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中国精品科技期刊2020

气相-离子迁移谱结合化学计量学方法快速区分不同年份酿造白酒

张敏敏 路岩翔 赵志国 崔莉 闫慧娇 王晓 赵恒强

张敏敏,路岩翔,赵志国,等. 气相-离子迁移谱结合化学计量学方法快速区分不同年份酿造白酒[J]. 食品工业科技,2021,42(14):226−232. doi:  10.13386/j.issn1002-0306.2020080205
引用本文: 张敏敏,路岩翔,赵志国,等. 气相-离子迁移谱结合化学计量学方法快速区分不同年份酿造白酒[J]. 食品工业科技,2021,42(14):226−232. doi:  10.13386/j.issn1002-0306.2020080205
ZHANG Minmin, LU Yanxiang, ZHAO Zhiguo, et al. Rapid Discrimination of Different Years of Brewing Liquor by Gas Chromatography-Ion Mobility Spectroscopy Combined with Chemometrics Method[J]. Science and Technology of Food Industry, 2021, 42(14): 226−232. (in Chinese with English abstract). doi:  10.13386/j.issn1002-0306.2020080205
Citation: ZHANG Minmin, LU Yanxiang, ZHAO Zhiguo, et al. Rapid Discrimination of Different Years of Brewing Liquor by Gas Chromatography-Ion Mobility Spectroscopy Combined with Chemometrics Method[J]. Science and Technology of Food Industry, 2021, 42(14): 226−232. (in Chinese with English abstract). doi:  10.13386/j.issn1002-0306.2020080205

气相-离子迁移谱结合化学计量学方法快速区分不同年份酿造白酒

doi: 10.13386/j.issn1002-0306.2020080205
基金项目: 山东省重点研发计划(医用食品)(2018YYSP012);山东省重点研发计划(2019GSF108062,2019GSF108035);山东省泰山学者岗位资助(郭兰萍);山东省科学院先导专项(郭兰萍)
详细信息
    作者简介:

    张敏敏(1990−),女,硕士研究生,研究方向:食品科学,E-mail:zhangminminff@163.com

    通讯作者:

    赵恒强(1980−),男,博士,副研究员,研究方向:食品及天然产物分析研究,E-mail:hqzhao2007@163.com

  • 中图分类号: TS261.7

Rapid Discrimination of Different Years of Brewing Liquor by Gas Chromatography-Ion Mobility Spectroscopy Combined with Chemometrics Method

  • 摘要: 目的:建立了气相色谱-离子迁移谱(Gas chromatography-ion mobility spectroscopy, GC-IMS)技术结合化学计量学分析快速区分不同年份酱香型白酒的方法。方法:采用GC-IMS技术对多批次不同年份的酱香型酿造白酒样本中挥发性有机物进行分析,通过对比挥发性有机物含量差异快速生成指纹图谱,并通过PCA-CA分析实现样本的快速区分。结果:将白酒中检测到的化合物峰利用NIST 2014气相保留指数数据库与IMS迁移时间数据库进行准确的二维定性后共鉴别出包含单体和二聚体在内的共53个挥发性有机物。挥发性有机物指纹图谱对比结果显示不同年份样本中所含化合物的种类和含量差异较大,采用PCA分析可以实现不同年份原酒和老熟酒的正确区分,采用主成分分析-聚类分析(Principal component analysis-cluster analysis, PCA-CA)处理结果进一步明确了区分结果的准确性。结论:该方法直观、快速、准确,为酿造白酒的年份区分提供了方法和技术支持。
  • 图  1  优化过程的气相-离子迁移谱图

    Figure  1.  Spectra of the optimization process

    图  2  样品的气相-离子迁移谱图(样本3-3)

    Figure  2.  Spectrogram of GC-IMS(sample 3-3)

    图  3  不同年份白酒样品的多成分差异性对比图

    Figure  3.  Comparison chart of multi-component differences of liquor samples

    注:每一行代表一个样品所选择的所有区域,每一列是不同样品间同一区域的对比。

    图  4  12个样品的PCA分析图谱

    Figure  4.  PCA analysis pattern of 12 samples

    图  5  12个样本的PCA-CA分析图谱

    Figure  5.  PCA-CA analysis spectrum of 12 samples

    表  1  GC-IMS 实验条件

    Table  1.   Test conditions of GC-IMS

    仪器项目GC-IMS参数
    样品孵育孵育时间10 min
    样品量1 mL
    孵育温度60 ℃
    进样口温度65 ℃
    GC色谱柱类型SE-54
    色谱柱柱长30 m
    柱温40 ℃
    运行时间30 min
    IMS电离源氚(6.5 KeV)
    电离模式正模式
    初始载气流量2 mL/min(N2, 99.999%)
    漂移气流量150 mL/min(N2, 99.999%)
    迁移管温度45 ℃
    采集均值12
    下载: 导出CSV

    表  2  酒样中检测出的VOCs

    Table  2.   VOCs detected in liquor samples

    编号化合物CAS号化学式分子量气相保留指数气相保留时间(s)迁移时间(RIPrel)
    1癸醛(decanal)C112312C10H20O156.31199.902087.912.06
    2癸醛(decanal)C112312C10H20O156.31200.702093.801.50
    3乙酸丙酯(Propyl hexanoate)C626777C9H18O2158.21106.801442.981.92
    4乙酸丙酯(Propyl hexanoate)C626777C9H18O2158.21107.401445.931.42
    5辛醛(Octanal)C124130C8H16O128.21021.001026.491.83
    6辛醛(Octanal)C124130C8H16O128.21022.001030.431.39
    7甲基己酮(Hexyl methyl ketone)C111137C8H16O128.21003.00955.601.35
    82,6-二甲基-4-庚酮(2,6-dimethyl-4-heptanone)C108838C9H18O142.2971.20857.141.34
    92,6-二甲基-4-庚酮(2,6-dimethyl-4-heptanone)C108838C9H18O142.2971.90859.111.79
    10α-蒎烯(α-Pinene)C80568C10H16136.2942.50779.971.72
    11α-蒎烯(α-Pinene)C80568C10H16136.2943.00781.301.31
    12庚醛(Heptanal)C111717C7H14O114.2903.10685.111.69
    132-庚酮(2-Heptanone)C110430C7H14O114.2899.60677.391.28
    142,5-二甲基吡嗪(2,5-Dimethylpyrazine)C123320C6H8N2108.1895.90669.201.13
    15乙酸异戊酯(3-Methylbutyl acetate)C123922C7H14O2130.2883.10644.991.30
    16乙酸异戊酯(3-Methylbutyl acetate)C123922C7H14O2130.2883.30645.351.75
    171-己醇(1-Hexanol)C111273C6H14O102.2870.20622.921.65
    181-己醇(1-Hexanol)C111273C6H14O102.2870.40623.281.33
    192-甲基吡嗪(2- Methyl pyrazine)C109080C5H6N294.1824.90551.361.33
    20正己醛(Hexanal)C66251C6H12O100.2797.60512.201.56
    212-甲基吡嗪(2- Methyl pyrazine)C109080C5H6N294.1826.80554.211.11
    222-己酮(2-Hexanone)C591786C6H12O100.2803.80520.741.21
    231-戊醇(1-Pentanol)C71410C5H12O88.1761.40464.851.52
    242,3-戊二酮(2,3-Pentanedione)C600146C5H8O2100.1701.70396.551.21
    25丙烯酸乙酯(Ethyl acrylate)C140885C5H8O2100.1702.00396.871.13
    262-戊酮(2-Pentanone)C107879C5H10O86.1687.20381.851.35
    27正丁醇(1-Butanol)C71363C4H10O74.1651.40354.041.37
    282-丁酮(2-Butanone)C78933C4H8O72.1598.10316.321.23
    29丙醇(1-Propanol)C71238C3H8O60.1584.00307.051.25
    302,3-丁二酮(2,3-butanedione)C431038C4H6O286.1581.60305.451.17
    31甲基叔丁基醚(tert-Butylmethylether)C1634044C5H12O88.1561.80292.981.14
    32丙酮(Acetone)C67641C3H6O58.1493.60253.671.14
    33苯甲醛(Benzaldehyde)C100527C7H6O106.1952.70806.521.47
    341-辛醇(1-Octanol)C111875C8H18O130.21062.901212.001.87
    351-辛醇(1-Octanol)C111875C8H18O130.21063.401214.551.42
    363-辛酮(3-Octanone)C106683C8H16O128.2982.40889.291.30
    374-甲基戊醇(4-Methylpentanol)C626891C6H14O102.2851.10591.781.65
    38乳酸乙酯(Ethyl lactate)C97643C5H10O3118.1814.40535.861.54
    39丁酸(Butanoic acid)C107926C4H8O288.1785.10495.231.39
    402,3-丁二醇(2,3-Butanediol)C513859C4H10O290.1791.20503.371.37
    41乙酸异丁酯(Isobutyl acetate)C110190C6H12O2116.2769.50475.071.62
    42异丁酸乙酯(Ethyl isobutyrate)C97621C6H12O2116.2755.80458.021.56
    431-戊醇(1-Pentanol)C71410C5H12O88.1763.10466.931.25
    442-甲基丁醇(2-methylbutanol)C137326C5H12O88.1725.70422.741.48
    45乙酸丙酯(Propyl acetate)C109604C5H10O2102.1712.10407.631.46
    46戊醛(Valeraldehyde)C110623C5H10O86.1662.80362.631.41
    47乙酸乙酯(Ethyl Acetate)C141786C4H8O288.1617.50329.541.34
    48异丙醇(Isopropyl alcohol)C67630C3H8O60.1501.90258.151.19
    49苯甲醛(Benzaldehyde)C100527C7H6O106.1953.00807.231.15
    502-庚醇(2-Heptanol)C543497C7H16O116.2891.50659.781.36
    51正戊酸(Pentanoic acid)C109524C5H10O2102.1891.10659.101.49
    52顺-3-己烯醇((Z)-3-hexenol)C928961C6H12O100.2846.00583.621.25
    532-甲基丁酸(2-methylbutyric acid)C116530C5H10O2102.1825.10551.661.45
    下载: 导出CSV

    表  3  相关矩阵的特征值

    Table  3.   Eigen-values of the correlation matrix

    成分方差贡献率(%)累积方差贡献率(%)特征值
    PC161.17661.1771.09E+07
    PC233.26494.4415946855.469
    PC33.21397.654574370.201
    PC40.94098.594168033.821
    PC50.52399.11593251.839
    PC60.34399.45961408.800
    下载: 导出CSV
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  • 收稿日期:  2020-08-21
  • 网络出版日期:  2021-06-07
  • 刊出日期:  2021-07-07

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