Design and Synthesis of Tri-substituted Chiral Pyrrolidin-2-one Derivatives as CCR4 Antagonists

A series of tri-substituted chiral pyrrolidin-2-one derivatives have been designed and synthesized as CC chemokine receptor 4 （CCR4） antagonists. The structure of CCR4 was built by homology modeling. Asymmetric synthesis was applied to synthesize the R,R configuration chiral pyrrolidin-2-one scaffold. The stereoisomeric con- figurations of the compounds were identified by 2D I H-~H COSY spectroscopy and 1D NOESY spectroscopy. This method was more economical and convenient than traditional X-ray single crystal diffraction. In addition, the inter- actions between these compounds and the N-terminal extracellular tail of CCR4 were studied using capillary zone electrophoresis. The CCR4 chemotaxis inhibition effect was tested in CCR4-transfected HEK293 cells. Several compounds showed potent activities as CCR4 antagonists. Among these compounds, lc is the most active one. Its apparent binding constant of CZE experiment result is （1.569±0.11）× 10s L·mol ^-1, and its percentage inhibition of the HEK293/CCR4 cells migration with the concentration of I gmol·L ^-1 in DMSO is 59%. And compound If has slightly higher affinity to N-terminal of CCR4 according to its apparent binding constant than lb because of the in- troduced ester linkage. Further studies on the mechanism of these compounds are in progress.     

Room-Temperature Bismuth-Catalyzed Bis-arylation of Carbonyl Compounds with Aryl Ethers and Phenols

Using Bi2（SO4）3 as the catalyst and TMSCl as the additive, a wide variety of aldehydes, ketones, and acetals were smoothly condensed with aryl ethers at room temperature to provide the corresponding diarylmethanes and triarylmethanes selectively in good to excellent yields.     

Triazole and Benzotriazole Derivatives as Novel Inhibitors for p90 Ribosomal S6 Protein Kinase 2： Synthesis, Molecular Docking and SAR Analysis

A series of triazole and benzotriazole derivatives as novel p90 ribosomal S6 protein kinase 2 （RSK2） inhibitors were designed and synthesized. The in vitro activities against RSK2 were evaluated, and among 14 compounds, compounds 5, 6, 11, 12, 13 and 14 exhibited enzyme IC50 values of 8.91, 2.86, 3.19, 3.05, 4.49 and 2.09 μmol/L re- spectively. The proposed binding modes were simulated using molecular docking method, and the docking results coupled with the stmcture-activi1：y relationship （SAR） analysis indicated that all these active compounds bound to the RSK2 ATP binding site at NTKD, and the electron-donating groups on the 4-position of phenyl were the deter- minant point for the inhibitory activity.     

两个由1H-苯并三氮唑-1-乙酸构筑的镉、银配合物的合成及晶体结构

合成了2个配位聚合物{[Cd(btaa)(phen)(CH₃COO)]·H₂O}_n(1)和{[Ag₂(btaa)(4,4-bpy)₂](NO₃)·2H₂O}_n(2)(Hbtaa=1H-苯并三氮唑-1-乙酸,phen=1,10-邻菲啰啉,4,4-bpy=4,4-联吡啶),采用单晶X-射线、红外光谱、元素分析和热重分析对配合物进行了表征。配合物1中的镉离子通过1H-苯并三氮唑-1-乙酸根桥连成一位螺旋链状结构。在配合物2中,银离子被4,4-联吡啶连接成一维链状结构,这些一维链通过1H-苯并三氮唑-1-乙酸根桥连以及Ag···Ag作用和π-π堆积连接成一维梯子状结构。此外,还研究了配合物1的荧光性质。     

Ir和IrPd催化剂的合成及结构调控对其甲醇氧化性能的影响

以三嵌段共聚物P123(聚环氧乙烷-聚环氧丙烷-聚环氧乙烷,PEO₂₀-PPO₇₀-PEO₂₀)为还原剂和保护剂,比较了水热法和溶剂热法对纯Ir和IrPd合金催化剂合成及其电催化氧化甲醇(MOR)性能的影响。对于纯Ir催化剂,在相同条件下,溶剂热法能更好地促进Ir前驱体的还原。对于IrPd合金催化剂,溶剂热法可制得表面富含Ir但MOR活性较低的核壳结构产物(IrPd-S)。水热反应得到的不同原子比(IrPd、Ir₂Pd、IrPd₂)的产物粒径更小,元素分布更均匀。其中比例为1∶1的IrPd (IrPd-H)催化剂的MOR电催化活性最高。上述结果表明,通过调节溶剂类型以及P123的结构诱导作用,可以有效地调节纯Ir和IrPd合金催化剂的结构、表面组成和电催化活性。     

稀土化合物TbCl3对成骨细胞系MC3T3-E1增殖、分化和矿化功能的影响

在细胞和分子水平上,研究了稀土化合物氯化铽(TbCl₃)对成骨细胞MC3T3-E1增殖、分化及矿化功能的影响。结果表明,细胞水平上,浓度为0.0001、0.001、0.01、0.1、1和10 μmol·L^-1的TbCl₃均促进MC3T3-E1细胞的增殖、分化及其矿化功能,然而,当浓度升至为100和1000 μmol·L^-1时,TbCl₃表现出抑制作用。分子水平上,浓度为0.0001和0.1 μmol·L^-1的TbCl₃明显上调成骨分化相关基因骨形成蛋白2(BMP-2),碱性磷酸酶(ALP),骨涎蛋白(BSP),Ⅰ型胶原蛋白(Col Ⅰ),骨钙素(OCN)和runt 相关转录因子2(Runx2)的表达。浓度为1 000 μmol·L^-1的TbCl₃则抑制上述成骨分化相关基因的表达。浓度为0.000 1、0.1和1 μmol·L^-1的TbCl₃促进成骨分化相关蛋白Runx2,BMP-2和OCN的表达;结果显示,低浓度的TbCl₃促进MC3T3-E1细胞的成骨分化及矿化功能,而高浓度TbCl₃则呈现出抑制作用。TbCl₃通过调控Runx2的表达刺激早期成骨分化相关基因BMP-2、Col Ⅰ和晚期成骨分化相关基因ALP、OCN的表达,从而诱导MC3T3-E1成骨分化。     

两种含大吸电子取代基的SnR_2Cl_2化合物的合成和晶体结构

以SnCl4和2,4,6-(CF3)3C6H2Li、2,6-(CF3)2C6H3Li为原料合成了两种含大吸电子取代基的化合物Sn[2,4,6-(CF3)3C6H2]2Cl2(缩写为SnAr2Cl2)和Sn[2,6-(CF3)2C6H3]2Cl2(缩写为Sn Ar′2Cl2),利用X射线衍射仪和核磁共振谱仪(19F NMR)表征了产物SnAr2Cl2和SnAr′2Cl2的晶体结构.     

用量子力学研究膦化三氢化铝储氢材料在磷化氢催化作用下的释氢反应机理

利用量子力学第一原理研究了储氢材料膦化三氢化铝(AlH3PH3)在催化剂膦(PH3)作用下的释氢反应机理;首先在MP2/aug-cc-pVDZ水平上计算了反应物、过渡态和产物的几何构型和频率,进而利用内禀反应坐标理论确定了反应的最小能量路径,随后在CCSD(T)/aug-cc-pVDZ水平上对基于MP2优化的几何构型进行了能量校正.结果表明,AlH3PH3释氢的能垒高于Al―P键的离解能,而催化剂PH3不能降低AlH3PH3的释氢能垒.因此,需要寻找其他的催化剂以使AlH3PH3成为一种合用的储氢材料.     

还原氧化石墨烯/碳纳米管/Co_3O_4三元复合材料的制备与电化学性能

将低温水热反应和低温热处理相结合,制备了含还原氧化石墨烯(RGO)、碳纳米管(CNTs)和Co3O4的三元纳米复合材料RGO-CNTs-Co3O4;利用X射线衍射仪、扫描电子显微镜、透射电子显微镜分析了合成产物的相组成和微观结构,分析了其形成过程;并利用电化学测试装置测定了其作为锂离子电池负极材料的电化学性能.结果表明,在合成反应过程中,氧化石墨烯被还原剂肼还原为石墨烯,同时在石墨烯和CNTs表面生成氢氧化钴;再经低温热处理得到RGO-CNTs-Co3O4三元复合材料.Co3O4纳米颗粒均匀分散在由RGO片层和CNTs组成的三维网络结构中;这种三维网络结构既有利于电子和离子的传输,又能够有效抑制Co3O4在脱嵌锂过程中因体积变化引起的结构破坏.总体而言,合成的新型三元复合材料具有高的比容量以及良好的循环性能与倍率性能.     

我国第三方食品检测实验室现状

(1)实验室的规划、布局和规模不到位。目前全国具有食品相关检验能力的技术机构有7000多家,多数隶属于卫生、农业、质检、粮食等部门,从业人数近16万人。因各部门