基于荧光光谱和拉曼光谱技术的中药检测研究

doi:10.3964/j.issn.1000-0593(2025)01-0139-07

摘要
参考文献
相关文章 (15)

全文: PDF (3657 KB)
输出: BibTeX | EndNote (RIS)

摘要：中医药是中华文化的瑰宝和中华文明的结晶，在全民健康中发挥着重要作用。由于中药生长环境受限及市场需求量的增大，市场上出现了许多以次充好、以假乱真的中药，这对中药发展及质量保障都极为不利。因此，对中药的检测和鉴定非常重要。为了探究中药的荧光光谱和拉曼光谱特性，选取白芷、苏木、山药、地榆四种中药进行分类检测研究。一方面，从化学成分和结构的角度分析中药白芷和苏木产生荧光的可能性，采用F-4600型荧光光谱仪（200~750 nm）分别在不同激发波长和不同浓度下测试了白芷和苏木水浸液的荧光光谱，探究了白芷和苏木水浸液的荧光光谱特性，并对荧光强度与不同浓度、激发波长的关系进行了探讨。另一方面，采用共聚焦显微拉曼光谱仪（100~4 000 cm^-1）对4种不同产地的山药和2种不同产地的地榆中药饮片的拉曼光谱分别进行测试研究。结果表明，白芷水浸液在波长260~350 nm的光激发下，产生较强荧光，最佳激发波长是340 nm，荧光峰值波长为420 nm，其荧光强度随浓度的增大而增强，且样品浓度较低时，荧光强度与浓度成线性关系；苏木水浸液在200~290 nm的光激发下，产生较强荧光，最佳激发波长为220 nm，荧光峰值波长为345 nm，随浓度的增加，荧光强度先增强后减弱，在浓度为0.175 mg·mL^-1时荧光强度达到最大。白芷水浸液和苏木水浸液的荧光强度都与激发波长的关系呈现高斯分布，符合荧光规律。分析山药和地榆的拉曼光谱，发现不同产地的拉曼特征基本一致，确认山药的拉曼特征峰主要集中在477、862、939、1 080、1 258、1 337和1 457 cm^-1处；地榆的拉曼特征峰主要集中在862和1 337 cm^-1处，主要归属与已有的化学成分研究结果相符。部分特征峰处拉曼活性出现差异，可以作为区分不同产地中药的依据。该研究结果不仅为荧光光谱在中药鉴定及质量分析中的应用提供了实验数据和方法参考，也为利用拉曼光谱技术实现中药的快速准确检测及产地归属奠定了基础。

关键词：白芷；苏木；山药；地榆；荧光光谱；拉曼光谱

Abstract：Traditional Chinese medicine is a treasure of Chinese culture and the crystallization of Chinese civilization, playing an important role in the health of the whole nation. Due to the limited growth environment of traditional Chinese medicine and the increasing market demand, numerous substandard and falsified traditional Chinese medicines have emerged in the market, which is extremely detrimental to the development and quality assurance of traditional Chinese medicine. Therefore, it is of utmost importance to detect and identify traditional Chinese medicine. Four medicinal herbs, angelica dahurica, Sappanwood, yam, and sanguinaria officinalis, were selected for classification and detection research to explore traditional Chinese medicine's fluorescent and Raman spectral characteristics. On the one hand, in this paper, we analyzed the possibility of angelica dahurica and sappanwood, traditional Chinese medicinal herbs, to exhibit fluorescence from the perspectives of chemical composition and structure. An F-4600 fluorescence spectrophotometer (200~750 nm) was used to measure the fluorescence spectra of aqueous extracts of angelica dahurica and sappanwood at different excitation wavelengths and concentrations, investigating the fluorescence spectral characteristics of aqueous extracts of angelica dahurica and sappanwood, and discussing the relationship between fluorescence intensity and different concentrations and excitation wavelengths. On the other hand, a confocal micro-Raman spectrometer (100~4 000 cm^-1) was used to conduct Raman spectroscopy tests on herbal slices of yam from four different regions and sanguisorba officinalis from two different regions, and then the Raman spectra were obtained. The results showed that the aqueous extract of angelica dahurica exhibited strong fluorescence under excitation wavelengths ranging from 260 to 350 nm. The optimal excitation wavelength is 340 nm, and the peak fluorescence wavelength is 420nm. The fluorescence intensity increased with the concentration increase, following a linear relationship at lower concentrations. The aqueous extract of sappanwood exhibited strong fluorescence under excitation wavelengths ranging from 200 to 290 nm, with the optimal excitation wavelength at 220 nm and the peak fluorescence wavelength at 345nm. With the increase inconcentration, the fluorescence intensity first increased and then decreased, reaching its maximum at 0.175 mg·mL^-1. Moreover, the fluorescence intensity of angelica dahurica and sappanwood aqueous extracts followed a Gaussian distribution about the excitation wavelength, followed by the fluorescence law. After analyzing the Raman spectra of yam and sanguisorba officinalis, it was found that the Raman characteristics of different producing areas were the same. The Raman characteristic peaks of yam were mainly concentrated at 477, 862, 939, 1 080, 1 258, 1 337, and 1 457 cm^-1. The Raman characteristic peaks of sanguisorba officinalis were mainly concentrated at 862, 1 337 cm^-1, consistent with the existing research results on chemical composition. Differences in Raman activity at certain characteristic peaks can be used to distinguish the origin of different traditional Chinese medicines. The research results provide experimental data and method references for applying fluorescence spectroscopy in the identification and quality analysis of traditional Chinese medicine, and they also lay the foundation for the rapid and accurate detection and origin attribution of traditional Chinese medicine by using Raman spectroscopy techniques.

Key words：Angelica dahurica; Sappanwood; Yam; Sanguisorba officinalis; Fluorescence spectra; Raman spectra

收稿日期: 2023-07-13 修订日期: 2024-03-20

中图分类号:

O657.37

基金资助: 国家自然科学基金项目（11905018），山西省高等学校教学改革创新项目（J20221074），山西省高等院校科技开发项目（2021L517）资助

作者简介: 逯美红，女，1979年生，长治学院物理系教授 e-mail: lmhxueer@126.com

引用本文:

逯美红，张凡，暴雅婷，王志军，雷海英，王翔宇，高鹏慧. 基于荧光光谱和拉曼光谱技术的中药检测研究[J]. 光谱学与光谱分析, 2025, 45(01): 139-145.
LU Mei-hong, ZHANG Fan, BAO Ya-ting, WANG Zhi-jun, LEI Hai-ying, WANG Xiang-yu, GAO Peng-hui. Research on Traditional Chinese Medicine Detection Based on Fluorescence Spectroscopy and Raman Spectroscopy Techniques. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2025, 45(01): 139-145.

链接本文:

https://www.gpxygpfx.com/CN/10.3964/j.issn.1000-0593(2025)01-0139-07 或 https://www.gpxygpfx.com/CN/Y2025/V45/I01/139

[1] ZHU Yi-xin, LI Bao-li, MA Hong-sheng, et al(朱艺欣, 李宝莉, 马宏胜, 等). China Medical Herald(中国医药导报), 2014, 11(31): 159.
[2] CHEN Meng-yu, LIU Wei, CHOU Gui-xin, et al(陈梦雨, 刘伟, 侴桂新, 等). Acta Chinese Medicine and Pharmacology(中医药学报), 2020, 48(2): 62.
[3] BAN Ji-fang, KE Rui(班纪芳, 客蕊). Lishizhen Medicine and Materia Medica Research(时珍国医国药), 2020, 31(8): 1963.
[4] WANG Ying-ying, ZHU Jie, LU Lan, et al (王英英, 朱洁, 鲁兰, 等). Journal of Sichuan of Traditional Chinese Medicine(四川中医), 2022, 40(8): 216.
[5] CHEN Yi-qing, SUN Fa-zhe(陈依晴, 孙发哲). Light Industry Science and Technology(轻工科技), 2020, 36(11): 77.
[6] LIU Zhi-rong, ZHANG Ming-tong, ZHANG Ping, et al(刘志荣, 张明童, 张平, 等). Chemical Reagents(化学试剂), 2022, 44(10): 1513.
[7] GAO Wei-ming, ZHAO Yue-xin, WANG Miao, et al(高维明, 赵悦新, 王淼, 等). Journal of Shenyang Pharmaceutical University(沈阳药科大学学报), 2019, 36(5): 394.
[8] SHEN Chao-bin, GU Jun, WANG Yan, et al(沈朝斌, 顾珺, 王雁, 等). Shanghai Journal of Traditional Chinese Medicine(上海中医药杂志), 2001, (2): 45.
[9] LI Xiu-mei, XU Fang-fang, ZHANG Xin, et al(李秀梅, 徐芳芳, 张欣, 等). Chinese Traditional and Herbal Drugs(中草药), 2023, 54(24): 8007.
[10] AO Dong-mei, XU Rong, LI Man-dian, et al(敖冬梅, 徐荣, 李曼钿, 等). China Journal of Traditional Chinese Medicine and Pharmacy(中华中医药杂志), 2023, 38(9): 4124.
[11] FAN Feng-jie, XUAN Feng-lai, BAI Yang, et al(樊凤杰, 轩凤来, 白洋, 等). Acta Metrologica Sinica(计量学报), 2020, 41(2): 263.
[12] JIN Xi-qing, YIN Hong, CHEN Song-qiang, et al(靳喜庆, 殷红, 谌松强, 等). China Brewing(中国酿造), 2023, 42(1): 203.
[13] CHEN Long, YUAN Ming-yang, MING Jing, et al(陈龙, 袁明洋, 明晶, 等). China Journal of Chinese Materia Medica(中国中药杂志), 2015, 40(18): 3608.
[14] SHENG Li-zhe, JI Ren-dong, WANG Xiao-yan, et al(盛立哲, 季仁东, 王晓燕, 等). The Journal of Light Scattering(光散射学报), 2022, 34(3): 244.
[15] ZHU Chun, XIE Xin, ZHAO Jin-chen, et al(朱纯, 谢心, 赵金辰, 等). Spectroscopy and Spectral Analysis(光谱学与光谱分析), 2017, 37(1): 141.
[16] ZHAO Wei, HE Jun, HOU Sen-lin, et al(赵伟, 何俊, 侯森林, 等). Journal of Terahertz Science and Electronic Information Technology(太赫兹科学与电子信息学报), 2023, 21(5): 586.
[17] MING Jing, CHEN Long, HUANG Bi-sheng, et al(明晶, 陈龙, 黄必胜, 等). Lishizhen Medicine and Materia Medica Research(时珍国医国药), 2016, 27(10): 2423.
[18] LIN Wen-shuo, CHEN Rong, CHEN Qiao-ling, et al(林文硕, 陈荣, 陈巧玲, 等). Chinese Journal of Spectroscopy Laboratory(光谱实验室), 2011, 28(2): 543.
[19] DONG Jing-jing(董晶晶). Strait Pharmaceutical Journal(海峡药学), 2017, 29(5): 49.
[20] DONG Jing-jing, QI Xue-yong, GE Yan-ru(董晶晶, 戚雪勇, 戈延茹). Strait Pharmaceutical Journal(海峡药学), 2016, 28(12): 55.
[21] SHI Fang-fang, ZHOU Meng-jiao, CUI Shi-yuan, et al(史芳芳, 周孟焦, 崔仕远, 等). Guiding Journal of Traditional Chinese Medicine and Pharmacy(中医药导报), 2020, 26(9): 34.
[22] FENG Shang-yuan, CHEN Rong, LI Yong-zeng, et al(冯尚源, 陈荣, 李永增, 等). Chinese Journal of Lasers(中国激光), 2010, 37(1): 121.
[23] ZHAN Rui-xue, FENG Shuai, ZHANG Tian-xi, et al(战瑞雪, 冯帅, 张天锡, 等). Journal of Shandong University of Traditional Chinese Medicine(山东中医药大学学报), 2022, 46(3): 393.
[24] CHEN Guo-qing, WU Ya-min, WANG Jun, et al(陈国庆, 吴亚敏, 王俊, 等). Spectroscopy and Spectral Analysis(光谱学与光谱分析), 2009, 29(9): 2518.
[25] ZHAO Nan-ming, ZHOU Hai-meng(赵南明, 周海梦). Biophysics(生物物理学). Beijing: Higher Education Press(北京：高等教育出版社), 2000. 297.
[26] XU Yi-ming(许以明). Raman Spectroscopy and Its Application in Structural Biology(拉曼光谱及其在结构生物学中的应用). Beijing: Chemical Industry Press(北京: 化学工业出版社), 2005. 96.
[27] Dollish F R, Fateley W G, Bentley F F. Characteristic Raman Frequencies of Organic Compounds(有机化合物的特征拉曼频率). Translated by ZHU Zi-ying(朱自莹, 译). Beijing: Chinese Chemical Society(北京: 中国化学会), 1980. 36.
[28] Bellamy L J. Infrared Spectra of Complex Molecules. Second ed. London: Methuen, 1954. 21.
[29] Bellamy L J. Advances in Infrared Group Frequencies. London: Methuen, 1968. 152.