近红外光谱扣除背景误差的研究
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摘要
在近红外光谱分析技术中,影响近红外光谱的因素很多,如被测样品的组分之间的相互作用、光谱仪的影响等,这些因素在很大程度上破坏样品的光谱,必须将这些影响光谱测量的背景因素进行扣除,以提高光谱测量的准确性,从而保证校正模型的适用性和稳健性。本文通过对葡萄糖水溶液、牛奶溶液以及人体血糖进行近红外光谱检测的实验分析,对扣除背景误差方法的适用性进行研究。
论文的主要研究内容包括:
1.扣除背景方法原理及分析。首先介绍了近红外光谱测量原理;然后从双光路补偿和扣标准液方法上对扣除背景方法的原理进行介绍;最后介绍了近红外光谱的多元数据分析方法:多元线性回归(MLR)、主成分回归(PCR)以及偏最小二乘(PLS),并给出了校正模型的评价指标。
2.扣除背景方法在葡萄糖水溶液中的实验研究。实验结果表明:扣除水背景的影响后,模型的建模精度提高了37.9%,预测精度提高了22.5%。因此,在糖水溶液中采用扣除水背景的方法能够有效的消除一部分仪器漂移以及水的强吸收带来的影响,提高了近红外光谱测量的精度。
3.扣除背景方法在牛奶溶液中的实验研究。实验结果表明:扣除背景的方法在测量牛奶中的脂肪和蛋白浓度时,并不能够有效地扣除牛奶中其他成分相互干扰误差的影响,提高测量的精度。但是,在测量牛奶中的葡萄糖浓度时,扣除纯牛奶背景的影响后,模型的建模精度提高了26.2%,预测精度提高了68.4%。因此,在牛奶溶液中采用扣除纯牛奶背景的方法测量牛奶中的葡萄糖浓度,能够有效的消除牛奶中其他成分干扰误差的影响,提高了近红外光谱测量的精度。
4.扣除背景方法在人体血糖无创检测中的实验研究。OGTT实验结果表明:扣除背景后,模型的建模精度和预测精度都没有得到提高。因此,在人体血糖无创伤检测中,寻找一种合适的标准物作为背景以消除仪器漂移的影响,成为下一步工作的重点。
During the near-infrared spectroscopy analysis, the reciprocity of thecomponent in the sample and the influence of the spectrum instrument willdestroy the spectrum of the sample. So they must be deducted to increase theveracity of the spectrum measurement. This will ensure the suitability androbustness of the calibration models. In the dissertation, the method of deductingbackground error is studied by the experiment of aqueous matrix、milk andblood glucose of the body.
The main research content of the dissertation involves:
Firstly, the principle of the method of deducting background error isintroduced. First of all, the principle of near-infrared spectrum measurement isintroduced;then the principle of the method of deducting background error isintroduced by the compensation of both light-paths and deducting the standardsolution;the methods of multi-date analysis are introduced: the MultivariateLinear Regression, Principle Component Analysis and Partial Least Squire. Theevaluating guidelines of the calibration models are also presented.
Secondly, the suitability of the method of deducting background error in theaqueous matrix is studied. The results show that the modeling precisions ofanalytical model have raised 37.9% and the predictable precisions have raised22.5% after deducting the background error of water. So deducting thebackground error in the aqueous matrix to eliminate partially influences of theexcursion to the instrument and the strong absorption of water raises theprecision of near-infrared spectrum measurement.
Thirdly, the suitability of the method of deducting background error in themilk is studied. The results show that the method of deducting background errorcannot deduct effectively the error of the reciprocity of the other components ofthe milk when measuring the fat and the protein in the milk. But when measuringthe glucose in the milk, the modeling precisions of glucose model have raised26.2% and the predictable precisions have raised 68.4% after deducting the
background error of pure milk. So deducting the pure milk background errorwhen measuring the glucose in the milk can deduct effectively the error of thereciprocity of the other components of the milk and raises the precision of near-infrared spectrum measurement.Lastly, the suitability o the method of deducting background error in theblood glucose of the body measurement is studied. The OGTT result shows thatthe modeling and predictable precisions of analytical model aren't raisedobviously after deducting from the background. So looking for a suitablestandard matter as background to eliminate partially influence of the excursion tothe instrument is important for the noninvasive monitoring of the blood glucose.
论文的主要研究内容包括:
1.扣除背景方法原理及分析。首先介绍了近红外光谱测量原理;然后从双光路补偿和扣标准液方法上对扣除背景方法的原理进行介绍;最后介绍了近红外光谱的多元数据分析方法:多元线性回归(MLR)、主成分回归(PCR)以及偏最小二乘(PLS),并给出了校正模型的评价指标。
2.扣除背景方法在葡萄糖水溶液中的实验研究。实验结果表明:扣除水背景的影响后,模型的建模精度提高了37.9%,预测精度提高了22.5%。因此,在糖水溶液中采用扣除水背景的方法能够有效的消除一部分仪器漂移以及水的强吸收带来的影响,提高了近红外光谱测量的精度。
3.扣除背景方法在牛奶溶液中的实验研究。实验结果表明:扣除背景的方法在测量牛奶中的脂肪和蛋白浓度时,并不能够有效地扣除牛奶中其他成分相互干扰误差的影响,提高测量的精度。但是,在测量牛奶中的葡萄糖浓度时,扣除纯牛奶背景的影响后,模型的建模精度提高了26.2%,预测精度提高了68.4%。因此,在牛奶溶液中采用扣除纯牛奶背景的方法测量牛奶中的葡萄糖浓度,能够有效的消除牛奶中其他成分干扰误差的影响,提高了近红外光谱测量的精度。
4.扣除背景方法在人体血糖无创检测中的实验研究。OGTT实验结果表明:扣除背景后,模型的建模精度和预测精度都没有得到提高。因此,在人体血糖无创伤检测中,寻找一种合适的标准物作为背景以消除仪器漂移的影响,成为下一步工作的重点。
During the near-infrared spectroscopy analysis, the reciprocity of thecomponent in the sample and the influence of the spectrum instrument willdestroy the spectrum of the sample. So they must be deducted to increase theveracity of the spectrum measurement. This will ensure the suitability androbustness of the calibration models. In the dissertation, the method of deductingbackground error is studied by the experiment of aqueous matrix、milk andblood glucose of the body.
The main research content of the dissertation involves:
Firstly, the principle of the method of deducting background error isintroduced. First of all, the principle of near-infrared spectrum measurement isintroduced;then the principle of the method of deducting background error isintroduced by the compensation of both light-paths and deducting the standardsolution;the methods of multi-date analysis are introduced: the MultivariateLinear Regression, Principle Component Analysis and Partial Least Squire. Theevaluating guidelines of the calibration models are also presented.
Secondly, the suitability of the method of deducting background error in theaqueous matrix is studied. The results show that the modeling precisions ofanalytical model have raised 37.9% and the predictable precisions have raised22.5% after deducting the background error of water. So deducting thebackground error in the aqueous matrix to eliminate partially influences of theexcursion to the instrument and the strong absorption of water raises theprecision of near-infrared spectrum measurement.
Thirdly, the suitability of the method of deducting background error in themilk is studied. The results show that the method of deducting background errorcannot deduct effectively the error of the reciprocity of the other components ofthe milk when measuring the fat and the protein in the milk. But when measuringthe glucose in the milk, the modeling precisions of glucose model have raised26.2% and the predictable precisions have raised 68.4% after deducting the
background error of pure milk. So deducting the pure milk background errorwhen measuring the glucose in the milk can deduct effectively the error of thereciprocity of the other components of the milk and raises the precision of near-infrared spectrum measurement.Lastly, the suitability o the method of deducting background error in theblood glucose of the body measurement is studied. The OGTT result shows thatthe modeling and predictable precisions of analytical model aren't raisedobviously after deducting from the background. So looking for a suitablestandard matter as background to eliminate partially influence of the excursion tothe instrument is important for the noninvasive monitoring of the blood glucose.
引文
[1] Stark E., Luchter K., Near-Infrared Analysis:A Technology for Qantitative and Qanlititive Analysis, Applied Spectroscopy Review, 1986, 22 (4): 335～339
[2] 中华人民共和国国家技术监督局,GB 8322-87,中华人民共和国国家标准—分子吸收光谱法术语,北京:中国标准出版社,1987
[3] 中华人民共和国国家技术监督局,GB 9721-88,中华人民共和国国家标准—分子吸收分光光度法通则(紫外和可见光部分),北京:中国标准出版社,1984
[4] 吴瑾光,近代博里叶变换红外光谱技术及应用(上卷),北京:科学技术文献出版社,1994,251~281
[5] Herschel W., Investigation of the Powers of the prismatic Colours to heat and illuminate Objects;with Remarks that prove the different Refrangibility of radiant Heat. To which is added an Inquiry into the Method of viewing the Sun advantageously with Telescopes of large Apertures and high magnifying Powers, Philosophical Transactions, 1800, 90:255～326
[6] Abney W., Festing, E. R., On the Influence of the Atomic Grouping in the Molecules of Organic Bodies on their Absorption in the Infra-Red Region of the Spectrum, Philosophical Transactions, 1881, 172: 887
[7] F.S.Brackett, Proc. Natl. Acad. Sci. 1928,14:857
[8] W. Kaye, Theory and principles of near infrared spectroscopy, Spectrochim Acta, 1955, 7:181
[9] Ben-Gera I., K.H. Norris, Direct spectrophotometric determination of fat and moisture in meat products, Journal Food Science, 1968, 33:64
[10] 梁逸曾,俞汝勤,分析化学手册第十分册-化学计量学,北京: 化学工业出版社,2000,207～211
[11] 李庆波,汪曣,徐可欣等,臘讨饕煞趾拷焱夤馄卓焖俨?量法,食品科学,2002,23(6):121～124
[12] Vályi-Nagy István, Kaffka Károly J., Jákó János M., et al., Application of near infrared spectroscopy to the determination of haemoglobin, Clinica Chimica Acta, 1997, 264 (1): 117～125
[13] 李庆波,徐可欣,血糖无创伤光学检测的进展,世界医疗器械,2002,8(7):56～59
[14] 陆婉珍,袁洪福,徐广通,现代近红外光谱分析技术,北京:中国石化出版社,2000.1～201
[15] 柯以侃,董慧茹,分析化学手册第三分册-光谱分析,北京:化学工业出版社,1998.176～177
[16] 沙宪政,李明菊,近红外光谱无创血糖检测技术的研究,医疗卫生装备,2003,6:29～31
[17] Ronald E. Shaffer, Gary W. Small, Mark A. Arnold, Genetic Algorithm-Based Protocol for Couping Digital Filtering and Partial Least-Squares Regression: Application to the Near-Infrared Analysis of Glucose in Biological Matrices, Analytical, Chemistry, 1996, 68(15): 2663～2675
[18] 唐国新,近红外无创伤人体血糖浓度检测中的数据预处理方法,硕士学位论文,天津大学,2003
[19] P. J. DE Groot, G. J. Postma, W. J. Melssen, et al., Influence of wavelength selection and data preprocessing on near-infrared-based classification of demolition waste, Applied Spectroscopy, 2001, 55 (2): 173～181
[20] 郭硕鸿等,电动力学,北京:人民出版社,1979. 119～142
[21] 吴瑾光等,近代傅里叶变换红外光谱技术及应用(上卷),北京:科学技术文献出版社 1994. 253～255,686～687
[22] 张玉民 戚伯云,波谱学,超星数字图书馆,1997,9(1):1～55
[23] Amerov, et al., Method and device for non-invasive blood glucose measurement, Proceedings of SPIE, 3599: 33-42, 1999
[24] Elsner P, Berardesca E, Wilhelm K P, et al. Bioengineering of the skin: skin biomechanics, CRC Press, Boca Raton, London, New York, Washington D.C., 2002.
[25] 常敏,应用红外光谱技术进行牛奶成分检测的研究,硕士学位论文,天津大学,2004
[26] 廖延彪,物理光学,电子工业出版社,1986,4(1),169～171
[27] 陈民森,陈文亮,杜振辉等,近红外无创血糖测量的研究,现代仪器,2004,10(4):38～40
[28] 倪勇,生物组织中光分布特性的理论及实验研究,博士学位论文,天津大学,2003
[29] B. Walczak, Outlier detection in multivariate calibration, Chemometrics Intell. Lab. Syst., 1995, 28:259～272
[30] Randy J. Pell, Multiple outlier detection for multivariate calibration using robust statistical techniques, Chemo metrics Intell. Lab. Syst., 2000, 52: 87～104
[31] William J. Egan, Outlier Detection in Multivariate Analytical Chemical Data, Anal. Chem., 1998, 70(11): 2372～2379
[32] 梁逸曾,白灰黑复杂多组份分析体系及其化学计量学算法,长沙:湖南科学技术出版社,1996.1～10
[33] J. Cox, Alan J. DeWeerd, Jennifer Linden,An experiment to measure Mie and Rayleigh total scattering cross sections,Am. J. Phys.2002,70(6)
[34] Michael P. Schubmehl , Mie Scattering Utilities User's Guide,2002
[35] Omar S.Khall. Spectroscopic and clinical aspects of noninvasive glucose Measurement, Clinical Chemistry, 45(2): 165～177,1999.
[36] 王惠文,偏最小二乘回归方法及其应用,北京:国防工业出版社,2000. 28～110
[37] 刘蓉,近红外光谱分析中模型优化方法的初步研究,硕士学位论文,天津大学,2003
[38] Jonas Sjoblom, Olof Svensson, Mats Josefson, et al., An evaluation of orthogonal signal correction applied to calibration transfer of near infrared spectra, Chemometricsand Intelligent Laboratory Systems, 1998, 44: 229～244
[39] Mark A.Arnold, Determination of Physiological Levels of Glucose in an Aqueous Matrix with Digitally Filtered Fourier Transform Near-Infrared Spectra, Analytical Chemistry, 1990, 62 (14): 1457～1464
[40] 欧俊豪,王家生,徐漪萍,刘嘉焜,应用概率统计(第 二版),天津大学出版社,1999,98～113, 220～223, 309～327.
[41] 于秀林,多元统计分析及程序,中国统计出版社,1993.6～28,145～172
[42] 崔继承,丁东,张洪艳等,葡萄糖溶液近红外光谱的测量与分析,光谱实验室,2003,20(2):257～259
[43] 丁东,张洪艳,王弼陡等,血浆中葡萄糖浓度的近红外光谱测量和分析,光学技术,2003,29(6):693～695
[44] 秦剑伟,中红外 ATR 光谱法测量血糖浓度的方法研究及仪器研制,硕士学位论文,天津大学,2003
[45] Kim H. ESbensen, Hit/TF, Multivariate Data Analysis-in practice. 4th Edition, CAMO ASA 2000
[46] 郭 本 恒 , 吴 昊 , 范 陈 剑 , 乳 品 化 学 , 北 京 : 中 国 轻 工 业 出 版 社,1998.1～7
[47] 蒋景英,人体内成分无创光谱检测中测量条件的研究,博士学位论文,天津大学,2002
[2] 中华人民共和国国家技术监督局,GB 8322-87,中华人民共和国国家标准—分子吸收光谱法术语,北京:中国标准出版社,1987
[3] 中华人民共和国国家技术监督局,GB 9721-88,中华人民共和国国家标准—分子吸收分光光度法通则(紫外和可见光部分),北京:中国标准出版社,1984
[4] 吴瑾光,近代博里叶变换红外光谱技术及应用(上卷),北京:科学技术文献出版社,1994,251~281
[5] Herschel W., Investigation of the Powers of the prismatic Colours to heat and illuminate Objects;with Remarks that prove the different Refrangibility of radiant Heat. To which is added an Inquiry into the Method of viewing the Sun advantageously with Telescopes of large Apertures and high magnifying Powers, Philosophical Transactions, 1800, 90:255～326
[6] Abney W., Festing, E. R., On the Influence of the Atomic Grouping in the Molecules of Organic Bodies on their Absorption in the Infra-Red Region of the Spectrum, Philosophical Transactions, 1881, 172: 887
[7] F.S.Brackett, Proc. Natl. Acad. Sci. 1928,14:857
[8] W. Kaye, Theory and principles of near infrared spectroscopy, Spectrochim Acta, 1955, 7:181
[9] Ben-Gera I., K.H. Norris, Direct spectrophotometric determination of fat and moisture in meat products, Journal Food Science, 1968, 33:64
[10] 梁逸曾,俞汝勤,分析化学手册第十分册-化学计量学,北京: 化学工业出版社,2000,207～211
[11] 李庆波,汪曣,徐可欣等,臘讨饕煞趾拷焱夤馄卓焖俨?量法,食品科学,2002,23(6):121～124
[12] Vályi-Nagy István, Kaffka Károly J., Jákó János M., et al., Application of near infrared spectroscopy to the determination of haemoglobin, Clinica Chimica Acta, 1997, 264 (1): 117～125
[13] 李庆波,徐可欣,血糖无创伤光学检测的进展,世界医疗器械,2002,8(7):56～59
[14] 陆婉珍,袁洪福,徐广通,现代近红外光谱分析技术,北京:中国石化出版社,2000.1～201
[15] 柯以侃,董慧茹,分析化学手册第三分册-光谱分析,北京:化学工业出版社,1998.176～177
[16] 沙宪政,李明菊,近红外光谱无创血糖检测技术的研究,医疗卫生装备,2003,6:29～31
[17] Ronald E. Shaffer, Gary W. Small, Mark A. Arnold, Genetic Algorithm-Based Protocol for Couping Digital Filtering and Partial Least-Squares Regression: Application to the Near-Infrared Analysis of Glucose in Biological Matrices, Analytical, Chemistry, 1996, 68(15): 2663～2675
[18] 唐国新,近红外无创伤人体血糖浓度检测中的数据预处理方法,硕士学位论文,天津大学,2003
[19] P. J. DE Groot, G. J. Postma, W. J. Melssen, et al., Influence of wavelength selection and data preprocessing on near-infrared-based classification of demolition waste, Applied Spectroscopy, 2001, 55 (2): 173～181
[20] 郭硕鸿等,电动力学,北京:人民出版社,1979. 119～142
[21] 吴瑾光等,近代傅里叶变换红外光谱技术及应用(上卷),北京:科学技术文献出版社 1994. 253～255,686～687
[22] 张玉民 戚伯云,波谱学,超星数字图书馆,1997,9(1):1～55
[23] Amerov, et al., Method and device for non-invasive blood glucose measurement, Proceedings of SPIE, 3599: 33-42, 1999
[24] Elsner P, Berardesca E, Wilhelm K P, et al. Bioengineering of the skin: skin biomechanics, CRC Press, Boca Raton, London, New York, Washington D.C., 2002.
[25] 常敏,应用红外光谱技术进行牛奶成分检测的研究,硕士学位论文,天津大学,2004
[26] 廖延彪,物理光学,电子工业出版社,1986,4(1),169～171
[27] 陈民森,陈文亮,杜振辉等,近红外无创血糖测量的研究,现代仪器,2004,10(4):38～40
[28] 倪勇,生物组织中光分布特性的理论及实验研究,博士学位论文,天津大学,2003
[29] B. Walczak, Outlier detection in multivariate calibration, Chemometrics Intell. Lab. Syst., 1995, 28:259～272
[30] Randy J. Pell, Multiple outlier detection for multivariate calibration using robust statistical techniques, Chemo metrics Intell. Lab. Syst., 2000, 52: 87～104
[31] William J. Egan, Outlier Detection in Multivariate Analytical Chemical Data, Anal. Chem., 1998, 70(11): 2372～2379
[32] 梁逸曾,白灰黑复杂多组份分析体系及其化学计量学算法,长沙:湖南科学技术出版社,1996.1～10
[33] J. Cox, Alan J. DeWeerd, Jennifer Linden,An experiment to measure Mie and Rayleigh total scattering cross sections,Am. J. Phys.2002,70(6)
[34] Michael P. Schubmehl , Mie Scattering Utilities User's Guide,2002
[35] Omar S.Khall. Spectroscopic and clinical aspects of noninvasive glucose Measurement, Clinical Chemistry, 45(2): 165～177,1999.
[36] 王惠文,偏最小二乘回归方法及其应用,北京:国防工业出版社,2000. 28～110
[37] 刘蓉,近红外光谱分析中模型优化方法的初步研究,硕士学位论文,天津大学,2003
[38] Jonas Sjoblom, Olof Svensson, Mats Josefson, et al., An evaluation of orthogonal signal correction applied to calibration transfer of near infrared spectra, Chemometricsand Intelligent Laboratory Systems, 1998, 44: 229～244
[39] Mark A.Arnold, Determination of Physiological Levels of Glucose in an Aqueous Matrix with Digitally Filtered Fourier Transform Near-Infrared Spectra, Analytical Chemistry, 1990, 62 (14): 1457～1464
[40] 欧俊豪,王家生,徐漪萍,刘嘉焜,应用概率统计(第 二版),天津大学出版社,1999,98～113, 220～223, 309～327.
[41] 于秀林,多元统计分析及程序,中国统计出版社,1993.6～28,145～172
[42] 崔继承,丁东,张洪艳等,葡萄糖溶液近红外光谱的测量与分析,光谱实验室,2003,20(2):257～259
[43] 丁东,张洪艳,王弼陡等,血浆中葡萄糖浓度的近红外光谱测量和分析,光学技术,2003,29(6):693～695
[44] 秦剑伟,中红外 ATR 光谱法测量血糖浓度的方法研究及仪器研制,硕士学位论文,天津大学,2003
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