Study on the Extraction, Geometry Structure and Spectral Characterization of Piperine Alkaloid
LI Xin1, SHI Jin-ru3, YANG Meng-shi1, LU Yi1, CHEN Liang1, CAO Hua-ru1,2*
1. School of Engineering, Zhejiang A&F University, Lin’an 311300, China 2. Zhejiang Provincial Key Laboratory of Chemical Utilization of Forestry Biomass, Zhejiang A&F University, Lin’an 311300, China 3. College of Life Sciences, Zhengzhou University, Zhengzhou 450001, China
Abstract：Using pepper fruit of Hainan as raw material and 95% ethanol as solvent, the alkaloid in pepper is extracted with reflux method in this paper. The piperonylic acid is removed by adjusting the pH; the fat-soluble substance being removed by adding ethyl ether; the piperine alkaloid being purified with acetone by recrystallization anddetected with HPLC, as well as characterized with IR. The characterizations of piperine are discussed. Meanwhile, B3LYP/6-31G (d,p) method of DFT is applied to optimize the structure, calculate frequency and energy of pepper alkaloid, then obtain four kinds of configurations (configuration Ⅰ as Piperine, configuration Ⅱ as Iso Piperine, configuration Ⅲ as Iso Chavicine, configuration Ⅳ as Chavicine) with 64 kinds of stability conformational structure. The distribution of the thermodynamic equilibrium of stable conformations of four kinds of configurations of the molecular is calculated with Gibbs free energy at room temperature (298.15 K). And IR spectra of the experimental were compared with the IR spectra of the theoretical. The results show that the alkaloid extracted from pepper is mainly conformer 1 in configuration Ⅰ, that is, Piperine; after purifying, the content of piperine is 7% with the purity of 99%. With analysis, the methods of extraction, separation and purification of piperine in this paper achieve good results. Established models are in good agreement with the experimental results. This research is of great significance in guiding extracting process, building structural model and the characterization and application of piperine.
Key words：Piperine alkaloid;Separation and purification;Structural model;Thermodynamic distribution;IR spectrum
李 鑫1，史金儒3，羊梦诗1，鲁 燚1，陈 亮1，曹华茹1,2* . 胡椒生物碱提取、几何结构以及红外光谱的研究 [J]. 光谱学与光谱分析, 2016, 36(07): 2082-2088.
LI Xin1, SHI Jin-ru3, YANG Meng-shi1, LU Yi1, CHEN Liang1, CAO Hua-ru1,2* . Study on the Extraction, Geometry Structure and Spectral Characterization of Piperine Alkaloid. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2016, 36(07): 2082-2088.
[1] Pino J，Rodriguez-Feo G，Borges P，et al. Die Nahrung，1990，34(6): 555. [2] Koul I B，Kapil A. Planta Med.，1993，59(5): 413. [3] LONG Yu-zhou(龙宇宙). Processing and Utilizing of Product of Tropical Unique Spice and Beverage Crops(热带特色香辛饮料作物农产品加工与利用). Haikou: Hainan Press(海口: 海南出版社)，2007. 63. [4] WEI Kun，DOU De-qiang，PEI Yu-ping，et al(韦 琨，窦德强，裴玉萍，等). Chinese Materia Medica(中国中药杂志)，2002，27(5): 328. [5] Govindarajan V S. Crit. Rev. Food Sci. Nutr.，1977，9: 117. [6] Mittal R，Gupta R L. Methods Find Exp. Clin. Pharmacol.，2000，22(5): 271. [7] Vijayakumar R S，Surya D，Nalini N. Redox. Rep.，2004，9(2): 105. [8] Ramasamy S V，Namasivayam N. Cell Biochemicalistry and Function，2006，24(6): 491. [9] Lee C S，Han E S，Kim Y K. Eur. J. Pharmacol.，2006，537(1-3): 37. [10] Bajad S，Bedi K L，Singla A K，et al. Planta Med.，2001，67(3): 284. [11] Bajad S，Bedi K L，Singla A K，et al. Planta Med.，2001，67(2): 176. [12] Capasso R，Izzo A A，Borrelli F，et al. Life Science，2002，71(19): 2311. [13] Lee S A，Hong S S，Han X H，et al. Chem. Pharm. Bull.(Tokyo)，2005，53(7): 832. [14] Kong L D，Cheng C H，Tan R X. J. Ethnopharmacol，2004，91(2-3): 351. [15] Pathak N，Khandelwal S. Biochemieal Pharmacol，2006，72(4): 486. [16] Dogra R K，Khalma S，Shanker R. Toxicology，2004，196(3): 229. [17] Pradeep C R，Kuttan G. Clin. Exp. Metastas.，2002，19(8): 703. [18] Menon A N，Padmakumari K. J. Essent Oil Res.，2005，2(17): 153. [19] Bai Y F，Xu H. Acta Pharmacologica Sinica，2000，21(4): 357. [20] Pradeep C R，Kuttan G. Int Immunopharmacol，2004，4(14): 1795. [21] Selvendiran K，Banu S M，Sakthisekaran D. Clin. Chim. Acta，2004，350(1-2): 73. [22] Sunila E S，Kuttan G. J. Ethnopharmacol，2004，90 (2-3): 339. [23] Khajuria A，Thusu N，Zutshi U. Phytomedicine，2002，9(3): 224. [24] Subramanian R，Subbramaniyan P，Noorul Ameen J，et al. Arabian Journal of Chemistry，2011，doi:10.1016/j.arabjc.2011.06.022. [25] MENG Zhao-hui，WANG Zhen-hui，ZHOU Shu-ping(孟召辉，汪振辉，周漱萍). J. Anal. Chem.(分析化学)，1994，22(12): 1163. [26] Kanaki N，Dave M，Padh H，et al. J. Nat. Med.，2008，62: 281. [27] FAN Xiu-yu，YIN Ai-qun，SU Wei-guo，et al(范秀玉，尹爱群，苏维国，等). Drug Standards of China(中国药品标准)，2004，5(5): 28. [28] Girija R，Vilas G G. Ind. Eng. Chem. Res.，2002，41(10): 2521. [29] CHEN Jian-hua，WENG Shao-wei，LI Zhong，et al(陈建华，翁少伟，李 忠，等). Fine Chemicals(精细化工)，2010，27(10): 991. [30] Cao X J，Ye X M，Lu Y B，et al. Anal. Chim. Acta，2009，640: 47. [31] Ternes W，Krause E L. Anal. Bioanal. Chem.，2002，374: 155. [32] Kozukue N，Park M S，Choi S H，et al. J. Agric. Food Chem.，2007，55: 7131. [33] Huang Z J，Yu W B，Lin Z J. J. Mol. Struct. THEOCHEM，2006，81: 7. [34] Zhang M L，Huang Z J，Lin Z J. J. Chem. Phys.，2005，122: 134313. [35] Huang Z J，Yu W B，Lin Z J. J. Mol. Struct. THEOCHEM，2006，758:195. [36] Ling S L，Yu W B，Huang Z J，et al. J. Phys. Chem. A，2006，110: 12282. [37] Huang Z J，Lin Z J. J. Phys. Chem. A，2005，109: 2656. [38] Yu W B，Lin Z J，Huang Z J. Chem. Phys. Chem.，2006，7: 828. [39] Yu W B，Liang L，Lin Z J，et al. J. Comput. Chem.，2009，30: 589. [40] Yu W B，Wu Z Q，Chen H B，et al. J. Comput. Chem.，2009，30: 2105. [41] Yu W B，Xu X E，Li H B，et al. J. Phys. Chem. B，2012，116: 2269. [42] LI Xin，YANG Meng-shi，YE Zhi-peng，et al(李 鑫，羊梦诗，叶志鹏，等). Acta Phys. Sin.(物理学报)，2013，15: 156103-1. [43] Li X，Yu S，Yang M S，et al. Physica E，2014，57: 63. [44] LI Xin，ZHANG Liang，YANG Meng-shi，et al(李 鑫，张 梁，羊梦诗，等). Acta Phys. Sin.(物理学报)，2014，7: 076102-1. [45] LI Xin，YANG Meng-shi，XU Can，et al(李 鑫，羊梦诗，徐 灿，等). Spectroscopy and Spectal Analysis(光谱学与光谱分析)，2014，34(9): 2331. [46] Li X，Yang M S，Shi X，et al，Physica E，2015，69: 273. [47] Von Weizsacker C F，Z. Phys.，1935，96: 431. [48] Becke A D. Phys. Rev. A，1988，38: 3098. [49] Lee C，Yang W，Parr R G. Phys. Rev. B，1998，37: 785. [50] Frisch M J，Trucks G W，Schlegel H B，et al. Gaussian09, Revision C. 01, Gaussian, Inc., Wallingford CT，2009. [51] Stepanian S G，Reva I D，Radchenko E D，et al. J. Phys. Chem. A，1999，103：4404.
