基于化学计量学鉴定不同甜橙精油挥发性成分

摘要/Abstract

摘要： 不同提取方式导致精油风味成分差异，进而影响其功效。本文采用感官定量描述分析、气相离子迁移色谱（gas chromatography-ion mobility spectrometry，GC-IMS）及超快速气相电子鼻并结合化学计量学，对冷压法（cold pressing，CP）、微波辅助水蒸气蒸馏法（microwave-assisted hydrodistillation，MADH）和旋转锥蒸馏塔法（spinning cone column，SCC）等不同方法提取的甜橙（血橙和脐橙为代表）精油进行挥发性成分差异分析。结果表明，三种方式提取的甜橙精油风味存在明显差异，CP精油喜爱度最高且具有更强的果香、甜香和花香，MADH精油具有更强的脂香、青香和木香，而SCC萃取液香气浓度较低。GC-IMS一共鉴定出64种挥发性化合物，主要为萜烯类、醇类和醛类，其次是酸类、酯类和其他化合物。指纹图谱直观地展示出不同样品的成分差异，萜烯类在CP和MADH精油中含量明显高于SCC萃取液，而醇类和醛类在MADH精油和SCC萃取液中含量明显高于CP精油。基于相对气味活性值（relative odor activity value，ROAV）鉴定出β-月桂烯和芳樟醇是甜橙精油风味的主要贡献者。GC-IMS结合偏最小二乘法判别分析（partial least square discriminant analysis，PLS-DA）和变量重要性投影（variable importance in projection，VIP）筛选出15种区分六种精油的标志性差异挥发性化合物。此外，超快速气相电子鼻结合主成分分析（principal component analysis，PCA）和判别因子分析（discriminant factor analysis，DFA）也能够成功区分六种甜橙精油挥发物差异。本研究为甜橙精油的提取及应用提供数据支撑。

关键词: 脐橙, 血橙, 精油, 挥发性化合物, 化学计量学

Abstract: he extraction methods affect the flavor components of essential oils, thereby affect their efficacy. Sensory quantitative description analysis, gas chromatography-ion mobility spectrometry (GC-IMS) and Heracles NEO e-nose combined with chemometrics were used to investigate the volatile compounds of different sweet orange essential oils (EOs). The EOs from blood orange and navel orange were extracted by three extraction methods, i.e. cold pressing (CP), microwave-assisted hydrodistillation (MADH) and spinning cone column (SCC). The results indicated that the extraction method greatly influenced the flavor profiles and aroma compounds of EOs. CP EOs exhibited the strongest fruity, sweet and floral aroma with the highest preference, MADH EOs had strongest fatty, green and woody aroma, and SCC extract had a low aroma intensity. A total of 64 volatiles were identified by GC-IMS, primarily terpenes, alcohols and aldehydes, followed by acids, esters and other compounds. The fingerprint directly highlighted the composition variations among six samples. The contents of terpenes were significantly higher in CP and MADH EOs compared to SCC extracts, whereas the contents of alcohols and aldehydes were significantly higher in MADH EOs and SCC extracts compared to CP EOs. Based on relative odor activity value (ROAV), β-myrcene and linalool were identified as the main contributors to the flavor of sweet orange EOs. Moreover, GC-IMS combined with partial least square discriminant analysis (PLS-DA) and variable importance in projection (VIP) screened out 15 aroma markers that distinguish six EOs. Additionally, the e-nose combined with principal component analysis (PCA) and discriminant factor analysis (DFA) also successfully distinguished the six EOs. This study provides data support for the extraction and application of sweet orange EOs.

Key words: navel orange, blood orange, essential oil, volatile compounds, chemometrics

中图分类号:

TQ651.2

刘菲斐陈晋陈健乐刘东红叶兴乾程焕. 基于化学计量学鉴定不同甜橙精油挥发性成分[J]. 食品科学.

Fei-Fei LIU Donghong LIU Ye Xingqian Huan 无CHENG. Identification of Volatiles in Different Sweet Orange Essential Oils by Chemometrics[J]. FOOD SCIENCE.

参考文献

[1] 成传香. 不同品种柑橘汁中香气物质的比较及其加工方式的影响[D]. 西南大学, 2020.
[2] 张雅. 甜橙果实品质综合评价分析系统的开发与验证[D]. 湖南农业大学, 2021.
[3] 张静. 温州蜜柑和几种晚熟柑橘理化品质及功能成分研究[D]. 西南大学, 2019.
[4] SINGH B, SINGH J P, KAUR A, et al. Insights into the chemical composition and bioactivities of citrus peel essential oils[J]. Food Research International, 2021, 143: 110231. DOI: 10.1016/j.foodres.2021.110231.
[5] MAHATO N, SHARMA K, KOTESWARARAO R, et al. Citrus essential oils: Extraction, authentication and application in food preservation[J]. Critical Reviews in Food Science and Nutrition, 2019, 59(4): 611-625. DOI: 10.1080/10408398.2017.1384716.
[6] LIU N, LI X, ZHAO P, et al. A review of chemical constituents and health-promoting effects of citrus peels[J]. Food Chemistry, 2021, 365: 130585. DOI: 10.1016/j.foodchem.2021.130585.
[7] 李贵节. 柑橘果汁和精油中的氧杂环化合物：分析方法学、化学表征和降血压活性研究[D]. 西南大学, 2018.
[8] 赵凯. 脐橙果皮精油与果胶的联产工艺研究[D]. 浙江大学, 2018.
[9] FERHAT M A, MEKLATI B Y, CHEMAT F. Comparison of different isolation methods of essential oil from Citrus fruits: cold pressing, hydrodistillation and microwave ‘dry’ distillation[J]. Flavour and Fragrance Journal, 2007, 22(6): 494-504. DOI: 10.1002/ffj.1829.
[10] HARLOVELEEN KAUR SANDHU, SINHA P, EMANUEL N, et al. Effect of Ultrasound-Assisted Pretreatment on Extraction Efficiency of Essential Oil and Bioactive Compounds from Citrus Waste By-Products[J]. Separations, 2021, 8(12): 244. DOI: 10.3390/separations8120244.
[11] JEYARATNAM N, NOUR A H, KANTHASAMY R, et al. Essential oil from Cinnamomum cassia bark through hydrodistillation and advanced microwave assisted hydrodistillation[J]. Industrial Crops and Products, 2016, 92: 57-66. DOI: 10.1016/j.indcrop.2016.07.049.
[12] LUO Y, WANG K, ZHUANG H, et al. Elucidation of aroma compounds in passion fruit (Passiflora alata Ait) using a molecular sensory approach[J]. Journal of Food Biochemistry, 2022, 46(9): e14224. DOI: 10.1111/jfbc.14224.
[13] WEI Y, PANG Y, MA P, et al. Green preparation, safety control and intelligent processing of high-quality tea extract[J]. Critical Reviews in Food Science and Nutrition, 2023, 0(0): 1-25. DOI: 10.1080/10408398.2023.2239348.
[14] SAM F E, MA T Z, SALIFU R, et al. Techniques for Dealcoholization of Wines: Their Impact on Wine Phenolic Composition, Volatile Composition, and Sensory Characteristics[J]. Foods, 2021, 10(10): 2498. DOI: 10.3390/foods10102498.
[15] GRABER M F, PéREZ-CORREA J R, VERDUGO G, et al. Spinning cone column isolation of rosemary essential oil[J]. Food Control, 2010, 21(5): 615-619. DOI: 10.1016/j.foodcont.2009.09.005.
[16] XIAO Z, WU Q, NIU Y, et al. Characterization of the Key Aroma Compounds in Five Varieties of Mandarins by Gas Chromatography–Olfactometry, Odor Activity Values, Aroma Recombination, and Omission Analysis[J]. Journal of Agricultural and Food Chemistry, 2017, 65(38): 8392-8401. DOI: 10.1021/acs.jafc.7b02703.
[17] SHUI M, FENG T, TONG Y, et al. Characterization of Key Aroma Compounds and Construction of Flavor Base Module of Chinese Sweet Oranges[J]. Molecules, 2019, 24(13): 2384. DOI: 10.3390/molecules24132384.
[18] LIU F, CHEN Y, CHEN J, et al. Characteristic aroma improvement mechanisms of heat-sterilized bayberry juice regulated by exogenous polyphenols[J]. Food Chemistry, 2023, 427: 136644. DOI: 10.1016/j.foodchem.2023.136644.
[19] 倪瑞洁, 詹萍, 田洪磊. 基于GC-IMS结合多元统计方法分析炸制时间对花椒调味油挥发性物质的影响[J]. 食品科学, 2022, 43(6): 279-286. DOI:10.7506/spkx1002-6630-20210429-417
[20] 刘盼盼, 郑鹏程, 龚自明, 等. 橘红茶香气特征及风味成分分析[J]. 食品科学, 2021, 42(8): 198-205. DOI:10.7506/spkx1002-6630-20191102-013.
[21] NGUYEN H, CAMPI E M, ROY JACKSON W, et al. Effect of oxidative deterioration on flavour and aroma components of lemon oil[J]. Food Chemistry, 2009, 112(2): 388-393. DOI: 10.1016/j.foodchem.2008.05.090.
[22] CHENG Y, HAN L, HUANG L, et al. Association between flavor composition and sensory profile in thermally processed mandarin juices by multidimensional gas chromatography and multivariate statistical analysis[J]. Food Chemistry, 2023, 419: 136026. DOI: 10.1016/j.foodchem.2023.136026.
[23] HOU J, LIANG L, WANG Y. Volatile composition changes in navel orange at different growth stages by HS-SPME–GC–MS[J]. Food Research International, 2020, 136: 109333. DOI: 10.1016/j.foodres.2020.109333.
[24] 余汉谋, 姜兴涛, 肖海鸿. 旋转锥体柱技术及其在食品和香精香料行业中的应用进展[J]. 食品工业科技, 2013, 34(24): 372-375. DOI: 10.13386/j.issn1002-0306.2013.24.087.
[25] JIA X, REN J, FAN G, et al. Citrus juice off-flavor during different processing and storage: Review of odorants, formation pathways, and analytical techniques[J]. Critical Reviews in Food Science and Nutrition, 2022, 0(0): 1-26. DOI: 10.1080/10408398.2022.2129581.
[26] 李湘, 江靖, 李高阳, 等. GC-IMS结合化学计量学分析不同采后处理对柑橘果皮挥发性化合物的影响[J]. 食品科学, 2021, 42(20): 128-134. DOI:10.7506/spkx1002-6630-20200808-110.
[27] YU D, ZHANG X, GUO S, et al. Headspace GC/MS and fast GC e-nose combined with chemometric analysis to identify the varieties and geographical origins of ginger (Zingiber officinale Roscoe)[J]. Food Chemistry, 2022, 396: 133672. DOI: 10.1016/j.foodchem.2022.133672.