石斛属植物中石斛碱类成分的波谱学特征

doi:10.11938/cjmr20192757

摘要/Abstract

摘要： 石斛属（Dendrobium Sw.）植物中的石斛碱类（dendrobines）倍半萜生物碱（sesquiterpenoid alkaloids）以其独特的结构和显著的生理活性而受到广泛关注．本文对石斛碱类化合物的结构特点及波谱学特征，包括紫外光谱（UV）、红外光谱（IR）、质谱（MS）、核磁共振（NMR）波谱等进行总结，并归纳石斛碱类成分的结构解析方式，为其深入研究与开发提供参考依据．

关键词: 石斛属, 石斛碱类, 倍半萜生物碱, 核磁共振（NMR）

Abstract: Dendrobine-type sesquiterpenoid alkaloids from the Dendrobium plants have attracted many research interests due to their unique structures and remarkable physiological activities. This paper reviews the structural features and spectral (i.e., ultraviolet, infrared, mass and NMR) characteristics of dendrobines, and how their structures could be elucidated from the spectral data. The present work may provide a reference for further research and development of dendrobines.

Key words: Dendrobium Sw., dendrobines, sesquiterpenoid alkaloids, nuclear magnetic resonance (NMR)

中图分类号:

O482.53

尹田鹏, 李幸, 汪泽, 王雅溶, 王敏. 石斛属植物中石斛碱类成分的波谱学特征[J]. 波谱学杂志, 2020, 37(3): 381-389.

YIN Tian-peng, LI Xing, WANG Ze, WANG Ya-rong, WANG Min. A Review on Spectral Characteristics of Dendrobines from the Dendrobium Plants[J]. Chinese Journal of Magnetic Resonance, 2020, 37(3): 381-389.

参考文献

[1] ZHANG X Q, ZHAO T M, LIU J, et al. Advances in chemical compounds and pharmacological effects of Dendrobii Caulis[J]. Chinese Tradit Herbal Drugs, 2018, 49(13):3174-3182. 张雪琴, 赵庭梅, 刘静, 等. 石斛化学成分及药理作用研究进展[J]. 中草药, 2018, 49(13):3174-3182.
[2] XIAO S J, LIU Z, ZHANG M S, et al. A new bibenzyl compound from Dendrobium nobile[J]. Acta Pharm Sin, 2016, 51(7):1117-1120. 肖世基, 刘珍, 张茂生, 等. 金钗石斛中一个新的联苄类化合物[J]. 药学学报, 2016, 51(7):1117-1120.
[3] XU J, HAN Q B, LI S L, et al. Chemistry, bioactivity and quality control of Dendrobium, a commonly used tonic herb in traditional Chinese medicine[J]. Phytochem Rev, 2013, 12(2):341-367.
[4] LIU J K, HAN X W, WU D G, et al. 2D NMR studies on sesquiterpene alkaloids from Celastrus angulatus[J]. Chinese J Magn Reson, 1992, 9(3):289-295. 刘吉开, 韩秀文, 吴大刚, 等. 南蛇藤中倍半萜生物碱的二维NMR研究[J]. 波谱学杂志, 1992, 9(3):289-295.
[5] NG T B, LIU J, WONG J H, et al. Review of research on Dendrobium, a prized folk medicine[J]. Appl Microbiol Biotechnol, 2012, 93(5):1795-1803.
[6] GUO L, FREY W, PLIETKER B. Catalytic enantioselective total synthesis of the picrotoxane alkaloids (-)-dendrobine, (-)-mubironine B, and (-)-dendroxine[J]. Org Lett, 2018, 20(14):4328-4331.
[7] LI L S, LU Y L, NIE J, et al. Dendrobium nobile Lindl alkaloid, a novel autophagy inducer, protects against axonal degeneration induced by Aβ_25-35 in hippocampus neurons in vitro[J]. CNS Neurosci Ther, 2017, 23(4):329-340.
[8] YANG D, CHENG Z Q, YANG L, et al. Seco-dendrobine-type alkaloids and bioactive phenolics from Dendrobium findlayanum[J]. J Nat Prod, 2018, 81(2):227-235.
[9] 王锋鹏. 生物碱化学[M]. 北京:化学工业出版社, 2008:394-396.
[10] GÖSSINGER E. Picrotoxanes[M]. Springer, Vienna, 2010:71-210.
[11] HEDMAN K, LEANDER K. Studies on orchidaceae alkaloids. XXVII. Quaternary salts of the dendrobine type from Dendrobium nobile Lindl[J]. Acta Chem Scand, 1972, 26:3177-3180.
[12] INUBUSHI Y, NAKANO J. Structure of dendrine[J]. Tetrahedron Lett, 1965, 31:2723-2728.
[13] MORITA H, FUJIWARA M, YOSHIDA N, et al. New picrotoxinin-type and dendrobine-type sesquiterpenoids from Dendrobium snowflake ‘Red Star’[J]. Tetrahedron, 2000, 56(32):5801-5805.
[14] WANG D F, YU G X, ZHAO N Y, et al. Study on chemical constituents in stems of Dendrobium nobile[J]. Chin Tradit Herbal Drugs, 2012, 43(8):1492-1495.
[15] HEDMAN K, LEANDER K, LUNING B. Studies on orchidaceae alkaloids. XXV. N-isopentenyl derivatives of dendroxine and 6-hydroxydendroxine from Dendrobium friedricksianum Lindl. and Dendrobium hildebrandii Rolfe[J]. Acta Chem Scand, 1971, 25(3):1142-1144.
[16] OKAMOTO T, NATSUME M, ONAKA T, et al. The structure of dendramine (6-oxydendrobine) and 6-oxydendroxine the fourth and fifth alkaloid from Dendrobium nobile[J]. Chem Pharm Bull, 1966, 14(6):676-680.
[17] LIU W H, HUA Y F, ZHAN Z J. Moniline, a new alkaloid from Dendrobium moniliforme[J]. J Chem Res, 2007, 2007(6):317-318.
[18] BLOMQVIST L, BRANDANGE S, GAWEL L, et al. Studies on Orchidaceae alkaloids. XXXVII. dendrowardine, a quaternary alkaloid from Dendrobium wardianum Wr.[J]. Acta Chem Scand, 1973, 27(4):1439-1441.
[19] WANG H, ZHAO T, CHE C T. Dendrobine and 3-hydroxy-2-oxodendrobine from Dendrobium nobile[J]. J Nat Prod, 1985, 48(5):796-801.
[20] CHEN K K, CHEN A L. The alkaloid of Chin-shih-hu[J]. J Biol Chem, 1935, 111(3):653-658.
[21] GRANELLII, LEANDER K, LUNING B. Studies on Orchidaceae alkaloids. XVI. A new alkaloid, 2-hydroxydendrobine, from Dendrobium findlayanum par. et Rchb. f.[J]. Acta Chem Scand, 1970, 24(4):1209-1212.
[22] MENG C W, HE Y L, PENG C, et al. Picrotoxane sesquiterpenoids from the stems of Dendrobium nobile and their absolute configurations and angiogenesis effec[J]. Fitoterapia, 2017, 121:206-211.
[23] LIU Q F, ZHAO W M. A new dendrobine-type alkaloid from Dendrobium nobile[J]. Chinese Chem Lett, 2003, 14(3):278-279.
[24] OKAMOTO T, NATSUME M, ONAKA T, et al. Further studies on the alkaloidal constituents of Dendrobium nobile (Orchidaceae)-structure determination of 4-hydroxy-dendroxine and nobilomethylene[J]. Chem Pharm Bull, 1972, 20(2):418-421.
[25] YAMAMURA S, HIRATA Y. Structures of nobiline and dendrobine[J]. Tetrahedron Lett, 1964, 5(2):79-87.
[26] ELANDER M, LEANDER K. Studies on orchidaceae alkaloids. XXI. 6-hydroxynobiline, a new alkaloid from Dendrobium hildebrandii Rolfe[J]. Acta Chem Scand, 1971, 25(2):717-720.
[27] 丛浦玉, 李笋玉. 天然有机质谱学[M]. 北京:中国医药科技出版社, 2003:443-444.
[28] CHEN X M, ZHANG S S, MA J S, et al. A simple, rapid and reliable UFLC-MS/MS method for the determination of dendrobine in rat plasma and its application to a pharmacokinetic study[J]. Anal Methods, 2014, 6(4):1197-1202.
[29] XIA J, YANG Z, ZENG Q F, et al. Analysis of chemical constituents in Dendrobium nobile by UPLC-Q-TOF[J]. Chinese Med Mat, 2018, 41(3):600-607.夏杰, 杨洲, 曾庆芳, 等. UPLC-Q-TOF法分析金钗石斛化学成分[J]. 中药材, 2018, 41(3):600-607.
[30] HE Y Q, LU Y L, LI L S, et al. Analysis of alkaloids from Dendrobium nobile stem by UPLC-ESI-Orbitrap-MS[J]. Chinese J Exp Tradit Med Form, 2017, 23(20):30-35. 何芋岐, 鲁艳柳, 李利生, 等. 基于UPLC-ESI-Orbitrap-MS技术对金钗石斛生物碱的分析[J]. 中国实验方剂学杂志, 2017, 23(20):30-35.
[31] WANG Y H, AVULA B, ABE N, et al. Tandem mass spectrometry for structural identification of sesquiterpene alkaloids from the stems of Dendrobium nobile using LC-QToF[J]. Planta Med, 2016, 82(7):662-670.
[32] YIN T P, LUO Z H, CAI L, et al. Research progress and NMR spectral features of natural C₁₉-diterpenoid alkaloids[J]. Chinese J Magn Reson, 2018, 36(1):113-126.尹田鹏, 罗智慧, 蔡乐, 等. 天然C₁₉-二萜生物碱的研究进展及其核磁共振波谱特征[J]. 波谱学杂志, 2018, 36(1):113-126.