基于稳定一致波长筛选的无标样近红外光谱模型传递方法  

A Novel Calibration Transfer Method of Near Infrared Spectral Model Without Standard Samples Based on Screening Stable and Consistent Wavelengths

作　　者：倪力军[1] 韩明月 张立国[1] 栾绍嵘[1] NI Li-Jun;HAN Ming-Yue;ZHANG Li-Guo;LUAN Shao-Rong(College of Chemistry and Molecular Engineering,East China University of Science and Technology,Shanghai 200237,China)

机构地区：[1]华东理工大学化学与分子工程学院,上海200237

出　　处：《分析化学》2018年第10期1660-1668,共9页Chinese Journal of Analytical Chemistry

摘　　要：测量环境及仪器间光谱信号的差异导致近红外光谱模型从主机传递到从机后,经常会产生过大误差。本研究提出了一种基于稳定一致波长筛选的无标样近红外模型传递方法(Screening stable and consistent wavelengths,SSCW),剔除主从仪器间差谱的标准偏差大于样品精密度测试光谱标准偏差的波长,以及精密度测试偏差过大的波长,筛选出仪器间光谱信号一致性好且稳定的波长建立近红外光谱定标模型。分别以玉米和黄芩样本集对本算法的有效性进行了检验。结果表明,SSCW模型传递后对从机样品的预测均方根残差RMSEP较全波长PLS模型直接传递结果小一个量级,大部分情况下优于分段直接校正算法(Piecewise direct standardization,PDS)的结果和文献报道的无标样模型传递结果。本方法具有传递性能好、模型参数少、稳健等优点,在不同仪器间可实现近红外光谱模型的无标样传递。The change of measurement environment and spectral signals of spectroscopy instruments can lead to big error in the process of transferring the model of near infrared(NIR)spectra to slave instruments.Present work advanced a novel method of transferring NIR calibration models without standard samples basing on Screening stable and consistent wavelengths(SSCW).The method firstly eliminates the wavelengths at which the standard variation of difference spectra between master and slave instruments(SDDSI)is bigger than the standard variance of precision detection spectra(SDPDS)to screen the wavelengths at which the spectral signals of different instruments are consistent well.And then deletes the wavelengths at which the values of SDPDS are too high.Thus the spectral signals at the selected wavelengths are stable and consistent between instruments to build the NIR calibration models.Two datasets are applied to validate the method of SSCW:one is consisted of 72 radix scutellaria samples,whose NIR spectra are measured on two different types of NIR spectroscopy instruments,another one is consisted of 80 corn samples,whose NIR spectra measured on three NIR instruments are available online.The results show that the overall prediction effect of SSCW for salves′samples is much better than that of the full-wavelength PLS model.In most cases,the root mean square of error prediction(RMSEP)of salve samples of SSCW is lower than those given by the piecewise direct standardization(PDS)correction,and that of the other model transfer methods without standard samples.Therefore,the method of SSCW is of fewer parameters,robust and can maintain good prediction performance after transferring to salve instruments.It can be used to realize the sharing of PLS calibration model among spectroscopy instruments.

关 键 词：近红外光谱 无标样模型传递 波长筛选 标准偏差光谱分析 

分 类 号：O657.33[理学—分析化学]