基于红外光谱与聚类分析法的宁夏产地枸杞子品种鉴别研究

doi:10.3964/j.issn.1000-0593(2024)05-1386-06

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摘要：宁夏枸杞(Lycium barbarum L.)为宁夏传统道地中药材，因其良好的药食两用价值，已引种至甘肃、新疆、青海等省区。因长期引种和改良，宁夏枸杞品种繁多，是影响其质量的重要因素之一。本研究采用傅里叶变换红外光谱（FTIR）对宁夏中宁产地的宁杞1号、4号、5号、7号、0909号、10号共6个品种的枸杞子进行测定，一维红外光谱及二阶导数光谱范围均为4 000～650 cm^-1，得到图谱后进行图谱解析；采用谱带较密集的指纹区（1 800～650 cm^-1）计算红外光谱图的相似系数；然后结合SMICA聚类分析法对不同品种枸杞子的红外指纹图谱进行聚类比较。结果表明，不同品种枸杞子样品的一维红外光谱图较为相似，峰的位置、峰高和峰形都较为接近，其共同吸收峰较多，仅在3 282～3 288、1 239～1 242和1 143～1 147 cm^-1附近的吸收峰强度、峰位置、峰形状有所不同，说明不同品种枸杞子中多糖类、苷类、蛋白质类、脂类和黄酮类等成分的种类和含量有所差异。二阶导数光谱中，宁杞1号、4号、7号在2 880 cm^-1处吸收峰不明显，0909号在969 cm^-1处吸收峰不明显。不同品种枸杞子的相似度范围在0.948 9～0.992 8之间，说明不同品种枸杞子存在一定差异，其中，宁杞7号与其他品种的平均相似度系数最小，为0.964 0，说明其成分特异性最高。0909号与宁杞10号相似系数为0.992 8，相似度最高。采用Assure ID软件以各药材吸收波数为变量进行聚类分析，宁杞1号与其他品种的差异均较小，类间距在2.17～2.97范围内；0909号与其他品种间的差异最大，类间距在2.97～8.06范围内。聚类模型中，不同品种枸杞子的识别率均为100%，仅宁杞1号的拒绝率较低，为66%，易与其他品种枸杞子混淆，0909号的拒绝率和识别率均为100%，最易区分。类模型图中，0909号与宁杞5号、0909号与宁杞7号两两分开，可以明显鉴别出不同品种的样品。采用已知品种的枸杞子对聚类分析模型进行验证，其识别率和拒绝率与聚类分析模型相同。不同品种枸杞子类模型图与一维红外光谱、二阶导数图谱、相似度、类间距、识别率和拒绝率结果相互印证，佐证了宁杞1号为大多数宁杞系列品种的来源品种，而09系列品种0909号与其他品种有较大差异。因此，红外光谱与聚类分析法相结合可以快速、无损地鉴别不同品种枸杞子，对枸杞子药材生产和新品种选育具有一定的指导作用。

关键词：红外光谱法；聚类分析法；枸杞子；不同品种；鉴别

Abstract：Lycium barbarum(Lycii Fructus, wolfberry) is a valuable traditional Chinese medicinal material for medicine and food. Ningxia Zhongning wolfberry cultivars have been introduced to Gansu, Xinjiang, Qinghai and other provinces. Due to long-term introduction and improvement, there are many varieties of Lycium barbarum, one of the important factors affecting the quality of Lycii Fructus. This study used Fourier transforms infrared spectroscopy (FTIR) to determine the collected Lycii Fructus of Ningqi No.1, No.4, No.5, No.7, No.0909 and No.10 from Zhongning, Ningxia. The range of the one-dimensional infrared spectrum and the second derivative spectrum was 4 000~650 cm^-1. After obtaining the spectrum, the infrared spectrum's similarity coefficient was calculated using the fingerprint region (1 800~650 cm^-1) with dense spectral bands. Then, the infrared fingerprints of different varieties of Lycii Fructus were classified and compared with SMICA cluster analysis. The results show that the one-dimensional infrared spectroscopy of different varieties of Lycium barbarum samples are relatively similar, with the location, peak height and peak shape of the peaks being relatively close. Their common absorption peaks are more numerous, and only the intensity, peak location and peak shape of the absorption peaks at around 3 282～3 288, 1 239～1 242 and 1 143～1 147 cm^-1 are different, indicating that the polysaccharides, glycosides, proteins, lipids, and The types and contents of polysaccharides, glycosides, proteins, lipids, flavonoids and other components in different varieties of Lycium barbarum varied. In the second-order derivative spectra, the absorption peaks of NingQi 1, 4 and 7 were not apparentat 2 880 cm^-1, and 0909 at 969 cm^-1. The similarity of different varieties of Lycii Fructus ranges from 0.9489 to 0.9928, indicating certain differences among different varieties. Ningqi 7 has the lowest average similarity coefficient of 0.9640, indicating that its component specificity is the highest. The similarity coefficient of No.0909 and Ningqi 10 is 0.992 8, the two varieties with the highest similarity. The cluster analysis was carried out using the Assure ID software with the absorption wave number of each medicinal material as a variable. The class spacing between Ningqi No.1 and other varieties was small, ranging from 2.17 to 2.97. The class spacing between No.0909 and other varieties was the largest, ranging from 2.97 to 8.06. In the clustering model, the recognition rate of different varieties of Lycii Fructus is 100%, only the rejection rate of Ningqi No.1 is 66%, which can easy to be confused with other varieties of Lycii Fructus, and the rejection rate of No.0909 is 100%, which is the easiest to distinguish. In the class model diagram, No.0909 and Ningqi No.5, No.0909 and Ningqi No.7 are separated in pairs, which can identify the samples of different varieties. The cluster analysis model was verified using known varieties of Lycii Fructus, and its recognition and rejection rates were the same as those of the cluster analysis model. The results of the one-dimensional infrared spectrum, second derivative spectrum, similarity, class spacing, recognition rate and rejection rate of different varieties of Lycii Fructus showed that Ningqi No.1 was the original variety of other varieties of Lycii Fructus, and No.0909 was significantly different from other varieties. Therefore, the combination of infrared spectrum and cluster analysis can quickly and nondestructively identify different varieties of Lycii Fructus, which has a certain guiding role in the breeding and production of Lycii Fructus in Ningxia.

Key words：Infrared spectroscopy; Cluster analysis; Lycium barbarum; Different varieties; Identification

收稿日期: 2022-09-08 修订日期: 2023-09-22

中图分类号:

R282

基金资助: 国家“十四五”重点研发计划项目（2022YFC3501502），中国医学科学院医学与健康科技创新工程项目（CIFMS 2021-I2M-1-031），宁夏回族自治区重点研发计划重大（重点）项目（2019BBF02030）资助

通讯作者: 敖冬梅，徐常青 E-mail: admei302@163.com；cqxu@implad.ac.cn

作者简介: 徐荣，女，1981年生，中国医学科学院药用植物研究所研究员 e-mail: rxu@implad.ac.cn

引用本文:

徐荣，敖冬梅，徐鑫，王占林，胡颖，刘赛，乔海莉，徐常青. 基于红外光谱与聚类分析法的宁夏产地枸杞子品种鉴别研究[J]. 光谱学与光谱分析, 2024, 44(05): 1386-1391.
XU Rong, AO Dong-mei, XU Xin, WANG Zhan-lin, HU Ying, LIU Sai, QIAO Hai-li, XU Chang-qing. Study on the Identification Method of Lycium Barbarum Cultivars in Ningxia Based on Infrared Spectrum and Cluster Analysis. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2024, 44(05): 1386-1391.

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