從台灣市場購得舒黨Su-Dangshen (Codonopsis tubulosa)和紋黨Wun-Dang.(C. pilosula)，分別用水萃取後，再經solid phase extraction (SPE) 濃縮乾燥，利用核磁共振光譜儀(1H-NMR)分析時，從舒黨發現兩個新四級銨鹽codotubulosine A和codotubulosine B 生物鹼。
本篇論文將台灣及中國大陸市場收集各類黨參樣品共42個，利用1H-NMR分析定量各樣品中codotubulosine A、codotubulosine B 生物鹼及adenosine 和5-(hydroxymethyl)furfural之含量。分析結果在黨參、素花黨參、川黨參中以codotubulosine A 為主要成分，在管花黨參中以codotubulosine A 和B 為主要成分，新疆黨參、羊乳、金錢豹和球花黨參均未發現 codotubulosine A 和 B；目前台灣及中國大陸市場常用藥材，將黨參、舒黨、素花黨參和川黨參視為主要商品。因此本論文將codotubulosine A 和 B生物鹼，建議作為黨參之指標成分。
利用SPE結合1H-NMR可快速鑑定市售黨參藥材的品種，且可同時定量分析所含的黨參codotubulosine A、codotubulosine B生物鹼及adenosine 和5-(hydroxymethyl)furfural 成分的含量。
以1H-NMR作為分析工具，提供一快速、準確、方便的分析方法同時定性定量黨參生物鹼類似物。並且本方法可以應用於市售藥物、黨參製品及食品的檢驗

Su-Dangshen (Codonopsis tubulosa) and Wun-Dang.(C. pilosula), purchased from Taiwanese market, were individually extracted by water. The water extract was quantitatively analysed by 1H-NMR after manual solid phase extraction (SPE) procedure. Furthermore, two novel alkaloids, codotubulosine A and B were also isolated from C. tubulosa .
Using 1H-NMR spectroscopy, a qualitative and quantitative analysis of codotubulosine A, codotubulosine B, adenosine and 5-(hydroxymethyl) furfural was successfully developed toward each of the 42 samples of Codonopsis herbs which were collected from Taiwan and Mainland China. The result of our analysis reveals that codotubulosine A is the major constituent in C. pilosula, C. pilosula var. modesta and C. tangshen, while codotubulosine A and B were found to be the major constituents in C. tubulosa, but both compounds were not discovered in C. clematidea, C. lanceolota, Campanumoea javanica and C. subglobosa. Up to the present, C. pilosula, C. pilosula var. modesta, C. tangshen and C. tubulosa (Su-Dang.) were available traditional herbs on the market in Taiwan and China. The marker components, codotubulosine A and B, were proposed for qualitative and quantitative analysis of Codonopsis.
A rapid identification of the species of Codonopsis by 1H-NMR spectroscopy using manual solid phase extraction (SPE) as a pre-treatment allowed the quantitative analysis of codotubulosine A, codotubulosine B, adenosine and 5-(hydroxymethyl) furfural.
1H-NMR can be used as an analytical tool, and it provides a rapid, accurate, and convenient method for qualitative and quantitative analysis of alkaloid derivatives from Dangshen. This method can also be applied to the analysis of commercial pharmaceutics or related products as well as dietary supplements.

1. 國家中醫藥管理局《中華本草》編委會，中華本草，第七冊，上海科學技術出版社，上海，pp603-610，1999。
2. 中國藥材公司編著，中國常用中藥材，科學出版社，北京，pp437-446，1995。
3. Q. Hu; T. Zhou; G. Hu; Y. Fang. Determination of sugars in Chinese traditional drugs by CE with amperometric detection. J Pharm Biomed Anal. 30, 1047-1053, 2002.
4. 清朝 張璐 撰，《續修四庫全書》編纂委員會，上海古籍出版社，子部 醫家類，上海，pp252，2002。
5. YG. Lee; JY. Kim; JY. Lee; SE. Byeon; EK. Hong; J. Lee; MH. Rhee; HJ. Rhee; JY. Cho. Regulatory effects of Codonopsis lanceolata on macrophage-mediated immune responses. J Ethnopharmacol. 112, 180-188, 2007.
6. TB. Ng; F. Liu; HX. Wang.The antioxidant effects of aqueous and organic
extracts of Panax quinquefolium, Panax notoginseng, Codonopsis
pilosula, Pseudostellaria heterophylla and Glehnia littoralis. J
Ethnopharmacol. 93, 285-288, 2004.
7. 任勉芝，藥與方，南澳出版社，香港，pp94-95，100-101，1997。
8. Tzu-chao Lin; Chang-chun Vi; Yu-jen Ko ; Chun-chuan Chen; Chao-lin Kuo. A Pentsaological Resarch on Dangshen (Codonopsis spp.,Campanulaceae). J. Chin .Med. 18(1,2), 51-64, 2007.
9. JP. Yang; IS Yeo.A study on the true nature of "Chinese jinseng". Uisahak. 12, 144-66, 2003.
10. Zheng-tao Wang; Gl-yuan Ma; Peng-fel Tu; Guo-jun Xu. Chemotaxonomic
study of Codonopsis (Family Campanulaceae) and its related genera. Biochem.
Sys. and Ecol. 23, 809-812, 1995.
11. 中國科學院中國植物志編輯委員會，曾建飛，中國植物志，科學出版社，第
73卷，第二分冊，北京，pp33-37，1983。
12. Z. Wang; G. Xu; L. Xu. Macrological identification of Chinese drug
dangshen (Radix Codonopsis). Zhongguo Zhong Yao Za Zhi. 17(7), 390-393, 444, 1992.
13. 楊兆起，封秀娥，中華鑑別手冊，科學出版社，第三冊，北京，pp 405-413，1997。
14. 王綿之，許濟群，方劑學，知音出版社，台北，pp229-299，2001。
15. 莊松榮製藥廠有限公司研發部，莊松榮複方選輯。莊松榮製藥廠有限公司，高雄，2000。
16. K. Mizutani; M. Yuda; O. Tanaka; Y.- I. Saruwatari; M.-R. Jia; Y.-K. Ling; X.-F. Pu. Tangshenosides I and II from Chuan-Dangshen, The root of Codonopsis tangshen Oliv.Chem. Pharm. Bull. 36, 2726-2729, 1988.
17. K. Mizutani; M. Yuda; O. Tanaka; Y.-I. Saruwatari; T. Fuwa; M.-R. Jia; Y.-K. Ling; and X.-F. Pu. Chemical studies on chinese traditional medicine, Dangshen. I. Isolation of (Z)-3-and (E)-2-hexenyl β-D-glucosides. Chem. Pharm. Bull. 36, 2689-2690, 1988.
18. H. Norr; H. Wagner. New Constituents from Codonopsis pilosula. Planta Med. 60, 494-495, 1994.
19. S. F. Matkhalikolva; V. M. Malikov; S. Yu. Yunusov. A study of alkaloids of Codonopsis clematidea. Chem. Nat. Compd. 5, 24-25, 1969.
20. C. F. Matkhalikova; V. M. Malikov; S. Yu. Yunusov. The structure of codonopsine. Chem. Nat. Compd. 5, 528-529, 1969.
21. D. T. Asilbekova; S. D. Gusakova; A. I. Glushenkova; S. F. Aripova; and D. M. Atazhanov. Chemical composition of Codonopsis clematidea grown in vitro. Chem. Nat. Comp. 32, 529-531, 1996.
22. N. G. Alad’ina; Yu. N. El’kin; E. A. Chezhina. Structure of codonoside B. Chem. Nat. Compd. 25, 317-320, 1989.
23. N. G. Alad’ina; P. G. Gorovoi; G. B. Elyakov. Codonopside B － The main triterpene glycoside of Codonopsis lanceolata. Chem. Nat. Compd. 24, 124-125, 1988.
24. M. Yuda; K. Ohtani; K. Mizutani; R. Kasai; O. Tanaka; M.-R. Jia; Y.-R. Ling; X.-F. Pu; Y.-I. Saruwatri. Neolignan glycosides from roots of Codonopsis tangshen. Phytochemistry. 29, 1989-1993, 1990.
25. R.-Q. Mei; Q. Lu; Y.-F. Hu; H.-Y. Liu; F.-K. Bao; Y. Zhang; Y.-X. Cheng*. Three new polyyne (＝polyacetylene) glucosides from the edible roots of Codonopsis cordifolioidea. Helvetica Chimica Acta . 91, 90-96, 2008.
26. T. Liu; W. Liang; G. Tu. A β-carboline alkaloid from Codonopsis pilosula. Planta Med. 472-473, 1988.
27. XL. Zneg; XA. Li; BY. Zhang. Immunological and hematopoietic effect of
Codonopsis pilosula on cancer patients during radiotherapy.
Zhongguo Zhong Xi Yi Jie He Za Zhi. 12, 607-608, 581, 1992.
28. Y. Zhou; XZ. Yan. Experimental study of qi deficiency syndrome and Codonopsis pilosula and Astragalus injection on the immune response in mice. Zhong Xi Yi Jie He Za Zhi. 9, 286-288, 262, 1989.
29. XL. Mao; Y. Zhou. Preliminary study of the effects of extract of Codonopsis pilosula on immunological functions of normal and immunosuppressed mice introduced by cyclophosphamidum. Zhong Xi Yi Jie He Za Zhi. 5, 739-741, 709, 1985.
30. JY. Xie; GR. Tu. Effect of radix Codonopsis pilosulae on cytochemical changes in macrophages. Zhong Xi Yi Jie He Za Zhi. 5, 487-488, 453, 1985.
31. Y. Wu; JC Li.; LG. Mao. Study of Chinese herbal medicine in treating ascites
and their mechanism in regulating lymphatic stomata. Zhongguo Zhong Xi Yi Jie
He Za Zhi. 21, 677-679, 2001.
32. KW. Lee; HJ. Jung; HJ. Park; DG. Kim; JY. Lee; KT. Lee.
β-D-xylopyranosyl-(1-->3)- β-D-glucuronopyranosyl echinocystic acid isolated from the roots of Codonopsis lanceolata induces caspase-dependent apoptosis in human acute promyelocytic leukemia HL-60 cells. Biol. Pharm. Bull. 28, 854-859, 2005.
33. GT. Wang.Treatment of operated late gastric carcinoma with prescription of
strengthening the patient's resistance and dispelling the invading evil in combination with chemotherapy: follow-up study of 158 patients and experimental study in animals. Zhong Xi Yi Jie He Za Zhi. 10, 712-716, 707, 1990.
34. SK. Hu. Effect of the combination of Codonopsis pilosula and cyclophosphamide on the transplantable tumor and tumor-bearing mice. Zhong Xi Yi Jie He Za Zhi. 5, 618-621, 581, 1985.
35. JP. Li; ZM. Liang; Z. Yuan. Triterpenoid saponins and anti-inflammatory activity of Codonopsis lanceolata. Pharmazie. 62, 463-466, 2007.
36. B. Xiao; G. Chen; Z. Lan. Study on the effect of promoting intelligence development and preventing hypoxia/reoxygenation injury of selenium-banqiao-Codonopsis pilosula-overground part in mice. Zhong Yao Cai. 28, 688-690, 2005.
37. B. Singh; H. Song; XD. Liu; M. Hardy; GZ. Liu; SP. Vinjamury; CD. Martirosian. Dangshen (Codonopsis pilosula) and Bai guo (Gingko biloba) enhance learning and memory. Altern Ther Health Med. 10, 52-56, 2004.
38. JX. Chen; SR. Wang; MJ. Zhao; XY. Lu; Z. Zhang; Y. Qin. Effect of different
drug dosage to activate blood circulation and to nourish qi on cardiac function
and structure of congestive heart failure rats after acute myocardial infarction.
Zhongguo Zhong Yao Za Zhi. 28, 446-449, 2003.
39. LM. Qin; YF. Yan; ZC. Wang. Experimental study on the cardiotonic action of extract from Codonopsis pilosula (Franch.)Nannf.. Zhongguo Zhong Yao Za Zhi. 19, 238-240, 1994.
40. F. Sui; R. Wang; J. Wang ; Y. Li; Q. Du; Y. Wu. Effects of Dangshen root extract serum on intracellular free calcium in gastric parietal cells of dissociated rats. Zhong Yao Cai. 28, 900-903, 2005.
41. JH. Liu; YM. Bao; JJ. Song; LJ. An. Codonopsis pilosula (Franch) Nannf total alkaloids potentiate neurite outgrowth induced by nerve growth factor in PC12 cells. Acta Pharmacol Sin. 24, 913-917, 2003.
42. X. Xu; SR. Wang; Q. Lin. Clinical and experimental study on Codonopsis pilosula oral liquor in treating coronary heart disease with blood stasis . Zhongguo Zhong Xi Yi Jie He Za Zhi. 15, 398-400, 1995.
43. SR. Wang; ZQ. Guo; JZ. Liao. Experimental study on effects of 18 kinds of Chinese herbal medicine for synthesis of thromboxane A2 and PGI2. Zhongguo Zhong Xi Yi Jie He Za Zhi. 13, 167-70, 134, 1993.
44. H. Yang; T. Wu; K. Zhang. Effects of extracts of Chinese medicines on Ganoderma lucidum in submerged culture. Wei Sheng Wu Xue Bao. 43, 519-522, 2003.
45. TZ. Zheng; W. Li; SY. Qu; YM. Ma; YH. Ding; YL. Wei. Effects of Dangshen on isolated gastric muscle strips in rats. World J Gastroenterol. 4, 354-356, 1998.
46. S. Chen; Z. Zhou; S. Sun; Y. Li; X. Li. The effect of Codonopsis pilosula (Franch.) Nannf. on gastric acid, serum gastrin and plasma somatostatin concentration in dogs. Zhongguo Zhong Yao Za Zhi. 23, 299-301, 320, 1998.
47. JY. Hou; ZW. Jiang; ZZ. He. Effects of Codonopsis pilosula (Franch) Nannf on gastric electricity, gastric motility and gastric emptying. Zhong Xi Yi Jie He Za Zhi. 9, 31-312, 1989.
48. H. Li; MY. Jiang; EB. Jin. Effects of Codonopsis pilosula on experimental gastric
ulcers in the rat. Zhong Xi Yi Jie He Za Zhi. 7, 163-165, 134, 1987.
49. W. Wang; DZ. Zhao; BH. Sun. Study on effects of Codonopsis eupolyphaga anti-obesity powder in mice with nutritive obesity. Zhongguo Zhong Xi Yi Jie He Za Zhi. 17, 739-741, 1997.
50. L. Tun; L. Wenzao; T. Guoshi. Separation and determination of 8β-hydroxyasteroid and perlolyrine in Codonopsis pilosula by reversed-phase high- performance liquid chromatography. J. Chromatogr. 477, 458-462, 1989.
51. E. S. Ong; S. Len. Evaluation of surfactant-assisted pressurized hot water
extraction for marker compounds in Radix Codonopsis pilosula using liquid
chromatography and liquid chromatography/electrospray ionization mass
spectrometry. J. Sep. Sci. 26, 1533–1540, 2003.
52. 賀慶，朱恩圓，王崢濤，徐潞珊，胡之壁。 Determination of lobetyolin in Radix Codonopsis by high-performance liquid chromatography。中國藥學雜誌。40， 56-58，2005.
53. C. Zhao; G. Hao; H. Li; X. Luo; Y. Chen. Decontamination of organochlorine pesticides in Radix Codonopsis by supercritical fluid extractions and determination by gas chromatography. Biomed. Chromatogr. 20, 857-863, 2006.
54. C.-F. Qiao; Z.-D. He; Q.-B. Han; H.-X. Xu; R.-W. Jiang;
S.-L. Li; Y.-B. Zhang; P. P.-H. But; P.-C. Shaw. The Use of lobetyolin and
HPLC-UV fingerprints for quality assessment of Radix Codonopsis.
J. Food Drug Anal. 15, 258-264, 2007.
55. G. Han; C. Wang; X. Su; X. He; Y. Wang; M. Kenji; T. Osamu. Determination of tangshenoside I in Codonopsis pilosula Nannf. by TLC-UV spectrophotometric method. Zhongguo Zhong Yao Za Zhi. 15, 553-555, 577, 1990.
56. Q. Hu; T. Zhou; G. Hu; Y. Fang. Determination of sugars in Chinese traditional drugs by CE with amperometric detection. J. Pharm. Biomed. Anals. 30 , 1047-1053, 2002.
57. T. A.van Beek; G. P. Lelyveld. Thin layer chromatography of bilobalide and ginkgolides A, B, C and J on sodium acetate impregnated silica gel. Phytochem. Anal. 4, 109–114, 1993.
58. M. H. George. Determination of ephedrine, pseudoephedrine, and norephedrine in mixtures (bulk and dosage forms) by proton nuclear magnetic resonance spectroscopy. J. AOAC Int. 78, 946–954, 1995.
59. I. Duarte; A. N. Barros, P. S. Belton; R. Righelato; M. Spraul; E. Humpfer; A. M. Gil. High-resolution nuclear magnetic resonance spectroscopy and multivariate analysis for the characterization of Beer. J. Agric. Food Chem. 50, 2475–2481, 2002.
60. H. K. Kim; Y. H. Choi; W. T. Chang; R. Verpoorte. Quantitative analysis of ephedrine analogues from Ephedra species using 1H-NMR. Chem. Pharm. Bull. 51, 1382–1385, 2003.
61. Y. H. Choi; H. K. Choi; A. Hazekamp; P. Bermejo; Y. Schilder; C. Erkelens, R. Verpoorte. Quantitative analysis of bilobalide and ginkgolides from Ginkgo biloba leaves and ginkgo products using 1H-NMR. Chem. Pharm. Bull. 51, 158–161, 2003.
62. L. Bala; G. A. Nagana Gowda; U. C. Ghoshal; A. Misra; M. Bhandari; C. L. Khetrapal. 1H NMR spectroscopic method for diagnosis of malabsorption syndrome: a pilot study. NMR Biomed. 17, 69–75, 2004.
63. H. K. Kim; Y. H. Choi; Teus J. C. Luijendijk; R. A. Vera Rocha; R. Verpoorte. Comparison of extraction methods for secologanin and the quantitative analysis of secologanin from symphoricarpos albus using 1H-NMR. Phytochem. Anal. 15, 257–261, 2004.
64. K. M. Holtman; H. M. Chang; J. F. Kadla. Solution-state nuclear magnetic resonance study of the similarities between milled wood lignin and cellulolytic enzyme lignin. J. Agric. Food Chem. 52, 720–726, 2004.
65. G. L. Gall; I. J. Colquhoun; M. Defernez. Metabolite profiling using 1H NMR spectroscopy for quality assessment of green tea, Camellia sinensis (L.). J. Agric. Food Chem. 52, 692–700, 2004.
66. I. F. Duarte; A. N. Barros; C. U. Almeida; M. Spraul; A. M. Gil. Multivariate analysis of NMR and FTIR data as a potential tool for the quality control of beer. J. Agric. Food Chem. 52, 1031–1038, 2004.
67. Y. H. Choi; H. K. Kim; A. Hazekamp; C. Erkelens; A. W. M. Lefeber; R. Verpoorte. Metabolomic Differentiation of Cannabis sativa Cultivars Using 1H NMR Spectroscopy and Principal Component Analysis. J. Nat. Prod. 67, 953–957, 2004.
68. G. M. Hanna. NMR regulator analysis: determination and characterization of Chinese-herb aristolochic acids. Pharmazie. 59, 170–174, 2004.
69. C. Y. Li; C. H. Lin; C. C. Wu; K.H. Lee; T. S. Wu. Efficient 1H nuclear magnetic resonance method for improved quality control analyses of ginkgo constituents . J. Agric. Food Chem. 52, 3721–3725, 2004.