包合反应手性萃取分离芳香酸对映体及其动力学研究
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摘要
药物对映体的制备性分离研究是当前最热门的课题之一。手性溶剂萃取是药物对映体制备性分离的一种十分重要方法,相对于化学拆分法、酶或微生物法和色谱拆分法,手性溶剂萃取分离体系的选择有一定的规律可循,且适用范围也大大拓宽。包合反应手性萃取是近年发展起来的一种高效分离技术,受到众多研究者的重视。本论文主要工作是研究疏水性α-环己基扁桃酸(α-CHMA)和苯基琥珀酸(PSA)两种对映体在含有手性选择体的水—有机溶剂两相系统中的萃取分配行为；并在优化的萃取体系下用恒界面池法研究萃取过程的动力学,为药物对映体的萃取分离提供理论依据和技术参数。主要内容和结果如下：
1.α-CHMA和PSA对映体手性萃取分离的研究：采用具有工业应用前景的亲水性β-环糊精衍生物(β-CDs)作为手性选择体,从分配系数和分离因子上考察有机溶剂的种类、萃取剂种类及其浓度、对映体浓度、pH及温度等因素对α-CHMA和PSA对映体萃取性能的影响。研究不同种类的β-CDs手性选择体的萃取性能及手性识别规律。
结果表明：包合反应萃取具有很强的手性分离能力,水溶性萃取剂羟丙基-β-环糊精(HP-β-CD)、羟乙基-β-环糊精(HE-β-CD)、甲基-β-环糊精(Me-β-CD)均对S-α-CHMA的识别能力大于对R-α-CHMA的识别能力,而对PSA识别能力刚好相反；一级萃取分离后,S-α-CHMA和R-α-CHMA对映体的分配系数(ks和kR)分别为4.77和2.36,分离因子(α)达2.02；R-PSA和S-PSA对映体的分配系数(kR和kS)分别为2.38和1.00,分离因子(α)达2.38。同时有机溶剂、pH、温度、对映体和萃取剂浓度对手性分离能力有显著的影响。
2.HP-β-CD对α-CHMA、PSA对映体的包合反应萃取动力学研究：通过恒界面池法研究β-CDs对α-CHMA和PSA对映体反应萃取的动力学特性；考察了搅拌速率、界面面积、对映体浓度和萃取剂浓度等操作参数对α-CHMA和PSA对映体萃取动力学的影响。实验结果表明：HP-β-CD萃取α-CHMA对映体的反应为“快反应”；HP-β-CD萃取PSA对映体的反应也为“快反应”；萃取反应是对映体浓度的—级反应,是萃取剂浓度的二级反应；反应速率常数对S-α-CHMA,R-α-CHMA而言分别为70584.8 L2/mol2·s,18079.4 L2/mol2·s；而对R-PSA,S-PSA而言分别为32011.8 L2/mol2·s,7408.7 L2/mol2·s。这些数据对萃取过程的设计是很重要的。
Preparative techniques for the separation of drug enantiomers have a great interesting potential. Chiral extraction is a very important method for preparative separation of enantiomers. It has some regularity and a larger application range in contrasting to chemical resolution, fermentation and enzymatic transformation and chromatography. Reactive extraction is a very effective separation technique with great promise. In the thesis, distribution behaviors ofα-cyclohexyl-mandelic acid (α-CHMA) enantiomers and phenylsuccinic acid (PSA) enantiomers were examined in the aqueous-organic solvent of a two-phase systerm containing a chiral selector. And then, the extraction kinetics was studied using constant- interface area cell under the optimized system to provide theoretical bases and technique parameters for enantioseparation process. The main contents and results can be summarized as follows:
1. Study on chiral extraction ofα-CHMA enantiomers and PSA enantiomers:The influence of the types of organic solvents and P-cyclodextrin derivatives (β-CDs), the concentrations of the extractants and enantiomers, pH and temperature on distribution ratio (k) and enantioselectivity (α) forα-CHMA and PSA enantiomers, was separately investigated using hydrophilicβ-CDs as chiral selectors. The extraction performance and chiral recognition mechanism were studied.
The experimental results indicate that reactive extraction has strong chiral separation ability. hydroxypropyl-β-cyclodextrin(HP-β-CD), hydroxyethyl-β-cyclodextrin(HE-β-CD) and methyl-β-cyclodextrin (Me-β-CD) have higher recognition ability for S-α-CHMA enantiomer than that for R-α-CHMA enantiomer, among which HP-β-CD has the strongest separation ability. But theseβ-CDs have reversed recognition ability for phenylsuccinic acid enantiomers. In the optimized extraction process forα-CHMA enantiomers, the extraction performance ofα-CHMA is optimum by one stage extraction, and the distribution ratio for S-α-CHMAt(kS) and for R-α-CHMA(kR) and separation factor(α) are 4.77,2.36 and 2.02, respectively. In the extraction process for PSA enantiomers, the extraction performance of PSA is optimum by one stage extraction, and the distribution ratio for R-PSA (kR) and for S-PSA(kS) and separation factor(α) are 2.38,1.00 and 2.38, respectively. Meanwhile, organic solvents, concentration of extractants, pH and temperature have great effects on chiral separation ability.
2. Study on the reactive extraction kinetics ofα-CHMA enantiomers, PSA enantiomers using HP-β-CD as extractant:The reactive extraction kinetics was determined in a stirred cell with a constant interfacial area. The extraction process was measured at various stirring speeds, interfacial areas, initial enantiomers concentration in organic phase as well as HP-β-CD concentration in aqueous phase. The experimental results demonstrate that, the exraction reaction kinetics is 'fast' for HP-β-CD extractionα-CHMA enantiomers, and the reactions between HP-β-CD and PSA enantiomers are also fast. The reactions have been found to be first order with respect to enantiomers and second order with respect to HP-β-CD with forward rate constants of 70584.8 L2/mol2·s and 18079.4 L2/mol2·s for S-α-CHMA and R-α-CHMA, respectively. The rate constants of HP-β-CD extraction PSA enantiomers are 32011.8 L2/mol2·s and 7408.7 L2/mol2·s for R-PSA and S-PSA, respectively. These data will be useful in the design of extraction processes.
1.α-CHMA和PSA对映体手性萃取分离的研究：采用具有工业应用前景的亲水性β-环糊精衍生物(β-CDs)作为手性选择体,从分配系数和分离因子上考察有机溶剂的种类、萃取剂种类及其浓度、对映体浓度、pH及温度等因素对α-CHMA和PSA对映体萃取性能的影响。研究不同种类的β-CDs手性选择体的萃取性能及手性识别规律。
结果表明：包合反应萃取具有很强的手性分离能力,水溶性萃取剂羟丙基-β-环糊精(HP-β-CD)、羟乙基-β-环糊精(HE-β-CD)、甲基-β-环糊精(Me-β-CD)均对S-α-CHMA的识别能力大于对R-α-CHMA的识别能力,而对PSA识别能力刚好相反；一级萃取分离后,S-α-CHMA和R-α-CHMA对映体的分配系数(ks和kR)分别为4.77和2.36,分离因子(α)达2.02；R-PSA和S-PSA对映体的分配系数(kR和kS)分别为2.38和1.00,分离因子(α)达2.38。同时有机溶剂、pH、温度、对映体和萃取剂浓度对手性分离能力有显著的影响。
2.HP-β-CD对α-CHMA、PSA对映体的包合反应萃取动力学研究：通过恒界面池法研究β-CDs对α-CHMA和PSA对映体反应萃取的动力学特性；考察了搅拌速率、界面面积、对映体浓度和萃取剂浓度等操作参数对α-CHMA和PSA对映体萃取动力学的影响。实验结果表明：HP-β-CD萃取α-CHMA对映体的反应为“快反应”；HP-β-CD萃取PSA对映体的反应也为“快反应”；萃取反应是对映体浓度的—级反应,是萃取剂浓度的二级反应；反应速率常数对S-α-CHMA,R-α-CHMA而言分别为70584.8 L2/mol2·s,18079.4 L2/mol2·s；而对R-PSA,S-PSA而言分别为32011.8 L2/mol2·s,7408.7 L2/mol2·s。这些数据对萃取过程的设计是很重要的。
Preparative techniques for the separation of drug enantiomers have a great interesting potential. Chiral extraction is a very important method for preparative separation of enantiomers. It has some regularity and a larger application range in contrasting to chemical resolution, fermentation and enzymatic transformation and chromatography. Reactive extraction is a very effective separation technique with great promise. In the thesis, distribution behaviors ofα-cyclohexyl-mandelic acid (α-CHMA) enantiomers and phenylsuccinic acid (PSA) enantiomers were examined in the aqueous-organic solvent of a two-phase systerm containing a chiral selector. And then, the extraction kinetics was studied using constant- interface area cell under the optimized system to provide theoretical bases and technique parameters for enantioseparation process. The main contents and results can be summarized as follows:
1. Study on chiral extraction ofα-CHMA enantiomers and PSA enantiomers:The influence of the types of organic solvents and P-cyclodextrin derivatives (β-CDs), the concentrations of the extractants and enantiomers, pH and temperature on distribution ratio (k) and enantioselectivity (α) forα-CHMA and PSA enantiomers, was separately investigated using hydrophilicβ-CDs as chiral selectors. The extraction performance and chiral recognition mechanism were studied.
The experimental results indicate that reactive extraction has strong chiral separation ability. hydroxypropyl-β-cyclodextrin(HP-β-CD), hydroxyethyl-β-cyclodextrin(HE-β-CD) and methyl-β-cyclodextrin (Me-β-CD) have higher recognition ability for S-α-CHMA enantiomer than that for R-α-CHMA enantiomer, among which HP-β-CD has the strongest separation ability. But theseβ-CDs have reversed recognition ability for phenylsuccinic acid enantiomers. In the optimized extraction process forα-CHMA enantiomers, the extraction performance ofα-CHMA is optimum by one stage extraction, and the distribution ratio for S-α-CHMAt(kS) and for R-α-CHMA(kR) and separation factor(α) are 4.77,2.36 and 2.02, respectively. In the extraction process for PSA enantiomers, the extraction performance of PSA is optimum by one stage extraction, and the distribution ratio for R-PSA (kR) and for S-PSA(kS) and separation factor(α) are 2.38,1.00 and 2.38, respectively. Meanwhile, organic solvents, concentration of extractants, pH and temperature have great effects on chiral separation ability.
2. Study on the reactive extraction kinetics ofα-CHMA enantiomers, PSA enantiomers using HP-β-CD as extractant:The reactive extraction kinetics was determined in a stirred cell with a constant interfacial area. The extraction process was measured at various stirring speeds, interfacial areas, initial enantiomers concentration in organic phase as well as HP-β-CD concentration in aqueous phase. The experimental results demonstrate that, the exraction reaction kinetics is 'fast' for HP-β-CD extractionα-CHMA enantiomers, and the reactions between HP-β-CD and PSA enantiomers are also fast. The reactions have been found to be first order with respect to enantiomers and second order with respect to HP-β-CD with forward rate constants of 70584.8 L2/mol2·s and 18079.4 L2/mol2·s for S-α-CHMA and R-α-CHMA, respectively. The rate constants of HP-β-CD extraction PSA enantiomers are 32011.8 L2/mol2·s and 7408.7 L2/mol2·s for R-PSA and S-PSA, respectively. These data will be useful in the design of extraction processes.
引文
[1]尤启冬,林国强.手性药物[M].北京：化学工业出版社,2004.3-5
[2]杨振云,张贻亮.手性工业[J].中国医药工业杂志,1998,27(10)：469-475
[3]郭荷民,胡季平.手性药物的立体选择考虑[J].中国药理学报,1997,13(3)：284-287
[4]于平.手性化合物研究进展[J].化工进展,2002,21(9)：635-638
[5]Thalji R K, Ellman J A, Bergman R G. Highly efficient and enantioselective cyclization of aromatic lmines via directed C-H bond activation[J]. J. Am. Chem. Soc.,2004,126(23):7192-7193
[6]Ryu D H, Corey E J. Highly enantioselective cyanosilylation of aldehydes catalyzed by a chiral oxazaborolidinium ion[J]. J. Am. Chem. Soc.,2004, 126(26):8106-8107
[7]Horvath J D, Koritnik A K, Kamakoti P, Sholl D S, Gellman A J. Enantioselective separation on a naturally chiral surface[J]. J. Am. Chem. Soc.,2004,126(45): 14988-14994
[8]Pickering P J, Chaudhuri J B. Equilibrium and kinetic studies of the enantio-selective complexation of (D/L)-phenylalanine with copper(Ⅱ) N-decyl-(L)-hydro -xylproline [J]. Chem. Eng. Sci.,1997,52(3):377-386
[9]黄量,戴立信.手性药物的化学与生物学[M].北京：化学工业出版社,2004：1
[10]苑可,戴立信.关注“手性药物”[J].科技术语研究,2002,4(2)：46-48
[11]Mostafavi S A, Foster R T. Pharmacokinetics of metoprolol enantiomers following single and mutiple administration of racemate in rat[J]. Int. J. Pharm., 2000,202(1):97-102
[12]Guxman A, Yuste F, Toscano R A, et al. Absolute configuration of (-)-5-benzoyl-1,2-dihydro-3H-pyrrolo[1,2-alpha] pyrrole-1-carboxylic acid, the active enantiomer of ketorolac[J]. J. Med. Chem.,1986,29(4):589-591
[13]Mitscher L A, Sharma P N, Chu-Daniel T W, et al. Chiral DNA gyrase inhibitors 2.Asymmetric synthesis and biological activity of the enantiomers of 9-fluoro-3-methyl-10(4-methyl-1-piperacinyl)-7-oxo-2,3-dihydro-7H-pyrido[1,2,3-de]-1, 4-benzoxazine-6-carboxylic acid(ofloxacin)[J]. J. Med. Chem.,1987,30(12): 2283-2286
[14]Plenge P, Mellerup E T, Honore T, et al. The activity of 25 paroxetine/femoxetine structure variants in various reactions, assumed to be important for the effect of antidepressants[J]. J. Pharm. Pharmacol.,1987,39(11):877-882
[15]Shum W P, Chen J, Cannarsa M J. Synthesis and enantiomeric purity determination of chiral 3-benzylglycidol, a key synthon for hiv protease inhibitors[J]. Chirality,2004,6 (8):681-684
[16]Halabi A, Ferrayoli C, Palacio M, Dabbene V, Palacios S. Validation of a chiral HPLC assay for (R)-salbutamol sulfate[J]. J. Pharm. Biomed. Anal.,2004,34(1): 45-51
[17]曾苏,沈向忠,刘志强.手性药物的药理及其体内对映体的HPLC测定[J].浙江医科大学学报,1994,23(5)：235-239
[18]廖永卫,陈卫平.手性药物与单一对映体药物的发展[J].国外医药,制剂分册,1996,17(1)：9-15
[19]Blanco M, Valverde I. Chiral and non chiral determination of dopa by capillary electrophoresis[J]. J. Pharm. Biomed. Anal.,2003,31(3):431-438
[20]芮建中,吴锦芳,庞晓东.手性药物对映体选择性的药代动力学和药效学与临床合理用药[J].中国药理学通报,1998,14(1)：19-22
[21]Raffa R B, Friderichs E, Reimann W. Complementory and synergistic antinociceptive interaction between the enantiomers of tramadol[J]. J. Pharmacol. Exp. Ther.,1993,267(1):331-340
[22]林国强,杜灿屏.手性与手性研究中的若干科学问题.中国科学基金,2003,17(2)：72-76
[23]Sheldon R A. Organic Synthesis-Past, Present and Future[J]. Chem. Ind.,1992, 23(12):903-906
[24]Gimenez F, Pennie R A, Crevoisier C. Stereoselective pharmacokinetics of mefloquine in healty caucasinans after multiple does[J]. J. Pharm. Sci.,1994, 83(6):824-827
[25]邓金根,迟永祥,朱槿.化学拆分的新方法研究[J].合成化学,1999,7(4)：340-345
[26]Gihani E, Moharem T, Jonathan M J W. Dynamic kinetic resolution [J]. Curr. Opin. Chem. Biol,1999,3(1):11-15
[27]Allen J V, Williams J M J. Dynamic kinetic resolution with enzyme and palladium combinations [J]. Tetrahedron Lett.,1996,37(11):1859-1862
[28]姚传义,张金红,俞耀庭.酶法手性化合物的合成与拆分[J].化工进展,2000,19(6)：35-50
[29]杨柳青,何南.手性药物的生物转化[J].中国新药杂志,2000,9(12)：817-820
[30]Bevinakatti H S, Benerji A A. Practical chemoenzymatic synthesis of both enantiomers of propranolol[J]. J. Org. Chem.,1991,56(18):5372-5375
[31]LutjeSpelberg J H, Tang L X, Kellogg R M, et al. Enzymatic dynamic kinetic resolution of epihalohydrins[J]. Tetrahedron:Asymmetry,2004,15(7): 1095-1102
[32]Battistel E, Bianthi D, Cesti P, Pina C. Enzymatic resolution of (S)-(+)-Naproxen in a continuous reactor[J]. Biotechnol. Bioeng.,1991,38(6):659-664
[33]Joly S, Nair M S. Studies on the enzymatic kinetic resolution of β-hydroxy ketones[J]. J. Mol. Catal. B:Enzym.,2003,22(3-4):151-160
[34]Van Tol J, Bert A, Duine J, et al. Description of hydrolase enantioselectivity must be based on the actual kinetic resolution of glycidyl(2,3-epoxy-1-propyl) butyrate by pig pancreas lipase[J]. Biocatal. Biotransform.,1995,12(2):99-117
[35]Straathof A J J, Rakels J L L, van Tol B A J, Heijnen J J. Improvement of lipase catalyzed kinetic resolution by tandem transesterification[J]. Enzyme Microb. Technol.,1995,17(7):623-628
[36]徐诗伟,徐清.酶法拆分腈类制备光学活性2-芳基丙酸[J].微生物学通报,1995,22(3)：184-187
[37]徐刚,程咏梅,吴坚平,杨立荣.有机相酶催化拆分制备(S)-2-氯-1-(2-噻吩)-乙醇[J].有机化学,2007,27(7)：857-861
[38]Khan M, Viswanathan B, Rao D S, Reddy R. Chiral separation of Frovatriptan isomers by HPLC using amylose based chiral stationary phase[J]. J. Chromatogr. B,2007,846(1-2):119-123
[39]Xiong X, Baeyens W R G, Aboul-Enein H Y, Delanghe J R, Tu TT, Ouyang J. Impact of amines as co-modifiers on the enantioseparation of various amino acid derivatives on a tert-butyl carbamoylated quinine-based chiral stationary phase[J]. Talanta,2007,71(2):573-581
[40]Yan H Y, Row K H. Rapid chiral separation and impurity determination of levofloxacin by ligand-exchange chromatography[J]. Anal. Chim. Acta,2007, 584(1):160-165
[41]Zhou Shanshan, Ouyang Jin, Willy R G B, et al. Chiral separation of four fluoroquinolone compounds using capillary electrophoresis with hydroxypropyl-(3-cyclodextrin as chiral selector[J]. J. Chromatogr. A,2006, 1130(2):296-301
[42]Ma S L, Shen S, Haddad N, et al. Chromatographic and spectroscopic studies on the chiral recognition of sulfated β-cyclodextrin as chiral mobile phase additive: Enantiomeric separation of a chiral amine[J]. J. Chromatogr. A,2009,1216(8): 1232-1240
[43]傅若农,顾峻岭.近代色谱分析[M].北京：国防工业出版社,1998：25-27
[44]Ward T J, Farris Ⅲ A B. Chiral separations using the macrocyclic antibiotics:a review[J]. J. Chromatogr. A,2001,906(1-2):73-89
[45]Stanffer S T, Dessy R E. CHIRULE:a chiral chromatographic column selection system utilizing similarity searching[J]. J. Chromatogr. Sci.,1994,32(6): 228-235
[46]胡珊珊,吴怡祖,史美仁.β-环糊精衍生物手性流动相HPLC法拆分α-环己基扁桃酸对映体[J].精细化工,2004,21(10)：731-732
[47]马剑茵.手性药物的色谱分离方法[J].中国医药工业杂志,2002,33(4)：199-202
[48]Lin J Y. Comparison of the chiral resolution on cis-trans isomeric chiral stationary phases derived from (S)-1-(1-naphthyl)ethylamine[J]. J. Chromatogr. A,1996,740(2):183-193
[49]黄蓓,陈欢林.选择性扩散和选择性吸附手性拆分膜及其应用[J].功能高分子学报,2002,15(4)：480-486
[50]Thoelen C, M. De bruyn, Theunissen E, Kondo Y, Vankelecom I F J, Grobet P, Yoshikawa M, Jacobs P A. Membranes based on poly (γ-methyl-1-glutamate): synthesis, characterization and use in chiral separations [J]. J. Membr. Sci.,2001, 186(2):153-163
[51]Miyako E, Maruyama T, Kamiya F, Goto M. Highly enantioselective separation using a supported liquid membrane encapsulating surfactant-enzyme complex[J]. J. Am. Chem. Soc.,2004,126(28):8622-8623
[52]Keurentjes J T F, Nabuurs L J W, Vegter E A. Liquid membrane technology for the separation of racemic mixtures[J]. J. Membr. Sci.,1996,113(2):351-360
[53]Krieg H M, Lotter J, Keizer K, Breytenbach J C. Enrichment of chlorthalidone enantiomers by an aqueous bulk liquid membrane containing β-cyclodextrin[J]. J. Membr. Sci.,2000,167(1):33-45
[54]Rmaile H H, Schlenoff J B. Optically active polyeletrolyte multilayers as membranes for chiral separations[J]. J. Am. Chem. Soc.,2003,125(22): 6602-6603
[55]Yoshikawa M, Murakoshi K, Kogita T, Hanaoka K, Guiver M D, Robertson G P. Chiral separation membranes from modified polysulfone having myrtenal-derived terpenoid side groups[J]. Eur. Polym. J.,2006,42(10): 2532-2539
[56]唐课文,周春山,蒋新宇.支载液膜双有机相萃取分离氧氟沙星外消旋体[J].中国科学(B),2002,32(6)：491-496
[57]Lee N H, Frank C W. Separation of chiral molecules using polypeptide-modified poly (vinylidene fluoride) membranes[J]. Polymer,2002,43 (23):6255-6262
[58]Pirkle W H, Doherty E M. Enantioselective transport through a silicone-supported liquid membrane[J].J. Am. Chem. Soc.,1989,111(11):4113-4114
[59]李俊,蔡水洪,朱中南.手性化合物的萃取拆分研究[J].化学世界,2001,42(5)：233-236
[60]Vladimir P, Martin E. Lipophilic tartaric acid esters as enantioselective ionophores[J]. Angew. Chem. Int. Ed.,1989,28(9):1147-1152
[61]唐课文,周春山.疏水性L-酒石酸酯萃取分离氧氟沙星对映体[J].化工学报,2003,54(12)：1729-1732
[62]唐课文,周春山.L-酒石酸酯立体选择性萃取分离扁桃酸对映体[J].应用化学,2003,20(11)：1108-1110
[63]唐课文,周春山.疏水性L-酒石酸酯立体选择性萃取分离氯噻酮对映体[J].分析化学,2004,32(1)：63-66
[64]唐课文,陈国斌,周春山.手性配体立体选择性萃取分离扁桃酸对映体[J].无机化学学报,2004,20(3)：339-344
[65]Bauza R. Rios A, Valcarcel M. Supercritical fluid extraction with in situ chiral derivatization for the enantiospecific determination of ibuprofen in urine samples[J]. Anal. Chim. Acta,2001,450:1-11
[66]Bowman N S, McCloud G T, Schweitzer G K. Partial resolution of some organic racemates by solvent extraction [J]. J. Am. Chem. Soc.,1968,90(14):3848-3852
[67]岑仲浙,蔡水洪.手性溶剂萃取麻黄碱差向异构体[J].化工学报,2000,51(3)：418-420
[68]Viegas R M C, Afonso C A M, Crespo J G, Coelhoso I M. Modelling of the enantio-selective extraction of propranolol in a biphasic system[J]. Sep. Purif. Technol.,2007,53(3):224-234
[69]Tan B, Luo G S, Wang J D. Extraction separation of amino acid enantiomers with co-extractions of tartaric acid derivative and Aliquat-336[J]. Sep. Purif. Technol., 2007,53(3)：330-336
[70]唐课文,周春山.疏水性相转移手性溶剂萃取分离叔丁喘宁对映体[J].分析化学,2004,3(32)：278-282
[71]唐课文,陈国斌,易健民等.基于手性配体交换反应立体选择性萃取分离氧氟沙星对映体[J].化学学报,2004,62(17)：1621-1625
[72]Toshifumi T, Rikizo H, Takenori T. Enantioselective solvent extraction of neutral D,L-amino acids in two-phase systems containing N-n-alkyl-L -proline derivative and copper(Ⅱ)ion[J]. Anal. Chem.,1984,56(7):1152-1155
[73]Ding H B, Carr P W, Cussler E L. Racemic leucine separation by hollow-fiber extraction[J].AIChE J.,1992,38(10):1493-1498
[74]Koska J, Haynes C A. Modelling multiple chemicl equilibria in chiral partition systems[J]. Chem. Eng. Sci.,2001,56(20):5853-5864
[75]Colera M, Costero A M, Gavina P, Gil S. Synthesis of chiral 18-crown-6 ethers containing lipophilic chains and their enantiomeric recognition of chiral ammonium picrates[J]. Tetrahedron:Asymmetry,2005,16(15):2673-2679
[76]Jerome L, Catherine G G, Sonya T H. Efficient enantioselective extraction tris(diimine) ruthenium(Ⅱ) complexs by chiral, lipophilic trisphat anions[J]. Angew. Chem.,2000,39(20):3695-3697
[77]Erdal K, Aysegul K, Abdulkadir S. Synthesis of new chiral calix[4]arene diamide derivatives for liquid phase extraction of a-amino acid methylesters[J]. Tetrahedron:Asymmetry,2006,17(10):1514-1520
[78]Vladimir P, Stjepan M, Krunoslav K. Uber die. Enantiomer entrennung durch verteilung zwischen fussigen phasen[J]. Helv. Chim. Acta,1983,66(225): 2279-2284
[79]陈慧,王孙琴.环糊精类高效液相色谱固定相的研究进展[J].色谱,1999,17(6)：533-538
[80]刘育,尤长城,张衡益.超分子化学：合成受体的分子识别与组装[M].天津：南开大学出版社.2001,166-169
[81]Escandadr G M. Spectroscopic study of sadlicylate-cyclodextrin systems in the presence and absence of alcohols[J]. Spectrochim. Acta, Part A,1999,55(9): 1743-1752
[82]Liu Y, Song Y, Wang H, Zhang HY, Wada T, Inoue Y. Selective Binding of Steroids by 2,2'-Biquinoline-4,4'-dicarboxamide-Bridged Bis(β-cyclodextrin): Fluore -scence Enhancement by Guest Inclusion[J]. J.Org. Chem.2003,68(9): 3687-3690
[83]Liu Y, Li X Q, Chen Y, Guan X D. Spectrophotometric Study of Selective Binding Behaviors of Dye Molecules by Pyridineand Bipyridine-Modified β-Cyclodextrin Derivatives with a Functional Tether in Aqueous Solution[J]. J. Phys. Chem. B,2004,108(50):19541-19549
[84]Venema F, Nelissen H F M, Berthault P, et al. Synthesis, Conformation, and Binding Properties of Cyclodextrin Homo- and Heterodimers Connected through Their Secondary Sides[J]. Chem. Eur. J.,1998,4(11):2237-2250
[85]Szeman J, Ganzler K, Salgo A, Szejtli J. Effect of the degree of substitution of cyclodextrin derivatives on chiral separations by high-performance liquid chromatography and capillary electrophoresis[J]. J. Chromatogr. A,1996, 728(1-2):423-431
[86]Cladrowa-Runge S, Rizzi A. Enantioseparation of 6-aminoquinoly-N-Hydroxy-succinimidyl carbamate-derivatized-amino acids by capillary zone electrophoresis using native and substituted β-cyclodextrins as chiral additives 1. Discussion of optimum separation conditions[J]. J. Chromatogr. A,1997, 759(1-2):157-165
[87]Pak C, Marriott P J, Carpenier P D, Amiet R G. Enantiomeric separation of Propranolol and selected metabolites by using capillary electrophoresis with hydroxypropyl-β-cyclodextrin as chiral selector[J]. J. Chromatogr. A,1998, 793(2):357-364
[88]Herraez-Hernandez R, Campins-Falco P. Chiral separation of ephedrines by liquid chromatography using β-cyclodextrins[J]. Anal. Chim. Acta,2001,434(2): 315-324
[89]Healy L O, Murrihy J P, Tan A, et al. Enantiomeric separation of R,5-naproxen by conventional and nano-liquid chromatography with methyl-β-cyclodextrin as a mobile phase additive[J]. J. Chromatogr. A,2001,924(1-2):459-464
[90]Danesi P R. Armolex:an apparatus for solvent extraction kinetic measurements [J]. Sep. Sci. Tech.,1982,17(7):961-968
[91]Lewis J B. The mechanism of mass transfer of solutes across liquid-liquid interfaces:Part Ⅱ.-The transfer of organic solutes between solvent and aqueous phases[J]. Chem. Eng. Sci.,1954,3(6):260-278
[92]朱屯,陈长庆.新型恒界面池系统及其应用[J].化学通报,1988,2：32-33
[93]奚正楷,张天红,沈静兰.溶剂萃取过程动力学研究(Ⅱ)—HEH(EHP)从硫 酸盐溶液中萃取Zn(Ⅱ)[J].高等学校化学学报,1986,7(3)：248-250
[94]罗学辉,秦炜,戴猷元.三烷基胺萃取丙酸的动力学特性[J].化学工程,2003,31(4)：8-11
[95]钱惠芬,刘建兰，正辛基—对叔丁基苯基亚砜萃取钯(Ⅱ)的动力学研究[J].科技进展,2001,15(8)：33-36
[96]孙思修,薛梅等.溶剂萃取动力学的研究方法—恒界面池法[J].化学通报,1996，7：50-52
[97]郑佐西,顾忠茂,汪德熙.2-乙基己基膦酸单(2-乙基己基)酯萃取钴的动力学[J].化工学报,1996,47(1)：114-119
[98]杨天林,杨永会,孙思修.TOA萃取硫酸铀酰的动力学研究[J].核化学与放射化学,1999,21(4)：207-212
[99]陈慧峰,熊晓东,王胜国.三烷基氧膦萃取铱的动力学研究[J].稀有金属,2004,28(5)：832-834
[100]Petera J, Weatherley L R. Modelling of mass transfer from falling droplets[J]. Chem. Eng. Sci.,2001,56(16):4929-4947
[101]Brodkorb M J, Bosse D, vonReden C, Gorak A, Slater M J. Single drop mass transfer in ternary and quaternary liquid-liquid extraction systems[J]. Chem. Eng. Process.,2003,42(11):825-840
[102]Poposka F A, Prochazka J, Tomovska R, Nikolovski K, Grizo A. Extraction of tartaric acid from aqueous solutions with tri-iso-octylamine (HOSTAREXA 324).Equilibrium and kinetics[J]. Chem. Eng. Sci.,2000,55 (9):1591-1604
[103]Poposka F A, Nikolovski K, Tomovska R. Kinetics, mechanism and mathematical modelling of extraction of citric acid with isodecanol/n-paranssolutions of trioctyl amine[J]. Chem. Eng. Sci.,1998,53(18):3227-3237
[104]Whewell R J, Hughes M A, Hanson C. The kinetics of the solvent extraction of copper(Ⅱ) with LIX reagents-Ⅰ:Single drop experiments[J]. J. Inorg. Nucl. Chem.,1975,37(11):2303-2307
[105]陈同岳,张国莹,张洪.用于萃取动力学研究的流动注射自动分析系统[J].化学通报,1991,5：30-32
[106]Yulizar Y, Ohashi A, Watarai H. Kinetic complexation mechanisms of Ni(Ⅱ)and Zn(Ⅱ) with a pyridylazo-ligand at liquid-liquid interfaces[J]. Anal. Chim. Acta,2001,447:247-254
[107]Kolaik Z, Koch G, Kuhn W. The rate of lanthanide(Ⅲ) extraction by di (2-ethylh-exyl) phosphoric acid from complexing media[J]. J. Inorg. Nucl. Chem., 1974,36(4)：905-909
[108]郑辉东,吴燕翔,薛杭燕,任其龙.Cu2+在支撑液膜中的传质过程[J].过程工程学报,2009,9(1)：1-6
[109]Zheng Z, Lu J, Li D Q, Ma G X. The kinetics study in liquid-liquid systems with constant interfacial area cell with laminar flow[J]. Chem. Eng. Sci.,1998, 53(13):2327-2333
[110]Poole C F. New trends in solid-phase extraction[J]. Trends in Analytical Chemistry,2003,22(6):362-373
[111]汪家鼎,陈家墉.溶剂萃取手册[M].北京：化学工业出版社,2001,53-56
[112]於静芬,吉晨.有机磷酸混合萃取体系的界面化学及动力学控制机制研究[J].高等学校化学学报,1992,13(2)：224-226
[113]Senanayake C H, Grover P T. Stereoselective process for alkylphenylglycolic acids[P]. US:6180823
[114]Roger P B, Jorge L L, Francis X M, et al. Carbonate Intermediates useful in the preparation of optically active cyclohexylphenylglycolate [P]. US:5973182
[115]Feitsma K G, Bosman J, Drenth B F H, de Zeeuw R. A study of the separation of enantiomers of some aromatic carboxylic acids by high-performance liquid chromatography on a β-cyclodextrin-bonded stationary phase[J]. J. Chromatogr. A,1985,333:59-68
[116]Stephani R, Cesare V. Enantiomeric enrichment of non-racemic antihistamines by achiral high-performance liquid chromatography[J]. J. Chromatogr. A,1998, 813(1):79-84
[117]Steensma M, Kuipers N J M, de Haan A B, Kwant G. Modelling and experimental evaluation of reaction kinetics in reactive extraction for chiral separation of amines, amino acids and amino-alcohols[J]. Chem. Eng. Sci., 2007,62(5):1395-1407
[118]唐课文.药物对映体手性萃取及支载液膜分离理论与应用研究[D].长沙：中南大学,2003
[119]Tang K W, Chen Y Y, Huang K L, Liu J J. Enantioselective resolution of chiral aromatic acids by biphasic recognition chiral extraction[J]. Tetrahedron: Asymmetry,2007,18(20):2399-2408
[120]王晓东,姚金水,魏明星等.手性识别及氨基酸类手性固定相的研究进展[J].有机化学,2006,26(7)：912-921
[121]叶素芳.环糊精和环糊精包含物[J].化工时刊,2002,16(8)：1-8
[122]颜承农,上官云凤,臧旭,刑钧,吴采樱.气相色谱固定相研究进展[J].化学通报,1998,11：1～8
[123]陈慧,吕宪禹,黄君氓,高如瑜,王琴孙.衍生化环糊精键合固定相色谱保留和手性识别机理的研究(Ⅰ)[J].高等学校化学学报,2000,21(4)：562-565
[124]Wang F, Khaledi M G. Enantiomeric separations by nonaqueous capillary electrophoresis[J]. J. Chromatogr. A,2000,875(1):277-293
[125]Fanali S. Enantioselective determination by capillary electrophoresis with cyclodextrins as chiral selectors[J]. J. Chromatogr. A,2000,875(1-2):89-122
[126]Chankvetadze B, Blaschke G. Enantioseparations in capillary electromigration techniques-recent developments and future trends[J]. J. Chromatogr. A,2001, 906(1):309-363
[127]Deyl Z, Miksik I, Tagliaro F. Advances in capillary electrophoresis[J]. Forensic Sci. Int.,1998,92(2):89-124
[128]朱全红,邓芹英,曾陇梅.手性药物的薄层色谱拆分[J].药物分析杂志,2002,22(2)：155-158
[129]周志强,张红雁,于兆文.高效液相色谱法对外消旋药物的拆分[J].分析测试技术与仪器,1998,4(1)：1-7
[130]王钟辉,满瑞林,唐课文.HP-β-CD对苯基琥珀对映体色谱保留机制及拆分机理的研究[J].分析测试学报,2009,8(2)：162-167
[131]Steensma M, Kuipers N J M, de Haan A B, Kwant G. Selection of candidate enantioselective extractants for amines and amino-alcohols[J]. Chirality,2006, 18(5):314-328
[132]Bora M M, Borthakur S, Rao P G, Dutta N N. Study on the reactive extraction and stripping kinetics of certain β-lactam antibiotics[J]. Chem. Eng. Process., 2008,47(1):1-8
[133]Scarpello J T, Stuckey D C. The Reactive Extraction of Phenylalanine with Aliquat 336:Buffer Co-Extraction Equilibrium and Mass Transfer Kinetics[J]. Biotechnol. Bioeng.,2000,69(5):469-477
[134]Doraiswamy L K, Sharma M M. Heterogeneous Reactions:Analysis, Examples and Reactor Design, Fluid-fluid-Solid reactions. Wiley, New York.1984,2: 17-45
[135]张国丽,唐课文,黄可龙,易健民.紫外光谱研究β-环糊精衍生物与α-环己基扁桃酸的包结作用[J].光谱实验室,2007,24(2)：81-85
[136]Nikhade B P, Pangarkar V G. Equilibria and Kinetics of Extraction of Citric Acid from Aqueous Solutions in Alamine336-Cyclohexanone System[J]. Sep. Sci. Technol.,2005,40(12):2539-2554
[137]Danesi P R, Chiarizia R, Coleman C F. The kinetics of metal solvent extraction[J]. Crit. Rev. Anal. Chem.,1980,10(1):1-126
[138]EI-Hefny N E. Kinetics and mechanism of extraction and stripping of neodymium using a Lewis cell[J]. Chem. Eng. Process.,2007,46(7):623-629
[139]Zimmermann V, Masuck I, Kragl U. Reactive extraction of N-acetylneuraminic acid-kinetic model and simulation of integrated product removal[J]. Sep. Purif. Technol.,2008,63(1):129-137
[2]杨振云,张贻亮.手性工业[J].中国医药工业杂志,1998,27(10)：469-475
[3]郭荷民,胡季平.手性药物的立体选择考虑[J].中国药理学报,1997,13(3)：284-287
[4]于平.手性化合物研究进展[J].化工进展,2002,21(9)：635-638
[5]Thalji R K, Ellman J A, Bergman R G. Highly efficient and enantioselective cyclization of aromatic lmines via directed C-H bond activation[J]. J. Am. Chem. Soc.,2004,126(23):7192-7193
[6]Ryu D H, Corey E J. Highly enantioselective cyanosilylation of aldehydes catalyzed by a chiral oxazaborolidinium ion[J]. J. Am. Chem. Soc.,2004, 126(26):8106-8107
[7]Horvath J D, Koritnik A K, Kamakoti P, Sholl D S, Gellman A J. Enantioselective separation on a naturally chiral surface[J]. J. Am. Chem. Soc.,2004,126(45): 14988-14994
[8]Pickering P J, Chaudhuri J B. Equilibrium and kinetic studies of the enantio-selective complexation of (D/L)-phenylalanine with copper(Ⅱ) N-decyl-(L)-hydro -xylproline [J]. Chem. Eng. Sci.,1997,52(3):377-386
[9]黄量,戴立信.手性药物的化学与生物学[M].北京：化学工业出版社,2004：1
[10]苑可,戴立信.关注“手性药物”[J].科技术语研究,2002,4(2)：46-48
[11]Mostafavi S A, Foster R T. Pharmacokinetics of metoprolol enantiomers following single and mutiple administration of racemate in rat[J]. Int. J. Pharm., 2000,202(1):97-102
[12]Guxman A, Yuste F, Toscano R A, et al. Absolute configuration of (-)-5-benzoyl-1,2-dihydro-3H-pyrrolo[1,2-alpha] pyrrole-1-carboxylic acid, the active enantiomer of ketorolac[J]. J. Med. Chem.,1986,29(4):589-591
[13]Mitscher L A, Sharma P N, Chu-Daniel T W, et al. Chiral DNA gyrase inhibitors 2.Asymmetric synthesis and biological activity of the enantiomers of 9-fluoro-3-methyl-10(4-methyl-1-piperacinyl)-7-oxo-2,3-dihydro-7H-pyrido[1,2,3-de]-1, 4-benzoxazine-6-carboxylic acid(ofloxacin)[J]. J. Med. Chem.,1987,30(12): 2283-2286
[14]Plenge P, Mellerup E T, Honore T, et al. The activity of 25 paroxetine/femoxetine structure variants in various reactions, assumed to be important for the effect of antidepressants[J]. J. Pharm. Pharmacol.,1987,39(11):877-882
[15]Shum W P, Chen J, Cannarsa M J. Synthesis and enantiomeric purity determination of chiral 3-benzylglycidol, a key synthon for hiv protease inhibitors[J]. Chirality,2004,6 (8):681-684
[16]Halabi A, Ferrayoli C, Palacio M, Dabbene V, Palacios S. Validation of a chiral HPLC assay for (R)-salbutamol sulfate[J]. J. Pharm. Biomed. Anal.,2004,34(1): 45-51
[17]曾苏,沈向忠,刘志强.手性药物的药理及其体内对映体的HPLC测定[J].浙江医科大学学报,1994,23(5)：235-239
[18]廖永卫,陈卫平.手性药物与单一对映体药物的发展[J].国外医药,制剂分册,1996,17(1)：9-15
[19]Blanco M, Valverde I. Chiral and non chiral determination of dopa by capillary electrophoresis[J]. J. Pharm. Biomed. Anal.,2003,31(3):431-438
[20]芮建中,吴锦芳,庞晓东.手性药物对映体选择性的药代动力学和药效学与临床合理用药[J].中国药理学通报,1998,14(1)：19-22
[21]Raffa R B, Friderichs E, Reimann W. Complementory and synergistic antinociceptive interaction between the enantiomers of tramadol[J]. J. Pharmacol. Exp. Ther.,1993,267(1):331-340
[22]林国强,杜灿屏.手性与手性研究中的若干科学问题.中国科学基金,2003,17(2)：72-76
[23]Sheldon R A. Organic Synthesis-Past, Present and Future[J]. Chem. Ind.,1992, 23(12):903-906
[24]Gimenez F, Pennie R A, Crevoisier C. Stereoselective pharmacokinetics of mefloquine in healty caucasinans after multiple does[J]. J. Pharm. Sci.,1994, 83(6):824-827
[25]邓金根,迟永祥,朱槿.化学拆分的新方法研究[J].合成化学,1999,7(4)：340-345
[26]Gihani E, Moharem T, Jonathan M J W. Dynamic kinetic resolution [J]. Curr. Opin. Chem. Biol,1999,3(1):11-15
[27]Allen J V, Williams J M J. Dynamic kinetic resolution with enzyme and palladium combinations [J]. Tetrahedron Lett.,1996,37(11):1859-1862
[28]姚传义,张金红,俞耀庭.酶法手性化合物的合成与拆分[J].化工进展,2000,19(6)：35-50
[29]杨柳青,何南.手性药物的生物转化[J].中国新药杂志,2000,9(12)：817-820
[30]Bevinakatti H S, Benerji A A. Practical chemoenzymatic synthesis of both enantiomers of propranolol[J]. J. Org. Chem.,1991,56(18):5372-5375
[31]LutjeSpelberg J H, Tang L X, Kellogg R M, et al. Enzymatic dynamic kinetic resolution of epihalohydrins[J]. Tetrahedron:Asymmetry,2004,15(7): 1095-1102
[32]Battistel E, Bianthi D, Cesti P, Pina C. Enzymatic resolution of (S)-(+)-Naproxen in a continuous reactor[J]. Biotechnol. Bioeng.,1991,38(6):659-664
[33]Joly S, Nair M S. Studies on the enzymatic kinetic resolution of β-hydroxy ketones[J]. J. Mol. Catal. B:Enzym.,2003,22(3-4):151-160
[34]Van Tol J, Bert A, Duine J, et al. Description of hydrolase enantioselectivity must be based on the actual kinetic resolution of glycidyl(2,3-epoxy-1-propyl) butyrate by pig pancreas lipase[J]. Biocatal. Biotransform.,1995,12(2):99-117
[35]Straathof A J J, Rakels J L L, van Tol B A J, Heijnen J J. Improvement of lipase catalyzed kinetic resolution by tandem transesterification[J]. Enzyme Microb. Technol.,1995,17(7):623-628
[36]徐诗伟,徐清.酶法拆分腈类制备光学活性2-芳基丙酸[J].微生物学通报,1995,22(3)：184-187
[37]徐刚,程咏梅,吴坚平,杨立荣.有机相酶催化拆分制备(S)-2-氯-1-(2-噻吩)-乙醇[J].有机化学,2007,27(7)：857-861
[38]Khan M, Viswanathan B, Rao D S, Reddy R. Chiral separation of Frovatriptan isomers by HPLC using amylose based chiral stationary phase[J]. J. Chromatogr. B,2007,846(1-2):119-123
[39]Xiong X, Baeyens W R G, Aboul-Enein H Y, Delanghe J R, Tu TT, Ouyang J. Impact of amines as co-modifiers on the enantioseparation of various amino acid derivatives on a tert-butyl carbamoylated quinine-based chiral stationary phase[J]. Talanta,2007,71(2):573-581
[40]Yan H Y, Row K H. Rapid chiral separation and impurity determination of levofloxacin by ligand-exchange chromatography[J]. Anal. Chim. Acta,2007, 584(1):160-165
[41]Zhou Shanshan, Ouyang Jin, Willy R G B, et al. Chiral separation of four fluoroquinolone compounds using capillary electrophoresis with hydroxypropyl-(3-cyclodextrin as chiral selector[J]. J. Chromatogr. A,2006, 1130(2):296-301
[42]Ma S L, Shen S, Haddad N, et al. Chromatographic and spectroscopic studies on the chiral recognition of sulfated β-cyclodextrin as chiral mobile phase additive: Enantiomeric separation of a chiral amine[J]. J. Chromatogr. A,2009,1216(8): 1232-1240
[43]傅若农,顾峻岭.近代色谱分析[M].北京：国防工业出版社,1998：25-27
[44]Ward T J, Farris Ⅲ A B. Chiral separations using the macrocyclic antibiotics:a review[J]. J. Chromatogr. A,2001,906(1-2):73-89
[45]Stanffer S T, Dessy R E. CHIRULE:a chiral chromatographic column selection system utilizing similarity searching[J]. J. Chromatogr. Sci.,1994,32(6): 228-235
[46]胡珊珊,吴怡祖,史美仁.β-环糊精衍生物手性流动相HPLC法拆分α-环己基扁桃酸对映体[J].精细化工,2004,21(10)：731-732
[47]马剑茵.手性药物的色谱分离方法[J].中国医药工业杂志,2002,33(4)：199-202
[48]Lin J Y. Comparison of the chiral resolution on cis-trans isomeric chiral stationary phases derived from (S)-1-(1-naphthyl)ethylamine[J]. J. Chromatogr. A,1996,740(2):183-193
[49]黄蓓,陈欢林.选择性扩散和选择性吸附手性拆分膜及其应用[J].功能高分子学报,2002,15(4)：480-486
[50]Thoelen C, M. De bruyn, Theunissen E, Kondo Y, Vankelecom I F J, Grobet P, Yoshikawa M, Jacobs P A. Membranes based on poly (γ-methyl-1-glutamate): synthesis, characterization and use in chiral separations [J]. J. Membr. Sci.,2001, 186(2):153-163
[51]Miyako E, Maruyama T, Kamiya F, Goto M. Highly enantioselective separation using a supported liquid membrane encapsulating surfactant-enzyme complex[J]. J. Am. Chem. Soc.,2004,126(28):8622-8623
[52]Keurentjes J T F, Nabuurs L J W, Vegter E A. Liquid membrane technology for the separation of racemic mixtures[J]. J. Membr. Sci.,1996,113(2):351-360
[53]Krieg H M, Lotter J, Keizer K, Breytenbach J C. Enrichment of chlorthalidone enantiomers by an aqueous bulk liquid membrane containing β-cyclodextrin[J]. J. Membr. Sci.,2000,167(1):33-45
[54]Rmaile H H, Schlenoff J B. Optically active polyeletrolyte multilayers as membranes for chiral separations[J]. J. Am. Chem. Soc.,2003,125(22): 6602-6603
[55]Yoshikawa M, Murakoshi K, Kogita T, Hanaoka K, Guiver M D, Robertson G P. Chiral separation membranes from modified polysulfone having myrtenal-derived terpenoid side groups[J]. Eur. Polym. J.,2006,42(10): 2532-2539
[56]唐课文,周春山,蒋新宇.支载液膜双有机相萃取分离氧氟沙星外消旋体[J].中国科学(B),2002,32(6)：491-496
[57]Lee N H, Frank C W. Separation of chiral molecules using polypeptide-modified poly (vinylidene fluoride) membranes[J]. Polymer,2002,43 (23):6255-6262
[58]Pirkle W H, Doherty E M. Enantioselective transport through a silicone-supported liquid membrane[J].J. Am. Chem. Soc.,1989,111(11):4113-4114
[59]李俊,蔡水洪,朱中南.手性化合物的萃取拆分研究[J].化学世界,2001,42(5)：233-236
[60]Vladimir P, Martin E. Lipophilic tartaric acid esters as enantioselective ionophores[J]. Angew. Chem. Int. Ed.,1989,28(9):1147-1152
[61]唐课文,周春山.疏水性L-酒石酸酯萃取分离氧氟沙星对映体[J].化工学报,2003,54(12)：1729-1732
[62]唐课文,周春山.L-酒石酸酯立体选择性萃取分离扁桃酸对映体[J].应用化学,2003,20(11)：1108-1110
[63]唐课文,周春山.疏水性L-酒石酸酯立体选择性萃取分离氯噻酮对映体[J].分析化学,2004,32(1)：63-66
[64]唐课文,陈国斌,周春山.手性配体立体选择性萃取分离扁桃酸对映体[J].无机化学学报,2004,20(3)：339-344
[65]Bauza R. Rios A, Valcarcel M. Supercritical fluid extraction with in situ chiral derivatization for the enantiospecific determination of ibuprofen in urine samples[J]. Anal. Chim. Acta,2001,450:1-11
[66]Bowman N S, McCloud G T, Schweitzer G K. Partial resolution of some organic racemates by solvent extraction [J]. J. Am. Chem. Soc.,1968,90(14):3848-3852
[67]岑仲浙,蔡水洪.手性溶剂萃取麻黄碱差向异构体[J].化工学报,2000,51(3)：418-420
[68]Viegas R M C, Afonso C A M, Crespo J G, Coelhoso I M. Modelling of the enantio-selective extraction of propranolol in a biphasic system[J]. Sep. Purif. Technol.,2007,53(3):224-234
[69]Tan B, Luo G S, Wang J D. Extraction separation of amino acid enantiomers with co-extractions of tartaric acid derivative and Aliquat-336[J]. Sep. Purif. Technol., 2007,53(3)：330-336
[70]唐课文,周春山.疏水性相转移手性溶剂萃取分离叔丁喘宁对映体[J].分析化学,2004,3(32)：278-282
[71]唐课文,陈国斌,易健民等.基于手性配体交换反应立体选择性萃取分离氧氟沙星对映体[J].化学学报,2004,62(17)：1621-1625
[72]Toshifumi T, Rikizo H, Takenori T. Enantioselective solvent extraction of neutral D,L-amino acids in two-phase systems containing N-n-alkyl-L -proline derivative and copper(Ⅱ)ion[J]. Anal. Chem.,1984,56(7):1152-1155
[73]Ding H B, Carr P W, Cussler E L. Racemic leucine separation by hollow-fiber extraction[J].AIChE J.,1992,38(10):1493-1498
[74]Koska J, Haynes C A. Modelling multiple chemicl equilibria in chiral partition systems[J]. Chem. Eng. Sci.,2001,56(20):5853-5864
[75]Colera M, Costero A M, Gavina P, Gil S. Synthesis of chiral 18-crown-6 ethers containing lipophilic chains and their enantiomeric recognition of chiral ammonium picrates[J]. Tetrahedron:Asymmetry,2005,16(15):2673-2679
[76]Jerome L, Catherine G G, Sonya T H. Efficient enantioselective extraction tris(diimine) ruthenium(Ⅱ) complexs by chiral, lipophilic trisphat anions[J]. Angew. Chem.,2000,39(20):3695-3697
[77]Erdal K, Aysegul K, Abdulkadir S. Synthesis of new chiral calix[4]arene diamide derivatives for liquid phase extraction of a-amino acid methylesters[J]. Tetrahedron:Asymmetry,2006,17(10):1514-1520
[78]Vladimir P, Stjepan M, Krunoslav K. Uber die. Enantiomer entrennung durch verteilung zwischen fussigen phasen[J]. Helv. Chim. Acta,1983,66(225): 2279-2284
[79]陈慧,王孙琴.环糊精类高效液相色谱固定相的研究进展[J].色谱,1999,17(6)：533-538
[80]刘育,尤长城,张衡益.超分子化学：合成受体的分子识别与组装[M].天津：南开大学出版社.2001,166-169
[81]Escandadr G M. Spectroscopic study of sadlicylate-cyclodextrin systems in the presence and absence of alcohols[J]. Spectrochim. Acta, Part A,1999,55(9): 1743-1752
[82]Liu Y, Song Y, Wang H, Zhang HY, Wada T, Inoue Y. Selective Binding of Steroids by 2,2'-Biquinoline-4,4'-dicarboxamide-Bridged Bis(β-cyclodextrin): Fluore -scence Enhancement by Guest Inclusion[J]. J.Org. Chem.2003,68(9): 3687-3690
[83]Liu Y, Li X Q, Chen Y, Guan X D. Spectrophotometric Study of Selective Binding Behaviors of Dye Molecules by Pyridineand Bipyridine-Modified β-Cyclodextrin Derivatives with a Functional Tether in Aqueous Solution[J]. J. Phys. Chem. B,2004,108(50):19541-19549
[84]Venema F, Nelissen H F M, Berthault P, et al. Synthesis, Conformation, and Binding Properties of Cyclodextrin Homo- and Heterodimers Connected through Their Secondary Sides[J]. Chem. Eur. J.,1998,4(11):2237-2250
[85]Szeman J, Ganzler K, Salgo A, Szejtli J. Effect of the degree of substitution of cyclodextrin derivatives on chiral separations by high-performance liquid chromatography and capillary electrophoresis[J]. J. Chromatogr. A,1996, 728(1-2):423-431
[86]Cladrowa-Runge S, Rizzi A. Enantioseparation of 6-aminoquinoly-N-Hydroxy-succinimidyl carbamate-derivatized-amino acids by capillary zone electrophoresis using native and substituted β-cyclodextrins as chiral additives 1. Discussion of optimum separation conditions[J]. J. Chromatogr. A,1997, 759(1-2):157-165
[87]Pak C, Marriott P J, Carpenier P D, Amiet R G. Enantiomeric separation of Propranolol and selected metabolites by using capillary electrophoresis with hydroxypropyl-β-cyclodextrin as chiral selector[J]. J. Chromatogr. A,1998, 793(2):357-364
[88]Herraez-Hernandez R, Campins-Falco P. Chiral separation of ephedrines by liquid chromatography using β-cyclodextrins[J]. Anal. Chim. Acta,2001,434(2): 315-324
[89]Healy L O, Murrihy J P, Tan A, et al. Enantiomeric separation of R,5-naproxen by conventional and nano-liquid chromatography with methyl-β-cyclodextrin as a mobile phase additive[J]. J. Chromatogr. A,2001,924(1-2):459-464
[90]Danesi P R. Armolex:an apparatus for solvent extraction kinetic measurements [J]. Sep. Sci. Tech.,1982,17(7):961-968
[91]Lewis J B. The mechanism of mass transfer of solutes across liquid-liquid interfaces:Part Ⅱ.-The transfer of organic solutes between solvent and aqueous phases[J]. Chem. Eng. Sci.,1954,3(6):260-278
[92]朱屯,陈长庆.新型恒界面池系统及其应用[J].化学通报,1988,2：32-33
[93]奚正楷,张天红,沈静兰.溶剂萃取过程动力学研究(Ⅱ)—HEH(EHP)从硫 酸盐溶液中萃取Zn(Ⅱ)[J].高等学校化学学报,1986,7(3)：248-250
[94]罗学辉,秦炜,戴猷元.三烷基胺萃取丙酸的动力学特性[J].化学工程,2003,31(4)：8-11
[95]钱惠芬,刘建兰，正辛基—对叔丁基苯基亚砜萃取钯(Ⅱ)的动力学研究[J].科技进展,2001,15(8)：33-36
[96]孙思修,薛梅等.溶剂萃取动力学的研究方法—恒界面池法[J].化学通报,1996，7：50-52
[97]郑佐西,顾忠茂,汪德熙.2-乙基己基膦酸单(2-乙基己基)酯萃取钴的动力学[J].化工学报,1996,47(1)：114-119
[98]杨天林,杨永会,孙思修.TOA萃取硫酸铀酰的动力学研究[J].核化学与放射化学,1999,21(4)：207-212
[99]陈慧峰,熊晓东,王胜国.三烷基氧膦萃取铱的动力学研究[J].稀有金属,2004,28(5)：832-834
[100]Petera J, Weatherley L R. Modelling of mass transfer from falling droplets[J]. Chem. Eng. Sci.,2001,56(16):4929-4947
[101]Brodkorb M J, Bosse D, vonReden C, Gorak A, Slater M J. Single drop mass transfer in ternary and quaternary liquid-liquid extraction systems[J]. Chem. Eng. Process.,2003,42(11):825-840
[102]Poposka F A, Prochazka J, Tomovska R, Nikolovski K, Grizo A. Extraction of tartaric acid from aqueous solutions with tri-iso-octylamine (HOSTAREXA 324).Equilibrium and kinetics[J]. Chem. Eng. Sci.,2000,55 (9):1591-1604
[103]Poposka F A, Nikolovski K, Tomovska R. Kinetics, mechanism and mathematical modelling of extraction of citric acid with isodecanol/n-paranssolutions of trioctyl amine[J]. Chem. Eng. Sci.,1998,53(18):3227-3237
[104]Whewell R J, Hughes M A, Hanson C. The kinetics of the solvent extraction of copper(Ⅱ) with LIX reagents-Ⅰ:Single drop experiments[J]. J. Inorg. Nucl. Chem.,1975,37(11):2303-2307
[105]陈同岳,张国莹,张洪.用于萃取动力学研究的流动注射自动分析系统[J].化学通报,1991,5：30-32
[106]Yulizar Y, Ohashi A, Watarai H. Kinetic complexation mechanisms of Ni(Ⅱ)and Zn(Ⅱ) with a pyridylazo-ligand at liquid-liquid interfaces[J]. Anal. Chim. Acta,2001,447:247-254
[107]Kolaik Z, Koch G, Kuhn W. The rate of lanthanide(Ⅲ) extraction by di (2-ethylh-exyl) phosphoric acid from complexing media[J]. J. Inorg. Nucl. Chem., 1974,36(4)：905-909
[108]郑辉东,吴燕翔,薛杭燕,任其龙.Cu2+在支撑液膜中的传质过程[J].过程工程学报,2009,9(1)：1-6
[109]Zheng Z, Lu J, Li D Q, Ma G X. The kinetics study in liquid-liquid systems with constant interfacial area cell with laminar flow[J]. Chem. Eng. Sci.,1998, 53(13):2327-2333
[110]Poole C F. New trends in solid-phase extraction[J]. Trends in Analytical Chemistry,2003,22(6):362-373
[111]汪家鼎,陈家墉.溶剂萃取手册[M].北京：化学工业出版社,2001,53-56
[112]於静芬,吉晨.有机磷酸混合萃取体系的界面化学及动力学控制机制研究[J].高等学校化学学报,1992,13(2)：224-226
[113]Senanayake C H, Grover P T. Stereoselective process for alkylphenylglycolic acids[P]. US:6180823
[114]Roger P B, Jorge L L, Francis X M, et al. Carbonate Intermediates useful in the preparation of optically active cyclohexylphenylglycolate [P]. US:5973182
[115]Feitsma K G, Bosman J, Drenth B F H, de Zeeuw R. A study of the separation of enantiomers of some aromatic carboxylic acids by high-performance liquid chromatography on a β-cyclodextrin-bonded stationary phase[J]. J. Chromatogr. A,1985,333:59-68
[116]Stephani R, Cesare V. Enantiomeric enrichment of non-racemic antihistamines by achiral high-performance liquid chromatography[J]. J. Chromatogr. A,1998, 813(1):79-84
[117]Steensma M, Kuipers N J M, de Haan A B, Kwant G. Modelling and experimental evaluation of reaction kinetics in reactive extraction for chiral separation of amines, amino acids and amino-alcohols[J]. Chem. Eng. Sci., 2007,62(5):1395-1407
[118]唐课文.药物对映体手性萃取及支载液膜分离理论与应用研究[D].长沙：中南大学,2003
[119]Tang K W, Chen Y Y, Huang K L, Liu J J. Enantioselective resolution of chiral aromatic acids by biphasic recognition chiral extraction[J]. Tetrahedron: Asymmetry,2007,18(20):2399-2408
[120]王晓东,姚金水,魏明星等.手性识别及氨基酸类手性固定相的研究进展[J].有机化学,2006,26(7)：912-921
[121]叶素芳.环糊精和环糊精包含物[J].化工时刊,2002,16(8)：1-8
[122]颜承农,上官云凤,臧旭,刑钧,吴采樱.气相色谱固定相研究进展[J].化学通报,1998,11：1～8
[123]陈慧,吕宪禹,黄君氓,高如瑜,王琴孙.衍生化环糊精键合固定相色谱保留和手性识别机理的研究(Ⅰ)[J].高等学校化学学报,2000,21(4)：562-565
[124]Wang F, Khaledi M G. Enantiomeric separations by nonaqueous capillary electrophoresis[J]. J. Chromatogr. A,2000,875(1):277-293
[125]Fanali S. Enantioselective determination by capillary electrophoresis with cyclodextrins as chiral selectors[J]. J. Chromatogr. A,2000,875(1-2):89-122
[126]Chankvetadze B, Blaschke G. Enantioseparations in capillary electromigration techniques-recent developments and future trends[J]. J. Chromatogr. A,2001, 906(1):309-363
[127]Deyl Z, Miksik I, Tagliaro F. Advances in capillary electrophoresis[J]. Forensic Sci. Int.,1998,92(2):89-124
[128]朱全红,邓芹英,曾陇梅.手性药物的薄层色谱拆分[J].药物分析杂志,2002,22(2)：155-158
[129]周志强,张红雁,于兆文.高效液相色谱法对外消旋药物的拆分[J].分析测试技术与仪器,1998,4(1)：1-7
[130]王钟辉,满瑞林,唐课文.HP-β-CD对苯基琥珀对映体色谱保留机制及拆分机理的研究[J].分析测试学报,2009,8(2)：162-167
[131]Steensma M, Kuipers N J M, de Haan A B, Kwant G. Selection of candidate enantioselective extractants for amines and amino-alcohols[J]. Chirality,2006, 18(5):314-328
[132]Bora M M, Borthakur S, Rao P G, Dutta N N. Study on the reactive extraction and stripping kinetics of certain β-lactam antibiotics[J]. Chem. Eng. Process., 2008,47(1):1-8
[133]Scarpello J T, Stuckey D C. The Reactive Extraction of Phenylalanine with Aliquat 336:Buffer Co-Extraction Equilibrium and Mass Transfer Kinetics[J]. Biotechnol. Bioeng.,2000,69(5):469-477
[134]Doraiswamy L K, Sharma M M. Heterogeneous Reactions:Analysis, Examples and Reactor Design, Fluid-fluid-Solid reactions. Wiley, New York.1984,2: 17-45
[135]张国丽,唐课文,黄可龙,易健民.紫外光谱研究β-环糊精衍生物与α-环己基扁桃酸的包结作用[J].光谱实验室,2007,24(2)：81-85
[136]Nikhade B P, Pangarkar V G. Equilibria and Kinetics of Extraction of Citric Acid from Aqueous Solutions in Alamine336-Cyclohexanone System[J]. Sep. Sci. Technol.,2005,40(12):2539-2554
[137]Danesi P R, Chiarizia R, Coleman C F. The kinetics of metal solvent extraction[J]. Crit. Rev. Anal. Chem.,1980,10(1):1-126
[138]EI-Hefny N E. Kinetics and mechanism of extraction and stripping of neodymium using a Lewis cell[J]. Chem. Eng. Process.,2007,46(7):623-629
[139]Zimmermann V, Masuck I, Kragl U. Reactive extraction of N-acetylneuraminic acid-kinetic model and simulation of integrated product removal[J]. Sep. Purif. Technol.,2008,63(1):129-137