。萃取结束后分别用0.5 mL浓硫酸净化两次，净化液浓缩定容后，采用气相色谱-高分辨质谱测定，同位素内标法定量。32种多氯联苯在0.1~20 μg/L范围内平均相对响应因子（RRF）的相对标准偏差（RSD）值（n=7）均小于15%，定量限（S/N=10）为0.3~1.9 ng/kg。在草鱼和海鲈鱼空白基质中做加标回收试验，添加水平为5、20和50 ng/kg，得到的平均回收率为71.9%~119.0%（n=6），RSD为3.5%~19.6%。该方法背景干扰低，灵敏度高，重现性好，回收率稳定，适用于水产品中多氯联苯的检测。     

(R)-1，1′-联萘手性单元通过溶胶凝胶法合成杂化硅干凝胶(英)

Precursor molecule (R)-6,6′-bis(triethoxysilylethen-2-yl)-2,2′-di(methoxyethoxymethyloxy)-1,1′-binaphthyl (R-2) was synthesized by Pd-catalyzed Heck reaction of (R)-6,6′-dibromo-2,2′-di(methoxyethoxymethyloxy)-1,1′-binaphthyl (R-1) intermediate with vinyltriethoxysilane. The hydrolysis and polycondensation of the precursor R-2 produced the corresponding xerogel. Both precursor and xerogel were analysed by NMR, FTIR, UV, CD spectra, fluorescent spectroscopy, polarimetry and elemental analysis. The precursor and xerogel can emit strong blue fluorescence and are expected to have a potential application in the separation of chiral molecules as fluorescent sensor. The precursor exhibits strong Cotton effect in its circular dichroism (CD) spectrum indicating a highly rigid structure.     

盐酸拓扑替康与人血清白蛋白的相互作用及分子模拟

用荧光光谱法、分光光度法研究了盐酸拓扑替康(topotecan hydrochloride, 简记为THC)与人血清白蛋白(human serum albumins, HSA)的相互结合反应. 计算了反应的结合常数、结合位点数和热力学常数. 盐酸拓扑替康在人血清白蛋白上的结合位置与色氨酸残基间的距离为3.63 nm. 分子模型研究表明, 盐酸拓扑替康与人血清白蛋白的亚结构域IIA结合, 二者间的作用力主要为疏水作用, 此外, 蛋白质的丙氨酸(Ala-291)残基和天冬氨酸(Asp-256)残基与盐酸拓扑替康之间还存在氢键作用力.