太赫兹波谱在冬虫夏草检测中的应用
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摘要
利用太赫兹波谱技术对名贵中药冬虫夏草及其常见伪品进行太赫兹波谱检测、反射式切片成像及分析,得到冬虫夏草正品及其常见伪品的太赫兹图谱特征.结果表明,冬虫夏草4种正品在1. 10 THz和1. 13 THz频段均具有特征吸收峰,在0. 5～1. 5 THz频段,其折射率分布于[1. 55,1. 63].常见伪品地蚕在太赫兹频段没有特征吸收峰,其折射率与冬虫夏草正品差距较大(> 12%),可作为重要鉴别依据;另外两种常见伪品古力虫草和亚香棒虫草具有与正品相近的特征吸收峰,然而其折射率与正品有明显的差异(> 3%).冬虫夏草太赫兹反射成像时域切片图像表明,通过分析有效轮廓区域内相对信号强度的分布,可有效评估各自结构特点,为鉴别冬虫夏草真伪提供了新方法.
Terahertz spectroscopy and reflective imaging of Cordyceps sinensis and its common counterfeit samples are carried out for the analysis and authenticity assessment of the valuable traditional Chinese medicine. Typical terahertz spectral signatures and features are obtained. The results show that the four authentic Cordyceps share a refractive index range from 1. 55 to 1. 63( in the 0. 5-1. 5 THz frequency band) and common absorption peaks at 1. 10 THz and 1. 13 THz,respectively. There is no characteristic absorption peak in the terahertz frequency range for silkworms of a common fake Cordyceps,and its refractive index shows significant difference( > 12%) from that of authentic Cordyceps,which can be used as an important basis for identification of silkworms. The other two counterfeits were couli Cordyceps and asiatic Cordyceps,of which the absorption coefficient spectra shows similar characteristic absorption peaks with the authentic ones,whereas their refractive indices are significantly different from those of the authentic ones( > 3%). The time-domain slice-images of Cordyceps section samples obtained with the THz reflective imaging show that by analyzing the distribution of relative signal intensity within the effective region-of-interest of images,the structural characteristics of the authentic and counterfeits can be effectively evaluated,which provides a new idea and method for the authenticity identification of Cordyceps sinensis.
Terahertz spectroscopy and reflective imaging of Cordyceps sinensis and its common counterfeit samples are carried out for the analysis and authenticity assessment of the valuable traditional Chinese medicine. Typical terahertz spectral signatures and features are obtained. The results show that the four authentic Cordyceps share a refractive index range from 1. 55 to 1. 63( in the 0. 5-1. 5 THz frequency band) and common absorption peaks at 1. 10 THz and 1. 13 THz,respectively. There is no characteristic absorption peak in the terahertz frequency range for silkworms of a common fake Cordyceps,and its refractive index shows significant difference( > 12%) from that of authentic Cordyceps,which can be used as an important basis for identification of silkworms. The other two counterfeits were couli Cordyceps and asiatic Cordyceps,of which the absorption coefficient spectra shows similar characteristic absorption peaks with the authentic ones,whereas their refractive indices are significantly different from those of the authentic ones( > 3%). The time-domain slice-images of Cordyceps section samples obtained with the THz reflective imaging show that by analyzing the distribution of relative signal intensity within the effective region-of-interest of images,the structural characteristics of the authentic and counterfeits can be effectively evaluated,which provides a new idea and method for the authenticity identification of Cordyceps sinensis.
引文
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[6] MIYAZAKI T,NAOKO O,YAMADA H. Studies on fungal polysacehafides galactomannan of cordyceps sinensis[J]. Chemical&Pharmaceutical Bulletin,1977,25(12):3324-3328.
[7]朱喜艳,李振华.青海冬虫夏草脂肪酸含量分析[J].青海畜牧兽医杂志,2006:36(2):21.ZHU Xiyan,LI Zhenhua. Analysis of fatty acid content in Cordyceps of Qinghai Province[J]. Chinese Qinghai Journal of Animal and Veterinary Sciences,2006,36(2):21.(in Chinese)
[8]CHAN S,LIU Baoling,ZHAO Zhongzhen,et al. Studies on macroscopic and microscopic identification of Cordyceps sinensis and its counterfeits[J]. China Journal of Chinese Medica,2011,36(9):1141-1144.
[9]YANG Yanqing,DUAN Junhua. Discrimination of Cordyceps sinensis from the counterfeit[J]. World Journal of Integrated Traditional&Western Medicine, 2012, 29(1):1-7.
[10]康帅.冬虫夏草与其混淆品的生药学鉴别研究[D].北京:中国药品生物制品检定所,2011.KANG Shuai. Authentication study in pharmacognosy of Chinese caterpillar fungus and its adulterants[D]. Beijing:National Institute for Food and Drug Control,2011.(in Chinese)
[11]高明,王俊升,曾金玲,等.冬虫夏草与几种常见伪品的鉴别[J].中药材,2011,34(2):213-216.GAO Ming,WANG Junsheng,ZENG Jinling,et al. Identification of Cordyceps sinensis and several common counterfeits[J]. Jorunal of Chinese Medicinal Materials,2011,34(2):213-216.(in Chinese)
[12]姚建铨.太赫兹技术及其应用[J].重庆邮电大学学报自然科学版,2010,22(6):703-707.YAO Jianquan. Introduction of THz-wave and its applications[J]. Journal of Chongqing University of Posts and Telecommunications Natural Science Edition,2010,22(6):703-707.(in Chinese)
[13]刘乔,李泽仁,孟坤.太赫兹时域光谱技术用于药品检测[J].太赫兹科学与电子信息学报,2011,9(3):283-286.LIU Qiao,LI Zeren,MENG Kun. Medicine inspection by the terahertz time-domain spectroscopy technique[J].Journal of Terahertz Science and Electronic Information Technology,2011,9(3):283-286.(in Chinese)
[14]汪一帆,尉万聪,周凤娟,等.太赫兹(THz)光谱在生物大分子研究中的应用[J].生物化学与生物物理进展,2010,37(5):484-489.WANG Yifan,YU Wancong,ZHOU Fengjuan, et al.Applications of terahertz(THz)spectroscopy in biological macromolecules[J]. Progress in Biochemistry and Biophysics,2010,37(5):484-489.(in Chinese)
[15]葛宏义,蒋玉英,廉飞宇,等.小麦品质的太赫兹波段光学与光谱特性研究[J].光谱学与光谱分析,2014,34(11):2897-2900.GE Hongyi,JIANG Yuying,LIAN Feiyu,et al. Nondestructive evaluation of wheat quality using terahertz time domain spectroscopy,spectroscopy and spectral analysis[J]. Spectroscopy and Spectral Analysis,2014,34(11):2897-2900.(in Chinese)
[16]沈飞,应义斌.太赫兹光谱和成像技术在食品安全检测中的应用[J].光谱学与光谱分析,2009,29(6):1445-1449.SHEN Fei,YING Yibin. Applications of terahertz spectroscopy and imaging techniques in food safety inspection[J]. Spectroscopy and Spectral Analysis,2009,29(6):1445-1449.(in Chinese)
[17]杨光鲲,袁斌,谢东彦,等.太赫兹技术在军事领域的应用[J].激光与红外,2011,41(4):376-380.YANG Guangkun, YUAN Bin, XIE Dongyan, et al.Analysis on the use of THz technology in military application[J]. Laser&Infrared,2011,41(4):376-380.(in Chinese)
[18]刘盛纲,钟任斌.太赫兹科学技术及其应用的新发展[J].电子科技大学学报,2009,38(5):481-486.LIU Shenggang,ZHONG Renbin. Recent development of terahertz science and technology and it's applications[J].Journal of University of Electronic Science and Technology of China,2009,38(5):481-486.(in Chinese)
[19]杨玉平,董睿林,张振伟.六种生物药物分子的高分辨太赫兹光谱研究[J].光谱学与光谱分析,2012,32(11):3035-3039.YANG Yuping,DONG Ruilin,ZHANG Zhenwei. Highresolution terahertz spectra of six biological and pharmaceutical materials[J]. Spectroscopy and Spectral Analysis,2012,32(11):3035-3039.(in Chinese)
[20]杨帅,左剑,刘尚建,等.太赫兹光谱技术在中药大黄炮制品检测中的应用研究[J].光谱学与光谱分析,2016,36(12):3870-3874.YANG Shuai,ZUO Jian,LIU Shangjian,et al. Application of terahertz spectroscopy in the detection of Chinese medicine processed drugs of rhubarb[J]. Spectroscopy and Spectral Analysis,2016,36(12):3870-3874.(in Chinese)
[21]张建,黄婉霞,罗轶,等.莪术的太赫兹时域光谱研究[C]//第7届中国功能材料及其应用学术会议论文集.长沙,中国:中国仪器仪表学会仪表学会,2010:167-169.ZHANG Jian,HUANG Wanxia,LUO Yi,et al. Study of terahertz time-domain spectroscopy of rhizoma curcumae[C]//Proceedings of the 7th China National Conference on Functional Materials and Applications. Changsha,China:China Instrument and Control Society,2010:167-169.(in Chinese)
[22]李小霞,邓琥,廖和涛,等.室温下中药附子的太赫兹波谱分析[J].激光与红外,2013(11):1282-1285.LI Xiaoxia,DENG Hu,LIAO Hetao,et al. Analysis of the terahertz spectrum of Chinese herbal medicine aconite at room temperature[J]. Laser&Infrared,2013(11):1282-1285.(in Chinese)
[23] SHEN Y C,UPADHYA P C,LINFIELD E H,et al.Vibrational spectra of nucleosides studied using terahertz time-domain spectroscopy[J]. Vibrational Spectroscopy,2004,35(1/2):111-114.
[24]陈涛.基于太赫兹时域光谱的物质定性鉴别和定量分析方法研究[D].西安:西安电子科技大学,2013.CHEN Tao. Study on qualitative identification and quantitative analysis based on terahertz time domain spectroscopy[D]. Xi'an:Xidian University,2013.(in Chinese)
[25] WALTHER M,FISCHER B,SCHALL M,et al. Farinfrared vibrational spectra of all-trans,9-cis and 13-cis retinal measured by THz time-domain spectroscopy[J].Chemical Physics Letters,2000,332(3/4):389-395.
[2]李家实.中药鉴定学[M].上海:上海科学技术出版社,1996:395.LI Jiashi. Authentication of traditional Chinese medicine[M]. Shanghai:Shanghai Scientific&Technical Publishers,1996:395.(in Chinese)
[3]解军,郭欣,李培毅,等.冬虫夏草及人工菌丝体中虫草菌素的定性定量研究[J].山西中医,1994,10(4):36-38.XIE Jun,GUO Xin,LI Peiyi,et al. Qualitative and quantitative study of Cordycepin in Cordyceps sinensis and artificial mycelium[J]. Shanxi Journal of Traditional Chinese Medicine,1994,10(4):36-38.(in Chinese)
[4]纪莎,施小兵,易骏.冬虫夏草化学成分研究概况[J].福建中医学院学报,1999,9(2):46-47.JI Sha, SHI Xiaobing, YI Jun. Survey of chemical constituents of Cordyceps sinensis[J]. Journal of Fujian College of TCM,1999,9(2):46-47.(in Chinese)
[5]汪宝琪,庞志功.西藏冬虫夏草有效成分研究(之一)[J].西藏科技,1995,68(2):16-18.WANG Baoqi,PANG Zhigong. Study on the active ingredients of Tibetan Cordyceps sinensis(part one)[J].Tibet Science and Technology,1995,68(2):16-18.(in Chinese)
[6] MIYAZAKI T,NAOKO O,YAMADA H. Studies on fungal polysacehafides galactomannan of cordyceps sinensis[J]. Chemical&Pharmaceutical Bulletin,1977,25(12):3324-3328.
[7]朱喜艳,李振华.青海冬虫夏草脂肪酸含量分析[J].青海畜牧兽医杂志,2006:36(2):21.ZHU Xiyan,LI Zhenhua. Analysis of fatty acid content in Cordyceps of Qinghai Province[J]. Chinese Qinghai Journal of Animal and Veterinary Sciences,2006,36(2):21.(in Chinese)
[8]CHAN S,LIU Baoling,ZHAO Zhongzhen,et al. Studies on macroscopic and microscopic identification of Cordyceps sinensis and its counterfeits[J]. China Journal of Chinese Medica,2011,36(9):1141-1144.
[9]YANG Yanqing,DUAN Junhua. Discrimination of Cordyceps sinensis from the counterfeit[J]. World Journal of Integrated Traditional&Western Medicine, 2012, 29(1):1-7.
[10]康帅.冬虫夏草与其混淆品的生药学鉴别研究[D].北京:中国药品生物制品检定所,2011.KANG Shuai. Authentication study in pharmacognosy of Chinese caterpillar fungus and its adulterants[D]. Beijing:National Institute for Food and Drug Control,2011.(in Chinese)
[11]高明,王俊升,曾金玲,等.冬虫夏草与几种常见伪品的鉴别[J].中药材,2011,34(2):213-216.GAO Ming,WANG Junsheng,ZENG Jinling,et al. Identification of Cordyceps sinensis and several common counterfeits[J]. Jorunal of Chinese Medicinal Materials,2011,34(2):213-216.(in Chinese)
[12]姚建铨.太赫兹技术及其应用[J].重庆邮电大学学报自然科学版,2010,22(6):703-707.YAO Jianquan. Introduction of THz-wave and its applications[J]. Journal of Chongqing University of Posts and Telecommunications Natural Science Edition,2010,22(6):703-707.(in Chinese)
[13]刘乔,李泽仁,孟坤.太赫兹时域光谱技术用于药品检测[J].太赫兹科学与电子信息学报,2011,9(3):283-286.LIU Qiao,LI Zeren,MENG Kun. Medicine inspection by the terahertz time-domain spectroscopy technique[J].Journal of Terahertz Science and Electronic Information Technology,2011,9(3):283-286.(in Chinese)
[14]汪一帆,尉万聪,周凤娟,等.太赫兹(THz)光谱在生物大分子研究中的应用[J].生物化学与生物物理进展,2010,37(5):484-489.WANG Yifan,YU Wancong,ZHOU Fengjuan, et al.Applications of terahertz(THz)spectroscopy in biological macromolecules[J]. Progress in Biochemistry and Biophysics,2010,37(5):484-489.(in Chinese)
[15]葛宏义,蒋玉英,廉飞宇,等.小麦品质的太赫兹波段光学与光谱特性研究[J].光谱学与光谱分析,2014,34(11):2897-2900.GE Hongyi,JIANG Yuying,LIAN Feiyu,et al. Nondestructive evaluation of wheat quality using terahertz time domain spectroscopy,spectroscopy and spectral analysis[J]. Spectroscopy and Spectral Analysis,2014,34(11):2897-2900.(in Chinese)
[16]沈飞,应义斌.太赫兹光谱和成像技术在食品安全检测中的应用[J].光谱学与光谱分析,2009,29(6):1445-1449.SHEN Fei,YING Yibin. Applications of terahertz spectroscopy and imaging techniques in food safety inspection[J]. Spectroscopy and Spectral Analysis,2009,29(6):1445-1449.(in Chinese)
[17]杨光鲲,袁斌,谢东彦,等.太赫兹技术在军事领域的应用[J].激光与红外,2011,41(4):376-380.YANG Guangkun, YUAN Bin, XIE Dongyan, et al.Analysis on the use of THz technology in military application[J]. Laser&Infrared,2011,41(4):376-380.(in Chinese)
[18]刘盛纲,钟任斌.太赫兹科学技术及其应用的新发展[J].电子科技大学学报,2009,38(5):481-486.LIU Shenggang,ZHONG Renbin. Recent development of terahertz science and technology and it's applications[J].Journal of University of Electronic Science and Technology of China,2009,38(5):481-486.(in Chinese)
[19]杨玉平,董睿林,张振伟.六种生物药物分子的高分辨太赫兹光谱研究[J].光谱学与光谱分析,2012,32(11):3035-3039.YANG Yuping,DONG Ruilin,ZHANG Zhenwei. Highresolution terahertz spectra of six biological and pharmaceutical materials[J]. Spectroscopy and Spectral Analysis,2012,32(11):3035-3039.(in Chinese)
[20]杨帅,左剑,刘尚建,等.太赫兹光谱技术在中药大黄炮制品检测中的应用研究[J].光谱学与光谱分析,2016,36(12):3870-3874.YANG Shuai,ZUO Jian,LIU Shangjian,et al. Application of terahertz spectroscopy in the detection of Chinese medicine processed drugs of rhubarb[J]. Spectroscopy and Spectral Analysis,2016,36(12):3870-3874.(in Chinese)
[21]张建,黄婉霞,罗轶,等.莪术的太赫兹时域光谱研究[C]//第7届中国功能材料及其应用学术会议论文集.长沙,中国:中国仪器仪表学会仪表学会,2010:167-169.ZHANG Jian,HUANG Wanxia,LUO Yi,et al. Study of terahertz time-domain spectroscopy of rhizoma curcumae[C]//Proceedings of the 7th China National Conference on Functional Materials and Applications. Changsha,China:China Instrument and Control Society,2010:167-169.(in Chinese)
[22]李小霞,邓琥,廖和涛,等.室温下中药附子的太赫兹波谱分析[J].激光与红外,2013(11):1282-1285.LI Xiaoxia,DENG Hu,LIAO Hetao,et al. Analysis of the terahertz spectrum of Chinese herbal medicine aconite at room temperature[J]. Laser&Infrared,2013(11):1282-1285.(in Chinese)
[23] SHEN Y C,UPADHYA P C,LINFIELD E H,et al.Vibrational spectra of nucleosides studied using terahertz time-domain spectroscopy[J]. Vibrational Spectroscopy,2004,35(1/2):111-114.
[24]陈涛.基于太赫兹时域光谱的物质定性鉴别和定量分析方法研究[D].西安:西安电子科技大学,2013.CHEN Tao. Study on qualitative identification and quantitative analysis based on terahertz time domain spectroscopy[D]. Xi'an:Xidian University,2013.(in Chinese)
[25] WALTHER M,FISCHER B,SCHALL M,et al. Farinfrared vibrational spectra of all-trans,9-cis and 13-cis retinal measured by THz time-domain spectroscopy[J].Chemical Physics Letters,2000,332(3/4):389-395.