甘蔗初压汁FTIR/ATR光谱分析的数学建模与稳定性
|
摘要
采用FTIR/ATR光谱和化学计量学方法,建立、优化甘蔗初压汁锤度定量分析的数学模型,并研究模型的稳定性。基于全体样品的最优单点模型预测效果给出定标和预测样品集的一种划分方法,在此基础上,分别采用单点回归、直接PLS、Savitzky-Golay平滑PLS、移动窗口PLS和等间隔移动窗口MLR方法建立定量分析的数学模型,以预测均方根误差(RMSEP)和预测相关系数(R_p)为优化目标,进行多种相关模型参数的联合优化设计,经过大量计算机数值实验,在大范围内进行模型优选,并讨论模型的稳定性。
结果表明:所采用的定标和预测样品集的划分方法具有良好的建模代表性、客观性和稳定性;Savitzky-Golay平滑可以较大提高模型的预测精度;移动窗口PLS方法可以遴选高信噪比的光谱特征波段;等间隔移动窗口MLR模型可以遴选简便有效的特征波数组合模型并具有最好的预测精度,大大降低模型的复杂性。最优模型预测效果的RMSEP、RRMSEP、R_p的值分别达到0.4690°Bx、2.38%、0.8456,为FTIR/ATR光谱技术应用于甘蔗初压汁定量分析提供优秀稳定的数学模型。
The mathematical models of quantitative analysis for Brix in sugarcane initial-pressed juice were established and optimized by FTIR/ATR spectroscopy and chemometrics method, and the stability of the models were also discussed. A sort of classified method for the calibration and prediction samples was gotten, which based on predictive effect of the best single-point model with all samples. On this condition, the calibration models were established by single-point regression, direct PLS, Savitzky-Golay smoothing PLS, moving window PLS and moving window MLR with fixed interval, respectively. The model parameters were designed according to the root-mean-square error (RMSEP) and the correlation coefficient (R_P) which were the optimum objective. Through a large number of computer experiments, we selected out the optimum models on a large scale and discussed the stability of models.
The results showed that the classified method for the calibration and prediction samples was representative, objective and stable. Savitzky-Golay smoothing method can improve model's predictive accuracy greatly. Moving window PLS method can be used to select the high Signal to Noise Ratio spectra bands. MLR method with fixed interval moving window can be used to select combination wavenumbers effectively and have the best predictive accuracy, so that the complexity of the model was reduced greatly. The RMSEP, RRMSEP and R_P for the best predictive effect of optimum models reached 0.4690°Bx, 2.38%, 0.8456, respectively. The results provided excellent and stable models for quantitative analysis Brix in sugarcane initial-pressed juice by FTIR/ATR spectroscopy technology.
结果表明:所采用的定标和预测样品集的划分方法具有良好的建模代表性、客观性和稳定性;Savitzky-Golay平滑可以较大提高模型的预测精度;移动窗口PLS方法可以遴选高信噪比的光谱特征波段;等间隔移动窗口MLR模型可以遴选简便有效的特征波数组合模型并具有最好的预测精度,大大降低模型的复杂性。最优模型预测效果的RMSEP、RRMSEP、R_p的值分别达到0.4690°Bx、2.38%、0.8456,为FTIR/ATR光谱技术应用于甘蔗初压汁定量分析提供优秀稳定的数学模型。
The mathematical models of quantitative analysis for Brix in sugarcane initial-pressed juice were established and optimized by FTIR/ATR spectroscopy and chemometrics method, and the stability of the models were also discussed. A sort of classified method for the calibration and prediction samples was gotten, which based on predictive effect of the best single-point model with all samples. On this condition, the calibration models were established by single-point regression, direct PLS, Savitzky-Golay smoothing PLS, moving window PLS and moving window MLR with fixed interval, respectively. The model parameters were designed according to the root-mean-square error (RMSEP) and the correlation coefficient (R_P) which were the optimum objective. Through a large number of computer experiments, we selected out the optimum models on a large scale and discussed the stability of models.
The results showed that the classified method for the calibration and prediction samples was representative, objective and stable. Savitzky-Golay smoothing method can improve model's predictive accuracy greatly. Moving window PLS method can be used to select the high Signal to Noise Ratio spectra bands. MLR method with fixed interval moving window can be used to select combination wavenumbers effectively and have the best predictive accuracy, so that the complexity of the model was reduced greatly. The RMSEP, RRMSEP and R_P for the best predictive effect of optimum models reached 0.4690°Bx, 2.38%, 0.8456, respectively. The results provided excellent and stable models for quantitative analysis Brix in sugarcane initial-pressed juice by FTIR/ATR spectroscopy technology.
引文
[1]潘涛,李仕萍,罗运平,黄泳,黄富荣,陈星旦.甘蔗清汁锤度的近红外光谱定量分析[M]//陆婉珍等编.当代中国近红外光谱技术.北京:中国石化出版社,2006:517-523.
[2]胡愉华,潘涛,陈星旦,梁家杰,陈华舟.甘蔗初压汁锤度近红外光谱分析的波段优选[J].光谱实验室,2009,26(1):90-95.
[3]曹干,谭中文,梁计南,龙永惠,周学秋.甘蔗品质成分的傅里叶变换近红外分析数学模型[J].中国农业科学,2003,36(3):254-258.
[4]曹干,周学秋.近红外光谱法快速测定甘蔗蔗汁蔗糖分[J].甘蔗,2001,8(3):20-25.
[5]曹干,谭中文等.甘蔗蔗汁锤度和还原糖分傅立叶变换近红外定量分析数学模型[J].华南农业大学学报(自然科学版),2004,25(2):1-4.
[6]陈洁梅,潘涛,陈星旦.二阶导数光谱预处理在用FTIR/ATR方法定量测定葡萄糖262磷酸和果糖262磷酸中的应用[J].光学精密工程,2006,14(1):1-7.
[7]潘涛,陈洁梅.解离性代谢物和pH值同时定量分析的FTIR/ATR光谱方法[J].光谱学与光谱分析,2008,28(10):31-32.
[8]尹浩,潘涛,田佩玲等.FTIR/ATR光谱应用于人体血液血红蛋白的快速定量分析[J].光谱实验室,2009,26(2):431-436.
[9]Hao Yin,Tao Pan,et al.A Simultaneous Quantification Method of Thalassemia Screening Multiple Indicators Using FTIR/ATR Spectroscopy[J].Accepted by The Proceedings of The International Symposium on Photonics and Optoelectronics,2009.
[10]Mirabella FM and Harrick NJ.Internal Reflection Spectroscopy:Review and Supplement[M].New York:Harrick Scientific Corporation,1985.
[11]Wilson R H.Fourier Transform Mid-infrared Spectroscopy for Food Analysis[J].Trends in Analyical Chemistry,1990,9:127-131.
[12]Nakanishi K,Hashimoto A,Pan T,et al.Mid-infrared Spectroscopic Measurement of Ionic Dissociative Materials in Metabolic Pathway[J].Applied Spectroscopy,2003,57(12):1510-1516.
[13]Pan T,Hashimoto A,Kanou M,etal.Development of a quantification system of ionic dissociative metabolites using an FTIR/ATR method[J].Bioprocess and Biosystems Engineering,2003,26(2):133-139.
[14]Axelsen PH,Braddock WD,Brockman HL,etal.Use of internal reflectance infrared spectroscopy for in situ study of supported lipid monolayers[J].Applied Spectroscopy,1995,49(5):526-531.
[15]Fujii T,Miyahara Y.Infrared ATR Spectroscopy of Substrates in Aqueous Solution Using Cryoenrichment and its Application in Enzyme-activity Assays[J].Applied Spectroscopy,1998,52(2):128-133.
[16]Savitzky A,Golay M J E.Smoothing and Differentiation of Data by Simplified Least Squares Procedures[J].Analytical Chemistry,1964,36:1627-1637.
[17]陆婉珍.现代近红外光谱分析技术[M].中国石化出版社,2007.
[18]邵学广,蔡文生.化学信息学[M].科学出版社,2001.
[19]许禄,邵学广.化学计量学方法[M].科学出版社,2004.
[20]曹璞,潘涛,陈星旦.小型近红外玉米蛋白质成分分析仪器设计的波段选择[J].光学精密工程,2007,15(12):1952-1958.
[21]潘涛,罗运平,陈星旦,谢军,梁家杰,胡愉华.人体血糖近红外光谱分析的等间隔波数组合的优选[C]//当代中国近红外光谱技术—全国第二届近红外光谱会议论文集.湖南,长沙,2008:663-667.
[22]赵强,张工力,陈星旦.多元散射校正对近红外光谱分析定标模型的影响[J].光学精密工程,2007,15(12):1946-1951.
[23]G Haberhauer,B Feigl,M H Gerzabek and C Cerri.FTIR Spectroscopy of Organic Matter in Tropical Soils,Changes induced through Deforestation[J].Appl Spectrosc,2000,54(2):221-224.
[24]James B Reeves,Ⅲ,Gregory W McCarty,Valerie B.Reeves.Mid-infrared Diffuse Reflectance Spectroscopy for the Quantitative Analysis of Agricultural Soils[J].J Agric Food Chem,2001,49:766-772.
[25]Gei Adi P,Macdougalld,Martens H.Linearization and Scatter-Correction for Near Infrared Reflectance Spectra of Meat[J].Appl Spectrosc,1985,39(3):491-500.
[26]Burns D A,Ciurczak E W.Handbook of Near-Infrared Analysis,Second Edition,Revised and Expanded[M].New York:Marcel Dekker,Inc,2001.
[27]Kim Y J,and Yoon G.Multicomponent Assay for Human Serum Using Mid-infrared Transmission Spectroscopy based on Component-optimized Spectral Region Selected by a first Loding Vector Analysis in Partial Lsast-squares Regression[J].Applied spectroscopy,2002,56(5):625-632..
[28]Peter Snoer Jensen,Jimmy Bak,Stefan Andersson-engels.Infreuence of Temperature on Water and Aqueous Glucose Absorption Spectra in the Near and Mid-infrared Regions at Physiologically Relevant Temperatures[J].Appl Spectrosc,2003,57(1):28-36.
[29]Rai S Kookana,Les J Janik,Mohsen Forouzangohar,Sean T Forrester.Prediction of Atrazine Sorption Coefficients in Soils using Mid-infrared Spectroscopy and Partial Least-squares Analysis[J].JAgric Food Chem,2008,56:3208-3213.
[30]James B Reeves,Ⅲ,Gregory W McCarty,David W Rutherford,Robert L Wershaw.Mid-infrared Diffuse Reflectance Spectroscopic Examination of Charred Pine Wood,Bark,Cellulose,and Lignin,Implications for the Quantitative Determination of Charcoal in Soils [J].Appl Spectrosc,2008,62(2):182-189.
[31]Raphael Linker and Leah Tsror (Lahkim).Discrimination of Soil-borne Fungi Using Fourier Ransform Infrared Attenuated Total Reflection Pectroscopy[J].Appl Spectrosc,2008,62(3):302-305.
[32]Raphael Linker,Amit Kenny,Avi Shaviv,Liviu Singher,Itzhak Shmulevich.Fourier Transform Infrared-attenuated Total Reflection Nitrate Determination of Soil Pastes Using Principal Component Regression,Partial Least Squares,and Cross-correlation [J].Appl Spectrosc,2004,58(5):516-520.
[2]胡愉华,潘涛,陈星旦,梁家杰,陈华舟.甘蔗初压汁锤度近红外光谱分析的波段优选[J].光谱实验室,2009,26(1):90-95.
[3]曹干,谭中文,梁计南,龙永惠,周学秋.甘蔗品质成分的傅里叶变换近红外分析数学模型[J].中国农业科学,2003,36(3):254-258.
[4]曹干,周学秋.近红外光谱法快速测定甘蔗蔗汁蔗糖分[J].甘蔗,2001,8(3):20-25.
[5]曹干,谭中文等.甘蔗蔗汁锤度和还原糖分傅立叶变换近红外定量分析数学模型[J].华南农业大学学报(自然科学版),2004,25(2):1-4.
[6]陈洁梅,潘涛,陈星旦.二阶导数光谱预处理在用FTIR/ATR方法定量测定葡萄糖262磷酸和果糖262磷酸中的应用[J].光学精密工程,2006,14(1):1-7.
[7]潘涛,陈洁梅.解离性代谢物和pH值同时定量分析的FTIR/ATR光谱方法[J].光谱学与光谱分析,2008,28(10):31-32.
[8]尹浩,潘涛,田佩玲等.FTIR/ATR光谱应用于人体血液血红蛋白的快速定量分析[J].光谱实验室,2009,26(2):431-436.
[9]Hao Yin,Tao Pan,et al.A Simultaneous Quantification Method of Thalassemia Screening Multiple Indicators Using FTIR/ATR Spectroscopy[J].Accepted by The Proceedings of The International Symposium on Photonics and Optoelectronics,2009.
[10]Mirabella FM and Harrick NJ.Internal Reflection Spectroscopy:Review and Supplement[M].New York:Harrick Scientific Corporation,1985.
[11]Wilson R H.Fourier Transform Mid-infrared Spectroscopy for Food Analysis[J].Trends in Analyical Chemistry,1990,9:127-131.
[12]Nakanishi K,Hashimoto A,Pan T,et al.Mid-infrared Spectroscopic Measurement of Ionic Dissociative Materials in Metabolic Pathway[J].Applied Spectroscopy,2003,57(12):1510-1516.
[13]Pan T,Hashimoto A,Kanou M,etal.Development of a quantification system of ionic dissociative metabolites using an FTIR/ATR method[J].Bioprocess and Biosystems Engineering,2003,26(2):133-139.
[14]Axelsen PH,Braddock WD,Brockman HL,etal.Use of internal reflectance infrared spectroscopy for in situ study of supported lipid monolayers[J].Applied Spectroscopy,1995,49(5):526-531.
[15]Fujii T,Miyahara Y.Infrared ATR Spectroscopy of Substrates in Aqueous Solution Using Cryoenrichment and its Application in Enzyme-activity Assays[J].Applied Spectroscopy,1998,52(2):128-133.
[16]Savitzky A,Golay M J E.Smoothing and Differentiation of Data by Simplified Least Squares Procedures[J].Analytical Chemistry,1964,36:1627-1637.
[17]陆婉珍.现代近红外光谱分析技术[M].中国石化出版社,2007.
[18]邵学广,蔡文生.化学信息学[M].科学出版社,2001.
[19]许禄,邵学广.化学计量学方法[M].科学出版社,2004.
[20]曹璞,潘涛,陈星旦.小型近红外玉米蛋白质成分分析仪器设计的波段选择[J].光学精密工程,2007,15(12):1952-1958.
[21]潘涛,罗运平,陈星旦,谢军,梁家杰,胡愉华.人体血糖近红外光谱分析的等间隔波数组合的优选[C]//当代中国近红外光谱技术—全国第二届近红外光谱会议论文集.湖南,长沙,2008:663-667.
[22]赵强,张工力,陈星旦.多元散射校正对近红外光谱分析定标模型的影响[J].光学精密工程,2007,15(12):1946-1951.
[23]G Haberhauer,B Feigl,M H Gerzabek and C Cerri.FTIR Spectroscopy of Organic Matter in Tropical Soils,Changes induced through Deforestation[J].Appl Spectrosc,2000,54(2):221-224.
[24]James B Reeves,Ⅲ,Gregory W McCarty,Valerie B.Reeves.Mid-infrared Diffuse Reflectance Spectroscopy for the Quantitative Analysis of Agricultural Soils[J].J Agric Food Chem,2001,49:766-772.
[25]Gei Adi P,Macdougalld,Martens H.Linearization and Scatter-Correction for Near Infrared Reflectance Spectra of Meat[J].Appl Spectrosc,1985,39(3):491-500.
[26]Burns D A,Ciurczak E W.Handbook of Near-Infrared Analysis,Second Edition,Revised and Expanded[M].New York:Marcel Dekker,Inc,2001.
[27]Kim Y J,and Yoon G.Multicomponent Assay for Human Serum Using Mid-infrared Transmission Spectroscopy based on Component-optimized Spectral Region Selected by a first Loding Vector Analysis in Partial Lsast-squares Regression[J].Applied spectroscopy,2002,56(5):625-632..
[28]Peter Snoer Jensen,Jimmy Bak,Stefan Andersson-engels.Infreuence of Temperature on Water and Aqueous Glucose Absorption Spectra in the Near and Mid-infrared Regions at Physiologically Relevant Temperatures[J].Appl Spectrosc,2003,57(1):28-36.
[29]Rai S Kookana,Les J Janik,Mohsen Forouzangohar,Sean T Forrester.Prediction of Atrazine Sorption Coefficients in Soils using Mid-infrared Spectroscopy and Partial Least-squares Analysis[J].JAgric Food Chem,2008,56:3208-3213.
[30]James B Reeves,Ⅲ,Gregory W McCarty,David W Rutherford,Robert L Wershaw.Mid-infrared Diffuse Reflectance Spectroscopic Examination of Charred Pine Wood,Bark,Cellulose,and Lignin,Implications for the Quantitative Determination of Charcoal in Soils [J].Appl Spectrosc,2008,62(2):182-189.
[31]Raphael Linker and Leah Tsror (Lahkim).Discrimination of Soil-borne Fungi Using Fourier Ransform Infrared Attenuated Total Reflection Pectroscopy[J].Appl Spectrosc,2008,62(3):302-305.
[32]Raphael Linker,Amit Kenny,Avi Shaviv,Liviu Singher,Itzhak Shmulevich.Fourier Transform Infrared-attenuated Total Reflection Nitrate Determination of Soil Pastes Using Principal Component Regression,Partial Least Squares,and Cross-correlation [J].Appl Spectrosc,2004,58(5):516-520.