Synthesis of Chiral Nitrogen-containing Tetradentate Ligands and their Applications in Asymmetric Transfer Hydrogenation

不对称催化反应的效率取决于手性催化剂。长期以来，开发高活性、高选择性的优秀手性催化剂一直是不对称催化研究的重要组成部分。本论文研究开发了四个新手性配体或手性催化体系，并有效实现了一系列芳香酮的不对称氢转移氢化。1、含氮手性配体由于其原料来源广泛、合成简便，因而是不对称转移氢化领域研究最多的一类手性配体。本研究首先以8-羟基喹啉为反应原料，简便地合成了手性含氮四齿配体(R,R)-C6N4，并分别与钌、铑或铱等组合，考察它们在芳香酮不对称氢转移氢化反应的性能。结果表明，其催化活性和对映选择性均不高；改变碱添加量或配体用量对提高对映选择性效果甚微。降低底物与催化剂的摩尔比(S/C)可较大地提高选择性...The efficiency of asymmetric catalysis lies on chiral catalysts. Therefore, developing excellent catalysts with high activity as well as high enantioselectivity has long been an indispensable part of asymmetric catalysis. In this dissertation, four new chiral ligands or chiral catalytic systems have been developed and employed in asymmetric transfer hydrogenation of aromatic ketones. 1. Nitroge...学位：理学博士院系专业：化学化工学院化学系_物理化学(含化学物理)学号：B20032503

重量-压强法在大输液配制系统定容中的应用

目的建立医院大输液制剂配制系统定容方法。方法拟定纯化水体积与定容参数的相关性,测定输液的相对密度,计算配制量输液等同于同重量纯化水的体积,计算理论定容参数。结果采用重量-压强法能准确对医院大输液制剂配制系统进行定容。结论该方法操作简便,迅速,可用于大输液系统定容

手性铁催化体系在不对称催化中的应用研究

本文介绍了手性铁催化体系在酮及亚胺的不对称还原、烯烃及硫醚的不对称氧化、不对称环加成、不对称环丙烷化以及不对称frIEdEl-CrAfTS烷基化等反应中的应用.国家自然科学基金(No.20423002;20703034);福建省自然科学基金(No.2008J0235

Asymmetric Transfer Hydrogenation of Ketones Catalyzed by Chiral Carbonyl Iron Systems

手性羰基铁络合物很少被用于芳香酮的不对称氢转移氢化 .利用不同的羰基铁络合物与手性双胺双膦配体现场络合 ,形成手性胺膦铁催化体系 .考察了它们对多种芳香酮的不对称氢转移催化氢化性能 .结果表明 ,三核的手性胺膦铁簇合物是催化芳香酮不对称氢转移氢化的较好体系 .当用三核的铁簇合物 [Et3 NH] + [HFe3 (CO) 11] -体系催化 1,1 二苯基丙酮的氢化时 ,最高可获得 98%的对映选择性 .通过现场红外光谱测定 ,揣测羰基铁簇合物Fe3 (CO) 12 在催化反应过程中保持三核的簇合物的簇骼不变 .Chiral carbonyl iron systems have seldom been used in asymmetric transfer hydrogenation of aromatic ketones. In this study, new chiral iron catalytic systems were synthesized in situ from different carbonyl iron complexes with chiral diaminodiphosphine ligands, respectively. These catalytic systems have been used for the asymmetric transfer hydrogenation of various aromatic ketones under mild conditions. The results indicated that trinuclear iron complexes were the best systems for the reactions. When the [Et 3NH]+[HFe 3(CO) 11]- as catalyst was used for asymmetric reduction of 1,1-diphenylacetone, high enantioselectivity up to 98% was achieved. Monitoring the reaction in situ by infrared spectroscopy, it could be conjectured that the carbonyl iron cluster Fe 3(CO) 12 kept its trinuclear skeleton unchanged during the catalytic reaction.国家自然科学基金 (No.2 0 3730 56);; 福建省科技厅重大科技项目 (No.2 0 0 2F0 1 6);; 福建省厦门市科技局重大科技项目 (No .350 2Z2 0 0 2 1 0 4 4 )资

噻唑烷二酮类降糖药的研究进展及临床评价

糖尿病是以慢性高血糖为特征的一组异质性代谢性疾病,由胰岛素分泌不足和(或)胰岛素作用缺陷所引起,以慢性高血糖伴糖类、脂肪和蛋白质的代谢障碍为特征。目前,根据药理作用机制,常见的口服降糖药可分为7类:磺酰脲类、非磺酰脲类胰岛素促泌剂、α-葡萄糖苷酶抑制剂、噻唑烷二酮类、双胍类、胰高糖素样肽1(glP-1)相关降糖药及还原酶抑制剂[1]。本文主要就噻唑烷二酮类降糖药的研究进展及临床评价作

本土化人格特质与工作绩效的关系:线性与非线性

采用跨文化(中国人)个性测量表(Cross-CulturalChinesePersonalityAssessmentInventory,简称CPAI-2)对182名服务企业员工进行本土化人格特质测查,并同时获得其直接上级主管对他/她工作绩效的评定。目的是探讨本土化人格特质与工作绩效之间的关系模式(线性或非线性)。结果表明:和谐性与工作绩效具有正向的线性关系;面子与工作绩效具有倒U曲线关系;人情与工作绩效具有正U曲线关系;其他本土化人格特质与工作绩效的关系均不显著

The Relationships between Indigenous Personality Traits and Job Performance： Linear and Nonlinear

采用跨文化(中国人)个性测量表(Cross-Cultural[Chinese]PersonalityAssessmentInventory,简称CPAI-2)对182名服务企业员工进行本土化人格特质测查,并同时获得其直接上级主管对他/她工作绩效的评定。目的是探讨本土化人格特质与工作绩效之间的关系模式(线性或非线性)。结果表明:和谐性与工作绩效具有正向的线性关系;面子与工作绩效具有倒U曲线关系;人情与工作绩效具有正U曲线关系;其他本土化人格特质与工作绩效的关系均不显著

无机热化学数据库中复氧化物热力学性质的计算机预报

建立了估算复氧化物高温热力学性质的数学模型.按照此模型,可以预报若干复氧化物四项高温热力学性质的数值.本法预报值的均方根偏差与实验值误差相当

Design of micro-arrayed multichannel optical filter for multispectral colposcope

设计了一种可与阴道镜中的图像传感器集成的微型化多通道滤光片,以使阴道镜具有光谱成像能力。采用微光刻技术及真空多层镀膜技术制成微滤光片,内部微滤光单元的通光波长与病灶标志物反射光谱或荧光光谱的特征峰相对应,与图像传感器集成后,能够获取几幅与光谱特征峰对应的特征波长图像,这些图像凸显了病变组织与正常组织的差异,提供了宫颈组织上皮表面形态变化及上皮组织内病灶标志物含量变化的信息。已加工出通光波长为λ1=630nM、λ2=460nM、λ3=515nM、λ4=577nM的微滤光片,微滤光单元面积为10μMx10μM,各通道带宽约为40nM,透射率为30%~40%。实验显示微滤光片的光学性能已达到光谱成像的基本要求,与阴道镜集成后,能有效提高其诊断的灵敏度与特异性,减少活检频率。A micro-arrayed multichannel optical filter is proposed to allow the colposcopy to have an ability of multispectral imaging.The micro-arrayed filter is fabricated by micro-lithographic procedures and vacuum multilayer thin film coatings,and the wavelengths of light passing through the filter correspond to the characteristic peaks of the biomarkers in the reflectance or fluorescence spectra.After integrating the filter with an image sensor on colposcopy,multiple spectral images centered at different wavelengths can be obtained to provide the information about morphological changes on cervical surface and the quantitative variation of the biomarkers in cervical tissues.The micro-arrayed filter with four kinds of filter cells(λ1=630 nm,λ2=460 nm,λ3=515 nm,λ4=577 nm) has been fabricated successfully with an area of 10 μm×10 μm for each filter cell.The bandwidth of each filter cell is about 40 nm,and the transmittance is between 30% and 40%.Experiments demonstrate that the optical properties of micro-arrayed filter satisfy the basic requirements of multispectral imaging.After integrating with a colposcope,the sensitivity and specificity of colposcope diagnosis is improved significantly,which can reduce the biopsy frequencies for patients.国家自然科学基金资助项目(No.61172046);福建省自然科学基金资助项目(No.2011J01363

Asymmetric Transfer Hydrogenation of Propiophenone Catalyzed by Chiral Nitrogen-containing Tetradentate Ligand

利用8-羟基喹啉与手性环己基二胺的反应,合成了对空气和水稳定的手性含氮四齿配体(R,R)-C6N4;进而分别与钌、铑或铱等金属络合物组合,现场生成催化体系,用于苯丙酮的不对称氢转移氢化反应;考察了碱添加量、配体用量和底物与催化剂用量摩尔比对反应性能的影响.结果表明,该配体与RhHCO(PPh3)3的混合体系效果较好,可得到68%ee的对映选择性.This paper describes a new chiral nitrogen-containing tetradentate ligand(R,R)-C6N4 synthesized by the interaction of 8-aminoquinoline and chiral cyclohexyl-1,2-diamine in refluxing water.The chiral ligand as a pale-yellow pillar crystals are very stable to air and water.The mixed systems combined from the ligand and various Ru,Rh or Ir complexes have been used as catalyst precursors for asymmetric transfer hydrogenation of propiophenone.The effects of chiral catalytic efficiency on various metal complexes,amount of addition of base and the molar ratios of ligand/metal were also observed.The results indicate that chiral system RhH(CO)(PPh3)3/(R,R)-C6N4 is a better catalyst for the reduction of propiophenone,leading to the corresponding optically active alcohol up to 68% ee.国家自然科学基金(20373056,20423002);; 福建省重大专项前期科研项目(2005YZ1020)资