基于顶空气相色谱-离子迁移谱技术的冷冻猪肉贮藏时间快速判别方法
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摘要
通过分析冷冻猪肉在贮藏过程中发生劣变的主因、位置、产生的物质及检测方法的繁简程度,选择顶空气相色谱-离子迁移谱(headspace-gas chromatography-ion mobility spectroscopy,HS-GC-IMS)技术作为冷冻猪肉气味劣变的检测手段,采集和分析冷冻猪IV号肉表层或浅表层脂肪氧化所产生的挥发性有机物(volatile organic compounds,VOCs),并采用主成分分析对不同贮藏时间冷冻猪肉的VOCs数据进行维度压缩,利用K均值聚类分析算法建立判别模型,以此作为判别冷冻猪肉贮藏时间的方法。研究表明,HS-GC-IMS可有效分离冷冻猪肉中极性相近的VOCs,对VOCs组分的数据采集及分析可在600 s内完成,并筛选出29种离子峰强度变化明显的VOCs,通过二维数据可视化方式显示各VOCs离子峰的差异。经数据降维处理后所构建的聚类判别模型,可将冷冻猪肉检验样品根据贮藏时间的不同归类到对应的时间簇。
Considering the main cause and positions of quality deterioration and the complexity of detecting newly generated compounds in pork during frozen storage, headspace-gas chromatography-ion mobility spectroscopy (HS-GC-IMS) was chosen as a method for odor deterioration analysis to acquire and analyze the volatile organic compounds (VOCs) generated from lipid oxidation on the surface layer and shallow layer of frozen pork. Dimensionality reduction of the VOCs data of frozen pork stored for different periods was performed by principal component analysis (PCA), and the processed data were applied to establish a discriminant analysis model by K-means algorithm. The model was used to assess frozen pork stored for different periods. The results showed that the VOCs with similar polarity in frozen pork were separated effectively, and the data acquisition and analysis of VOCs were completed within 600 s by HS-GC-IMS. After data screening, 29 VOCs showed obvious changes in ion peak intensity, which could be displayed in the 2-dimension mode of data visualization. The model developed in this study could classify samples of frozen pork at different storage times into the corresponding clusters.
Considering the main cause and positions of quality deterioration and the complexity of detecting newly generated compounds in pork during frozen storage, headspace-gas chromatography-ion mobility spectroscopy (HS-GC-IMS) was chosen as a method for odor deterioration analysis to acquire and analyze the volatile organic compounds (VOCs) generated from lipid oxidation on the surface layer and shallow layer of frozen pork. Dimensionality reduction of the VOCs data of frozen pork stored for different periods was performed by principal component analysis (PCA), and the processed data were applied to establish a discriminant analysis model by K-means algorithm. The model was used to assess frozen pork stored for different periods. The results showed that the VOCs with similar polarity in frozen pork were separated effectively, and the data acquisition and analysis of VOCs were completed within 600 s by HS-GC-IMS. After data screening, 29 VOCs showed obvious changes in ion peak intensity, which could be displayed in the 2-dimension mode of data visualization. The model developed in this study could classify samples of frozen pork at different storage times into the corresponding clusters.
引文
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[30]袁凯,张龙,谷东陈,等.肉品中的蛋白质氧化机制及其影响因素[J].食品科学,2018,39(5):329-335.DOI:10.7506/spkx1002-6630-201805048.
[31]CHENG J H.Lipid oxidation in meat[J].Journal of Nutrition&Food Sciences,2016,6(3):494-496.DOI:10.4172/2155-9600.1000494.
[2]国家质量监督检验检疫总局,国家标准化管理委员会.鲜、冻四分体牛肉:GB/T 9960-2008[S].北京:中国标准出版社,2008:5.
[3]国家质量监督检验检疫总局,国家标准化管理委员会.鲜、冻兔肉:GB/T 17239-2008[S].北京:中国标准出版社,2008:6.
[4]商务部.中央储备冻卷羊肉:SB/T 11093-2014[S].北京:中国标准出版社,2014:2.
[5]商务部,财政部.2007年第9号《中央储备肉管理办法》[EB/OL].(2007-08-13)[2018-05-25].http://www.mofcom.gov.cn/article/b/d/200708/20070804990649.shtml.
[6]佚名.国家储备猪肉财务管理办法[J].中国财政,1996(2):52-53.
[7]COOK G W,LAPUMA P T,HOOK G L,et al.Using gas chromatography with ion mobility spectrometry to resolve explosive compounds in the presence of interferents[J].Journal of Forensic Sciences,2010,55(6):1582-1591.DOI:10.1111/j.1556-4029.2010.01522.x.
[8]BURYAKOV I A.Express analysis of explosives,chemical warfare agents and drugs with multicapillary column gas chromatography and ion mobility increment spectrometry[J].Journal of Chromatography B-Analytical Technologies in the Biomedical and Life Sciences,2004,800(1/2):75-82.DOI:10.1016/j.jchromb.2003.10.064.
[9]KWAN C,SNYDER A P,ERICKSON R P,et al.Chemical agent detection using GC-IMS:a comparative study[J].IEEE Sensors Journal,2010,10(3):451-460.DOI:10.1109/JSEN.2009.2038128.
[10]SIELEMANN S,XIE Z,SCHMIDT H,et al.Determination of MTBEnext to benzene,toluen and xylene within 90 s using GC/IMS with multi-capillary column[J].International Journal for Ion Mobility Spectrometry,2001,4(2):69-73.
[11]VERA L,COMPANIONI E,MEACHAM A,et al.Real time monitoring of VOC and odours based on GC-IMS at wastewater treatment plants[J].Chemical Engineering Transactions,2016,54:79-84.DOI:10.3303/CET1654014.
[12]LANGEJUERGEN J,WAGNER C,BEUTEL S,et al.Non-invasive monitoring of bacterial growth and auto-induced protein production in a bioreactor with a closed-loop GC-IMS[J].International Journal for Ion Mobility Spectrometry,2015,18(1/2):9-15.DOI:10.1007/s12127-014-0163-7.
[13]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.
[14]林若川,邓榕,许丽蓉.基于GC-IMS技术的绿茶风味鉴别方法可行性的研究[J].广东化工,2017(23):19-21.
[15]陈通,陆道礼,陈斌.GC-IMS技术结合化学计量学方法在食用植物油分类中的应用[J].分析测试学报,2017,36(10):1235-1239.DOI:10.3969/j.issn.1004-4957.2017.10.012.
[16]GARRIDO-DELGADO R,MERCADER-TREJO F,SIELEMANNS,et al.Direct classification of olive oils by using two types of ion mobility spectrometers[J].Analytica Chimica Acta,2011,696(1/2):108-115.DOI:10.1016/j.aca.2011.03.007.
[17]GARRIDO-DELGADO R,DOBAO-PRIETO M M,ARCE L,et al.Ion mobility spectrometry versus classical physico-chemical analysis for assessing the shelf life of extra virgin olive oil according to container type and storage conditions[J].Journal of Agricultural&Food Chemistry,2015,63(8):2179-2188.DOI:10.1021/jf505415f.
[18]ARROYO-MANZANARES N,MARTíN-GóMEZ A,JURADO-CAMPOS N,et al.Target vs spectral fingerprint data analysis of Iberian ham samples for avoiding labelling fraud using headspace-gas chromatography-ion mobility spectrometry[J].Food Chemistry,2018,246:65-73.DOI:10.1016/j.foodchem.2017.11.008.
[19]GERHARDT N,BIRKENMEIER M,SCHWOLOW S,et al.Volatilecompound fingerprinting by headspace-gas-chromatography ionmobility spectrometry(HS-GC-IMS)as a benchtop alternative to1H NMR profiling for assessment of the authenticity of honey[J].Analytical Chemistry,2018,90(3):1777-1785.DOI:10.1021/acs.analchem.7b03748.
[20]国家卫生和计划生育委员会.食品中挥发性盐基氮的测定:GB5009.228-2016[S].北京:中国标准出版社,2016:1-8.
[21]国家卫生和计划生育委员会.食品中酸价的测定:GB 5009.229-2016[S].北京:中国标准出版社,2016:1-13.
[22]国家卫生和计划生育委员会.食品中过氧化值的测定:G B5009.227-2016[S].北京:中国标准出版社,2016:1-6.
[23]李强,史晓宁,候顺利,等.不同冷藏期猪肉的挥发性盐基氮、pH值变化的研究[J].肉类工业,1992(7):47-48.
[24]国家卫生和计划生育委员会.食用动物油脂:GB 10146-2015[S].北京:中国标准出版社,2015.
[25]鞠波,王方宪,管恩平,等.出口冻猪肉过氧化值检测方法的探讨[J].肉类研究,2000,14(4):43-47.DOI:10.3969/j.issn.1001-8123.2000.04.016.
[26]沈路,任道援.影响肉类食品冷冻质量的若干因素[J].保鲜与加工,2006,6(5):9-12.DOI:10.3969/j.issn.1009-6221.2006.05.007.
[27]杜江萍.冷冻肉品储藏期间品质变化及控制措施[J].肉类研究,2009,23(11):14-17.DOI:10.3969/j.issn.1001-8123.2009.11.006.
[28]张丽,余群力,孙宝忠.肌肉蛋白氧化对肉类品质的影响[J].食品与发酵工业,2017,43(5):268-276.DOI:10.13995/j.cnki.11-1802/ts.201705043.
[29]黄莉,孔保华,李菁,等.氧化引起肉及肉制品品质劣变的机理及影响因素[J].食品科学,2011,32(9):319-323.
[30]袁凯,张龙,谷东陈,等.肉品中的蛋白质氧化机制及其影响因素[J].食品科学,2018,39(5):329-335.DOI:10.7506/spkx1002-6630-201805048.
[31]CHENG J H.Lipid oxidation in meat[J].Journal of Nutrition&Food Sciences,2016,6(3):494-496.DOI:10.4172/2155-9600.1000494.