多齿胺膦钌配合物催化苯乙酮的氢转移氢化

利用Ｃ２－对称的双胺双膦钌（Ⅱ）配合物ＲｕＣｌ２（Ｐ２Ｎ２Ｈ４）为催化剂，研究了苯乙酮的氢转移还原反应。在苯乙酮、钌配合物和异丙氧基钾的摩尔比为２００：１：１２的条件下，于６５℃反应２ｈ后，苯乙酮的转化率高达９９％。讨论了苯乙酮的氢转移氢化机理。     

新马兜铃内酯的晶体结构

从绵毛马兜铃的根茎中分离出一种新的倍半萜内酯, 它的分子式由高分辨质谱数据确定为C~1~5H~2~0O~2, 它的结构用单晶X射线衍射法测定, 晶体属三斜晶系, 空间群为P1, a=0.6275(3)nm, b=0.8057(4)nm, c=1.3622(6)nm; α=88.78(4)°,β=91.44(4)°, γ=105.20(4)°; Z=2.3107。     

Michael Addition of Thiols to á,(a)-Unsaturated Carbonyl Compounds Catalyzed by Bifunctional Organocatalysts:Asymmetric Michael Addition and Asymmetric Protonation

Recently the hydrogen-bond activated reactions have attracted much attention.1 Takemoto2 reported a highly enantioselective Michael addition of manolate to nitroolefins catalyzed by a bifunctional organocatalyst with tertiary amine and thiourea moiety. As we known,stereoselective conjugate additions of thiols are interesting due to the standpoint of biological and synthetic importance, however, only very limited good results have been obtained except for the works of Shibasaki3, Kanemasa4 and Deng5 et al.In this letter, we report an efficient catalytic asymmetric Michael reactions of thiols to a,a-unsaturated carbonyl compounds promoted by bifunctional organocatalysts. A series of organocatalysts with chiral amine and thiourea structures were designed and synthesized and have been successfully applied in the conjugated additions of thiols to a,a-unsaturated imides and enones.The reactions got quantitative yields and the ee values were up to 84%. It is noteworthy that the a-asymmetric protonation (up to 43% ee) also could be achieved.The Michael addition between aromatic thiols and a,a-unsaturated carbonyl compounds isdescribed as follows:Works to further increase the enantioselectivity is under investigation in our laboratory.     

芳香基团修饰的三联吡啶钌(Ⅱ)配合物光物理性质及其光损伤CT-DNA研究

钌(Ⅱ)多吡啶配合物具有丰富的光物理和光化学性质,在无机生物光化学的发展和应用中发挥了重大作用.例如,作为高效DNA光断裂试剂,钌(Ⅱ)多吡啶配合物已经得到广泛而深入的研究.     

GC-MS测定中的小体积样品浓缩技术

在GC-MS仪器分析中,采用窄孔毛细管分析柱(0.25 mm id/0.32.mm id),能引进样品的柱容量很小(约20～60μL气体),为了有效地完成进样过程并获得较高分辨的测定结果(离子色谱图),通常采用的技术主要有柱前"冷聚焦"、柱前分流等,以纯化和减少进样体积,确保进样过程与GC-MS系统的载气流量匹配.     

层状LiMnO_2的溶胶凝胶法合成及其改性

采用溶胶凝胶法合成了锂离子电池正极材料层状锰酸锂(o-L iMnO2),并对其进行了N i2+掺杂改性研究,优化了层状L iMnO2的合成路径及制备条件.采用XRD、充放电实验和交流阻抗测试方法研究了N i2+的掺入对o-L iMnO2充放电容量的影响.结果表明N i2+的掺入明显提高了锰酸锂的放电比容量和循环性能,抑制了循环过程中电池阻抗的增加.     

Hydrothermal Synthesis and Crystal Structure of a Highly Reduced Mixed Molybdenum-vanadium Polyoxometalate with Phosphorus-centered [Ni(phen)3]2H2·[PmoⅤ4MoⅥ4VⅣ6M2M44]5-·4H2O(M=0.78MoⅤ+0.22VⅣ)

Polyoxometalates(POMs0) containing Keggin moieties exhibit a wide variety of compositions and have considerable structrral versatility as well as important magnetic, optical,and catalytic proper-ties[1-6].     

Keggin类杂多化合物催化α,β-不饱和羰基化合物环氧化

在乙睛溶剂中考察了一系列杂多化合物和过氧化氢水溶液催化的各种缺电子的α,β-不饱和羰基化合物的环氧化反应.在所研究的杂多化合物中,二缺位的[γ-SiW10(H2O)2O34](Bu4N)4显示出了最高的活性.     

对固体圆二色光谱测试方法的再认识——兼谈“浓度效应”

对近期发展的固体圆二色(CD)光谱测试方法进行了概述、评价和比较, 着重探讨了“浓度效应”的存在使固体CD光谱失真的原因. 通过对本课题组和其他作者已报道的四种化合物的固体CD谱再测试的反思, 强调了依手性化合物的手性光谱学性质不同, 根据浓度梯度实验选择其合适测试浓度的必要性. 对固有手性的阻转异构化合物(S)-1,1'-联二萘酚(S-BINOL)进行了成膜法固体CD谱浓度梯度测试, 发现所得固体薄膜CD谱中也存在着“浓度效应”     

主体分子六次甲基四胺与客体分子二氯化六水合钴(Ⅱ)和结晶水包结物的研究

用X射线单晶衍射分析法研究主体分子六次甲基四胺与客体分子二氯化六水合钴（Ⅱ）和结晶水包结物晶体结构。其分子式为［（CH2）6N4］2·［（Co（H2O）6］Cl2·4H2O，Mr＝59038。晶体属三斜晶系，空间群为P1。晶胞参数：3341个衍射点，其中3148个独立衍射点，2754（F0＞6σ（F0））为可观察反射点。在晶胞内，客体分子和结晶水形成氢键：，客体分子与主体分子形成氢键晶胞之间形成氢键晶胞之内和晶胞之间主体分子和客体分子以及结晶水以氢键和范德华力相联系形成稳定的晶格。