基于静态顶空气相离子迁移谱技术的果啤种类判别

龚霄; 周伟; 李积华; 涂京霞; 杨涛华; 霍羽佳

doi:10.13386/j.issn1002-0306.2020060261

基于静态顶空气相离子迁移谱技术的果啤种类判别

doi: 10.13386/j.issn1002-0306.2020060261

龚霄^{1, 2, 3,},
周伟^{1, 2},
李积华^{1, 2, ,},
涂京霞^3, ,,
杨涛华^{1, 2},
霍羽佳⁴

1.
中国热带农业科学院农产品加工研究所，农业农村部热带作物产品加工重点实验室，广东湛江 524001
2.
海南省果蔬贮藏与加工重点实验室，广东湛江 524001
3.
广州珠江啤酒股份有限公司，广东广州 510308
4.
山东海能科学仪器有限公司GAS事业部，山东德州 251500

基金项目: 广东省优稀水果现代农业产业技术体系创新团队项目（2019KJ116）；中国热带农业科学院基本科研业务费专项资金（1630122017013）；广州珠江啤酒股份有限公司技术中心研究开发项目（RD20-02）

详细信息

作者简介:
龚霄（1984−），男，博士，副研究员，研究方向：食品代谢组学，E-mail：gongxiaocau@126.com

通讯作者:
李积华（1979−），男，博士，研究员，研究方向：食品科学，E-mail：foodpaper@126.com

涂京霞（1973−），女，硕士，教授级高工，研究方向：啤酒酿造学，E-mail：tujingxia@zhujiangbeer.com

中图分类号: TS255.3
计量
- 文章访问数: 16
- HTML全文浏览量: 15
- PDF下载量: 6
- 被引次数: 0
出版历程
- 收稿日期: 2020-06-22
- 网络出版日期: 2021-01-28
- 刊出日期: 2021-04-01

Identification of Fruit Beers Based on Static Headspace-Gas Chromatography-Ion Mobility Spectroscopy (SH-GC-IMS)

Xiao GONG^{1, 2, 3
,},
Wei ZHOU^{1, 2},
Jihua LI^{1, 2
, ,},
Jingxia TU^{3
, ,},
Taohua YANG^{1, 2},
Yujia HUO⁴

1.
Key Laboratory of Tropical Crop Products Processing of Ministry of Agriculture and Rural Affairs, Agricultural Products Processing Research Institute, Chinese Academy of Tropical Agricultural Sciences, Zhanjiang 524001, China
2.
Hainan Key Laboratory of Storage & Processing of Fruits and Vegetables, Zhanjiang 524001, China
3.
Guangzhou Zhujiang Brewery Co., Ltd., Guangzhou 510308, China
4.
G.A.S. Department of Shandong Hanon Science Instrument Co., Ltd., Dezhou 251500, China

摘要

摘要: 以菠萝、苹果和蔓越莓等三种果啤为研究对象，采用静态顶空气相离子迁移谱（static headspace-gas chromatography-ion mobility spectrometry, SH-GC-IMS）对样品中的挥发性有机物（volatile organic compounds, VOCs）进行分析，采用主成分分析（principal component analysis, PCA）方法对VOCs数据进行判别和分类。结果表明：基于GC-IMS指纹图谱的二维数据可视化方法筛选出乙醇、乙酸异戊酯、己酸乙酯、异戊醇、丁酸乙酯、苯甲醛、辛酸乙酯等35个香气特征离子峰，可以作为表征三种果啤产品风味差异信息的特征变量；三组果啤样品在PCA图中离散性好，均得到不同的归属区域，两个主成分累积贡献率达到98%，可以有效区分三种不同果啤产品的主要香气。这为果啤生产过程的质量控制、产品溯源、品牌鉴定与保护提供了一种新方法。
- 静态顶空气相离子迁移谱 /
- 果啤 /
- 挥发性有机物 /
- 主成分分析 /
- 风味鉴别
Abstract: The volatile organic compounds (VOCs) of three kinds of fruit beer, namely pineapple, apple and cranberry beers were investigated, and the VOCs data was discriminated and classified by using principal component analysis (PCA) method. The results showed that a total of 35 effective characteristic ionic peaks of the VOCs mainly ethanol, isoamyl acetate, ethyl hexanoate, isoamyl alcohol, ethyl butyrate, benzaldehyde, and ethyl octanoate were selected by the two-dimensional mode of data visualization based on the SH-GC-IMS fingerprint, which could be used to characterize the flavor differences among the selected fruit beers. Discrimination and classification of the three kinds of fruit beer was effectively performed by using PCA method with good dispersion, and all groups had corresponding attribution areas in the PCA map and the cumulative contribution rate of the first two PCs was 98%, which could be used to distinguish the aroma characteristics of different fruit beer products. Anyway, the results offer a new method for process control, product traceability, brand identification and protection in fruit beer industry.
- static headspace-gas chromatography-ion mobility spectroscopy (SH-GC-IMS) /
- fruit beers /
- volatile organic compounds (VOCs) /
- principal component analysis (PCA) /
- flavor identification

HTML全文

图 1 不同果啤样品的GC-IMS图谱

注：a. 菠萝; b. 苹果; c. 蔓越莓。

Figure 1. GC-IMS chromatogram of different fruit beer samples

下载: 全尺寸图片幻灯片

图 2 不同果啤样品中挥发性化合物的指纹图谱

注：a. 菠萝; b. 苹果; c. 蔓越莓。

Figure 2. Volatile fingerprints of different fruit beer samples

下载: 全尺寸图片幻灯片

图 3 不同果啤样品PCA分析的得分图和载荷图

注：a. 菠萝; b. 苹果; c. 蔓越莓。

Figure 3. The score and loading map of PCA analysis of different fruit beer samples

下载: 全尺寸图片幻灯片

表 1 GC-IMS鉴别不同果啤样品中的挥发性成分

Table 1. Identification of volatile compounds in different fruit beers by GC-IMS

	挥发性成分	化学式	分子量	RI^a	Rt(s)^b	Dt [RIPrel]^c
1	辛酸甲酯（Methyl octanoate）	C₉H₁₈O₂	158.2	1119.8	508.622	1.4607	M^d
2	辛酸甲酯（Methyl octanoae）	C₉H₁₈O₂	158.2	1117.0	504.495	2.0183	D^e
3	乙酸庚酯（Heptyl acetate）	C₉H₁₈O₂	158.2	1111.0	495.555	1.937	D
4	乙酸庚酯（Heptyl acetate）	C₉H₁₈O₂	158.2	1112.4	497.618	1.4092	M
5	己酸丙酯（Propyl hexanoate）	C₉H₁₈O₂	158.2	1091.1	465.982	1.3827	M
6	己酸丙酯（Propyl hexanoate）	C₉H₁₈O₂	158.2	1090.6	465.294	1.859	D
7	庚酸乙酯（Ethyl heptanoate）	C₉H₁₈O₂	158.2	1063.5	425.405	1.4092	M
8	庚酸乙酯（Ethyl heptanoate）	C₉H₁₈O₂	158.2	1066.4	429.531	1.9353	D
9	己酸乙酯（Ethyl hexanoate）	C₈H₁₆O₂	144.2	1007.5	350.44	1.3428	M
10	己酸乙酯（Ethyl hexanoate）	C₈H₁₆O₂	144.2	1007.5	350.44	1.7959	D
11	苯甲醛（Benzaldehyde）	C₇H₆O	106.1	965.1	305.737	1.1486
12	乙酸异戊酯（Isopentyl acetate）	C₇H₁₄O₂	130.2	883.5	246.59	1.3046	M
13	乙酸异戊酯（Isopentyl acetate）	C₇H₁₄O₂	130.2	884.7	247.278	1.7494	D
14	丁酸乙酯（Ethyl butanoate）	C₆H₁₂O₂	116.2	799.6	205.325	1.2067	M
15	丁酸乙酯（Ethyl butanoate）	C₆H₁₂O₂	116.2	801.2	206.013	1.5569	D
16	异戊醇（3-Methyl-1-butanol）	C₅H₁₂O	88.1	740.2	180.919	1.5109
17	乙酸乙酯（Ethyl acetate）	C₄H₈O₂	88.1	616.0	146.42	1.3359
18	乙醇（Ethanol）	C₂H₆O	46.1	473.2	118.598	1.1402
19	异丁醇（2-Methylpropanol）	C₄H₁₀O	74.1	636.5	150.649	1.3736
20	辛酸乙酯（Ethyl octanoate）	C₁₀H₂₀O₂	172.3	1265.1	724.544	1.4826
21	甲基麦芽酚（Maltol）	C₆H₆O₃	126.1	1107.5	490.345	1.2104
22	反-2-辛烯醛（(E)-2-Octenal）	C₈H₁₄O	126.2	1048.2	403.534	1.3291	M
23	反-2-辛烯醛（(E)-2-Octenal）	C₈H₁₄O	126.2	1049.4	405.292	1.8171	D
24	乙酸甲酯（Methyl hexanoate）	C₇H₁₄O₂	130.2	932.8	278.933	1.6752	D
25	乙酸甲酯（Methyl hexanoate）	C₇H₁₄O₂	130.2	932.8	278.933	1.2882	M
26	戊酸乙酯（Ethyl pentanoate）	C₇H₁₄O₂	130.2	909.0	262.288	1.275	M
27	戊酸乙酯（Ethyl pentanoate）	C₇H₁₄O₂	130.2	907.3	261.154	1.6752	D
28	2-甲基丁酸乙酯（Ethyl 2-methylbutanoate）	C₇H₁₄O₂	130.2	853.7	230.512	1.6449
29	2-甲基丁酸甲酯（Methyl 2-methylbutanoate）	C₆H₁₂O₂	116.2	773.8	194.371	1.53
30	丙酸乙酯（Ethyl propanoate）	C₅H₁₀O₂	102.1	712.0	170.749	1.4516
31	丙酸（Propionic acid）	C₃H₆O₂	74.1	687.6	163.164	1.3504
32	3-甲基-1-戊醇（3-Methylpentanol）	C₆H₁₄O	102.2	851.9	229.612	1.6008
33	2-甲基丙酸乙酯（Ethyl 2-methylpropanoate）	C₆H₁₂O₂	116.2	752.3	185.618	1.5575	D
34	异戊醛（3-Methylbutanal）	C₅H₁₀O	86.1	652.8	154.265	1.4036	D
35	异戊醛（3-Methylbutanal）	C₅H₁₀O	86.1	653.9	154.518	1.1881	M
36	2-甲基丙酸乙酯（Ethyl 2-methylpropanoate）	C₆H₁₂O₂	116.2	754.9	186.629	1.2006	M
37	丁醛（Butanal）	C₄H₈O	72.1	656.1	155.024	1.2896
38	柠檬烯（Limonene）	C₁₀H₁₆	136.2	1022.5	369.053	1.2134
39	庚醛（Heptanal）	C₇H₁₄O	114.2	901.1	257.174	1.6984
40	乙酸丁酯（Butyl acetate）	C₆H₁₂O₂	116.2	811.9	210.745	1.618	D
41	乙酸丁酯（Butyl acetate）	C₆H₁₂O₂	116.2	807.5	208.801	1.2387	M
42	乙酸异丁酯（Isobutyl acetate）	C₆H₁₂O₂	116.2	763.5	190.125	1.6108
43	丙酸2-甲基丁酯（2-Methylbutyl propionate）	C₈H₁₆O₂	144.2	976.0	316.091	1.3544	M
44	丙酸2-甲基丁酯（2-Methylbutyl propionate）	C₈H₁₆O₂	144.2	976.7	316.812	1.8392	D
45	丁酸异丁酯（Isobutyl butyrate）	C₈H₁₆O₂	144.2	943.5	287.276	1.7523	D
46	丁酸异丁酯（Isobutyl butyrate）	C₈H₁₆O₂	144.2	942.2	286.226	1.3093	M
47	异丁酸甲酯（Methyl isobutyrate）	C₅H₁₀O₂	102.1	680.7	161.252	1.4405
48	丁酸甲酯（Methyl butanoate）	C₅H₁₀O₂	102.1	720.5	173.677	1.4292
49	壬醛（Nonanal）	C₉H₁₈O	142.2	1099.8	478.93	1.9368
注：a表示保留指数；b表示毛细管气相色谱柱中的保留时间；c表示漂移管中的迁移时间；d 表示dimer，二聚体；e表示monome单体。

下载: 导出CSV

参考文献(28)

[1]	苗方, 康健, 王德良. 果啤的研究进展[J]. 酿酒,2010,37(3):75−77. doi: 10.3969/j.issn.1002-8110.2010.03.026
[2]	王松廷. 西瓜精酿啤酒酿造工艺的研究及其风味物质分析[D]. 郑州: 河南大学, 2016.
[3]	莫芬. 小麦面筋蛋白水解物对酵母增殖代谢及啤酒发酵的影响研究[D]. 广州: 华南理工大学, 2014.
[4]	Prasad M. In-vitro evaluation of antioxidant properties of fermented fruit beer samples[J]. International Journal of Science and Research,2014,3(11):1545−1550.
[5]	Ghasemi-Vamamkhasti M, Mohtasebi S S, Siadat M, et al. Aging fingerprint characterization of beer using electronic nose[J]. Sensors and Actuators B: Chemical,2011,159(1):51−59. doi: 10.1016/j.snb.2011.06.036
[6]	Ceto X, Gutierrez-Capitan M, Calvo D, et al. Beer classification by means of a potentiometric electronic tongue[J]. Food Chemistry,2013,141(3):2533−2540. doi: 10.1016/j.foodchem.2013.05.091
[7]	Augusto D S L, Luiz F D, Gomes T A, et al. Discrimination of Brazilian lager beer by ¹H NMR spectroscopy combined with chemometrics[J]. Food Chemistry,2019,272:488−493. doi: 10.1016/j.foodchem.2018.08.077
[8]	Anderson H E, Santos I C, Hildenbrand Z L, et al. A review of the analytical methods used for beer ingredient and finished product analysis and quality control[J]. Analytica Chimica Acta,2019,1085:1−20. doi: 10.1016/j.aca.2019.07.061
[9]	Kishimoto T, Noba S, Yako N, et al. Simulation of Pilsner-type beer aroma using 76 odor-active compounds[J]. Journal of Bioscience and Bioengineering,2018,126(3):330−338. doi: 10.1016/j.jbiosc.2018.03.015
[10]	Krechmer J E, Groessl M, Zhang X, et al. Ion mobility spectrometry-mass spectrometry (IMS-MS) for on-and offline analysis of atmospheric gas and aerosol species[J]. Atmospheric Measurement Techniques,2016,9(7):3245−3262. doi: 10.5194/amt-9-3245-2016
[11]	Sheibani A, Haghpazir N. Application of ion mobility spectrometry for the determination of tramadol in biological samples[J]. Journal of Food and Drug Analysis,2014,22(4):500−504. doi: 10.1016/j.jfda.2014.02.001
[12]	Sobel J D, Karpas Z, Lorber A. Diagnosing vaginal infections through measurement of biogenic amines by ion mobility spectrometry[J]. European Journal of Obstetrics & Gynecology and Reproductive Biology,2012,163(1):81−84.
[13]	Hernandez-Mesa M, Escourrou A, Monteau F, et al. Current applications and perspectives of ion mobility spectrometry to answer chemical food safety issues[J]. Trac Trends in Analytical Chemistry,2017,94:39−53. doi: 10.1016/j.trac.2017.07.006
[14]	Hernandez-Mesa M, Ropartz D, Garcia-Campana A M, et al. Ion mobility spectrometry in food analysis: Principles, current applications and future trends[J]. Molecules,2019,24:2706. doi: 10.3390/molecules24152706
[15]	Wang S Q, Chen H T, Sun B G. Recent progress in food flavor analysis using gas chromatography-ion mobility spectrometry (GC-IMS)[J]. Food Chemistry,2020,315:126158. doi: 10.1016/j.foodchem.2019.126158
[16]	葛含光, 温华蔚, 宋旭, 等. 离子迁移谱法检测蒸馏酒中4种风味成分[J]. 食品安全质量检测学报,2016,7(2):834−838.
[17]	黄星奕, 吴梦紫, 马梅, 等. 采用气相色谱-离子迁移谱技术检测黄酒风味物质[J]. 现代食品科技,2019,35(9):271−276, 226.
[18]	Tang Z S, Zeng X A, Margaret A, et al. Characterization of aroma profile and characteristic aromas during lychee wine fermentation[J]. Journal of Food Processing and Preservation,2019,43(8):e14003.
[19]	Garrido-Delgado R, Arce L, Guaman A V, et al. Direct coupling of a gas-liquid separator to an ion mobility spectrometer for the classification of different white wines using chemometrics tools[J]. Talanta,2011,84(2):471−479. doi: 10.1016/j.talanta.2011.01.044
[20]	Vautz W, Baumbach J I, Jung J. Beer fermentation control using ion mobility spectrometry-results of a pilot study[J]. Journal of the Institute of Brewing, 2006, 112(2): 157−164.
[21]	张俊杰, 尚益民, 彭姗姗, 等. 产香酵母的筛选及其苹果酒发酵特性[J]. 中国酿造,2019,38(8):31−35. doi: 10.11882/j.issn.0254-5071.2019.08.007
[22]	潘咏梅. 菠萝汁及加工、发酵过程中风味变化的研究[D]. 北京: 北京化工大学, 2007.
[23]	Siebert T E, Smyth H E, Capone D L, et al. Stable isotope dilution analysis of wine fermentation products by HS-SPME-GC-MS[J]. Analytical & Bioanalytical Chemistry,2005,381(4):937−947.
[24]	Yan X, Fan W, Qian M C. Characterization of aroma compounds in apple cider using solvent-assisted flavor evaporation and headspace solid-phase microextraction[J]. Journal of Agricultural & Food Chemistry,2007,55(8):3051−3057.
[25]	Pino J A, Queris O. Analysis of volatile compounds of pineapple wine using solid-phase microextraction techniques[J]. Food Chemistry,2010,122(4):1241−1246. doi: 10.1016/j.foodchem.2010.03.033
[26]	Takeoka G, Rg B, Flath R, et al. Volatile constituents of pineapple (Ananas Comosus [L. ] Merr.)[J]. ACS Symposium Series,1989,388(1):223−237.
[27]	Sancho M F, Rao M A, Downing D L. Infinite dilution activity coefficients of apple juice aroma compounds[J]. Journal of Food Engineering,1997,34(2):145−158. doi: 10.1016/S0260-8774(97)89919-0
[28]	Zhang J, Kilmartin P A, Peng Y, et al. Identification of key aroma compounds in cranberry juices as influenced by vinification[J]. Journal of Agricultural and Food Chemistry,2020,68(1):279−291. doi: 10.1021/acs.jafc.9b07165