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全二维气相色谱—飞行时间质谱用于中药挥发油的研究
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摘要
全二维气相色谱(GCxGC)是九十年代发展起来的分离复杂混合物的一种全新手段。自1991年其思想及其装置问世后,得到了迅速的发展。
     本论文首先以石油产品为样品研究了全二维气相色谱-飞行时间质谱(GCxGC-TOFMS)的特性,讨论了柱系统的匹配、调制条件等对分离的影响,并提出了柱系统优化的策略及两维分辨率的概念,
    为GCxGC用于解决复杂样品分析提供了技术基础。
     在上述研究的基础上,本论文首次应用GCxGC-TOFMS于中药挥发油的研究。首先优化了适合中药挥发油分析的柱系统和操作条件,并考察了用于指纹分析的适用性和方法学。以三种挥发油为例,
    基于多次调制(定性)信息,加上两维保留时间和峰纯度数据,鉴定了其中的重要组分,含量累加均超过90%。进一步对广藿香进行研究,药效成分得以完全分离和正确定量。评价中药挥发油的3种方法得以建立,
    其中根据族分离特性的用药效分子群代替个别药效组分评价中药质量的方法充分体现了中药的复杂性和中医用药的整体性。最后以姜黄挥发油的快速族组成分析为例,显示GCxGC在中药挥发油筛选和质控中的应用前景。
GCxGC is a novel separation method for complex samples emerging in the 1990's. After the idea was prompted and implemented, it is experiencing rapid development.
    In the thesis, we firstly demonstrated characteristics of GCxGC-TOFMS using petroleum samples, discussed influence of column match and modulation conditions on separation, and gave a strategy of system optimization and suggested the concept of two dimensional resolution, providing technological foundation for separation of complex samples.
    On the above basis, GCxGC-TOFMS was applied to study volatile oils of Traditional Chinese Medicines (TCMs). Column system and operation conditions were optimized. Applicability of GCxGC and its methodology for TCMs was investigated. Components of three volatile oils were identified with 2D Rts, peak purity and multiple modulation information from TOFMS, concentration sums of which were more than 90% for each sample. Further study of patchouli was carried out with curative components completely separated and accurately quantified. Three assessing methods of TCMs were suggested; especially the method based on effective group separation can reflect the complexity and the entirety of TCMs to the most. With GCxGC alone, fast group identification of a curcuma volatile oil was achieved, which indicates the prospective of GCxGC to screening and quality control of TCMs.
引文
1 Bertsch W,J.High Resol.Chromatogr.,1999,22:647-665
    2 Davis J,M.J.High Resol.Chromatogr.,1999,23,(3) :235~244
    3 Nishimura O,Agric J,Food Chem.,1995,43:2941
    4 Wright D W,Mahler K O,Ballard L B,J.Chromatogr.Sci.,1986,24:60
    5 Bicchi C,Amato A D,Frattini C,Nano G M,Pisciotta A,J.High Resol.Chromatogr.,1989,12:705
    6 Bushey M.M.,Jorgenson J.W.,Anal.Chem.1990,62:161-167
    7 Liu Z.,Phillips J.B.,J.Chromatogr.Sci.,1991,29:227-231
    8 Venkatramani C.J.,Xu J.,Phillips J.B.,Anal.Chem.,1996,68:1486-1492
    9 Beens J.,Blomberg J.,Tijssen R.,J.Chromatogr.A,1998,882:233-251
    10 Phillips J.B.,Luu D.,Pawliszyn J.B..Carle G.C.,Anal.Chem.1985,57:2779-2787
    11 Geus H,J.J.Chromatogr.A.,1997,767:137-151
    12 Kinghorn,R.M.,Marriott,P.J.,J.High Resol.Chromatogr.,1999,23,(3) :245-252
    13 Marriott,P.J.,Kinghorn,R.M.,J.High Resol.Chromatogr.,1999,23,(3) :253-258
    14 Schoenmakers P.J.,Jeroen L.M.M.Oomen,J.Chromatogr.A,2000,892:29-46
    15 Ledford E.B.,Billesbach C.,J.High Resol.Chromatogr.,1999,23,(3) :202~204
    16 Phillips J B,Beens J,J.Chromatogr.A,1999,856:331
    17 Venkatramani C J,Xu J,Phillips J B.Anal Chem.,1996,68:1468
    18 Phillips J.B.,J.Xu,J.Chromtogr.A,1995,703:327-334
    
    
    19 Kinghorn R.M,Marriott P.J.,J.HRC&CC.1999,22:235-238
    20 Phillips John B.,Gaines R.B.,Blomberg J.,et al.J.HRC&CC.1999,22:3-10
    21 Bruckner C.A.,Prazen B.J.,Synovec R.E.,Anal.Chem.1998,70:2796-2804
    22 Phillips J.B.,Liu Z.,United States Patent,5,196,039,1993.
    23 Phillips J.B.,Liu Z.,United States Patent,5,135,,549,1992
    24 Phillips J.B.,Xu J.,J.Chromtogr.A,1995,703:327-334
    25 Marriott P.J.,Kinghorn R.M.,Anal.Chem.1997,69:2582-2588
    26 Kinghorn R.M.,Marriott P.J.,J.HRC&CC.1998,21:620~622
    27 Kinghorn R.M.,Marriott P.J.,J.HRC&CC.1999,22:235-238
    28 Geus H.De,Boer J.De,U.A.Th.Brinkman,J.Chromatogr.A,1997,767:137-151
    29 Frysinger G.S.,Gaines R.B.J.High Resol.Chromatogr.1999,22:251-255
    30 Deursen M.V.,Beens J.etc.J.High Resol.Chromatogr.2000,23,(7/8) :507~510
    31 Shellie R.,Marriott P.,Morrison P.Anal.Chem.2001,73:1336-1344
    32 许国旺,叶芬,孔宏伟,路鑫,赵欣捷,全二维气相色谱技术及其进展,色谱2001,19:132-136
    33 Frysinger G S,Gaines R B,J.High Resol Chromatogr.,1999,22(4) :195-200
    34 Neumann H.J.,Paczynska-Lahme B.,Severin D.,Compositional Properties of Petroleum,Ferdinand Enke Publ.,Stuttgart,Germany,1981.
    35 Xu J.,Ph.D.Dissertation,Southern Illinois University,1997
    36 Gaines R.B.,Frysinger G.S.,Hendrick-Smith M.S.,Stuart J.D.,Environ.Sci.Technol.1999,33:2106
    37 Frysinger G.S.,Gaines R.B.,J.Sep.Sci.,2001,24(2) :87-96
    38 Frame G.,Anal.Chem.,1997,69:468A~475A
    
    
    39 Frame G. M., Fresenius Z. Anal. Chem., 1997, 357:701~713
    40 Phillips J. B., Xu J., Organohalogen Compounds, 1997, 31:199~201
    41 Liu Z., .Sirimanne S. R, Patterson D. G Jr.., Needham L. L., Phillips J. B., Anal. Chem., 1994, 66:3086~3092
    42 Gaines R. B., Ledford Jr. E. B., Stuart J. D., J. Microcol. Sep., 1998, 10:597~600
    43 Gaines R. B., Frysinger G. S., Hendfick-Smith M. S., Stuart J. D., Environ. Sci. Technol., 1999, 33:2106~2108
    44 Frysinger G. S., Gaines R. B. J. Sep. Sci. 2001, 24:87.
    45 Marriott P. J., Ony R. C. Y., Kinghom R. M., Morrison P. D., J. Chromatogr. A. 2000, 892:15
    46 Marriott P. J., Shellie R., Jfergeus, R. Ong, Morrison P., Flavour Fragr. J. 2000, 15: 225
    47 Dimandja J.-M., Standfill S. B., Grainger J., Paterson Jr. D. G., J. High Resolu. Chromatogr., 2000, 23:54.
    48 Shellie R., Marriott P., J. High Resolu. Chromatogr., 2000, 23, (9):554~560.
    49 de Geus H. J., Aidos I., J. Chromatogr. A, 2001, 910:95~103
    50 许有玲,中药基础性研究的现状、发展趋势与对策、建议,全球华人中药现代化学术研讨会论文集,1998,7,南京,33~37
    51 惠永正.历史的机遇人民的责任“全球华人中药现代化学术研讨会”开幕词.世界科学技术—中药现代化杂志,1999,1(1):1
    52 张兰桐.中药现代化研究与发展战略.河北医科大学学报,2000,21,(4)
    53 科技部,国家中医药管理局课题组.中药现代化发展战略.世界科学技术—中药现代化杂志,1999,1,(1):5
    54 吴风锷,吴蔚,田军.中药现代化理论和方法研究[J].天然产物研究与开发,1999,11(2):93
    
    
    55 王本祥,周秋丽.关于中药活性成分的认识及其研究方法[J].中国中药杂志,2001,26(1):10~13
    56 吕文海.中药炮制学.第一版.北京:科学出版社,1982.18~21.
    57 李石生等.中药现代化研究的关键在于建立科学的现代中药理论体系——分子药性假说的提出.中国中西医结合杂志.2000,20,(2)
    58 梁生旺,刘伟.中药制剂定量分析[M].北京:中国中医药出版社,1997
    59 ECDR of FDA. Guidance for Industry Botanical Drug products (Draft guidance). 2000
    60 国家药品监督局.中药注射剂指纹图谱研究的技术要求(暂行)[J].中成药杂志,2000,22(10):671
    61 Branka Barl. Quality Analysis and Standardized Extracts of Medicinal Herbs [M]. PMAP Conference, 1997
    62 Rudolf Bauer. Quality Criteria and Phytopharmaceuticals: Can Acceptable Drug Standards be achieved: [J] Drug Information Journal, 1998, 32:101:110
    63 罗国安,王义明.中药指纹图谱的分类和发展.中国新药杂志.2002,11(1):46~51.
    64 谢培山.现代化中药产业关键技术系列研讨会(一)国际色谱指纹图评价中药质量研讨会学术报告论文集[C].广州,2001 i3~1,i3~27
    65 果德安.第四届国际周“中药与天然药物国际论坛”.Internet来源.
    66 胡平,罗国安,王如骥,等.药学学报,1997,32(7):549
    67 林明美,罗燕.药物分析杂志,1987,7(1):13
    68 凌大奎,朱永新,王维,等.药物分析杂志,1995,15(4):13
    69 卢佩章,梁鑫淼,肖红斌.中药组分智能统一指纹数据库.化学进展,1993,18(11):650
    
    
    70 张子忠,梁鑫淼,卢佩章.色谱,2001,19(2):157-160
    71 张子忠,梁鑫淼,张青,卢佩章.药学学报,2001,36(7):523-527
    72 徐智秀,肖红斌,王加宁,梁鑫淼.色谱,2000,18(6):521-524
    73 常建华,董绮功,波谱原理及解析.北京:科学出版社,2001
    74 姜大成,张洁,邓明鲁.中草药,1999,30(2):137
    75 张亮,马国祥,张正行,等.药学学报,1994,29(4):290
    76 秦海林,赵天增.药学学报.1999,34(1):58
    77 秦海林,尚玉俊,赵伟,等.中草药,2000,31(1):48
    78 秦海林,赵天增,袁卫梅,等.药学学报,1999,34(11):828
    79 陈耀祖,涂亚平.第一版.有机质谱原理及应用.北京:科学出版社,2001
    80 阴健.中药现代研究与临床应用Ⅲ.北京:中国古籍出版社,1997
    81 Karas M, Hillencamp F. Laser desorption ionization of proteins with molecular masses exceeding 1000 daltons. Anal Chem, 1998, 60:2299
    82 袁湘林,张玉奎,邹汉法.基体辅助激光解吸电离飞行时间质谱用于中草药黄芪鉴别的研究.药物分析杂志,2001,21(1):7~9
    83 梁惠玲.中草药,1996,27(6):367:369
    84 吕扬,郑启泰,吕楠,等.中草药,2000,31(3):214
    85 周俊国,蔡金娜,吕扬,等.中草药,1998,30(12):59
    86 王树春,吕扬,吴楠,等.中草药,2000,31(3):214
    87 肖小河,刘峰群,袁海龙,等.中药DNA分子标识鉴定研究进展.中草药,2000,31(8):561
    88 Ozeki y, Wake H, Yoshimatsuk, et al. NaturalMed, 1996, 50:24
    89 Shaw P. C., But P. P. H. Planta Med, 1995, 61:466
    
    
    90 曹晖,毕培曦,邵鹏柱.中药材,1996,19:608
    91 曹晖,毕培曦,邵鹏柱.J. Chin Pharm Sci, 1996, 5:186
    92 曹晖,毕培曦,邵鹏柱.药学学报,1996,31:543
    93 陈永久,王文,杨跃雄,等.遗传学报,1997,24(5):410
    94 Chen K. T., Tsay H. S., Chen C. F., et al. Planta Med, 1998, 64:563
    95 Hakamatsuka T., Tanaka N. Biol Pharm. Bull, 1997, 20:464
    96 秦海林,王峥涛等.中药材特征性总成分指纹鉴定.中国中药杂志,2001,(261):4~8
    97 梁鑫淼,肖红斌,卢佩章.世界科学技术-中药现代化与基础研究,2000,2(4):18-22
    98 Beens J., Tijssen R., Blomberg J., J. Chromatogr. 1998, 822:233
    99 俞惟乐,欧庆瑜.毛细管气相色谱和分离分析新技术.北京:科学出版社,1999
    100 姚新生.天然药物化学[M].北京:轻工业出版社,1985
    101 肖崇厚.中药化学[M].上海:上海科学技术出版社,1993
    102 傅乃武.揽香烯的抗肿瘤作用和药理学研究[J].中药通报,1984,9(2):35~38
    103 李应红,李啸红,王毓美.中药莪术接抗致突变作用的初步研究.中国优生与遗传杂志,1999,7(1):22~23
    104 李爱群,胡学军,邓远辉,等.温莪术挥发油的成分,2001,32(9):782~783
    105 姜建萍.莪术抗肿瘤研究概况,吉林中医药,2000,2:62~64
    106 方洪钜,苏秀玲,刘红岩.香叶天竺葵精油的化学成分及抗肿瘤作用[J].药学学报,1989,24(5):480
    107 董玉山,傅建熙,许平安,等.植物精油研究进展.河南林业科技,1999,19(4):23~26
    
    
    108 汤敏燕,汪洪武,孙凌峰.具有抗肿瘤活性的天然萜类化合物.江西师范大学学报(自然科学版),1997,21(2):146-150
    109 张莉,方洪钜.药用挥发油的气相色谱分析.药物分析杂志,1994,14(3):52~60
    110 方洪钜.高分辨气相色谱法及其在药物分析中的应用.药学学报,1990:869~880
    111 中华人民共和国药典一部.北京:化学工业出版社,2000
    112 杨得坡,Chaumont J. P., Millet Joelle. 藿香和广藿香挥发油对皮肤藓菌和条件致病真菌的抑制作用.中国药学杂志,2000,35(1):9~11
    113 罗集鹏,冯毅凡,郭晓玲.石牌藿香的挥发油成分分析.中草药,2001,32(4):299~302
    114 卫世安,贾彦龙.连翘果皮和种子挥发油化学成分的分析研究.药物分析杂志,1992,12(6):329~332
    115 俞崇灵.连翘抗菌成分的研究.药学学报,1960,8(6):241-243
    116 石素贤,何福江.连翘挥发油化学成分的研究.药物分析杂志,1995,15(3):10~12
    117 苏镜娱,张文广,李核,等.广藿香精油化学成分分析与抗菌活性研究(Ⅰ).中草药,2001,32(3):204~205
    118 杨赞熹,谢培山.中药广藿香抗真菌成分—广藿香酮的分离与结构测定[J].科学通报,1977,22(7):318
    119 陈士林,肖小河,等.中国药用植物的数值区划.资源开发与市场,1994,10(1):8~10
    120 分析化学手册,化学计量学分册,北京:化学工业出版社,2000
    121 罗旭,毕开顺,王玺,等.中药质量化学模式识别研究的进展.药学学报,1993,28(12):936~940
    
    
    122 王建勤,张兴运.基于内容的图象检索原理与应用于中药显微鉴定的前景展望.中草药,2001,32(2):180~181
    123 唐立军,段立娟,高文.基于内容的图象检索系统.计算机应用研究.2001,7:41~45
    124 白雪生,徐光佑,Jesse S.Jin.基于内容的图象检索及其相关技术的研究.机器人,1997,5:231~240
    125 徐金昌,赵荣春,冯大淦,用形状相似性进行基于内容的图像检索.中国体视学与图像分析.2000,5(1):44~48
    126 凌云,闻一渝,钟国跃.中药学图像和文字数据库的建立.中国中药杂志,1995,20(1):58~59

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