不同提取方法与GC-MS进样方式对柚皮精油挥发性成分分析结果的影响
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摘要
采用冷压榨、水蒸汽蒸馏及机械磨皮三种方法制备柚皮精油,比较直接进样和固相微萃取两种进样方式对柚皮精油挥发性成分种类和数量的影响,并利用主成分分析(PCA)和偏最小二乘法判别分析(PLS-DA)对三种方法提取的精油挥发性成分进行统计分析并找出特征挥发性成分。结果表明:直接进样法结合GC-MS从柚皮精油中共分离鉴定出69种物质,SPME结合GC-MS共鉴定出51种物质,直接进样比SPME进样更全面地反映出精油挥发性成分的组成。PCA分析能对直接进样法检测的三种柚皮精油进行很好的区分,其中冷榨油与磨皮油挥发性成分更为接近。PLS-DA分析发现能够将三种精油区分开的特征挥发性成分有:冷榨油中的桧烯、D-柠檬烯、α-松油醇、β-月桂烯、α-蒎烯以及4-萜品醇;水提油中芳樟醇、(R)-氧化柠檬烯、8,9-二氢新异长叶烯;磨皮油中的圆柚酮,n-棕榈酸以及(Z,Z)-9,12-十八二烯酸。其中水提油中特征挥发性物质氧化柠檬烯(5.19%)具有不良气味,磨皮油中保留指数大于2000的挥发性成分相对含量(4.61%)较高,影响澄清度和稳定性。综合以上成分分析得出,冷压榨法制备的柚皮精油的品质相对较好。
In this study,pomelo peel essential oil was prepared by cold pressing,steam distillation and mechanical dermabrasion.The effects of direct injection and solid phase microextraction(SPME) on the type and amount of volatile components of pomelo peel essential oil were compared.Principal component analysis(PCA) and partial least squares discriminant analysis(PLS-DA) were applied to analyze the volatile components in essential oils extracted from the three methods and identify the characteristic volatile compounds.The results showed that totally 69 compounds were identified by the approach involving direct injection combined with GC-MS,and 51 compounds by SPME combined with GC-MS,with the direct injection approach showing the volatile profile of essential oil more comprehensively than SPME.For the volatile profiles obtained by the direct injection method,PCA analysis can distinguish the three kinds of pomelo peel essential oils with those derived from cold pressing and mechanical dermabrasion being more similar.PLS-DA analysis revealed that the characteristic volatile components in the three essential oils can be distinguished:Sabinene,D-limonene,α-terpineol,β-myrcene,α-pinene,and 4-terpineol in cold pressed oil;Linalool,(R)-limonene oxide and 8,9-dihydroneisoxylene in steam distillation oil;Nootkatone,n-palmitic acid,and(Z,Z)-9,12-octadienoic acid in dermabrasion oil.Among them,the characteristic volatile compound limonene oxide(5.19%) in steam distillation oil exhibited an irritating odor.The volatile components with a retention index greater than 2000 was higher(4.61%) in dermabrasion oil,which affected the clarity and stability of essential oils.Based on the above analyses,the quality of the pomelo peel oil prepared by cold pressing was better.
In this study,pomelo peel essential oil was prepared by cold pressing,steam distillation and mechanical dermabrasion.The effects of direct injection and solid phase microextraction(SPME) on the type and amount of volatile components of pomelo peel essential oil were compared.Principal component analysis(PCA) and partial least squares discriminant analysis(PLS-DA) were applied to analyze the volatile components in essential oils extracted from the three methods and identify the characteristic volatile compounds.The results showed that totally 69 compounds were identified by the approach involving direct injection combined with GC-MS,and 51 compounds by SPME combined with GC-MS,with the direct injection approach showing the volatile profile of essential oil more comprehensively than SPME.For the volatile profiles obtained by the direct injection method,PCA analysis can distinguish the three kinds of pomelo peel essential oils with those derived from cold pressing and mechanical dermabrasion being more similar.PLS-DA analysis revealed that the characteristic volatile components in the three essential oils can be distinguished:Sabinene,D-limonene,α-terpineol,β-myrcene,α-pinene,and 4-terpineol in cold pressed oil;Linalool,(R)-limonene oxide and 8,9-dihydroneisoxylene in steam distillation oil;Nootkatone,n-palmitic acid,and(Z,Z)-9,12-octadienoic acid in dermabrasion oil.Among them,the characteristic volatile compound limonene oxide(5.19%) in steam distillation oil exhibited an irritating odor.The volatile components with a retention index greater than 2000 was higher(4.61%) in dermabrasion oil,which affected the clarity and stability of essential oils.Based on the above analyses,the quality of the pomelo peel oil prepared by cold pressing was better.
引文
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[9]Asli G,Ismai K,Gülay K.Comparison of lemon oil composition after using different extraction methods[J].Journal of Essential Oil Research,2015,27(1):17-22
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[11]施迎春,杨颖,周锦云,等.提取方法对葡萄柚精油性质与组成的影响[J].浙江农业学报,2012,24(2):305-309SHI Ying-chun,YANG Ying,ZHOU Jin-yun,et al.Effects of extraction methods on the properties and composition of grapefruits essential oil[J].Acta Agriculturae Zhejiangensis,2012,24(2):305-309
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[13]苗延林.气相色谱分析啤酒中风味成分最简单的方法-直接进样法[J].中国酿造,2004,134(5):35-37Miao Yan-lin.Direct-injection technique in gas chromatograph-the easiest method of analyzing flavor components in beer[J].China Brewing,2004,134(5):35-37
[14]Marta F,Gabriel M,JoséC.Evaluation of diagnosis methods in PCA-based multivariate statistical process control[J].Chemometrics and Intelligent Laboratory Systems,2018,175(15),194-210
[15]Pizarro C,Rodríguez-Tecedor S,Pérez-del-Notario N,et al.Classification of Spanish extra virgin olive oils by data fusion of visible spectroscopic fingerprints and chemical descriptors[J].Food Chemistry,2013,138(2-3):915-922
[16]古彦.梅县沙田柚营销策略优化研究[D].仲恺农业工程学院,2015GU Yan.Mei xian District of Shatian pomelo marketing strategy optimization research[D].Zhongkai University of Agriculture and Engineering,2015
[17]陈晓水,候宏卫,边照阳,等.气相色谱-串联质谱(GC-MS)的应用研究进展[J].质谱学报,2013,34(5):308-318CHEN Xiao-shui,HOU Hong-wei,BIAN Zhao-yang,et al.Research progress on application of GC-MS[J].Journal of Chinese Mass Spectrometry Society,2013,34(5):308-318
[18]Wenjing L,Bo H,Zuojing L,et al.GC-MS method for determination and pharmacokinetic study of seven volatile constituents in rat plasma after oral administration of the essential oil of Rhizoma curcumae[J].Journal of Pharmaceutical and Biomedical Analysis,2018,149(5):577-585
[19]Cheong M,Chong Z,Liu S,et al.Characterisation of calamansi(Citrus microcarpa).part I:volatiles,aromatic profiles and phenolic acids in the peel[J].Food Chemistry,2012,134(2):686-695
[20]Dharmawan J,Kasapis S,Curran P,et al.Characterization of volatile compounds in selected citrus fruits from asia.part I:freshly-squeezed juice[J].Flavour and Fragrance Journal,2007,22(3):228-232
[21]LIU C,CHENG Y,ZHANG H,et al.Volatile constituents of wild citrus mangshanyegan(Citrus nobilis Lauriro)peel oil[J].Journal of Agricultural and Food Chemistry,2012,60(10):2617-2628
[22]Espina L,Somolinos M,Lorán S,et al.Chemical composition of commercial citrus fruit essential oils and evaluation of their antimicrobial activity acting alone or in combined processes[J].Food Control,2011,22(6):896-902
[23]洪鹏,陈峰,杨远帆,等.三种柚子精油的香味特征及挥发性成分[J].现代食品科技,2014,30(10):274-281HONG Peng,CHEN Feng,YANG Yuan-fan,et al.Sensory characteristics and volatile components of three pummelo(Citrus maxima)essential oils[J].Modern Food Science and Technology,2014,30(10):274-281
[24]傅曼琴,肖更生,陈于陇,等.改进型Clevenger装置提取柠檬果皮精油及成分分析[J].食品科学,2016,38(2):170-175FU Man-qin,XIAO Geng-sheng,CHEN Yu-long,et al.Volatile components of lemon peel essential oils extracted by an improved clevenger apparatus[J].Food Science,2016,38(2):170-175
[25]刘晔,葛丽琴,王远兴.三个产地不同等级庐山云雾茶挥发性成分主成分分析[J].食品科学,2017,24(9):1-16LIU Ye,GE Li-qin,WANG Yuan-xing.Study of principal components analysis of volatile compounds in different grades Lu mountain clouds-mist tea from three regions[J].Food Science,2017,24(9):1-16
[26]唐军,廖享,童红,等.基于气质与PLS-DA对新疆薰衣草精油判别分析[J].计算机与应用化学,2014,31(6):701-704TANG Jun,LIAO Xiang,TONG Hong,et al.GC-MScombined with PLS-DA to discriminate the varieties of Xinjiang Lavender essential oil[J].Computers and Applied Chemistry,2014,31(6):701-704
[27]Omori H,Nakahara K,Umano K.Characterization of aroma compounds in the peel extract of Ja(Citrus jabara Hort ex Tanaka)[J].Flavour and Fragrance Journal,2011,6(6):396-402
[28]Choi H,Sawamura M,Kondo Y.Characterization of the key aroma compounds of Citrus flaviculpus Hort.ex Tanaka by aroma extraction dilution analysis[J].Journal of Food Science,2002,67(5):1713-1718
[29]孙浩,陈峰,倪辉,等.制备工艺对柚皮精油产品香味特征及挥发性成分的影响[J].中国食品学报,2014,14(9):117-123SUN Hao,CHEN Feng,NI Hui,et al.Effect of preparation technology on the odour characteristic and volatile compounds of the essential oil products from pomelo peel[J].Journal of Chinese Institute of Food Science and Technology,2014,14(9):117-123
[2]徐慧,吕金顺,沈茜茜,等.柚子皮精油提取分离方法及其成分分析[J].淮阴师范学院学报(自然科学版),2015,14(1):43-46XU Hui,LYU Jin-shun,SHEN Xi-xi,et al.The extraction and separation methods of the essential oil of Citrus maxima peel and its chemical composition[J].Journal of Huaiyin Normal University(Natural Science Edition),2015,14(1):43-46
[3]谢婧,宋新辉,许少丹.柚子活性成分的研究进展[J].广州化工,2013,41(7):14-16XIE Jing,SONG Xin-hui,XU Shao-dan.Research progress of grapefruit active ingredients[J].Guangzhou Chemical Industry,2013,41(7):14-16
[4]杨宁.柚子全果综合利用及生物活性研究进展[J].广州化工,2015,43(5):9-11YANG Ning.Research progress of comprehensive utilization and biological activity of grapefruit fruit[J].Guangzhou Chemical Industry,2015,3(5):9-11
[5]臧燕燕,张明霞,刘国杰,等.不同品种中国柚果皮中挥发性物质的组成及质量分数比较[J].中国农业大学学报,2011,16(6):52-57ZANG Yan-yan,ZHANG Ming-xia,LIU Guo-jie,et al.Comparison of volatile compounds in flavedos of Chinese pummeios[J].Journal of China Agricultural University,2011,16(6):52-57
[6]杨愈丰,柳敦耀,向红英,等.柚子皮精油提取及其驱蚊效果研究[J].天然产物研究与开发,2017,27:867-872YANG Yu-feng,LIU Dun-yao,XIANG Hong-ying,et al.Extraction and mosquito repellent activity of essential oil from Citrus maxima(Burm)Merr.Cv.Shatian Yu peels[J].Natural Product Research and Development,2017,27:867-872
[7]张帅,张少平,郑云云,等.柚皮有效成分提取及综合利用研究进展[J].中国农学学报,2017,10:158-164ZHANG Shuai,ZHANG Shao-ping,ZHENG Yun-yun,et al.Extraction techniques and comprehensive utilization of pomelo peel[J].Chinese Agricultural Science Bulletin,2017,10:158-164
[8]邓桂兰,魏强华,刘冬梅.柚子皮的综合利用研究[J].食品工业,2013,34(9):180-184DENG Gui-lan,WEI Qiang-hua,LIU Dong-mei.Research on the comprehensive utilization of pomelo peel[J].Food Industry,2013,34(9):180-184
[9]Asli G,Ismai K,Gülay K.Comparison of lemon oil composition after using different extraction methods[J].Journal of Essential Oil Research,2015,27(1):17-22
[10]樊荣,曾新安,关昕.不同方法提取的柚皮精油质量评价[J].食品工业科技,2012,7:202-205FANG Rong,ZENG Xin-an,GUAN Xin.Quality assessment of essential oils of Citrus grandis peel obtained by different extraction methods[J].Science and Technology of Food Industry,2012,7:202-205
[11]施迎春,杨颖,周锦云,等.提取方法对葡萄柚精油性质与组成的影响[J].浙江农业学报,2012,24(2):305-309SHI Ying-chun,YANG Ying,ZHOU Jin-yun,et al.Effects of extraction methods on the properties and composition of grapefruits essential oil[J].Acta Agriculturae Zhejiangensis,2012,24(2):305-309
[12]Andrzej L,Dawidowicz N,Joanna S,et al.Modified application of HS-SPME for quality evaluation of essential oil plant materials[J].Talanta,2016,146(1):195-202
[13]苗延林.气相色谱分析啤酒中风味成分最简单的方法-直接进样法[J].中国酿造,2004,134(5):35-37Miao Yan-lin.Direct-injection technique in gas chromatograph-the easiest method of analyzing flavor components in beer[J].China Brewing,2004,134(5):35-37
[14]Marta F,Gabriel M,JoséC.Evaluation of diagnosis methods in PCA-based multivariate statistical process control[J].Chemometrics and Intelligent Laboratory Systems,2018,175(15),194-210
[15]Pizarro C,Rodríguez-Tecedor S,Pérez-del-Notario N,et al.Classification of Spanish extra virgin olive oils by data fusion of visible spectroscopic fingerprints and chemical descriptors[J].Food Chemistry,2013,138(2-3):915-922
[16]古彦.梅县沙田柚营销策略优化研究[D].仲恺农业工程学院,2015GU Yan.Mei xian District of Shatian pomelo marketing strategy optimization research[D].Zhongkai University of Agriculture and Engineering,2015
[17]陈晓水,候宏卫,边照阳,等.气相色谱-串联质谱(GC-MS)的应用研究进展[J].质谱学报,2013,34(5):308-318CHEN Xiao-shui,HOU Hong-wei,BIAN Zhao-yang,et al.Research progress on application of GC-MS[J].Journal of Chinese Mass Spectrometry Society,2013,34(5):308-318
[18]Wenjing L,Bo H,Zuojing L,et al.GC-MS method for determination and pharmacokinetic study of seven volatile constituents in rat plasma after oral administration of the essential oil of Rhizoma curcumae[J].Journal of Pharmaceutical and Biomedical Analysis,2018,149(5):577-585
[19]Cheong M,Chong Z,Liu S,et al.Characterisation of calamansi(Citrus microcarpa).part I:volatiles,aromatic profiles and phenolic acids in the peel[J].Food Chemistry,2012,134(2):686-695
[20]Dharmawan J,Kasapis S,Curran P,et al.Characterization of volatile compounds in selected citrus fruits from asia.part I:freshly-squeezed juice[J].Flavour and Fragrance Journal,2007,22(3):228-232
[21]LIU C,CHENG Y,ZHANG H,et al.Volatile constituents of wild citrus mangshanyegan(Citrus nobilis Lauriro)peel oil[J].Journal of Agricultural and Food Chemistry,2012,60(10):2617-2628
[22]Espina L,Somolinos M,Lorán S,et al.Chemical composition of commercial citrus fruit essential oils and evaluation of their antimicrobial activity acting alone or in combined processes[J].Food Control,2011,22(6):896-902
[23]洪鹏,陈峰,杨远帆,等.三种柚子精油的香味特征及挥发性成分[J].现代食品科技,2014,30(10):274-281HONG Peng,CHEN Feng,YANG Yuan-fan,et al.Sensory characteristics and volatile components of three pummelo(Citrus maxima)essential oils[J].Modern Food Science and Technology,2014,30(10):274-281
[24]傅曼琴,肖更生,陈于陇,等.改进型Clevenger装置提取柠檬果皮精油及成分分析[J].食品科学,2016,38(2):170-175FU Man-qin,XIAO Geng-sheng,CHEN Yu-long,et al.Volatile components of lemon peel essential oils extracted by an improved clevenger apparatus[J].Food Science,2016,38(2):170-175
[25]刘晔,葛丽琴,王远兴.三个产地不同等级庐山云雾茶挥发性成分主成分分析[J].食品科学,2017,24(9):1-16LIU Ye,GE Li-qin,WANG Yuan-xing.Study of principal components analysis of volatile compounds in different grades Lu mountain clouds-mist tea from three regions[J].Food Science,2017,24(9):1-16
[26]唐军,廖享,童红,等.基于气质与PLS-DA对新疆薰衣草精油判别分析[J].计算机与应用化学,2014,31(6):701-704TANG Jun,LIAO Xiang,TONG Hong,et al.GC-MScombined with PLS-DA to discriminate the varieties of Xinjiang Lavender essential oil[J].Computers and Applied Chemistry,2014,31(6):701-704
[27]Omori H,Nakahara K,Umano K.Characterization of aroma compounds in the peel extract of Ja(Citrus jabara Hort ex Tanaka)[J].Flavour and Fragrance Journal,2011,6(6):396-402
[28]Choi H,Sawamura M,Kondo Y.Characterization of the key aroma compounds of Citrus flaviculpus Hort.ex Tanaka by aroma extraction dilution analysis[J].Journal of Food Science,2002,67(5):1713-1718
[29]孙浩,陈峰,倪辉,等.制备工艺对柚皮精油产品香味特征及挥发性成分的影响[J].中国食品学报,2014,14(9):117-123SUN Hao,CHEN Feng,NI Hui,et al.Effect of preparation technology on the odour characteristic and volatile compounds of the essential oil products from pomelo peel[J].Journal of Chinese Institute of Food Science and Technology,2014,14(9):117-123