白酒基酒中典型醇的近红外预测模型构建
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摘要
采用气相色谱法测定白酒基酒中的正丙醇、正丁醇、正戊醇和异戊醇的含量作为建立近红外预测模型的化学值,将近红外光谱图结合偏最小二乘法和内部交互验证法建立基酒中典型醇的快速检测模型,并进一步优化模型。确定了最优光谱预处理方法和最佳谱区,正丙醇、正丁醇、正戊醇和异戊醇的校正集样品的真实值与近红外预测值的决定系数(R~2)分别为0.952、0.981、0.963和0.981,内部交互验证均方根误差分别为0.27、0.49、0.101 mg/100 mL和0.67 mg/100 mL;验证集的决定系数(R~2)分别为0.947、0.980、0.928和0.952,预测均方根误差分别为0.40、0.81、0.49 mg/100 mL和1.35 mg/100 mL。结果表明建立的典型醇近红外快速检测模型的准确度、稳定性及预测性能均呈现良好,为白酒基酒的醇类物质品质分析方法研究提供了新的思路。
In this paper,the contents of n-propanol,n-butanol,amyl alcohol and isoamyl alcohol in base liquor were determined by gas chromatography and used as chemical values for the establishment of calibration and validation sets for a rapid predictive model based on near infrared spectroscopy(NIR) to measure typical alcohols in base liquor.The model was developed using partial least squares(PLS) regression with internal cross validation and optimized.The optimal spectral pretreatment method and the optimal spectral region were determined.The coefficients of determination(R~2) between the actual and the NIR predicted values of n-propanol,n-butanol,amyl alcohol and isoamyl alcohol for the calibration set were 0.952,0.981,0.963 and 0.981,and the root mean square error of cross-validation(RMSECV) were 0.27,0.49,0.101 and 0.67 mg/100 mL,respectively; the R~2 values for the validation set were 0.947,0.980,0.928 and 0.952,and RMSEPs were 0.40,0.81,0.49 and 1.35 mg/100 mL,respectively.Results showed that the predictive model exhibited good accuracy,stability and prediction performance and could provide a new approach for the analysis of alcohols in base liquor.
In this paper,the contents of n-propanol,n-butanol,amyl alcohol and isoamyl alcohol in base liquor were determined by gas chromatography and used as chemical values for the establishment of calibration and validation sets for a rapid predictive model based on near infrared spectroscopy(NIR) to measure typical alcohols in base liquor.The model was developed using partial least squares(PLS) regression with internal cross validation and optimized.The optimal spectral pretreatment method and the optimal spectral region were determined.The coefficients of determination(R~2) between the actual and the NIR predicted values of n-propanol,n-butanol,amyl alcohol and isoamyl alcohol for the calibration set were 0.952,0.981,0.963 and 0.981,and the root mean square error of cross-validation(RMSECV) were 0.27,0.49,0.101 and 0.67 mg/100 mL,respectively; the R~2 values for the validation set were 0.947,0.980,0.928 and 0.952,and RMSEPs were 0.40,0.81,0.49 and 1.35 mg/100 mL,respectively.Results showed that the predictive model exhibited good accuracy,stability and prediction performance and could provide a new approach for the analysis of alcohols in base liquor.
引文
[1]FAN W,QIAN M C.Characterization of aroma compounds of Chinese“Wuliangye”and“Jiannanchun”liquors by aroma extract dilution analysis[J].Journal of Agricultural&Food Chemistry,2006,54(7):2695-2704.DOI:10.1021/jf052635t.
[2]ZHU S,LU X,JI K,et al.Characterization of flavor compounds in Chinese liquor Moutai by comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry[J].Analytica Chimica Acta,2007,597(2):340-348.DOI:10.1016/j.aca.2007.07.007.
[3]FAN W,XU Y,QIAN M C.Identification of aroma compounds in Chinese“Moutai”and“Langjiu”liquors by normal phase liquid chromatography fractionation followed by gas chromatography/olfactometry[J].Flavor Chemistry of Wine and Other Alcoholic Beverages,2012,1104:303-308.DOI:10.1021/bk-2012-1104.ch017.
[4]刘明,刘传贺,吕志远,等.白酒产品关键感官特征与质量性价比研究[J].食品安全质量检测学报,2016,7(3):1102-1108.
[5]范文来,徐岩.白酒风味物质研究方法的回顾与展望[J].食品安全质量检测学报,2014,5(10):3073-3078.
[6]罗杰,敖宗华,王松涛,等.浓香型白酒不同类别基酒中杂醇油相关性研究[J].酿酒科技,2015(1):43-44.
[7]陆婉珍,袁洪福,徐广通.现代近红外光谱分析技术[M].北京:中国石化出版社,2000.
[8]余丽娟,郑建明,朱文雷.傅里叶变换红外光谱法测定白酒中乙醇含量[J].广州化工,2011,39(4):112-113.DOI:10.3969/j.issn.1001-9677.2011.04.041.
[9]VERSARI A,LAGHI L,THORNGATE J H,et al.Prediction of colloidal stability in white wines using infrared spectroscopy[J].Journal of Food Engineering,2011,104(2):239-245.DOI:10.1016/j.jfoodeng.2010.12.015.
[10]苟静瑜,贾智勇,闫宗科,等.降低白酒中高级醇含量的研究进展[J].酿酒,2016,43(4):25-29.DOI:10.3969/j.issn.1002-8110.2016.04.006.
[11]GAO W,FAN W,XU Y.Characterization of the key odorants in light aroma type Chinese liquor by gas chromatography-olfactometry,quantitative measurements,aroma recombination,and omission studies[J].Journal of Agricultural&Food Chemistry,2014,62(25):5796-5804.DOI:10.1021/jf501214c.
[12]姚晶,王海瑞,姚丽萍.毛细管柱气相色谱外标法测定白酒中的醇类和己酸乙酯[J].西南农业学报,2013,26(4):1674-1676.
[13]ZHONG J,QIN X.Rapid quantitative analysis of corn starch adulteration in konjac glucomannan by chemometrics-assisted FTNIR spectroscopy[J].Food Analytical Methods,2016,9(1):61-67.DOI:10.1007/s12161-015-0176-9.
[14]JIANG H,LIU G,XIAO X,et al.Classification of Chinese soybean paste by Fourier transform near-infrared(FT-NIR)spectroscopy and different supervised pattern recognition[J].Food Analytical Methods,2012,5(4):928-934.DOI:10.1007/s12161-011-9331-0.
[15]邓波,沈才洪,敖宗华,等.基于主成分分析与近红外光谱技术的窖泥聚类研究[J].酿酒科技,2011(8):36-38.
[16]熊雅婷,李宗朋,王健,等.近红外光谱波段优化在白酒酒醅成分分析中的应用[J].光谱学与光谱分析,2016,36(1):84-90.
[17]SMYTH H E,COZZOLINO D,CYNKAR W U,et al.Near infrared spectroscopy as a rapid tool to measure volatile aroma compounds in riesling wine:possibilities and limits[J].Analytical and Bioanalytical Chemistry,2008,390(7):1911-1916.DOI:10.1007/s00216-008-1940-0.
[18]许家胜,张杰.近红外光谱法测定柴油硫含量方法研究[J].化学研究与应用,2013,25(3):355-358.DOI:10.3969/j.issn.1004-1656.2013.03.017.
[19]丁美珍,宋岑,胡志明.近红外光谱技术在酒类产品分析中的应用[J].酿酒科技,2013(4):68-70.DOI:10.3969/j.issn.1001-9286.2005.08.020.
[20]吴同,谭超.近红外光谱同时测定白酒中总酯和杂醇油[J].化学研究与应用,2016(10):1460-1463.DOI:10.3969/j.issn.1004-1656.2016.10.017.
[21]周杨,刘杰,王纪元.中国酿酒行业中近红外光谱技术的应用进展[J].食品安全质量检测学报,2014,5(4):1100-1104.
[22]CAI J J.Computer note:PGEToo Ibox:a Matlab toolbox for population genetics and evolution[J].Journal of Heredity,2008,99(4):438-440.DOI:10.1093/jhered/esm127.
[23]王豪,邬蓓蕾,林振兴,等.傅立叶变换近红外光谱法快速测定葡萄酒中的酒精度[J].中国酿造,2008,27(7):72-74.DOI:10.3969/j.issn.0254-5071.2008.04.024.
[24]李军会.现代近红外光谱分析的信息处理技术[J].光谱学与光谱分析,2000,20(6):777-780.DOI:10.3964/j.is sn.1000-0593(2009)10-2646-05.
[25]李水芳,单杨,朱向荣,等.近红外光谱结合化学计量学方法检测蜂蜜产地[J].农业工程学报,2011,27(8):350-354.DOI:10.3969/j.issn.1002-6819.2011.08.061.
[26]FAN W,SHEN H,XU Y.Quantification of volatile compounds in Chinese soy sauce aroma type liquor by stir bar sorptive extraction and gas chromatography-mass spectrometry[J].Journal of the Science of Food and Agriculture,2011,91(7):1187-1198.
[27]彭帮柱,龙明华,岳田利,等.傅立叶变换近红外光谱法检测白酒总酸和总酯[J].农业工程学报,2006,22(12):216-219.DOI:10.3321/j.issn:1002-6819.2006.12.045.
[28]王动民,纪俊敏,高洪智.多元散射校正预处理波段对近红外光谱定标模型的影响[J].光谱学与光谱分析,2014,34(9):2387-2390.DOI:10.3964/j.issn.1000-0593(2014)09-2387-04.
[29]ZHANG C,XU N,LUO L,et al.Detection of aspartic acid in fermented cordyceps powder using near infrared spectroscopy based on variable selection algorithms and multivariate calibration methods[J].Food and Bioprocess Technology,2014,7(2):598-604.DOI:10.1007/s11947-013-1149-x.
[30]SHEN F,YANG D,YING Y,et al.Discrimination between shaoxing wines and other Chinese rice wines by near-infrared spectroscopy and chemometrics[J].Food and Bioprocess Technology,2012,5(2):786-795.DOI:10.1007/s11947-010-0347-z.
[2]ZHU S,LU X,JI K,et al.Characterization of flavor compounds in Chinese liquor Moutai by comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry[J].Analytica Chimica Acta,2007,597(2):340-348.DOI:10.1016/j.aca.2007.07.007.
[3]FAN W,XU Y,QIAN M C.Identification of aroma compounds in Chinese“Moutai”and“Langjiu”liquors by normal phase liquid chromatography fractionation followed by gas chromatography/olfactometry[J].Flavor Chemistry of Wine and Other Alcoholic Beverages,2012,1104:303-308.DOI:10.1021/bk-2012-1104.ch017.
[4]刘明,刘传贺,吕志远,等.白酒产品关键感官特征与质量性价比研究[J].食品安全质量检测学报,2016,7(3):1102-1108.
[5]范文来,徐岩.白酒风味物质研究方法的回顾与展望[J].食品安全质量检测学报,2014,5(10):3073-3078.
[6]罗杰,敖宗华,王松涛,等.浓香型白酒不同类别基酒中杂醇油相关性研究[J].酿酒科技,2015(1):43-44.
[7]陆婉珍,袁洪福,徐广通.现代近红外光谱分析技术[M].北京:中国石化出版社,2000.
[8]余丽娟,郑建明,朱文雷.傅里叶变换红外光谱法测定白酒中乙醇含量[J].广州化工,2011,39(4):112-113.DOI:10.3969/j.issn.1001-9677.2011.04.041.
[9]VERSARI A,LAGHI L,THORNGATE J H,et al.Prediction of colloidal stability in white wines using infrared spectroscopy[J].Journal of Food Engineering,2011,104(2):239-245.DOI:10.1016/j.jfoodeng.2010.12.015.
[10]苟静瑜,贾智勇,闫宗科,等.降低白酒中高级醇含量的研究进展[J].酿酒,2016,43(4):25-29.DOI:10.3969/j.issn.1002-8110.2016.04.006.
[11]GAO W,FAN W,XU Y.Characterization of the key odorants in light aroma type Chinese liquor by gas chromatography-olfactometry,quantitative measurements,aroma recombination,and omission studies[J].Journal of Agricultural&Food Chemistry,2014,62(25):5796-5804.DOI:10.1021/jf501214c.
[12]姚晶,王海瑞,姚丽萍.毛细管柱气相色谱外标法测定白酒中的醇类和己酸乙酯[J].西南农业学报,2013,26(4):1674-1676.
[13]ZHONG J,QIN X.Rapid quantitative analysis of corn starch adulteration in konjac glucomannan by chemometrics-assisted FTNIR spectroscopy[J].Food Analytical Methods,2016,9(1):61-67.DOI:10.1007/s12161-015-0176-9.
[14]JIANG H,LIU G,XIAO X,et al.Classification of Chinese soybean paste by Fourier transform near-infrared(FT-NIR)spectroscopy and different supervised pattern recognition[J].Food Analytical Methods,2012,5(4):928-934.DOI:10.1007/s12161-011-9331-0.
[15]邓波,沈才洪,敖宗华,等.基于主成分分析与近红外光谱技术的窖泥聚类研究[J].酿酒科技,2011(8):36-38.
[16]熊雅婷,李宗朋,王健,等.近红外光谱波段优化在白酒酒醅成分分析中的应用[J].光谱学与光谱分析,2016,36(1):84-90.
[17]SMYTH H E,COZZOLINO D,CYNKAR W U,et al.Near infrared spectroscopy as a rapid tool to measure volatile aroma compounds in riesling wine:possibilities and limits[J].Analytical and Bioanalytical Chemistry,2008,390(7):1911-1916.DOI:10.1007/s00216-008-1940-0.
[18]许家胜,张杰.近红外光谱法测定柴油硫含量方法研究[J].化学研究与应用,2013,25(3):355-358.DOI:10.3969/j.issn.1004-1656.2013.03.017.
[19]丁美珍,宋岑,胡志明.近红外光谱技术在酒类产品分析中的应用[J].酿酒科技,2013(4):68-70.DOI:10.3969/j.issn.1001-9286.2005.08.020.
[20]吴同,谭超.近红外光谱同时测定白酒中总酯和杂醇油[J].化学研究与应用,2016(10):1460-1463.DOI:10.3969/j.issn.1004-1656.2016.10.017.
[21]周杨,刘杰,王纪元.中国酿酒行业中近红外光谱技术的应用进展[J].食品安全质量检测学报,2014,5(4):1100-1104.
[22]CAI J J.Computer note:PGEToo Ibox:a Matlab toolbox for population genetics and evolution[J].Journal of Heredity,2008,99(4):438-440.DOI:10.1093/jhered/esm127.
[23]王豪,邬蓓蕾,林振兴,等.傅立叶变换近红外光谱法快速测定葡萄酒中的酒精度[J].中国酿造,2008,27(7):72-74.DOI:10.3969/j.issn.0254-5071.2008.04.024.
[24]李军会.现代近红外光谱分析的信息处理技术[J].光谱学与光谱分析,2000,20(6):777-780.DOI:10.3964/j.is sn.1000-0593(2009)10-2646-05.
[25]李水芳,单杨,朱向荣,等.近红外光谱结合化学计量学方法检测蜂蜜产地[J].农业工程学报,2011,27(8):350-354.DOI:10.3969/j.issn.1002-6819.2011.08.061.
[26]FAN W,SHEN H,XU Y.Quantification of volatile compounds in Chinese soy sauce aroma type liquor by stir bar sorptive extraction and gas chromatography-mass spectrometry[J].Journal of the Science of Food and Agriculture,2011,91(7):1187-1198.
[27]彭帮柱,龙明华,岳田利,等.傅立叶变换近红外光谱法检测白酒总酸和总酯[J].农业工程学报,2006,22(12):216-219.DOI:10.3321/j.issn:1002-6819.2006.12.045.
[28]王动民,纪俊敏,高洪智.多元散射校正预处理波段对近红外光谱定标模型的影响[J].光谱学与光谱分析,2014,34(9):2387-2390.DOI:10.3964/j.issn.1000-0593(2014)09-2387-04.
[29]ZHANG C,XU N,LUO L,et al.Detection of aspartic acid in fermented cordyceps powder using near infrared spectroscopy based on variable selection algorithms and multivariate calibration methods[J].Food and Bioprocess Technology,2014,7(2):598-604.DOI:10.1007/s11947-013-1149-x.
[30]SHEN F,YANG D,YING Y,et al.Discrimination between shaoxing wines and other Chinese rice wines by near-infrared spectroscopy and chemometrics[J].Food and Bioprocess Technology,2012,5(2):786-795.DOI:10.1007/s11947-010-0347-z.