3-苯基-1-丁炔-3-醇质谱碎裂中[C8H7]^+的结构及分子内质子迁移反应

报道了3-苯基-1-丁炔-3-醇的常规电子轰击质谱(EIMS)。利用碰撞诱导解离(CID)技术研究了质谱碎裂过程中产生的[C8H7]^+的气相离子结构。同时, 氘代同位素交换、亚稳(MI)和CID实验进一步证实了m/z 103离子的形成并不是分子离子的质谱碎裂中顺次失去甲基自由基和中性CO分子的直接氢迁移的协同反应, 而是在失去CO分子前后发生了二次质子迁移反应的逐步过程。在此基础上提出了一种独特的双分子质子键合复合物中间体的碎裂机理。     

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     

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.     

(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.     

DNA光复活作用机理研究中的模型化合物

用模型化合物模拟光解酶诱导的DNA光复活作用，能深入认识其作用机理。介 绍了用于DNA光复活机理研究的各种模型化合物的合成，并综述了由模型化合物研 究得到的光复活机理，以及底物嘧啶二聚体的修复效率受外界因素的影响。     

Selection of Anodic Material Used in Electrolytic Process for Producing Hypophosphorous Acid

Black lead, Ti-Ru and Ti-PbO2 were used as anode and stainless steel was used as cathode The electrolytic process of producing hypophosphorous acid with four-compartment electrodialytic cell was studied. The comparison of some factors, such as anodic voltage, product concentration and current efficiency, of black lead, Ti-Ru, and Ti-PbO2 electrodes was conducted. As a result, theTi-PbO2 electrode is the optimal anode material used, it can be in electrolytic process for producing hypophosphorous acid.