长寿金丹——锰

锰是人体不可缺少的微量元素。锰是丙酮酸脱羧酶的组成部分，也是许多酶系统的重要活化剂，它能促进、增强人体内许多重要的代谢反应。人体如缺锰，会导致生长发育障碍、身体矮小、瘦弱、智力下降、反应迟钝、贫血、面色苍白、无力以及共济失调、平衡障碍等中枢神经系统症状。由于锰参与人体内胆固醇的合成，而胆固醇是性激素的前体，所以缺锰可引起性激素缺乏，导致不育症。     

Design of Agents Interacting with Immunoregulating Proteins：Potential Inhibitors of the Phenylpyruvate Tautomerase Activity Catalysed by Macrophage Migration Inhibitory Factor （MIF）

The macrophage migration inhibitory factor has been implicated in a number of immune and inflammatory processes. MIF presents particular opportunities for drug design and development with potential therapeutic applications. Drug design strategies taking into consideration of specific stereochemical and tautomeric requirements in the interaction of MIF with substrates and inhibitors allow several novel structures to be de-signed. Our investigations successfully explored the tautomeric and stereochemical aspects of new compounds of the 2-phenylpyruvic acid type, both experimentally, through synthe-sis and structural investigations and computationally, through molecular mechanics and quantum mechanics calculations.     

弱桥联二聚体丙酮酸异烟酰腙合锡(Ⅳ)配合物[(p-CNC6H4CH2)2Sn(C9H7N3O3)(H2O)]2的合成、表征和晶体结构

Diorganotin(Ⅳ) compound [(p-CNC₆H₄CH₂)₂Sn(C₉H₇N₃O₃)(H₂O)]₂ was synthesized by the reaction of tri-p-cyanobenzyltin chloride with Schiff base ligand pyruvic acid isonicotinyl hydrazone. The compound was characterized by elemental analysis, IR, ¹H NMR. The crystal structure was determined by X-ray single crystal diffraction. The crystal belongs to monoclinic space group C2/c, with a=3.143 1(3) nm, b=0.989 99(10) nm, c=1.785 68(18) nm, β=114.908 0(13)°, V=5.039 6(9) nm³, Z=4, μ=1.054 mm^-1, D_c=1.513 Mg·m^-3, F(000)=2 304, R=0.042 8, wR=0.090 3, GOF=0.997. In this compound, the Sn atom exists in a distorted octahedral coordination environment in which one water molecule, one tridentate pyruvic acid isonicotinyl hydrazone ligand, and two trans p-cyanobenzyl groups coordinate to each Sn center, the angle of the axial C10-Sn1-C18 is 166.1(2)°. Two molecules form a weak-bridged dimmer with weak interactions of Sn…O bonding and hydrogen bonds. CCDC: 270796.     

预处理和修饰条件对负载型铑纳米簇催化丙酮酸甲酯不对称加氢性能的影响

 将PVP保护的铑纳米簇合物负载于钛硅分子筛上制得了负载型Rh／PVP－TS－1催化剂．以辛可尼定（CD）作为手性诱导剂时，考察了预处理和修饰条件，如溶剂、温度、氢压、修饰气体及反应时间等因素对催化丙酮酸甲酯不对称加氢反应性能的影响．以THF为溶剂，催化剂在140℃和5．0MPa的氢气中进行预处理1h，并在c（CD）＝4．0mmol／L，20℃和5．0MPa的氢气中修饰0．5h后，在20℃和7．0MPa的氢气中反应1h，丙酮酸甲酯的转化率和对映选择性分别为40．8％和39．9％．     

四氮杂大环铜(Ⅱ)参与的新型振荡反应实验研究

本文报道了以5,7,12,14-四乙基-7,14-二甲基-1,4,8,11-四氮杂环十四-4,11-二烯铜(Ⅱ)配合物为催化剂,NaBrO₃为氧化剂,丙酮酸为有机底物,稀硫酸为介质的振荡反应新体系。对该体系的振荡特性进行了描述,并研究了Ag⁺、Hg²⁺,还原性物质,自由基抑制剂,四氯化碳以及温度对振荡反应的影响。     

辛可尼定修饰的铂纳米簇合物催化丙酮酸甲酯不对称加氢反应的研究

研究了辛可尼定(cinchonidine)作手性修饰剂修饰的氧化铝负载铂纳米簇合物(Pt-PVP-γ-Al2O3)催化丙酮酸甲酯不对称氢化反应,采用甲醇的碱溶液做溶剂,着重考察了低温条件下催化剂的活性和对映选择性的变化.优化的反应条件为0℃,5.0MPaH2,[cinchonidine]=3.24×10-3mol/L,[KOH]=0.02mol/L,1h内丙酮酸甲酯不对称加氢的转化率为32.2%,对映选择性达到52.2%;     

Me［14］－N_4大环四烯镍（Ⅱ）催化、BrO_3~－氧化丙酮酸的振荡化学反

本文报道了一种以２，３，９，１０－四甲基－１，４，８．１１－四氮杂环十四－１３，８，１０－四烯镍（Ⅱ）配合物［Ｎｉ［ＴＩＭ］２＋为催化剂、ＮａＢｒＯ３为氧化剂、丙酮酸为有机底物、稀硫酸为介质的振荡化学反应新体系．对该体系的振荡特性进行了描述．研究了Ａｇ＋、Ｈｇ２＋、还原性物质、自由基抑制剂、四氯化碳以及温度对振荡的影响．     

（Cu（Me6（14）4,11—dieneN4）^2＋——丙酮酸—溴酸钠—硫酸体系的新型振…

报道一种以５，７，７，１２，１４，１４－六甲基－１，４，８，１１－四氮杂环十四－４，１１－二烯酮（Ⅱ）配合物为催化剂，丙酮酸为有机底物，溴酸钠作氧化剂，硫酸为介质的振荡化学反应新体系，描述了该体系的振荡特性，得到了振荡范围，详细研究了各物种的初始浓度，温度等对振荡行为的影响，通过研究还原性物质（维生素Ｃ和葡萄糖）自由基抑制剂（丙烯酰胺，丙烯腈和Ｈ２Ｏ２），Ａｇ＾＋，Ｈｇ＾２＋和ＣＣｌ４等对振荡的影     

介孔载体负载Pt催化剂上α-酮酸酯的不对称氢化

以介孔材料SBA-15、经或未经Al2O3修饰的具有三维立方孔道结构的SiO2为载体,制备了负载型Pt催化剂,并用于催化α-酮酸酯底物2-氧代-4-苯基-丁酸乙酯(EOPB)和丙酮酸乙酯(Etpy)的不对称氢化反应中.结果表明,当SBA-15孔径由6.2,7.6和9.2nm依次增加时,EOPB不对称氢化的活性和手性选择...     

One-pot multicomponent synthesis of novel tricyclic pyrrolo[2, 1-c][1, 4]benzoxazines

A simple and efficient synthetic protocol has been developed using a one-pot multicomponent reaction （MCR） involving 2-aminophenols, dialkyl acetylenedicarboxylates, and ethyl bromopyruvate in poly（ethyleneglycol）. This protocol was utilized to prepare novel pyrrolo[2,1-c][1,4]benzoxazines in excellent yields.