摘要
我国蕴藏着丰富的药用植物资源,在防病治病中发挥着重要的作用。本研究就地取材利用药用天然化学成分做色谱配体,设计开发新型色谱固定相,并进行相关的基础应用研究。直接利用这些天然配体不仅能降低制备成本,还可避免繁杂的合成与纯化过程,对深层次开发利用我国丰富的中草药资源具有重要意义。本论文以天然产物大黄的药用成分大黄素为配体,将大黄素稳定地键合到硅胶表面,制备了一种具有抗菌和多作用位点的新型色谱固定相-大黄素配体键合硅胶固定相(EDSP),采用红外光谱、元素分析和热重分析进行结构表征,并评价了新固定相基本的色谱性能,探讨了该固定相的分离机制,为将来的开发利用提供理论依据。主要研究内容如下：
1、从色谱固定相的基质选择、配体键合方法、色谱保留机理及应用研究的角度,较全面地总结了近年来国内外新型高效液相色谱键合硅胶固定相的研究进展,其中对传统固定相和新型固定相的研究开发进行了较详细的评述,以此作为本论文工作的理论依据。
2、采用有机溶剂提取法,从药用大黄中提取并纯化得到大黄素。采用固液表面连续反应法,以γ-[(2,3)-环氧丙氧]丙基三甲氧基硅烷(KH-560)为偶联剂,首次将大黄素配体键合到球形硅胶表面,制备得到一种新的大黄素键合硅胶固定相。对配体的选择、制备路线的设计和反应条件的优化进行了探讨。并采用红外光谱、元素分析和热重分析表征了新固定相的结构。结果表明,通过蒽醌环上的配羟基与环氧基的开环反应,大黄素配体被成功地键合到球形硅胶表面,测得大黄素配体的键合量是0.180 mmol/g,不同批次的产品有良好的重现性,该制备方法简便,所制备的固定相色谱性能稳定。
3、采用高压泵将固定相的匀浆直接填入不锈钢柱中(4.6 i.d.×150mm),以联苯为溶质探针,甲醇-水为流动相(50:50, v/v,0.8 mLmin-1,室温),测得EDSP的柱效为8227块/米。采用纯有机溶剂或酸性流动相长时间冲洗,发现该固定相对溶质的保留能力和柱效变化较小。采用Kimata等建立的一种国际上公认的C18反相键合硅胶固定相的色谱性能综合评价方法,评价了大黄素键合固定相的基本色谱性能。其中包括疏水性能、氢键能力、立体选择性和离子交换能力等。然后以中性的多环芳烃、酸性的酚类化合物和碱性硝基苯胺异构体等为溶质探针,初步研究EDSP对芳香性溶质的分离能力,并在相同条件下与传统的反相色谱固定相ODS进行比较,从不同的角度较系统地表征出EDSP对不同类型化合物的色谱分离性能和特点,结合色谱数据来探讨其分离机理,为新固定相实际应用提供理论依据。上述结果表明,所制备的大黄素键合硅胶固定相具有良好的反相色谱性能,除与溶质间的疏水作用外,还能提供氢键、n-π或π-π电荷转移作用以及偶极-偶极作用,这与大黄素配体的多羟基蒽醌环大π平面性结构有关,多位点的协同作用使得大黄素键合固定相不仅拥有类似ODS的反相色谱优良的色谱选择性和广泛的分离对象,同时在极性化合物的分离方面显示出较强的分离能力和快速分离等特点。
4、进一步评价EDSP对极性芳香性化合物的分离能力,溶质包括9种嘧啶、4种嘌呤、3种核苷、4种蝶呤和5种农药等药物或生物活性密切相关的极性化合物,分别研究了它们在大黄素键合硅胶色谱固定相(EDSP)上的色谱行为,考察了流动相中常见的溶剂甲醇含量和pH对分离选择性的影响,并以ODS做对照,探讨了EDSP对这类含氮的碱性极性化合物的色谱分离机理。结果表明,采用通用和价廉的甲醇-水体系流动相,大黄素键合硅胶固定相能在较短的时间内分别实现上述物质的基线分离。在相同的流动相中,5-硝基尿嘧啶、异黄蝶呤、敌稗在EDSP上的洗脱顺序与ODS不同,说明EDSP和ODS对上述溶质的保留机理存在差异。明显地,由于EDSP中大黄素配体中含有蒽醌大π共轭体系,丰富的π电子与溶质间能发生ππ-π作用,羟基和羰基上的孤电子与溶质之间发生氢键作用和偶极-偶极作用,多种作用力的分离机制使得EDSP能够克服ODS单一疏水性作用的缺陷,在对极性化合物中显示其特有的优越性能。
5、为考察新制备的EDSP固定相对复杂样品的分离能力,选用常见的中草药如虎杖、葛根、半枝莲和半边莲提取液做实际分离样品,采用液相色谱质谱电喷雾离子化联用技术,在分离的同时,对相关色谱峰进行了初步的质谱定性分析。结果表明,在未经前处理的情况下,EDSP对上述植物中复杂的提取液有较好的分离能力,明显地,这与多作用位点有关。此外,因地取材得到的天然大黄素配体的药物功能和分离功能相结合,更能满足工业色谱的需要。
It is well known that there is abundant medicinal plants in our country, which play an important role in disease prevention. In this study, we make use of narural active components in Traditional Chinese Medicine as chromatographic ligands to design, prepare and apply new-style chromatographic separation materials. Direct exploitation of the natural ligands can not only reduce production cost, but also to avoid the complicate synthesis and purification process, and it also has an importantance in the development and utilization of Chinese herbal medicine deeply. In this thesis, a new emodin-bonded silica gel stationary phase (EDSP) with the ligand from Rheum officinale Baill for HPLC was prepared for the first time. Its structure were characterized by Fourier transform infrared spectrometry, elemental analysis and thermal analysis. The chromatographic performance of EDSP were evaluated. Related separation mechanism was systematically studied. The new stationary phase was used for the separations of complicate samples. The major contents are as follows.
1. The recent advance in the proceeding from the matrix, preparation, chromatographic retention mechanism and their application of novel bonded silica gel stationary phases for HPLC at home and abroad, were reviewed. The study of bonded silica gel stationary phases for HPLC was reviewed from two aspects, including the improvement of traditional bonded-silica gel stationary phases and the design of new bonded phases. Above all will contribute to the research basis and start point of this thesis.
2. Emodin was extracted and purfied from Rheum officinale Baill by organic solvent extraction method. And emodin was chemically immobilized to the surface of silica gel as stationary phase by the solid-liquid phase reaction with y-glycidoxy-propyltrimethoxy-silane (KH-560) coupling reagent for high performance liquid chromatography(HPLC). The new emodin-bonded stationary phase (EDSP) was brown-red monodispersal particles. According to. the preparative scheme, the reaction conditions were also partially optimized via investigation under different reaction ratios. The structure of new emodin-bonded stationary phase (EDSP) was characterized by Fourier transform infrared spectrometry, elemental analysis and thermal analysis. The results showed that emodin was successfully immobilized onto the surface of spherical silica gel with a 0.18 mmolg-1 of bonded amount and highly physical and chemical stability. In addition, the bonded amounts of the packings in different batches were similar to each other, which indicated that the above preparation procedure was practical and reliable.
3. The slurry of EDSP was packed into a stainless steel column by using common LC pressure pump. The column efficiency was 8827 plates/m by using biphenyl as probe in methanol-water (50/50, v/v) mobile phase at room temperature. The chromatographic stability of EDSP in strong organic solvent and acidic mobile phase were investigated, respectively. That an authorized column validation method proposed by Kimata's group was used to systematically evaluate the basic chromatographic properties of EDSP, including hydrophobicity, charge transfer ability, hydrogen-bonding, steric selectivity and ion exchange interactions. The chromatographic performance of new EDSP was studied in detail by using different structural solutes as probes and ODS as reference. These chromatographic data can be used as the theoretical basis for its applications in future. The tested solutes included neutral aromatics, acid phenols and basic aromatic amines etc. The results indicated that EDSP performed as a versatile reversed-phase material with a relatively weak hydrophobicity, especially, various sites located in the emodin ligand, such as hydrophobic, hydrogen bonding,π-πor n-πcharge transfer and dipole-dipole interactions. EDSP has excellent abilities for the fast separations of neutral, acid and basic compounds. It is related with the existence of largeπsystem and planar rigid structure of EDSP. Hence, EDSP was endowed advantage over only hydrophobic ODS in rapid separations of polar compounds.
4. In order to further evaluate chromatographic performance in the separation of polar compounds, the behavior of nine pyrimidines, four purines, three nucleosides, four pterins and five pesticides on EDSP were studied by HPLC. Meanwhile, the comparative study in the retention behavior of the above solutes on both EDSP and ODS were also done under the same conditions. The influence of mobile phase variables, such as methanol content and pH value on the retention behavior of the polar compounds were investigated. The results showed that baseline separation on EDSP were easily achieved by using common and cheap methanol-water mobile phases. The elution orders of 5-nitrouracil, isoxanthopterin and propanil were very different on EDSP and ODS under the same condition, which showed that EDSP and ODS had different retention mechanism. Obviously, the EDSP exhibited advantage over only hydrophobic ODS in seperations of the above polar compounds. The results can be explained as follows:theπ-πinteraction, hydrogen bonding, n-πinteraction existed between phenolic hydroxyl or carbonyl groups of emodin anthraquinone ligands containingπ-conjugated system and the solutes.
5. To investigate the chromatographic performance in the separation of complicate compounds, EDSP was also employed for the separation of complex samples, which were extracted from common herbs, including polygonum cuspidatum S. et Z., Radices puerarire, Scutellaria barbatat and lobelia. Some major components were identified by LC-ESI-MS in the absence of standard substances. Good separations of the above samples were achieved without pre-treatment, which was because the carbonyl and hydroxyl on emodin anthraquinone ligands could provide various sites. In addition, new separation material with natural emodin ligand will exhibit a bright future for industrial chromatography separation applications because it has both pharmaceutical and chromatographic functions.
引文
[1]Fishbein L. Chromatography of environmental hazards. Amsterdam, Elsevier Pub. Co.,1982
[2]师治贤,王俊德.生物大分子的液相色谱分离和制备.北京：科学出版社,1992,173-205
[3]Snyder L R, Kirkland J J, Glajch J L. Practical HPLC method development.2nd. Chichester, England:John Wiley & Sons Inc.,1997
[4]邹汉法,张玉奎,卢佩章.高效液相色谱法.北京：科学出版社,1998,79-125
[5]达世禄.色谱学导论(第二版).武汉：武汉大学出版社,1999,307-343
[6]于世林.高效液相色谱方法及应用.北京：化学工业出版社,2000,245-322
[7]杨新立,王俊德,熊博晖.高效液相色谱用硅质填料的进展.色谱,2000,18(4)：381-312
[8]刘国诠,余兆楼.色谱柱技术.北京：化学工业出版社,2001
[9]W H Pirkle, D L Sikkenga. Resolution of optical isomers by liquid chromatography. J. Chromatogr. A,1976,123:400-404
[10]F Mikes, G Boshart, J Gil-Ar. Resolution of optical isomers by high-performance liquid chromatography, using coated and bonded chiral charge-transfer complexing agents as stationary phases. J. Chromatogr. A,1976,122:205-221
[11]J.M Hawkins, T A Lewis, S D Loren. Organic chemistry of C60 (buckminsterfullerene): chromatography and osmylation. J. Org. Chem.,1990,55 (26):6250-6252
[12]王俊德,商振华,郁蕴璐.高效液相色谱法.北京：中国石化出版社,1992
[13]C H Lochmuller, D B Marshall. The effect of end-capping reagent on liquid chromatographic performance. Anal. Chim. Acta,1982,142:63-72
[14]B Bogudlaw, J Marta, O G Barbara. Silicon dioxide surface modified with cholesterol derivatives. Materials Chemistry and Physis,2001,72 (1):30-41
[15]H A Claessens. Trends and progress in the characterization of stationary phases for reversed-phase liquid chromatography. Trends in Analytical Chemistry,2001,20(10): 563-583
[16]Klaus Albert, Bettina Pfleiderer, Ernst Bayer, et al. Characterization of chemically modified glass surfaces by 13C and 29Si CP/MAS NMR spectroscopy. Journal of Colloid and Interface Science,1991,142(1):35-40
[17]Nobuo Tanaka, Hiroshi Kinoshita, Mikio Araki, et al. On-column preparation of chemically bonded stationary phase with maximum surface coverage and high reproducibility, and its application to packed microcapillary columns. J. Chromatogr. A,1985,332(20):57-69
[18]丁彦蕊,蔡宇杰等.十二烷基键合固定相的制备及在青霉素降解研究中的应用.中国医药工业杂志,2002,33(12)：580-582
[19]刘英,冯钰琦,达世禄等.C60键合硅胶液相色谱固定相的合成及其性能评价.色谱, 1998,16(3)：115-117
[20]冯钰琦,达世禄.混合型烷基键合硅胶液相色谱固定相的合成与性能评价.应用化学,1999,16(4)：55-57
[21]景玉清,王利娟,杨更亮等.醚型十八烷基键合硅胶整体柱的制备及其评价.化学通报,1-5
[22]喻昕,赵睿,刘国诠.一种新型C18酯型反相高效液相色谱填料的制备.色谱,2000,18(1)：25
[23]喻昕,赵睿,刘国诠.十八烷基醚型高效液相反相色谱填料的制备.高等学校化学学报,2000,21(7)：1043-1044
[24]Hirayama C, Ihara H, Mukai T. Lipid-membrane analogs-specific retention behavior in comb-shaped telomer-immobilized porous silica-gels. Macromolecules,1992,25 (23): 6375-6376
[25]Fukumoto T, Ihara H, Sakaki S, et al. Chromatographic separation of geometrical isomers using highly oriented polymer-immobilized silica gels. J. Chromatogr. A,1994,672: 237-241
[26]O'Gara J F, Alden B A, Walter T H, et al. Simple preparation of a C18 HPLC stationary phase with an internal polar functional group. Anal Chem,1995,67(3):3809-3813
[27]Liu X D, Bordunov A V, Pohl C A. Preparation and evaluation of a hydrolytically stable amide-embedded stationary phase. J. Chromatogr. A,2006,1119:128-134
[28]Kirkland J J, Henderson J W. Reversed-phase HPLC selectivity and retention characteristics of conformationally different bonded alkyl stationary phases. J. Chromatogr. Sci.,1994, vol. 32(11):473-480
[29]Kirkland J J, Henderson J W, Martosella J D, et al. A highly stable alkyl-amide silica-based column packing for reversed-phase HPLC of polar and ionizable compounds. LC GC N. Am., 1999, vol.7(17):634-636
[30]Kirkland J J, Adams J B, van Straten M A, et al. Bidentate silane stationary phases for reversed phase high-performance liquid chromatography. Anal. Chem,1998, vol.70(20): 4344-4352
[31]黄晓佳,王俊德,刘学良.新型烷基醚型键合固定相的制备及评价.色谱,2001,19(6)：485-488
[32]黄晓佳,刘学良,王俊德等.新型酯型反相高效液相色谱填料的制备表征及性能评价.高等学校化学学报,2002,23(9)：1684-1687
[33]黄晓佳,王俊德,刘学良.酰胺型键合相的简便制备及评价.色谱,2002,20(3)：19-222
[34]黄晓佳,王俊德,刘学良等.胺型键合反相固定相的制备及评价.分析化学,2002,30(8)：962-966
[35]黄晓佳,王俊德,刘学良等.双胺型键合固定相的制备及评价.分析化学,2002,30(9)：1048-1052
[36]龙远德,杨晓晔,黄天宝.十四烷基胺键合固定相的反相色谱性能.色谱,1999,17(4)：339-341
[37]景玉青,龙远德,黄天宝.一种新型液相色谱屏蔽键合相的色谱性能.高等学校化学学报,2002,23(2)：210-212
[38]马言顺,龙远德,翦英红等.新型高效液相色谱酰胺键合固定相的制备与评价.分析化学,2004,32(2)：232-236
[39]王萍,王俊德,丛润滋等.用于碱性物质分离的高效液相色谱键合相的制备及评价.色谱,1997,15(3)：189-192
[40]R M Smith. Separation of aromatic compounds on phenyl-bonded silica. J. Chromatogr. A, 1982,237:144-147
[41]R Doms, W E Lambert, K M Clauwaert, et al. Comparison of phenyl-type columns in the development of a fast liquid chromatographic system for eighteen opiates commonly found in forensic toxicology. J. Chromatogr. A,2000,896:311-319
[42]J Szeman, K Csabai, K Kekesi, et al. Novel stationary phases for high-performance liquid chromatography analysis of cyclodextrin derivatives. J. Chromatogr. A,2006,1116:76-82
[43]刘旭.高效液相色谱芳基键合硅胶固定相的制备与评价：硕士论文.南昌：南昌大学,2005
[44]李来生,刘旭,黄志兵等.3,5-二硝基苯甲酰基高效液相色谱键合硅胶固定相的制备与评价.色谱,2005,23(2)：123-128
[45]刘旭,李来生,黄志兵等.高效液相色谱喹啉醚基键合硅胶固定相的制备及评价.分析试验室,2005,24(4)：1-6
[46]T Hanai, F Ahamed, I Rustamor, D Babusis. Seleetivity of Phenylhexyl-bonded silica gel for liquid chromatography. J. liq. Chrom.& Rel. Technol,1999,22:501-511
[47]Buszewski B, Schmid J, Albert K, Bayer E. Chemically bonded phases for the reversed-phase high-performance liquid chromatographic separation of basic substances. J Chromatogr,1991,552(1/2):415-427
[48]C. P. Jaroniec, M. Jaroniec, M. Kruk. Comparative studies of structural and surface properties of porous inorganic oxides used in liquid chromatography. Journal of Chromatography A,1998,797(1/2):93-102
[49]B. Buszewski, P. Kasturi, R. K. Gilpin, M. E. Gangoda, M. Jaroniec. Chromatographic and related studies of alkylamide phases. Chromatographia,1994,39(3/4):155-161
[50]Monika Waksmundzka-Hajnos, Anna Petruczynik, et al. Comparison of chromatographic properties of cyanopropyl-, diol-and aminopropyl-polar-bonded stationary phases by the retention of model compounds in normal-phase liquid chromatography systems. J. Chromatogr. A,2001,919:39-50
[51]John E. O'Gara, Bonnie A.Alden, Thomas H.Walter, John S. Petersen, et al. Simple preparation of a C8 HPLC stationary phase with an internal polar functional group. Anal. Chem.,1995,67 (20):3809-3813
[52]Kensuke Okusa, H. Tanaka, M. Ohira. Development of a new cyano-bonded column for high-performance liquid chromatography. J. Chromatogr. A,2000,869:143-149
[53]L W Yu, T R Floyd, R A Hartwick. The synthesis and characterization of chemically bonded. silica-based zwitterion-exchangers for HPLC. J. Chromatogr. Sci.,1986,24 (5):177-182
[54]P.J. Davis, R.J. Ruane, I.D. Wilson. Chromatographia,1993,37:60
[55]M Caude, R Rosset. Comparison of new hing capacity ion exchange silicas of the spherosil type and normal microparticulate ion exchangers of the polystyrene divinylbenzene type in high performance liquid chromatography. J. Chromatogr. Sci.,1977,15 (9):405-412
[56]Raquel Nogueira, Michael Lammerhofer, Wolfgang Lindner. Alternative high-performance liquid chromatographic peptide separation and purification concept using a new mixed-mode reversed-phase/weak anion-exchange type stationary phase. J. Chromatogr. A,2005,1089: 15-169
[57]Mei-Hui Yang, Kuo-Chang Chang, Jer-Yann Lin. Multifunctional ion-exchange stationary phases for high-performance liguid chromatography. J. Chromatogr. A,1996,722:87-96.
[58]雷晓玲,王俊德,丛润滋.新型离子交换硅胶键合相的制备及评价.色谱,1999,17(5)：431-434
[59]雷晓玲,王俊德,丛润滋.无孔单分散离子交换硅胶键合相用于蛋白质的高效液相色谱分离.分析测试学报,1999,18(4)：1-4
[60]小田良平,庄野利之,田伏岩夫.冠醚化学.北京：原子能出版社.1985
[61]化学分离富集方法及应用编委.化学分离富集方法及应用.长沙：中南工业大学出版社,2000
[62]C J Pederson. The synthesis of crown. Am. Chem. Soc.,1967,89:7017
[63]Shinbo T, Yamaguchi T, Nishimura K, Sugiura M. Chromatographic separation of racemic amino acids by use of chiral crown ether-coated reversed-phase packings. J Chromatogr, 1987,405:145-53
[64]Myung Ho Hyun, Jong Sung Jin, Wonjae Lee. Liquid chromatographic resolution of racemic amino acids and their derivatives on a new chiral stationary phase based on crown ether. Journal of Chromatography A,1998,882(1):155-161
[65]Hyun M H, Han S C, Jin J S, et al. Separation of the stereoisomers of racemic fluoroquinolone antibacterial agents on a crown-ether-based chiral HPLC stationary phase. Chromatographia,2000,52 (7/8):473-476
[66]Myung Ho Hyun, Jong Sung Jin, Hye Jin Koo, Wonjae Lee. Liquid chromatographic resolution of racemic amines and amino alcohols on a chiral stationary phase derived from crown ether. Journal of Chromatography A,1999,837(1/2):75-82
[67]Hyun M H, Han S C, Lipshutz B H, et al. New chiral crown ether stationary phase of the liquid chromatographic resolution of a-amino acid enantiomers. J Chromatogr. A,2001, 910(2):359-365
[68]Hyun M H, Min H J, Cho Y J. Enantiomeric separation of tocainide and its analogues on an optically active crown ether-based stationary phase by liquid chromatography. J Chromatogr. A,2003, vol.996 (1/2):233-237
[69]Lauth M, Gramain P. Ion chromatographic-separation on silica grafted with benzo-18-c-6 crown ether. J. Liq. Chromatogr,1985,8 (13):2403-2415
[70]Bradshaw J S, Bruening R L, Krakowiak K E, Tarbet B J, Bruening M L, Izatt R M, Christensen J J. Preparation of silica gel-bound macrocycles and their cation-binding properties. J. Chem. Soc. Chem. Commun.,1988,12:812-814
[71]Steffeck R J, Zelechonok Y, Gahm K H. Enantioselective separation of racemic secondary amines on a chiral crown ether-based liquid chromatography stationary phase. J Chromatogr. A,2002,947 (2):301-305
[72]Hirose K, Nakamura T, Nishioka R, et al. Preparation and evaluation of novel chiral stationary phases covalently bound with chiral pseudo-18-crown-6 ethers. Tetrahedron Letters,2003, vol.44(8):1549-1551
[73]Lee W, Bang E, Lee W. Chiral resolution of diphenylalanine by high-performance liquid chromatography on a crown-ether-based chiral stationary phase and by NMR spectroscopy. Chromatographia,2003,57 (7/8):457-461
[74]Farkas V, Toth T, Orosz G, et al. Enantioseparation of protonated primary arylalkylamines and amino acids containing an aromatic moiety on a pyridino-crown ether based new chiral stationary phase. Tetrahedron-asymmetry.,2006,17(12):1883-1889
[75]达世禄,何国亮.高效液相色谱二氮杂冠醚键合相的合成及性能研究.高等学校化学学报,1993,14(12).1677-1681
[76]达世禄,范畴.多功能基和氮杂冠醚键合固定相的制备与鉴定.色谱,1995,13(3)：161-165
[77]Da S L, Feng Y Q, Da H N, et al. Preparation and characterization of 3-(Aza-18-crown-6) propylsilyl bonded phase for reversed-phase liquid chromatography. J. Chromatogr. Sci., 1999, vol.37(5):137-144
[78]达世禄,齐广才.氮杂冠醚键合固定相的RP-HPLC色谱性能研究.高等学校化学学报,1995,16(8)：1219-1223
[79]Da S L, Yue W G, Wen Y F, et al. Preparation and characterization of bonded stationary phases of nitrogen-containing crown ether for high-performance liquid chromatography. Anal. Chim. Acta,1994, vol.299(2):239-247
[80]龚银汉.高效液相色谱氮杂冠醚键合固定相的合成及性能研究.高等学校化学学报,1998,19(5)：720-722
[81]Armstrong D W. U S. patent, No.4539399,1985.
[82]Armstrong D W, DeMond W J. J. Chromatogr. Sci,1984,22,411-415
[83]旷昌渝,吴邦桂,周竞先.β-环糊精键合相的制备及其在液相色谱中的应用.色谱,1989,7：21-23
[84]黄天宝等.中国专利,90105779
[85]黄天宝等.β-环糊精键合固定相的制备和评价.分析化学,1991,19(11)：1257-1260
[86]Tanaka M, et al. Unmodified and acylated cyclodextrin stationary phases for liquid chromatographic separation of aromatic compounds. Journal of chromatography,1984,301: 345-353
[87]Tanaka M, et al. Liquid chromatographic separation of racemates on acetylated or carbamoylated β-cyclodextrin-bonded stationary phases. Journal of chromatography,1989, 469:429-433
[88]Tanaka M, et al. Retention behaviour of disubstituted benzene isomers on acetylated cyclodextrin stationary phases. Journal of chromatography A,1983,267:285-292
[89]Tanaka, et al. Methylated cyclodextrin-bonded stationary phases for liquid chromatography. Journal of chromatography A,1986,370:293-301
[90]Hattori K, et al. Novel high-performance liquid chromatographic adsorbents prepared by immobilization of modified cyclodextrins. Journal of chromatography A,1986,355: 383-391
[91]Hattori K, et al. Novel HPLC adsorbents by immobilization of modified cyclodextrins. Journal of Inclusion Phenomena and Macrocyclic Chemistry,1987,5:73-76
[92]Kazumi Fujimura, Teruhisa Ueda, Teiichi Ando. Retention behavior of some aromatic compounds on chemically bonded cyclodextrin silica stationary phase in liquid chromatography. Analytical Chemistry,1983,55 (3):446-450
[93]Fujimura K, Kitagawa M, Takayanagi H. High-performance liquid chromatographic separation of aromatic carboxylic acids with β-cyclodextrin-bonded stationary phases. Journal of chromatography A,1985,350:371-380
[94]Fujimura K. Optical resolution of some mandelic derivatives on a chemically bonded cyclodextrin stationary phase. Journal of liquid chromatography,1986,9:607-620
[95]Armstrong D W. Derivatized cyclodextrins for normal-phase liquid chromatographic separation of enantiomers. Analytical chemistry,1986,62:1610-1615
[96]Armstrong D W, et al. (R)-and (S)-naphthylethylcarbamate-subsituted β-cyclodextrin bonded stationary phase for the reversed-phase liquid chromatrography separation of enantiomers. Journal of chromatography A,1991,539,83-90
[97]Stalcup A M, San Chun Chang, Armstrong D W. Effect of the configuration of the substituents of derivatized β-cyclodextrin bonded phases on enantioselectivity in normal-phase liquid chromatography. Journal of chromatography A,1991,540:113-128
[98]Stalcup A M, Chang S C, Armstrong D W, Pitha J. (S)-2-hydroxypropyl-beta-cyclodextrin, a new chiral stationary phase for reversed-phase liquid chromatography. Journal of chromatography,1990,513:181-194
[99]黄天宝,吴邦桂,龙远德等.β-环糊精键合固定相的制备和评价.分析化学,1991,19：1257-1260
[100]陈慧,吕宪禹,黄君珉等.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).高等学校化学学报,2000,21(4)：562-565
[101]黄君珉,陈慧,高如瑜等.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(Ⅱ).高等学校化学学报,2000,22(11)：1838-1842
[102]贺湘凌,谭天伟等.利用β-环糊精键合固定相分离纯化葛根素.色谱,2003,21：610-613
[103]冯钰琦,达世禄.甘氨酸衍生化β-环糊精键合硅胶液相色谱固定相的合成与评价.色 谱,2000,1 8(3)：224-228
[104]冯钰琦,谢敏杰,达世禄.8-羟基喹啉衍生化β-环环糊精键合硅胶液相色谱固定相的合成与评价.高等学校化学学报,1999,20：1708-1713
[105]罗爱芹,刘立文,戴荣继等.2,6-二-O-苄基-β-环糊精键合硅胶固定相的合成与色谱性能.北京理工大学学报,2005,25(1)：87-90
[106]罗爱芹,侯爱军,戴荣继等.七(2,6-二-O-丁基)-β-环糊精键合硅胶固定相的合成与评价.北京理工大学学报,2005,25(8)：745-748
[107]刘立文,罗爱芹,戴荣继等.2,6-二-O-戊基-β-环糊精键合硅胶固定相的合成与色谱性能考察.色谱,2004,22(6)：630-633
[108]罗爱芹,刘立文,戴荣继等.对联苯二酚桥联环糊精键合硅胶固定相的合成与色谱性能测试.北京理工大学学报,2004,24(7)：646-649
[109]耿利娜,罗爱芹等.丝氨酸衍生化β-环糊精色谱柱的制备及色谱性能研究.北京理工大学学报,2007,27(12)：1022-1026
[110]方敏,周智明,罗爱芹.新型α-希夫碱衍生化β-环糊精键合硅胶手性固定相的合成与色谱性能研究.高等学校化学学报,2005,26(8)：1443-1445
[111]罗爱芹,钱伟等.利胆醇在新型多肽键合环糊精硅胶手性柱上分离条件的优化.北京理工大学学报,2007,27(7)：646-649
[112]孙立权,罗爱芹等.新型苄氧羰基苯丙氨酸环糊精衍生物键合硅胶手性固定相的合成与评价.北京理工大学学报,2008,28(8)：749-752
[113]Gutsche C D, Muthukrishnan R. Calixarenes. Analysis of the product mixtures produced by the base-catalyzed condensation of formaldehyde with para-substituted phenols. J. Org. Chem,1978,43:4905-4906
[114]Park J K, Lee Y H, Cheong N Y. Reversed phase liquid chromatographic separation of some mono-substituted phenols with calix[6]arene-p-sulfonate-modified eluents. Chromatographia,1993,37:221-223
[115]Glennon J D, O'Connor K, Srijaranai S, et al. Enhanced chromatographic selectivity for sodium ions on a calixarene-bonded stationary silica phase.Anal. Lett.,1993, vol.26: 153-162
[116]Glennon J D, Home E, Hall K, D Cocker, A Kuhn, S J Harris, M A McKervey. Silica-bonded calixarene in chromatography. Ⅱ.Chromatographic retention of metal ions and amino-acid ester hydrochlorides. J.Chromatogr. A,1996,731:47-55
[117]S Friebe, S Gebauer, G J Krauss, et al. HPLC on calixarene bonded silica gels.I.Characteriz ation and applications of the p-tert-butyl-calix[4]arene bonded material. J. Chromatogr. Sci.,1995,33:281-289
[118]S Gebauer, S Friebe, G. Giibitz, G. J Krauss. High performance liquid chromatography on calixarene-bonded silica gels. Ⅱ.separation of regio-and stereoisomers on p-tert-butyl-calix[n] phase. J. Chromatogr. Sci,1998,36:383-287
[119]Glennon J D, O'Connor K, Eorne E. Analytical Proceedings including Chromatographic selectivity for amino acid esters and alkali metal ions on a silica bonded calix[4]arene tetraester stationary phase. Analytical Proceedings including Analytical Communications, 1994,31:33-35
[120]粟学俐,李仁杰,吴彩樱.叔丁基和脱叔丁基环酰胺杯[4]芳烃聚硅氧烷固定相的合成.阜阳师范学院学报(自然科学版),2002,19：23-25
[121]张岩,肖湘竹,冯钰琦等.硅胶键合杯[4]芳烃固定相的合成和核磁共振表征.物理化学学报,2000,16：65-69
[122]李文智,王霞,张红丽等.对-叔丁基杯[4]芳烃键合固定相的制备及表征.分析测试学报,2004,23(1)：19-22
[123]李文智,敦惠娟,韩小茜等.对-叔丁基杯[6]芳烃键合固定相的制备和评价.色谱,2003,21(5)：483-486
[124]李文智,柳春辉,张红丽等.对-叔丁基杯[8]芳烃键合固定相的制备及表征.分析测试技术与仪器,2004,10(1)：24-29
[125]李文智,王霞,窦建民等.新型杯[4]芳烃高效液相色谱固定相的制备及表征.化学学报,2004,62(4)：405-409
[126]Li L S, Da S L, Feng Y Q, et al. Preparation and evaluation of a new calix[4]arene-bonded stationary phase for HPLC. J. Liq. Chromatogr. R. T,2004, vol.27 (14):2167-2188
[127]李来生,达世禄,冯钰琦,刘敏.脱叔丁基杯[8]芳烃键合固定相的制备及其液相色谱性能.高等学校化学学报,2005,26(2)：241-243
[128]Li L S, Da S L, Feng Y Q, et al. Preparation and Characterization of a New p-tert-Butyl-calix[8] arene-bonded Stationary Phase for High-Performance Liquid Chromatography. Anal. Sci.,2004, vol.20(3):561-564
[129]Liu M., Li L S, Da S L, et al. Preparation of p-tert-Butyl-Calix[8]arene bonded silica stationary phase and separation for steroid hormone medicines. Anal. Lett.,2004,37(14): 3017-3031
[130]Li L S, Da S L, Feng Y Q, Liu M. HPLC separation of neutral, acidic, and basic compounds on a p-tert-butyl-calix[8]arene-bonded stationary phase. Anal. Lett.,2004, vol. 37 (13):2805-2817
[131]Li L S, Da S L, Feng Y Q, et al. Study on the chromatographic behavior of water-soluble vitamins on p-tert-butyl-calix[8]arene-bonded silica gel stationary phase by HPLC. Talanta, 2004, vol.64 (2):373-379
[132]李来生,刘敏,达世禄等.大黄蒽醌衍生物在杯[8]芳烃键合固定相上色谱行为的研究.分析化学,2004,32(4)：511-515
[133]刘敏,达世禄,冯钰琦等.杯[8]芳烃键合硅胶固定相的制备、表征及色谱性能.高等学校化学学报,2004,25(7)：1254-1256
[134]Li L S, Liu M, Da S L, et al. High performance liquid chromatography of aromatic carboxylic acids on p-tert-butyl-calix[8]arene-bonded silica gel stationary phase. Talanta, 2004,62 (3):643-648
[135]Li L S, Liu M, Da S L, et al. Studies on the chromatographic behavior of nucleosides and bases on p-tert-butyl-calix[8]arene-bonded silica gel stationary phase by HPLC. Talanta, 2004, vol.63 (2):443-451
[136]Li L S, Da S L, Feng Y Q, et al. Preparation and characterization of a p-tert-butyl-calix[6]-1,4-benzocrown-4-bonded silica gel stationary phase for liquid chromatography. J. Chromatogr. A,2004, vol.1040(1):53-61
[137]Behrend R, Meyer E, Rusche F. Ueber condensationsprodukte aus glycoluril und formaldehyd. Liebigs Ann. Chem.,1905,339:1-37
[138]Freeman W A, Mock W L, Shih N Y. Cucurbituril. J. Am. Chem. Soc.,1981,103 (24): 7367-7368
[139]杨辉,谭业邦等.葫芦脲的研究进展.化学进展,2009,21(1)：164-173
[140]Jon S Y, Selvapalam N, Oh D H, Kang J K, Kim S Y, Jeon Y J, Lee J W, Kim K. Facile synthesis of cucurbit[n]uril derivatives via direct functionalization:Expanding utilization of cucurbit[n]uril. J. Am. Chem. Soc.,2003,125 (34):10186-10187
[141]Liu S M, Xu. L, Wu C T, Feng Y Q. Preparation and characterization of perhydroxyl-cucurbit[6]uril bonded silica stationary phase for hydrophilic-interaction chromatography. Talanta,2004,64,929-934
[142]Nagarajan E R, Oh D H, Selvapalam N, Ko Y H, Park K M, Kim K. Cucurbituril anchored silica gel. Tetrahedron Letter,2006,47,2073-2075
[143]Kim K, Balaji R, Oh D H, Ko Y H, Jon S Y. PCT WO2004/072151 A1,2004; KR 0008453,2003
[144]Si-Min Liu, Li Xu, Cheng-Tai Wu, Yu-Qi Feng. Preparation and characterization of perhydroxyl-cucurbit[6]uril bonded silica stationary phase for hydrophilic-interaction chromatography. Talanta,2004,64(4):929-934
[145]王上文,李来生,易绣光.嘌呤衍生物在葫芦[6]脲单轮烷键合固定相上的色谱行为.色谱,2007,25(6)：838-843
[146]李来生,王上文,黄丽芳,刘妙芬.葫芦[6]脲单轮烷键合固定相的制备、表征及色谱性能.化学学报,2008,66(1)：63-72
[147]S G Nerurkar, S V Dighe, R L Williams. Bioequivalence of racemicdrugs. J. Clin. Pharmacol.1992,32 (10):935-943.
[148]Jamali F, Mehvar R, Pasutto F M. Enantioselective aspects of drug action disposition: therapeutic pitfalls. J Pharm Sci,1989,78 (9):695
[149]Pirkle W H, and House D W. Chiral high-performance liquid chromatographic stationary phases.1. Separation of the enantiomers of sulfoxides, amines, amino acids, alcohols, hydroxy acids, lactones, and mercaptans. J Org, Chem,1979, vol.44(12):1957-1960
[150]Hyun M Ho, Na M S, Min C S. Improved chiral stationary phase derived from (S)-naproxen for the liquid chromatographic resolution of enantiomers. J. Chromatogr. A, 1996, vol.732:209-214
[151]Oi S, Ono H, Tanka H, et al. Axially dissymmetric bianthracene-based chiral stationary phase for the high-performance liquid chromatographic separation of enantiomers. J.Chromatogr. A,1994, vol.679:35-46
[152]M H Hyun, M S Na, J S Jin. Chiral recognition models for the liquid chromatographic resolution of π-acidic racemates on a chiral stationary phase derived from N-phenyl-N-alkylamide of (S-naproxen). J.Chromatogr. A,1996,752:77-84
[153]蔡小军,徐秀珠,张大同等.高效液相色谱手性固定相法分离酸性化合物对映体.分析化学,2004,32(2)：134-138
[154]潘春秀,吴清洲,沈报春等.芳氧苯氧丙酸类除草剂在两种手性柱上的分离.分析化学,2006,34(2)：159-164
[155]Zhang D D, Li F M, Hyun M H. Preparation and application of a novel Pirkle-type chiral stationary phase in liquid chromatography. Pharmazie,2007, vol.62 (4):258-261
[156]唐琴,宋航,付超等.高效液相色谱手性固定相法拆分克伦特罗对映体.分析化学,2004,32(6)：755-758
[157]Okamoto Y, Kawashima M, HATADA K. Chromatographic resolution. XI:Controlled chiral recognition of cellulose triphenylcarbamate derivatives supported on silica gel. Journal of chromatography A,1986,363:173-186
[158]Blaschke G. Chromatographic resolution of chiral drugs on polyamides and cellulose triacetate. Journal of liquid chromatography A,1986,9:341-368
[159]Shibata T, Okamoto I, Ishii K. Chromatographic optical resolution on polysaccharides and their derivatives. Journal of liquid chromatography A,1986,9:313-340
[160]Francotte E, In:Aboul-Enein H Y, Wainer I W(Ed). The Impact of Stereochemistry on Drug Development and Use. New York:Wiley,1997,23,633-683
[161]G Hesse, R Hagel. A complete separation of a racemic mixture by elution chromatography on cellulose triacetate. Chromatographia,1973,6:277-280
[162]Okamoto Y, Aburatani R, Hatada K. Chromatographic chiral resolution. XIV:Cellulose tribenzoate derivatives as chiral stationary phases for high-performance liquid chromatography. Journal of chromatography A,1987,389:95-102
[163]Y Okamoto, R Aburatani, S Miura, et al. Chiral stationary phases for HPLC:Cellulose tris(3,5-dimethylphenylcarbamate) and tris(3,5-dichlorophenylcarbamate) chemically bonded to silica gel. J. Liq. Chromatogr.,1987,10:1613-1628
[164]E Yashima, H Fukaya, Y Okamoto.6,6'-Dinitrobiphenyl-2,2'-dicarboxylic acid ionically bonded to aminopropyl silica:New axially chiral phase of C2 symmetry for high-performance liquid chromatographic separation of enantiomeric amino alcohol derivatives. J. Chromatogr. A,1994,667:11-17
[165]T Kubota, T Kusano, C Yamamoto, et al. Cellulose 3,5-dimethylphenylcarbamate immobilized onto silica gel via copolymerization with a vinyl monomer and its chiral recognition ability as a chiral stationary phase for HPLC. Chem. Lett.,2001,7:724-725
[166]C Minguillon, P Franco, L Oliveros, et al. Bonded cellulose-derived high-performance liquid chromatography chiral stationary phases I. Influence of the degree of fixation on selectivity. J. Chromatogr. A,1996,728:407-414.
[167]邵保海,徐秀珠,吕建德等.三种甲氧基黄烷酮在纤维素衍生物手性柱上的对映体分 离及手性识别机理研究.化学学报,2003,61(3)：440-444
[168]杨丽萍,王立新,徐艳丽等.纤维素类手性固定相高效液相色谱法拆分三唑类手性化合物.分析测试学报,2004,23(5)：25-28
[169]陈小明,毛希琴,张曾子等.键合型纤维类手性固定相高效液相色谱法拆分对映异构体.化学学报,2002,60(1)：93-97
[170]Yoshio Okamoto, Hideaki Sakamoto, Koichi Hatada, Masahiro Irie. Resolution of enantionmers by HPLC on cellulose trans-and cis-tris(4-phenylazophenylcarbamate). Chemistry Letters,1986,15(6):983-986
[171]Yoshio Okamoto, Ryo Aburatani, Tohru Fukumoto, Koichi Hatada. Useful Chiral Stationary Phases for HPLC. Amylose Tris(3,5-dimethylphenylcarbamate) and Tris(3,5-dichlorophenylcarbamate) Supported on Silica Gel. Chemistry Letters,1987,16: 1857-1860
[172]Stephen A Matlin, M Elizabeth Tiritan, Quezia B Cass, Derek R Boyd. Enantiomeric resolution of chiral sulfoxides on polysaccharide phases by HPLC. Chirality,1996,8(1): 147-152
[173]周志强,丁二润,胡雨来,于兆文等.直链淀粉手性固定相对8种外消旋硫代缩水甘油醚的直接拆分.高等学校化学学报,1998,19(11)：1755-1757
[174]周志强,于兆文,牛童等.涂敷型直链淀粉手性固定相直接拆分外消旋硫代缩水甘油醚.色谱,1999,17(2)：182-183
[175]周志强,胡雨来,丁二润,于兆文等.直链淀粉-三(苯基氨基甲酸酯)手性固定相的制备及对外消旋硫代缩水甘油醚的直接拆分.分析化学,1998,26(9)：1139-1141
[176]于兆文,周志强,蒋生祥等.高效液相色谱法直接分离硒代缩水甘油醚对映异构体.分析化学,1999,27(2)：206-209
[177]孔亮,邹汉法等.以人血清白蛋白为固定相的分子生物色谱分析几种中等活性成分的研究.高等学校化学学报,2000,21(1)：36-40
[178]封顺,张强,邹汉法等.羰基咪唑法合成牛血清白蛋白键合手性固定相.高等学校化学学报,2002,23(7)：1251-1254
[179]Millot M C, Taleb N L, Sebille B. Binding of human serum albumin to silica particles by means of polymers:a liquid chromatographic study of the selectivity of resulting chiral stationary phases. J. Chromatogr. B,2002,768:157-166
[180]Andrisano V, Gotti R, Recanatini M, et al. Stereoselective binding of 2-(4-biphenylyl)-3-substituted-3-hydroxy-propionic acids on an immobilised human serum albumin chiral stationary phase. J. Chromatogr. B,2002,768:137-145
[181]Jorgen Hermansson. Direct liquid chromatographic resolution of racemic drugs using al-acid glycoprotein as the chiral stationary phase. Journal of Chromatography A,1983, 269:71-80
[182]Miwa T. Ichikawa M, Tsuno M, et al. Direct liquid chromatographic resolution of racemic compounds. Use of ovomucoid as a column ligand. Chemical and pharmaceutical bulletin, 1987,35:682-686
[183]Miwa T, Miyakawa T, Miyake T. Characteristics of an avidin-conjugated column in direct liquid chromatographic resolution of racemic compounds. Journal of chromatography A, 1988,457:227-233
[184]Erlandsson P, Marle I, Hansson L, et al. Immobilized cellulase (CBH Ⅰ) as a chiral stationary phase for direct resolution of enantiomers. Journal of the American Chemical Society,1990,112:4573-4574
[185]Thelohan S, Jadaud P, Schombaum G R, et al. Immobilized enzymes as chromatographic phases for HPLC:the chromatography of free and derivatized amino acids on immobilized trypsin. Chromatographia (Wiesbaden) A,1989,28:551-555
[186]Wainer I W, Jadaud P, Schombaum G R, et al. Enzymes as HPLC stationary phases for chiral resolutions:initial investigations with α-chymotrypsin. Chromatographia (Wiesbaden) A,1988,25:903-907
[187]Haginaka J, Murashima T, Seyama C. Separation of enantiomers on a lysozyme-bonded silica column. Journal of chromatography A,1994,666:203-210
[188]Armstrong D W, Tang Y B, Chen S S, et al. Macrocyclic antibiotics as a new class of chiral selectors for liquid chromatography. Anal Chem,1994,66 (9):1473-1484
[189]Armstrong D W, Liu Y B, Erthoryott K H. A covalently bonded teicoplanin chiral stationary phase for HPLC enantioseparations. Chirality,1995,7(6):474-497
[190]Rundett K L, Gasper M P, Zhou E Y, Armstrong D W. Capillary electrophoretic enantiomeric separations using the glycopeptide antibiotic, teicoplanin. Chirality,1995,8(1): 88-107
[191]Armstrong D W, Zhou Y W. Use of a macrocyclic antibiotic as the chiral selector for enantiomeric separations by TLC. Journal of liquid chromatography,1994,17:1695-1707
[192]丁国生,黄晓佳,刘学良,王俊德.新型高效液相色谱手性固定相选择剂--大环抗生素.色谱,2002,20(6)：519-525
[193]Ward T J, Farris Ⅲ A B. Chiral separations using the macrocyclic antibiotics:a review. Journal of Chromatography A,2001,906:73-89
[194]Beesley T E, Lee J T, Wang A X. In:Subranian G. (Ed). Chiral Separation Technigues. New York:Wiley-VCH,2001,25
[195]丁国生,从润滋,王俊德.去甲万古霉素键合手性固定相在反相条件下拆分氨基酸类衍生物.分析化学,2004,32(5)：606-610
[196]丁国生,刘莺,从润滋,王俊德.去甲万古霉素键合手性固定相拆分-受体阻滞剂类药物及其结构类似物的研究.色谱,2004,22(4)：386-389
[197]G S Ding, X J Huang, Y Liu, J D Wang. Chiral Separation of Racemates of Drugs and Amino Acid Derivatives by High-Performance Liquid Chromatographyon a Norvancomycin-Bonded Chiral Stationary Phase. Chromatographia,2004,59:443-449
[198]丁国生,唐安娜,王俊德,包建民.替拉考宁键合手性固定相的制备及其在反相条件下对手性化合物的拆分.分析化学,2006,34(3)：338-342
[199]丁国生,唐安娜,王俊德,从润滋,包建民.替考拉宁键合手性固定相高效液相色谱 法直接拆分泮托拉唑钠对映体.色谱,2006,24(1)：46-48
[200]Timothy J. Ward, Alton B. Farris Ⅲ. Chiral separations using the macrocyclic antibiotics:a review. J. Chromatogr. A,2001,906:73-89
[201]Davankov V A. Chiral selectors with chelating properties in liquid chromatography: fundamental reflections and selective review of recent developments. Journal of chromatography A,1994,666:55-76
[202]Davankov V A, Meyer V R, Rais M. A vivid model illustrating chiral recognition induced by achiral structures. Chirality,1990,2(4):208-210
[203]Kurganov A A, Davankov V A, Kuzmenko O et al. Effects of polystyrene coating on pore, structural and chromatography properties of silica packings. Journal of chromatography, 1990,506:391-400
[204]Kurganov A A. Chiral chromatographic separations based on ligand exchange. Journal of chromatography A,2001,906:51-71
[205]Davankov V A. Journal of chromatographic science,1990,47:541-545
[206]Gubita G, Juffmann F, Jellenz W. Direct separation of amino enantiomers by high performance ligand exchange chromatography on chemically bonded chiral. Chromatographia,1982,16:103-106
[207]Gubitz G, Mihellyes S, Kobinger G et al. New chemically bonded chiral ligand-exchange chromatographic stationary phases. Journal of chromatography A,1994,666:91-97
[208]Katoh H, Ishida T, Kiniwa H. Optical resolution of 2-hydroxy acids by high-performance ligand exchange chromatography. Chromatographia,1989,28(9/10):481-486
[209]Francotte E, Junker-Buchheit A. Preparative chromatographic separation of enantiomers. Journal of Chromatography,1992,576(1):1-45
[210]祝馨怡,刘淑娟,肖小华等.L-苯丙氨酸键合手性配体交换色谱固定相的制备及手性拆分.分析测试学报,2002,21(6):62-64.
[211]祝馨怡,敦会娟,赵亮等.L-脯氨酸键合手性配体交换色谱固定相的制备及手性拆分.化学试剂,2002,24(3)：129-131
[212]祝馨怡,张玉华,孙伟等.L-羟基脯氨酸键合手性配体交换色谱固定相的制备及手性拆分.分析科学学报,2003,19(2)：124-126
[213]孟庆华,王圣庆等.异喹啉酸衍生物配体交换色谱手性固定相的制备及应用.分析化学,2006,34(3)：311-315
[214]王圣庆,孟庆华等.L-半光氨酸衍生物配体交换手性色谱固定相.高等学校化学学报,2005,26(9)：1631-1633
[215]黄晓佳,王秋泉,王俊德等.L-异亮氨酸型配体交换固定相对DL-氨基酸的拆分研究.色谱,2005,23(2)：172-175
[216]丁国生,黄晓佳,刘莺,王俊德.硅胶键合手性配体交换色谱固定相拆分α-氨基酸.分析测试学报,2003,22(6)：32-35
[217]黄晓佳,丁国生,王俊德等.新型手性配体交换色谱固定相的合成及其对DL-氨基酸的拆分.色谱,2003,21(3)：230-232
[218]吴邦桂,黄天宝,龙远德等.L-脯氨酸手性键合固定相的制备和表征.色谱,1993,11(3)：164-166
[219]王群标,龙远德,黄天宝.新型手性配体交换色谱固定相的制备及应用.色谱,2000,18(2)：112-117
[220]龙远德,王群标,黄天宝.新型手性配体交换色谱键合固定相.高等学校化学学报,2001,22(4)：566-568
[221]House D W. Chiral stationary phase based on yohimbine, United States Patent 6,132,606. 2000
[222]杨汉荣.大蒜新素二烯丙基三硫化物键合硅胶液相色谱固定相的制备与表征：硕士论文.南昌：南昌大学,2007
[223]陈雄泉.黄芩苷键合硅胶色谱固定相的制备、表征及应用：硕士论文.南昌：南昌大学,2007
[224]许丽丽.姜黄素键合硅胶色谱固定相的制备、表征及其应用：硕士论文.南昌：南昌大学,2007
[225]刘妙芬.靛红键合硅胶色谱固定相的制备、表征及其应用：硕士论文.南昌：南昌大学,2008
[226]肖崇厚,杨松松,洪筱坤,万德光.中药化学.上海：上海科学技术出版社,1999：196-197
[227]陆豫,黄志纾,谭嘉恒,丁岩,卜宪章,安林坤,马林,古练权.大黄素衍生物的合成及细胞毒性研究.有机化学,2005,25(8)：944-948
[228]T. Sokolieβ, U. Menyes, U. Roth, T. Jira. J. Chromatogr. A,2002,948,309-319
[229]Ward T J, Baker B A. Analytical Chemistry,2008,80 (12):4363-4372
[230]李来生,陈雄泉,样汉荣,吴宇梅.黄芩苷键合硅胶固定相的制备与表征.分析化学,2007,35(9)：44-49
[231]许丽丽,李来生,杨汉荣.姜黄素键合硅胶固定相的制备、表征及色谱性能.色谱,2007,25(3)：374-379
[232]宋小妹,唐志书.中药化学成分提取分离与制备.北京：人民卫生出版社,2004,
57-65
[233]侯晓东等.大黄素的研究现状和展望.中国热带医学,2005,5(8)：1738-1740
[234]陈定一,王静竹等.高效液相色谱法测定大黄及其炮制品中大黄素的含量.中国中药杂志,19(9)：538-539
[235]杜文彬,张洪.大黄中大黄素的提取条件优化.时珍国医国药,2008,9(11)：2757-2758
[236]王乃利,陈英杰.大黄中蒽醌类成分分离方法的改进.中药通报,1995,8(8)：28-30
[237]汪显阳,孙作民.从大黄中提取大黄素的研究.中国现代应用化学,1997,14(4)：16-18
[238]肖艳,杜智敏.大黄中有效成分提取分离条件的优化.中国临床药理学与治疗学,2003,8(1)：98-100
[239]Kimata K, Iwaguchi K, Onishi S, et al. Chromatographic characterization of silica C18 packing materials. Correlation between a preparation method and retention behavior of stationary phase. J. Chromatogr. Sci.,1989,27 (12):721-728
[240]Sane R T, Doshi V J, Joshi S K. Simple colorimetric method for determination of pyridoxine hydrochloride(vitamin B6) in pharmaceuticals. J. Assoc. Off. Anal. Chem.,1983, vol.66(1):158-160
[241]Wang E, Hou W. Determination of water-soluble. vitamins using high-performance liquid chromatography and electrochemical or absorbance detection. J. Chromatogr.,1988,447(1): 256-262
[242]Singh J, Upadhyay A K, Prasad K, et al. Variability of carotenes vitamin C, E and phenolics in Brassica vegetables. Journal of Food Composition and Analysis,2007,20(2): 106-112
[243]Weissinger E M, Nguyen-Khoa T, Fumeron C, et al. Effects of oral vitamin C supplementation in hemodialysis patients. A proteomic assessment. Proteomics,2006,6 (3): 993-1000
[244]Lai-Sheng Li, Min Liu, Shi-Lu Da, Yu-Qi Feng. Studies on the chromatographic behavior of nucleosides and bases on p-tert-butyl-calix [8] arene-bonded silica gel stationary phase by HPLC. Talanta,2004,63(2):433-441
[245]Lai-Sheng Li, Shi-Lu Da, Yu-Qi Feng, Min Liu. Study on the chromatographic behavior of water-soluble vitamins on p-tert-butyl-calix[8]arene-bonded silica gel stationary phase by HPLC. Talanta,2004,64(2):373-379
[246]Tomonari Umemura, Kin-ichi Tsunoda, Akira Koide, et al. Amphoteric surfactant-modified stationary phase for the reversed-phase high-performance liquid chromatographic separation of nucleosides and their bases by elution with water. Analytica Chimica Acta, 2000,419(1):87-92
[247]Hibiya M, Teradaira R, Sugimoto T, et al. Journal of Chromatography B,1995,672 (1): 143-148
[248]Solichova D,Melichar B, Klejna M, et al. Talanta,2003,60:459-465
[249]Tomandl J, Tallova J, Tomandlova M, et al. J.Sep.Sci.,2003,26 (8):674-678
[250]Fekkes D, Voskuilen-Kooijman A. Clinical Biochemistry,2007,40 (5):411-413
[251]Huber J F K, Lamprecht G. Journal of Chromatography B,1995,666:223-232
[252]de Cadtro M R, Di Marco G S, Arita D Y, et al. Journal of Biochem. Biophys. Methods, 2004,59 (3):275-283
[253]Schroecksnadel K, Winkler C, Fuchs D. Journal of Biochemical and biophysical methods, 2006,66 (1):99-100
[254]Sawada M, Yamaguchi T, Sugimoto T, et al. Clin. Chim. Acta.,1984,138 (3):1325-1334
[255]Mayersbach P, Augustin R, Schennach H, et al. Clinical Chemistry,1994,40 (2):265-266
[256]Han F T, Huynh B H, Shi H G, et al. Anal. Chem.,1999,71 (7):1265-1269
[257]Kocmid U, Padolak M, Coupek J, et al. Collect. Czech. Chem. Commun.,1986,51(1): 34-44
[258]Espinosa-Mansilla A, Duran-Meras I, Salinas F. Journal of Pharmaceutical and Biomedical Analysis,1998,17:1325-1334
[259]Venkateswara R J. Ecotoxicol Environ Saf,2004,59:217-222
[260]Andrew Campbell. Regulatory Toxicology and Pharmacology,2009,53; 195-204
[261]Graciela P. Zanini. Carolina Maneiro, et al. Geoderma,2009,149:110-115
[262]Eneida Reyes Perez, St'ephane Le Calv', Philippe Mirabel. Journal of Photochemistry and Photobiology A:Chemistry,2008,193:237-244
[263]Robert Kro"ger Richard E, Lizotte Jr. (?)E Matthew T. Moore. Bull Environ Contam Toxicol, 2009,83:369-373
[264]P R. Brown, C.S. Robb, S. E. Geldart. Perspectives on analyses of nucleic acid constituents: The basis of genomics. J. Chromatogr. A,2002,965:163-173
[265]刘春丽,刘满仓,朱彭龄.高效液相色谱分析中药及植物药的进展.分析化学,2000,28(5)：631-643
[266]Huang X D, Kong L, Li X, et al. Strategy for analysis and screening of bioactive compound in traditional Chinese medicines. J. Chromatogr. B, Analyt. Technol. Biomed Life Sci.,2004,812(1/2):71-84
[267]肖凯,宣利江,徐亚明等.虎杖的化学成分研究.中国药学杂志,2003,38(1)：12-14
[268]董静,王弘,万乐人等.高效液相色谱/电喷雾-离子阱-飞行时间质谱分析鉴定中药虎杖中的主要化学成分.色谱,2009,27(4)：425-430
[269]朱立贤.虎杖中白藜芦醇(苷)和蒽醌类化合物的研究：博士论文.无锡：江南大学,2005.
[270]柳航,李占林,郭捷等.葛根的化学成分.沈阳药科大学学报,2009,26(11)：882-885
[271]王慕邹,陈毓享,相乐和彦等.常用中草药高效液相色谱分析.北京：科学出版社,1999：57-58,354-357
[272]李家实.中药鉴定.上海：上海科学技术出版社,1996
[273]李宇航,戴海学,李晓蓉等.葛根素的电喷雾电离裂解规律解析.质谱学报,2007,28(4)：224-229
[274]梁剑武.有关葛根的黄酮类成分分析与研究.广东化工,2004,6：1-4
[275]田宏哲,王华,关亚风.液质联用分析葛根提取物及中药片剂中异黄酮类化合物.色谱,2005,23(5)：477-481
[276]王艳萍.薛兴亚,张秀莉等.HPLC/ESI-MS法鉴定半枝莲乙酸乙酯组分中黄酮苷元类化合物.质谱学报,2009,30(3)：130-138
[277]王英峰,焦燕,王慧彬等.半枝莲中黄酮成分的提取纯化及LC-MS检测.首都师范大学学报(自然科学版),2009,30(5)：32-34
[278]国家药典委员会.中华人民共和国药典：第一部(2005版).北京：化学工业出版社,2005：77.
[279]周颖,王彦,王刃锋.半边莲药材HPLC指纹图谱研究.中成药,2009,29(12)：1717-1720
[280]姜艳艳,石任兵,刘斌等.半边莲中黄酮类化学成分研究.北京中医药大学学报,2009, 32(1)：59-61
[281]周颖.现代液相色谱和质谱联用技术用于半边莲药材的研究：硕士论文.上海：上海交通大学,2008.
[282]韩景兰,张凤岭,李志宏等.半边莲化学成分的研究.中国中药杂志,2009,34(17)：2200-2202
