香附饮片与4种醋制香附饮片的快速鉴别

Quick Identification of Xiangfu(Cyperi Rhizoma)Decoction Pieces and Four Types of Vinegar-Processed Decoction Pieces

目的建立香附饮片与4种醋制香附饮片的傅里叶变换红外光谱图,快速鉴别香附饮片与4种醋制香附饮片;建立香附饮片与4种醋制香附饮片的高效液相指纹图谱,并测定α-香附酮、香附烯酮、5-羟甲基糠醛(5-HMF)、对香豆酸、阿魏酸、木犀草素的含量。方法建立25批香附样品的红外光谱图,利用OMNIC 9.2软件分析其平均红外光谱间的差异,采用Spectrum for Window 3.02软件标定共有峰,计算相对峰高;采用《中药色谱指纹图谱相似度评价系统(2012版)》建立香附饮片与4种醋制香附饮片的高效液相指纹图谱,进行相似度评价,确定共有峰个数;采用SIMCA 14.1软件进行聚类分析、主成分分析、正交偏最小二乘法-判别分析,判断红外光谱图结果与高效液相指纹图谱结果是否相互验证;测定α-香附酮、香附烯酮、5-HMF、对香豆酸、阿魏酸、木犀草素的含量。结果25批香附样品的红外光谱图的相关系数为0.9347~0.9829,共标定16个共有峰,1500~1300 cm^(-1)波段处差异明显。正态分布分析结果显示,2928、1649、995 cm^(-1)波段处可分别将醋煮品、醋炙品、醋蒸品与饮片区分;高效液相指纹图谱结果显示25批样品共有21个共有峰,相似度均大于0.9。指认出3号峰为5-HMF,7号峰为对香豆酸,8号峰为阿魏酸,14号峰为木犀草素,19号峰为香附烯酮,21号峰为α-香附酮;红外光谱图与高效液相指纹图谱聚类分析结果、主成分分析结果与正交偏最小二乘法-判别分析结果一致,均可聚为五类,即能够相互验证;5-HMF的含量经炮制后均有增加。对香豆酸、阿魏酸、木犀草素在饮片中含量最低,经炮制后均有增加。香附烯酮经醋炙、醋煮、醋蒸、醋煮蒸后均有减少,在香附饮片中含量最高。α-香附酮经醋炙后含量略有增加,经醋煮、醋蒸、醋煮蒸后均减少。结论香附饮片与4种醋制香附饮片的红外光谱图之间存在明显差异,能够快速鉴别香附饮片与4种醋制香附饮片;所建立的高效液相指纹图谱与含量测定方法操作简单、准确。

Objective To establish the fourier transform infrared spectra of Xiangfu(Cyperi Rhizoma)decoction pieces and 4 types of vinegar-processed Xiangfu(Cyperi Rhizoma)decoction pieces and quickly identify Xiangfu(Cyperi Rhizoma)decoction pieces and 4 types of vinegar-processed Xiangfu(Cyperi Rhizoma)decoction pieces.To establish high-performance liquid chromatography fingerprints of Xiangfu(Cyperi Rhizoma)decoction pieces and 4 types of vinegar-processed decoction pieces and determine the contents of-ketone,enone,5-hydroxymethylfurfural(5-HMF),p-coumaric acid,ferulic acid and luteolin in Xiangfu(Cyperi Rhizoma).Methods The infrared spectra of 25 batches of samples were established,the difference between the average infrared spectra was analyzed by OMNIC 9.2 software,and the common peak was calibrated by Spectrum for Window 3.02 software to calculate the relative peak height.Chromatographic Fingerprint Similarity Evaluation System of Traditional Chinese Medicines(2012 Edition)was used to establish the high-performance liquid fingerprint of Xiangfu(Cyperi Rhizoma)decoction pieces and four kinds of vinegar-processed decoction pieces,and the similarity evaluation was carried out to determine the numbers of common peaks.SIMCA 14.1 software was used for the hierarchical cluster analysis,principal component analysis and orthogonal partial least squares-discriminant analysis,and it was to determine whether the infrared spectrogram results and the high-performance liquid phase fingerprint results were mutually verified.The contents of α-gerinone,geranione,5-HMF,p-coumaric acid,ferulic acid and luteolin were determined.Results The correlation coefficient of the infrared spectra of 25 batches of samples was 0.9347~0.9829,and a total of 16 common peaks were calibrated,and the difference at 1500~1300 cm^(-1) band was obvious.The normal distribution analysis results showed that vinegar-boiled products,vinegar-fired products,vinegar-steamed products and Xiangfu(Cyperi Rhizoma)decoction pieces could be distinguished at the 2928 cm-1,1649 cm^(-1) and 995 cm-1 bands.The results of high performance liquid phase fingerprinting showed there were 21 common peaks in 25 batches of samples,and the similarity was greater than 0.9.Peak 3 was identified as 5-HMF,peak 7 as p-coumaric acid,peak 8 as ferulic acid,peak 14 as luteolin,peak 19 as geranienone and peak 21 as α-geronone.The infrared spectroscopy and high-performance liquid phase fingerprint hierarchical cluster analysis results,principal component analysis results,orthogonal partial least squares-discriminant analysis results were consistent,and can be clustered into five categories,and they can verify each other.The content of 5-HMF increased after processing.The contents of p-coumaric acid,ferulic acid and luteolin were the least in the decoction pieces,and they all increased after processing.Geranienone was reduced after vinegar frying,vinegar boiling,vinegar steaming and vinegar boiling steaming,and the content was the highest in the decoction pieces The content ofα-vanillone increased slightly after vinegar processing,and reduced after vinegar boiling,vinegar steaming and boiling.Conclusion There are obvious differences between the infrared spectra of Xiangfu(Cyperi Rhizoma)decoction pieces and the four vinegar-processed Xiangfu(Cyperi Rhizoma)decoction pieces,which can quickly identify Xiangfu(Cyperi Rhizoma)decoction piecesand the four vinegar-processed Xiangfu(Cyperi Rhizoma)decoction pieces.The established high-performance liquid phase fingerprint and content determination method are simple and accurate to operate.