Thermodynamic Studies on Mechanism of Chiral Resolution by Liquid Chromatography

手性识别是分子识别的一个重要组成部分。液相色谱手性拆分机理研究有助于色谱条件的优化和新型手性固定相的设计,也有助于理解手性识别机制。本文就线性色谱与非线性色谱条件下手性拆分过程对应热力学参数的推求方法进行了评述,阐述了相关热力学参数的涵义及其在色谱保留及手性拆分机理探讨中的应用,并展望了该领域的研究前景。Chiral recognition is an important part of molecular recognition.Studies of mechanistic aspects of chiral resolution by liquid chromatography are helpful to optimize chromatographic conditions,to design novel chiral stationary phases and to understand chiral recogniton mechanisms.In this paper,the methodologies for deriving corresponding thermodynamic parameters in the chiral resolution processes by linear or nonlinear chromatography are reviewed.The meaning of correlative parameters is explained.The applications of these parameters in the studies of mechanistic aspects of retentions and chiral resolutions by liquid chromatography are expatiated,and corresponding research prospects are put forward.福建省自然科学基金(No.C0540024);; 福建省教育厅课题(No.JA05301)资

苯氧异丁酸类化合物的合成及其体外抗糖尿病活性(英文)

目的设计及合成新型苯氧异丁酸类抗糖尿病化合物。方法关键步骤采用亲核取代反应或M itsunobu缩合反应把亲脂性片段和酸性片段连接成一体,共合成了8个新目标物。用核磁共振、红外、质谱进行结构确认。结果体外胰岛素增敏活性测试(3T3-L1脂肪细胞)结果显示,分别将罗格列酮、吡格列酮、目标物A和B加入已经存在胰岛素抵抗脂肪细胞培养液中,用GOD-POD方法分析得到上清液葡萄糖浓度分别为5.942,6.339,6.226和6.512mmol.L-1。结论目标物A在胰岛素抵抗实验(3T3-L1脂肪细胞)中抗糖尿病活性介于市售PPARγ激动剂罗格列酮和吡格列酮之间,而目标物B的活性略低于吡格列酮

Thermodynamic studies on mechanism of chiral resolution by liquid chromatography

Chiral recognition is an important part of molecular recognition. Studies of mechanistic aspects of chiral resolution by liquid chromatography are helpful to optimize chromatographic conditions, to design novel chiral stationary phases and to understand chiral recogniton mechanisms. In this paper, the methodologies for deriving corresponding thermodynamic parameters in the chiral resolution processes by linear or nonlinear chromatography are reviewed. The meaning of correlative parameters is explained. The applications of these parameters in the studies of mechanistic aspects of retentions and chiral resolutions by liquid chromatography are expatiated, and corresponding research prospects are put forward

Study on Enantioselective Sulfide Qxidation

光学纯的亚矾化合物具有广泛而重要的应用价值，它的用途分为三种：一是手性中间体和辅剂；二是手性配体和催化剂；三是手性药物，如Esomeprazole。手性亚砜合成方法主要有，一、酶或微生物的方法；二是化学方法。后者又分为拆分、手性辅剂诱导和不对称催化亚矾化。前两种有时还是很重要的方法，但是，不符合绿色化学和原子经济性。不对称催化硫醚氧化是今后发展的必然趋势。现在不对称亚砜化反应的催化剂体系主要有Ti/酒石酸酯、Ti/BINOL,Ti,Mn,V的Salen络合物，V,Fe的Schiff碱络合物。Bolm采用氨基醇衍生的Schiff碱与钒的原位催化剂、以H2O2做氧化剂取得不对称硫醚氧化的突破进展。...Optical pure sulfoxides have extensive and important application. They are used as chiralintermediates, auxiliaries, chiral ligands and catalysts, and chiral drugs, such as esomeprazole. Chiral sulfoxides are synthesized by enzymes and fungus, and by chemical methods,which include resolution, chiral auxiliary induction and enantioselective sulfoxidation. Theformer two methods sometimes are valu...学位：博士后院系专业：化学化工学院化学系_有机化学学号：X2004170

Mild and effective N-phthaloylation of amino acids

In the present work various free amino acids, including tryptophan and tyrosine, were effectively N-phthaloylated under reduced pressure and at lower temperature. Moreover, under these conditions, the presence of phthalic acid in phthalic anhydride did not hinder the N-phthaloylation of amino acids. This simple process is economic, environmentally friendly, and suitable for large-scale production

Enantioseparation of Sulphoxide Compounds with Cellulose-based Chiral Stationary Phase

在纤维素型手性固定相Ch iralcel OD-H正相条件下对6个亚砜化合物进行了拆分,考察了流动相中极性醇添加剂的含量、柱温等对保留及手性拆分效果的影响。与手性硫原子相连的苯环上含有吸电子取代基的化合物拆分效果不理想,而苯甲亚砜、苯乙亚砜及对甲氧基苯甲亚砜得到了基线分离。当流动相为正己烷:异丙醇(92.5∶7.5,V/V),流速1.0 mL/m in,柱温25℃时,3个化合物的分离因子分别为1.351、1.369和1.151,出峰时间在26 m in以内。利用热力学方法对手性拆分机理进行了深入探讨。Six sulphoxide compounds were enantioseparated with a cellulose-based chiral stationary phase,Chiralcel OD-H,in the normalphase mode.The effects of the amount of polar alcohol in the mobile phase and the column temperature on the retention and enantioseparation were studied.It showed that the substance(containing) electron-withdrawing substituent in the aromatic ring exhibited low enantioseparation.Methyl phenyl sulphoxide,ethyl phenyl sulphoxide and methyl 3-methoxyphenyl sulphoxide can be baseline separated,the separation factors are 1.351,1.369 and 1.151 respectively when n-hexane/2-propanol(92.5∶7.5,V/V) was used as eluent,at a flow rate of 1.0 mL/min at 25℃.The retention times were in 26 min.The mechanism of chiral recognition was discussed further by thermodynamic method.福建省高校重点科技项目基金(No.JA99210);; 福建省科技厅三项经费(No.K02092);; 福建省自然科学基金(No.C0540024)资

Study on the synthesis of sulfenylindoles with Dess -Martin periodinane - promoted

目的建立简单、高效制备吲哚硫醚类化合物的方法。方法以Dess- Martin试剂(DMP)为促进剂,异丙醇为溶剂,在室温下反应15 min,促进硫醇和吲哚反应来制备吲哚硫醚类化合物。结果和讨论合成了一系列吲哚硫醚类化合物,结构经~1HNMR、~(13)CNMR和HR- MS鉴定。该反应具有原子经济性好、反应条件温和、反应时间短等优点

JUNO Sensitivity on Proton Decay p→νˉK+p\to \bar\nu K^+ Searches

The Jiangmen Underground Neutrino Observatory (JUNO) is a large liquid scintillator detector designed to explore many topics in fundamental physics. In this paper, the potential on searching for proton decay in $p\to \bar\nu K^+$ mode with JUNO is investigated.The kaon and its decay particles feature a clear three-fold coincidence signature that results in a high efficiency for identification. Moreover, the excellent energy resolution of JUNO permits to suppress the sizable background caused by other delayed signals. Based on these advantages, the detection efficiency for the proton decay via $p\to \bar\nu K^+$ is 36.9% with a background level of 0.2 events after 10 years of data taking. The estimated sensitivity based on 200 kton-years exposure is $9.6 \times 10^{33}$ years, competitive with the current best limits on the proton lifetime in this channel

JUNO sensitivity on proton decay p → ν K + searches*

The Jiangmen Underground Neutrino Observatory (JUNO) is a large liquid scintillator detector designed to explore many topics in fundamental physics. In this study, the potential of searching for proton decay in the $p\to \bar{\nu} K^+$ mode with JUNO is investigated. The kaon and its decay particles feature a clear three-fold coincidence signature that results in a high efficiency for identification. Moreover, the excellent energy resolution of JUNO permits suppression of the sizable background caused by other delayed signals. Based on these advantages, the detection efficiency for the proton decay via $p\to \bar{\nu} K^+$ is 36.9% ± 4.9% with a background level of $0.2\pm 0.05({\rm syst})\pm$$0.2({\rm stat})$ events after 10 years of data collection. The estimated sensitivity based on 200 kton-years of exposure is $9.6 \times 10^{33}$ years, which is competitive with the current best limits on the proton lifetime in this channel and complements the use of different detection technologies