基于HPLC-UV和FT-NIR的不同贮藏年限余甘子质量评价与鉴别
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摘要
目的:探寻不同贮藏年限余甘子有效成分变化规律,为其保存策略提供理论依据。方法:采集7个不同贮藏年限的余甘子材料,高效液相色谱紫外光谱(HPLC-UV)测定没食子酸、柯里拉京、诃黎勒酸、鞣花酸、槲皮素的含量,阐明其主要活性成分累积特征;傅立叶变换近红外光谱(FT-NIR)记录样品整体光谱指纹图谱,偏最小二乘判别(PLS-DA)模型鉴别不同贮藏年限余甘子样品。结果:2015年版《中国药典》指标性成分没食子酸含量最高,其次是鞣花酸与诃黎勒酸,柯里拉京与槲皮素的含量较少;各成分在不同贮藏年限间样品中具有显著性差异(P<0.05),没食子酸和槲皮素均在贮藏6年时达最大值,分别为79.36和1.68 mg·g~(-1),贮藏4年样品中诃黎勒酸、柯里拉京、鞣花酸累积最高,分别是18.85,7.97,21.46 mg·g~(-1)。MSC+SG二阶求导(窗口参数为11,多项式次数为3)优化FT-NIR数据,不同贮藏年限样品的分类正确率为84.5%;以最低交叉验证均方根误差为准则,降维光谱数据为若干重要潜在变量并与5种活性成分含量数据融合,鉴别正确率提高到98.8%。结论:基于HPLC-UV和FT-NIR技术,该研究有效阐述不同贮藏年限余甘子5种主要代谢成分累积特征;结合数据融合策略,PLS-DA模型能较好鉴别不同质量样品。该结果可为不同贮藏年限余甘子的质量鉴别及评价提供一定的科学依据。
Objective:To explore the change rules of active ingredients in Phyllanthi Fructus of different storage years,in order to provide theory basis for storage.Method:Seven Phyllanthi Fruatus samples of different storage years were collected.HPLC-UV detection method was established to determine the contents of gallic acid,corilagin,chebulagic acid,ellagic acid and quercetin.Samples were fingerprinted by FT-NIR and identified by PLS-DA model.Result:Gallic acid,which was the bioactive marker in Chinese Pharmacopoeia,had the highest content.It was followed by ellagic acid and chebulagic acid,and corilagin and quercetin had the least content.The components had significant differences between samples of different storage years(P<0.05).Gallic acid and quercetin reached the maximum value at 6 years of storage,which were 79.36 and 1.68 mg·g~(-1)respectively.The contents of chebulagic acid,corilagin and ellagic acid reached a maximum at 4 years of storage,which were18.85,7.97,21.46 mg·g~(-1),respectively.FT-NIR data was optimized by MSC+SG(second derivative,the window parameter as 11,and the polynomial order as 3).The classification accuracy was 84.5%.Spectral data reduced to several important potential variables,and was fused with 5 active components based on minimum crossvalidation root mean square error,and the classification accuracy increased to 98.8%.Conclusion:The analysis of PLS-DA by HPLC-UV and FT-NIR could effectively explain the accumulation characteristics of active components in Phyllanthi Fruatus.According to the data fusion strategy,PLS-DA model could distinguish samples of different qualities.The results provide a scientific basis for the quality evaluation and identification of Phyllanthi Fruatus.
Objective:To explore the change rules of active ingredients in Phyllanthi Fructus of different storage years,in order to provide theory basis for storage.Method:Seven Phyllanthi Fruatus samples of different storage years were collected.HPLC-UV detection method was established to determine the contents of gallic acid,corilagin,chebulagic acid,ellagic acid and quercetin.Samples were fingerprinted by FT-NIR and identified by PLS-DA model.Result:Gallic acid,which was the bioactive marker in Chinese Pharmacopoeia,had the highest content.It was followed by ellagic acid and chebulagic acid,and corilagin and quercetin had the least content.The components had significant differences between samples of different storage years(P<0.05).Gallic acid and quercetin reached the maximum value at 6 years of storage,which were 79.36 and 1.68 mg·g~(-1)respectively.The contents of chebulagic acid,corilagin and ellagic acid reached a maximum at 4 years of storage,which were18.85,7.97,21.46 mg·g~(-1),respectively.FT-NIR data was optimized by MSC+SG(second derivative,the window parameter as 11,and the polynomial order as 3).The classification accuracy was 84.5%.Spectral data reduced to several important potential variables,and was fused with 5 active components based on minimum crossvalidation root mean square error,and the classification accuracy increased to 98.8%.Conclusion:The analysis of PLS-DA by HPLC-UV and FT-NIR could effectively explain the accumulation characteristics of active components in Phyllanthi Fruatus.According to the data fusion strategy,PLS-DA model could distinguish samples of different qualities.The results provide a scientific basis for the quality evaluation and identification of Phyllanthi Fruatus.
引文
[1]中国科学院《中国植物志》编辑委员会.中国植物志.44卷[M].北京:科学出版社,1994:87.
[2]贡保东知,郭伟晨,阿达,等.基于中医传承辅助平台的藏族医治疗浮肿用药规律分析[J].中国实验方剂学杂志,2017,23(12):208-213.
[3]Shukla R,Singh P,Prakash B,et al. Antifungal,aflatoxin inhibitory and free radical-scavenging activities of some medicinal plants extracts[J]. J Food Qual,2012,35(3):182-189.
[4]LIU X L,ZHAO M M,WEI L,et al. Identification of volatile components in Phyllanthus emblica L. and their antimicrobial activity[J]. J Med Food,2009,12(2):423-428.
[5]Chatterjee A,Chatterjee S,Biswas A,et al. Gallic acid enriched fraction of Phyllanthus emblica potentiates indomethacin-induced gastric ulcer healing via e-NOSdependent pathway[J]. J Evidence-Based Complementary Altern Med,2012,2012(4):487380.
[6]朱英环,孟宪生,包永睿,等.余甘子总酚酸和总黄酮配伍抑制肝癌细胞增殖及对免疫功能的调节作用[J].中国实验方剂学杂志,2012,18(3):132-135.
[7]Sumalatha D. Antioxidant and antitumor activity of Phyllanthus emblica in colon cancer cell lines[J]. Int J Curr Microbiol Appl Sci,2013,2(5):189-195.
[8]李萍,彭百承,杨政腾,等.余甘子抗免疫性肝纤维化大鼠的作用(Ⅱ)[J].中国实验方剂学杂志,2010,16(8):139-141.
[9]Pramyothin P,Samosorn P,Poungshompoo S,et al. The protective effects of Phyllanthus emblica Linn. extract on ethanol induced rat hepatic injury[J]. J Ethnopharmacol,2006,107(3):361-364.
[10]崔炳权,何震宇,杨泽民,等.余甘子提取物对小鼠免疫功能的影响[J].时珍国医国药,2010,21(8):1920-1922.
[11]Krishnaveni M,Mirunalini S. Therapeutic potential of Phyllanthus emblica(amla):the ayurvedic wonder.[J]. J Basic Clin Physiol Pharmacol,2010,21(1):93-105.
[12]国家药典委员会.中华人民共和国药典.一部[M].北京:中国医药科技出版社,2015:179.
[13]郑国栋,蒋林,杨雪,等.不同贮藏年限广陈皮黄酮类成分的变化规律研究[J].中成药,2010,32(6):977-980.
[14]陈宇航,郭巧生,刘丽,等.贮藏年限及药材分级对夏枯草药材品质的影响[J].中国中药杂志,2012,37(7):882-886.
[15]福建省医药研究所.福建中草药[M].福州:福建省医药研究所,1970:552.
[16]王琴琴,沈涛,左智天,等.基于数据融合和多指标定量对滇龙胆产地鉴别和质量评价[J].中国中药杂志,2018,43(6):1162-1168.
[17]吴瑶,岳显可,葛卫红,杨等.乌药不同部位乌药醚内酯、去甲异波尔定含量比较和FT-NIR光谱分析[J].中国实验方剂学杂志,2017,23(11):73-78.
[18]Bassbasi M,Luca M D,Ioele G,et al. Prediction of the geographical origin of butters by partial least square discriminant analysis(PLS-DA)applied to infrared spectroscopy(FTIR)data[J]. J Food Compos Anal,2014,33(2):210-215.
[19]Ballabio D, Consonni V. Classification tools in chemistry. Part 1:linear models. PLS-DA[J]. Anal Methods,2013,5(16):3790-3798.
[20]QI L M,ZHANG J,ZHAO Y L,et al. Characterization of Gentiana rigescens by ultraviolet–visible and infrared spectroscopies with chemometrics[J]. Anal Lett,2017,50(9):1497-1511.
[21]陆兔林,石上梅,蔡宝昌,等.基于一测多评的中药多成分定量研究进展[J].中草药,2012,43(12):2525-2529.
[22]Boots A W,Haenen G R,Bast A. Health effects of quercetin:from antioxidant to nutraceutical[J]. Eur J Pharmacol,2008,585(2/3):325-337.
[23]吴玲芳,袁永兵,王坤凤,等.可水解鞣质单体化学与药理作用研究进展[J].中草药,2014,45(2):290-299.
[24]Sinija V R,Mishra H N. FTNIR spectroscopic method for determination of moisture content in green tea granules[J]. Food Bioprocess Technol,2011,4(1):136-141.
[2]贡保东知,郭伟晨,阿达,等.基于中医传承辅助平台的藏族医治疗浮肿用药规律分析[J].中国实验方剂学杂志,2017,23(12):208-213.
[3]Shukla R,Singh P,Prakash B,et al. Antifungal,aflatoxin inhibitory and free radical-scavenging activities of some medicinal plants extracts[J]. J Food Qual,2012,35(3):182-189.
[4]LIU X L,ZHAO M M,WEI L,et al. Identification of volatile components in Phyllanthus emblica L. and their antimicrobial activity[J]. J Med Food,2009,12(2):423-428.
[5]Chatterjee A,Chatterjee S,Biswas A,et al. Gallic acid enriched fraction of Phyllanthus emblica potentiates indomethacin-induced gastric ulcer healing via e-NOSdependent pathway[J]. J Evidence-Based Complementary Altern Med,2012,2012(4):487380.
[6]朱英环,孟宪生,包永睿,等.余甘子总酚酸和总黄酮配伍抑制肝癌细胞增殖及对免疫功能的调节作用[J].中国实验方剂学杂志,2012,18(3):132-135.
[7]Sumalatha D. Antioxidant and antitumor activity of Phyllanthus emblica in colon cancer cell lines[J]. Int J Curr Microbiol Appl Sci,2013,2(5):189-195.
[8]李萍,彭百承,杨政腾,等.余甘子抗免疫性肝纤维化大鼠的作用(Ⅱ)[J].中国实验方剂学杂志,2010,16(8):139-141.
[9]Pramyothin P,Samosorn P,Poungshompoo S,et al. The protective effects of Phyllanthus emblica Linn. extract on ethanol induced rat hepatic injury[J]. J Ethnopharmacol,2006,107(3):361-364.
[10]崔炳权,何震宇,杨泽民,等.余甘子提取物对小鼠免疫功能的影响[J].时珍国医国药,2010,21(8):1920-1922.
[11]Krishnaveni M,Mirunalini S. Therapeutic potential of Phyllanthus emblica(amla):the ayurvedic wonder.[J]. J Basic Clin Physiol Pharmacol,2010,21(1):93-105.
[12]国家药典委员会.中华人民共和国药典.一部[M].北京:中国医药科技出版社,2015:179.
[13]郑国栋,蒋林,杨雪,等.不同贮藏年限广陈皮黄酮类成分的变化规律研究[J].中成药,2010,32(6):977-980.
[14]陈宇航,郭巧生,刘丽,等.贮藏年限及药材分级对夏枯草药材品质的影响[J].中国中药杂志,2012,37(7):882-886.
[15]福建省医药研究所.福建中草药[M].福州:福建省医药研究所,1970:552.
[16]王琴琴,沈涛,左智天,等.基于数据融合和多指标定量对滇龙胆产地鉴别和质量评价[J].中国中药杂志,2018,43(6):1162-1168.
[17]吴瑶,岳显可,葛卫红,杨等.乌药不同部位乌药醚内酯、去甲异波尔定含量比较和FT-NIR光谱分析[J].中国实验方剂学杂志,2017,23(11):73-78.
[18]Bassbasi M,Luca M D,Ioele G,et al. Prediction of the geographical origin of butters by partial least square discriminant analysis(PLS-DA)applied to infrared spectroscopy(FTIR)data[J]. J Food Compos Anal,2014,33(2):210-215.
[19]Ballabio D, Consonni V. Classification tools in chemistry. Part 1:linear models. PLS-DA[J]. Anal Methods,2013,5(16):3790-3798.
[20]QI L M,ZHANG J,ZHAO Y L,et al. Characterization of Gentiana rigescens by ultraviolet–visible and infrared spectroscopies with chemometrics[J]. Anal Lett,2017,50(9):1497-1511.
[21]陆兔林,石上梅,蔡宝昌,等.基于一测多评的中药多成分定量研究进展[J].中草药,2012,43(12):2525-2529.
[22]Boots A W,Haenen G R,Bast A. Health effects of quercetin:from antioxidant to nutraceutical[J]. Eur J Pharmacol,2008,585(2/3):325-337.
[23]吴玲芳,袁永兵,王坤凤,等.可水解鞣质单体化学与药理作用研究进展[J].中草药,2014,45(2):290-299.
[24]Sinija V R,Mishra H N. FTNIR spectroscopic method for determination of moisture content in green tea granules[J]. Food Bioprocess Technol,2011,4(1):136-141.