18 2Π3 2006 3 PROGRESS IN CHEMISTRY Vol. 18 No. 2Π3 Mar., 2006 3 3 ( 130022) (CE2AD) CE2AD CE2AD CE2AD : O657. 8 ; R28 : A : 10052281X(2006) 02Π320331206 Chinese Herb Medicines Analyses by Capillary Electrophoresis with Amperometric Detection Zhou Xiaoguang You Tianyan 3 Wang Erkang 3 (State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China) Abstract Capillary electrophoresis (CE) with amperometric detection (AD) has been widely used in various fields of analytical science, especially in the pharmaceutical industry recently due to its high separation efficiency and low detection limit. The determination of active ingredients in Chinese herb medicines by CE2AD is of great importance in developing the researches on pharmacology of herbs, quantitative analysis and quality control. Analyses of the effective components in Chinese herb medicines and compound Chinese herb medicine by CE2AD are reviewed in this paper. In contrast with other analysis methods, the advantage of CE2AD is discussed. The development in analyses of traditional Chinese medicine ( TCM) by CE2AD in future is mentioned. Key words capillary electrophoresis ; amperometric detection ; Chinese herb medicines 1 (CE) 20 80 ( ) (high performance liquid chromatography, 4 HPLC) (gas chromatography, GC) ] AD CE CE, : 25 m AD [1 ] CE : 2005 1, : 2005 7 3 e2mail :youty @ciac. jl. cn ; ekwang @ciac. jl. cn, (amperometric detection, AD) 3 [2
332 18 CE ( ultraviolet spectrophotometry, UV) ( nuclear magnetic resonance, NMR ) ( mass spectrum, MS) AD NMR [5 7 ], (laser2induced fluorescence, LIF) CE 10-12 10-16 molπl UV,CE2AD CE2AD UV 2 CE2AD AD ; AD CE, Fang Ye CE2 2. 1 2 GC HPLC CE HPLC HPLC CE2AD ( 1) ( 2) [9,10 ] 2. 2. 1 : (1), ; (2) 1 ; (3) ; (4) N HPLC,CE, CZE [11 ] GC HPLC ph [8 ] : (1), CE2AD ; (2) ; (3),Jin ; (4) [9 ] ; (5) ;Fang [10 ] 300 m ; (6) MS 40 AD ] [10,12 19,21 26,28 2. 2 CE2AD ph [12 18 ] 2. 2. 2
2Π3 333 1 CE-AD Table 1 High performance capillary electrophoresis-amperometric detection analyses of active compounds in Chinese herbs sort Chinese herbs sample component buffer working electrode alkaloids vincristine 117 10-2 molπl Na 2 HPO 4 2 flavons Flos sophorae buds, leaves of Ligustrum lucidum Ait., Cinnamomum camphora (L. ), Presl leaves 312 10-3 molπl NaH 2 PO 4 (ph = 715) carbon fiber microdisk bundle electrode codeine, morphine ph = 814 phosphate 300 m diameter pencil lead daidzein, rutin, 100 mmolπl borate (ph = 910) 300 m diameter detection limit (molπl) mode ref. 510 10-7 CZE2AD 9 116 10-7 CZE2AD 10 618 10-8 0119 10-6 CZE2AD 12 01434 10-6 Scutellariae radix, Astragali radix, Shuang2Huang2Lian oral liquid the vines of Pueraria lobata puerarin, daidzein, ( wild ) ohwi, Puerariae rutin radix Rhododendron dauricum L. farrerol, scopoletin, umbeliferone, hyperoside, kaempferol, baicalein, baicalin 100 mmolπl borate (ph = 910) 300 m diameter 50 mmolπl borate (ph = 910) 300 m diameter 70 mmolπl borate (ph = 912) 300 m diameter 5148 10-7 CZE2AD 13 2124 10-7 01241 10-6 CZE2AD 14 01511 10-6 210 10-8 210 10-7 gπml CZE2AD 15 Seme sojae preparatum, soy bean, soybean milk powder daidzein, genistein 100 mmolπl borate (ph = 1110) 300 m diameter 110 10-7 gπml CZE2AD 16 crude and parched Flos sophorae immaturus genistin, genistein, rutin, kaempferol, (ph = 910) 300 m diameter 111 10-7 218 10-7 gπml CZE2AD 17 Fructus sophorae, Flos sophorae immaturus genistin, genistein, rutin, kaempferol, 50 mmolπl borax (ph = 910) 300 m diameter 111 10-7 218 10-7 gπml CZE2AD 18 phenolic acids Rhododendron dauricum L. farrerol,, syringic acid, vanillic acid, 42hydroxybenzoic acid, protocatechuic acid turmeric curcumin 15 mmolπl phosphate (ph = 917) Pericarpium Citri Reticulatae Cephalanoplos segetum (Bge. ) Kitam., Cirsium japonicum DC 50 mmolπl borate (ph = 817) 300 m diameter 33 m diameter carbon fiber hesperidin, synephrine 50 mmolπl borate (ph = 910 ) 300 m diameter acacetin, rutin, chlorogenic acid,, caffeic acid, protocatechuic acid (ph = 814) 300 m diameter 9 10-7 CZE2AD 19 3 10-6 310 10-8 CZE2AD 20 4196 10-7 CZE2AD 21 6154 10-7 115 10-7 610 10-7 gπml CZE2AD 22 Lonicera japonica Thumb. hyperoside, chlorogenic acid, luteolin, caffeic acid 50 mmolπl borate (ph = 817) 300 m diameter 110 10-7 510 10-7 gπml CZE2AD 23 sugars Astragalus membranceus (Fish. ) Bge, Sngelica, Codonopsis pilosula (Franch) Nannf. Sucrose, glucose, fructose 0105 molπl NaOH (ph = 1217) 140 m diameter copper wire 110 10-6 CZE2AD 24 410 10-6 Ligustrum lucidum polysaccharides 01045 molπl NaOH 120 m diameter copper Angelica sinensis, flax polysaccharides 0108 molπl NaOH 100 m diameter copper 110 10-6 CZE2AD 25 912 10-7 CZE2AD 26 112 10-6
334 18 conti. sort Chinese herbs sample component buffer working electrode coumarins and else ash brak aesculin, aesculetin 10 mmolπl phosphate (ph = 910) 33 m diameter microdisc carbon electrode detection limit (molπl) mode ref. 610 10-8 CZE2AD 27 310 10-7 Radix seu Cortex Caraganae sinicae, the root of Caragana sinica (Buc hoz) Rehd hypaphorine, four oligomeric stilbenes 100 mmolπl borate (ph = 10) 300 m diameter 3185 10-8 1111 10-7 gπml CZE2AD 28 2 CE-AD Table 2 High performance capillary electrophoresis-amperometric detection analyses of active compounds in compound Chinese herb medicine compound Chinese herb medicines Scutellariae radix and Shuang2Huang2Lian oral liquids Apocynum venetum and its tablets component buffer working electrode baicalein, baicalin, d2catechin, rutin, 100 mmolπl borate (ph = 9. 0) (ph = 8. 4) detection limit (molπl) mode ref. 2. 24 10-7 CZE2AD 30 5. 48 10-7 3. 0 10-7 5. 0 10-7 gπml CZE2AD 31 Gastrodia rhizoma and its capsules 42hydroxybenzyl alcohol, vanillyl alcohol, 42 hydroxybenzylaldehyde, 100 mmolπl borate (ph = 912) 3. 0 10-7 CZE2AD 32 1. 8 10-6 vanillin, gastrodin, sucrose, glucose, fructose Puerariae radix, Jinfukang granules and Zhennaoling capsules puerarin, daidzein sodium dodecyl sulphate2borax (ph = 7. 8) 6. 0 10-7 MECC2 1. 1 10-6 AD 33 Ginkgo biloba L., its capsules and tablets Epicatechin, catechin, rutin, apigenin, luteolin, (ph = 9. 0) 1. 4 10-7 5. 0 10-7 gπml CZE2AD 34 Polygonum cuspidatum Sied. Et Zucc., Zijin capsule, trans2resveratrol 100 mmolπl H 3 BO 3 2Na 2 B 4 O 7 (ph = 9. 24) 5. 96 10-8 gπml CZE2AD 35 wines, health food Lycium Barbarum L. and its capsules, LIPOVIYAN beverage, milk powder taurine 50 mmolπl borate (ph = 9. 2) 1. 0 10-7 CZE2AD 36 Hippophae rhamnoides L. and its phytopharmaceuticals epicatechin, catechin, rutin, kaempferol, (ph = 9. 0) 1. 3 10-7 5. 9 10-7 gπml CZE2AD 37 Zhen Ju Jiang Ya Pian rutin, hydrochlorothiazide 25 mmolπl borax + 50 mmolπl phosphate (ph = 7. 9) 5. 0 10-7 CZE2AD 38 2. 0 10-7 Glycyrrhiza uralensis, Liquorice tablets, Liquorice mixture liquiritigenin, isoliquiritigenin 50 mmolπl borate (ph = 8. 7) 4. 7 10-7 CZE2AD 39 2. 9 10-7 Polygonum cuspidatum Sied. Et Zucc., Jindan tablets trans2resveratrol, emodin, chrysophanol, rhein borax (ph = 8. 7) 4. 2 10-7 CZE2AD 40 5. 0 10-8 Huangdan Yinchen Keli chlorogenic acid, caffeic acid, aloe2emodin, 30 mmolπl borate (ph = 9. 5) 1. 4 10-6 CZE2AD 41 3. 0 10-7 emodin, rhein
2Π3 335 Ye 37,39,40 ] 300 m,, CE2AD Fang [12] 300 m Fang [38,41 ] 300 m [13 Ye 18] 300 m 3 [19 23 ] 2. 2. 3, CE2, CE AD,AD, [19,21 Ye 23 ] 300 m Wang [20 ] [42 ] 33 m,ad [43 ],, CE2AD, 100 m ( ) CE2AD, [24 26 ] 2. 2. 4 [44,45 ], ( NaOH ) CE2AD Fang [24 26 ] [46 49 ] 140 m 120 m 100 m [27,28 ] 2. 2. 5 You [27 ] 33 m : (1) Ye [28 ] [50 300 m ] ; (2) 3 [51 ] ; (3),2004 Li [29 ] [52 ] CE2 AD (capillary zone electrophoresis-ad, CZE-AD) OH 6 OH 6 2. 3 CE2AD [29 40 ] [30 [ 1 ] (Luo G A), (Wang Y M). 21 CE2AD (Analytical Chemistry in 21st Century). : (Beijing : Science Press), 1999. 102 111
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