鱼粉近红外光谱模型传递应用研究

为探讨光栅型与傅里叶变换型近红外分析仪之间模型传递的应用效果,选取国产鱼粉为近红外光谱样本,DS2500F型近红外分析仪为源仪器,MPA型近红外分析仪为目标仪器,采用分段直接校正(PDS)方法实现近红外光谱传递。分别建立水分、粗蛋白质、粗脂肪、蛋氨酸和赖氨酸等组分的预测模型,通过交互验证决定系数(R2cv)、交互验证标准误差(RMSECV)、马氏距离(MD)、系统偏差(Bias)、预测均方根误差(RMSEP)和相对分析误差(RPD)等参数,多维度评估光谱传递后所建预测模型的效果。结果表明,DS2500F仪器的近红外光谱传递到MPA型仪器时,所建国产鱼粉的水分、粗蛋白质、粗脂肪、蛋氨酸、赖氨酸的预测模型与MPA型仪器原始预测模型各参数对比无显著差异,预测效果基本一致,说明国产鱼粉在DS2500F仪器上的近红外光谱通过传递可以替代MPA型仪器的原始光谱,间接实现了模型传递,且具有良好的适用性和共享性,可提高近红外预测模型的应用效率。     

基于光谱比值分析的无标样近红外模型传递方法

测量环境及光谱仪台间差异导致近红外光谱(NIRS)模型传递到从机后,常产生较大误差。该文使用标准正态变量变换(SNV)+微分处理光谱消除光谱散射和基线漂移的影响,提出通过仪器间光谱信号比值分析筛选波长的方法(Screening wavelengths based on spectrum ratio analysis,SWSRA),选出仪器间一致性较好且样本间差异大的光谱特征波长,采用筛选出的波长信号建立待测性质的偏最小二乘近红外光谱定标模型。以80个玉米样品中水分、油、蛋白质含量及72个黄芩样品中黄芩苷含量的NIRS预测对该方法进行了检验。结果表明,SWSRA主机模型预测从机样品的各成分含量的平均相对误差均小于4.3%,明显优于全波长模型直接传递的结果,且其预测均方根残差RMSEP与文献报道的其他模型传递方法的结果相当或更优。SWSRA方法具有模型参数少、稳健、简便易行等优点,可以在同类型近红外光谱仪器之间实现模型的无标样传递。     

正交信号校正用于傅里叶变换红外光谱的模型传递

利用正交信号校正（OSC）实现了4组分气体混合物的PLS模型,在两台傅里叶变换红外光谱（FTIR）仪上的传递,并与直接标准化（DS）、分段直接标准化（PDS）、多元分散校正（MSC）和有限脉冲响应（FIR）的传递效果进行了比较,确立了以源机的校正模型直接对目标机数据进行预测的传递方式。经过OSC校正,预测均方根误差（RMSEP）为10^-3左右。OSC可以有效地减小测量仪器间的差异,同时使PLS模型的潜变量个数降为4,使模型简单化。与DS和PDS相比,OSC不需要同一样品在两台仪器上测量,在支集大小为3时,得到一致的预测准确度,表现出稳健性。MSC和FIR处理的RMSEP为10^-1左右,效果远差于OSC。     

二进制蜻蜓算法-直接校正算法优选标样集在小麦粉蛋白质近红外模型传递中的应用

为了实现小麦粉蛋白质含量近红外分析模型的传递，探究二进制蜻蜓算法(Binary Dragonfly Algorithm, BDA)与直接校正算法(Direct Standardization, DS)相结合构成的BDA-DS算法挑选标样集对模型传递结果的影响。以棱光S450光栅型近红外光谱仪为主机，NeoSpectra Micro傅里叶变换型近红外光谱仪为从机，采集了126个小麦粉的近红外光谱，用偏最小二乘回归法建立了主机近红外光谱与小麦粉蛋白质的关联模型。经BDA-DS算法模型传递后，主机模型对从机样品预测决定系数为0.9812,预测标准偏差为0.1838,从机与主机的光谱集合平均马氏距离由22.34下降到1.40,均接近于主机模型精度水平。该研究同时与采用Kennard/Stone(K/S)挑选标样集再结合DS构成的传统K/S-DS算法进行了对比，结果表明：相对于K/S-DS算法，BDA-DS算法挑选出较少的标样集就能表征仪器的差异，有效地提高了主机模型对从机样品的预测精度，为近红外模型传递提供了一种更加有效的标样集选择方法。     

基于一元线性回归的近红外光谱模型传递研究

为解决近红外光谱分析中的模型传递问题,本研究提出了一元线性回归直接标准化算法(Simple linear regression direct standardization,SLRDS)。为验证算法的有效性,采用玉米样品的近红外光谱集进行实验,并与传统的直接标准化算法(Direct standardization,DS)、分段直接标准化算法(Piecewise direct standardization,PDS)进行比较。实验结果表明,SLRDS算法不仅能够有效消除近红外光谱仪之间的差异,很好地实现玉米样品的PLS校正模型在3台仪器之间的共享,而且与DS和PDS算法相比,具有传递性能高、模型简单及所求参数少等优点。     

段式正交信号校正方法及在小麦近红外光谱数据分析中的应用

针对光谱数据峰宽、局部效应显著、含有噪音、变量个数多及彼此间常存在严重的复共线性等问题,改进和设计一种光谱数据局部校正方法:基于窗口平滑的段式正交信号校正方法,并将之结合偏最小二乘回归,以实现光谱数据的预处理及定量分析。通过NIPALS算法初始化将滤去的正交成分,以近邻分段方式进行逐个波长点的正交信号校正。而后将去噪后的光谱矩阵作为新的自变量阵,通过偏最小二乘回归构建其与性质参变量间的校正模型。通过小麦近红外漫反射光谱数据的应用实验结果表明,本方法正交成分估计稳定,去噪明显,模型的预报性能优于其它方法,PLS成分数减少,模型更加简洁。     

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

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。     

近红外光谱分析模型传递简易方法研究

本文在不同时间安装的多台同型号近红外光谱仪上建立推进剂校正模型时,由于推进剂样品数量少且难于保存,新到仪器在建模时常遇到代表性样品数量严重不足.为此,提出将2台波长一致性好的近红外光谱仪器上采集的光谱组成一个混合校正样品光谱集,使用偏最小二乘法(PLS)建立模型的方法.结果表明,在用户缺少专业模型传递软件情况下,该方法...     

光谱预处理方法对混胺近红外定量模型影响的研究

本文探讨了一阶导数、Savitzky-Golay平滑、小波变换(WT)和正交信号校正(OSC)预处理方法对混胺组分近红外光谱的预处理效果。采用预测集标准偏差(SEP)对各种预处理方法的最佳参数进行选择。比较了各种预处理方法的去噪能力,对预处理方法组合后的效果进行了评价。研究表明,WT和OSC能有效去除噪声,提高分析模型的精度,WT和OSC结合后的预处理效果更好。     

基于小波变换动态时间规整的近红外光谱模型传递方法

为解决因测量环境及仪器差异而导致的近红外光谱模型通用性较差的不足,提出一种基于小波变换动态时间规整算法的模型传递方法(Wavelet transform combined with dynamic time warping,WDTW),从而实现不同仪器之间模型的共享。首先,该方法将光谱进行小波变换预处理,然后利用动态时间规整算法(Dynamic time warping,DTW)找到近红外光谱波长点之间最优的对应关系并建立回归方程。使用近红外药品光谱数据集和汽油数据集建立传递模型,验证了基于小波变换动态时间规整模型传递方法的有效性。汽油光谱数据集C7、C8、C9和C10成分的预测标准偏差(SEP)分别为0.414 4、0.801 1、1.090 4和1.290 8;药品光谱数据集活性、硬度和重量的SEP分别为2.585 6、0.434 5和2.270 3,均小于传统方法。上述实验结果表明,所建立的模型传递方法能有效消除源机光谱和目标机光谱之间的差异,提高模型的稳定性和准确性,实现模型传递的效果。     

基于尺度不变特征变换筛选稳定特征波长的近红外光谱模型传递方法

该研究利用一维尺度不变特征变换(SIFT)算法寻找烟叶近红外光谱(Near infrared spectroscopy,NIRS)的稳定特征波长,根据样品精密度测试光谱筛选的波长计算重现率和重现度,采用L_9(3~3)正交表优化SIFT算法中的相关参数,使重现率和重现度尽可能高。基于优化的参数和主机上10个代表性样品的光谱,筛选出10个稳定特征波长集合,以这些波长集合并集的光谱响应为自变量,采用偏最小二乘(PLS)方法构建烟叶总植物碱NIRS模型(简称SIFT-PLS)。该模型直接传递到3台从机后,对3台从机样品总植物碱的平均相对预测误差(MRE)均满足小于6%的企业内控要求,而全光谱模型(WW-PLS)直接转移后仅1台从机的MRE满足要求,经分段直接校正(PDS)方法校正从机光谱后,WW-PLS模型也仅对1台从机的MRE小于6%。采用SIFT算法筛选稳定特征波长建立的NIRS模型可在3台从机直接共享,无需转移集,不需对从机光谱或光谱模型进行校正,实现了真正意义的无标样NIRS模型的直接转移。     

Data fusion in multivariate calibration transfer

We report the use of stacked partial least-squares regression and stacked dual-domain regression analysis with four commonly used techniques for calibration transfer to improve predictive performance from transferred multivariate calibration models. The predictive performance from three conventional calibration transfer methods, piecewise direct standardization (PDS), orthogonal signal correction (OSC) and model updating (MUP), requiring standards measured on both instruments, was significantly improved from data fusion either by stacking of wavelet scales or by stacking of spectral intervals, as demonstrated by transfer of calibrations developed on near-infrared spectra of synthetic gasoline. Stacking did not produce as significant an improvement for calibration transfer using a finite impulse response (FIR) filter, but application of SPLS regression to FIR-transferred spectra improves predictive performance of the transferred model.     

基于波数校准下傅里叶红外气体分析仪模型传递的研究

傅里叶变换红外光谱仪具有扫描速度快、分辨率高、波数精度高、灵敏度高和光谱范围宽等优点,因而应用于各个领域.但在实际应用中,由于仪器间的差异、仪器自身随时间的变化或者样品特性等问题,导致在一台仪器上建立的校正模型不能推广至其他仪器长期使用,使得傅里叶变换红外光谱法(FTIR)的应用受到了校正模型的限制,因此如何实现整机的...     

对直接标准化算法的改进及其应用

由于各种仪器之间存在差异,主机上建立的定量模型用于从机会导致预测结果出现较大偏差。目前主要通过有标样方法和无标样方法来减小预测偏差。该文对现有标样方法中的直接标准化算法进行改进,在转移矩阵的建立过程中,对从仪器数据矩阵进行主成分分解,以预测均方差为判定标准,确定最终的转移矩阵。并以玉米和烟草数据为对象,测试了该法的有效性。玉米样品含有2种成分:水分和蛋白质;烟草样品含有4种成分:还原糖、总糖、总氮和总碱。结果表明,对于玉米样品中的2种成分,采用改进的方法可显著提高预测的准确度;对于烟草中的4种成分而言,采用改进的方法可获得稳健的预测结果。     

Application of orthogonal space regression to calibration transfer without standards

To transfer a calibration model in cases where the standardization samples are rare or unstable, a method based on orthogonal space regression (OSR) is proposed. It uses virtual standardization spectra to account for response changes between instruments or batches. A comparative study of the proposed OSR, piecewise direct standardization, finite impulse response, orthogonal signal correction, and model updating (MU) was conducted on both pharmaceutical tablet data and chlorogenic acid data. The results of these studies suggest that both the OSR and the MU are superior to the other transfer techniques in terms of root‐mean‐squared error of prediction and ratio of performance to interquartile distance. Moreover, OSR requires no identical standard samples, and it avoids re‐optimizing the transfer models. In conclusion, both the differences among spectra measured on different spectrometers and the differences between different batches can be corrected successfully using the OSR method. Copyright © 2013 John Wiley & Sons, Ltd.     

Determination of alcohol content in beverages using short-wave near-infrared spectroscopy and temperature correction by transfer calibration procedures

This paper reports the utilization of short-wave near-infrared (SW-NIR) transmission spectroscopy for rapid and conclusive analysis of alcoholic content (% v/v) in beverages. This spectral region is interesting because common visible diode array spectrometers can be utilized, reducing time and costs in comparison with traditional near-infrared or mid-infrared instruments. A correction of external temperature influence is necessary, and for this purposes two calibration transfer procedures were compared: piecewise direct standardization (PDS) and orthogonal signal correction (OSC). The RMSEP found for the alcoholic content model at 20 °C was 0.13% v/v and, after application of transfer calibration procedures at other temperatures (15, 25, 30 and 35 °C) using the model built at 20 °C, errors of the same order of magnitude were obtained.     

Calibration transfer of near‐IR partial least squares property models of fuels using virtual standards

Partial least squares (PLS) models of 10 important jet and diesel fuel properties were built using spectra from a master near‐IR dispersive instrument and then subsequently transferred to a secondary dispersive instrument via a novel calibration transfer method using virtual standards and a slope‐bias correction. Implementation of the transfer requires that only seven spectra of neat solvents be acquired on the master and secondary instruments. The spectra of the neat solvents are then used to digitally replicate spectra from the calibration set to generate virtual standards. Comparison of PLS predictions for the master and secondary instrument virtual standards provides a simple but effective slope‐bias correction for transfer. The transferred fuel properties include American Petroleum Institute gravity, % aromatics, cetane index, flashpoint, hydrogen content, % saturates, and distillation temperatures at 10%, 20%, 50%, and 90% volume recovered. Transfer error was lower than using either the pure solvents with a slope‐bias correction or than using a piecewise direct standardization calibration transfer using fuel spectra. Transfer error was higher than when using actual fuels to transfer the calibration. The use of virtual standards eliminates the need to maintain either complex fuel standards or the master instrument for future instrument calibration transfers. Copyright © 2011 John Wiley & Sons, Ltd.     

A comparative study of calibration transfer methods for determination of gasoline quality parameters in three different near infrared spectrometers

This work presents a comparative study of calibration transfer among three near infrared spectrometers for determination of naphthenes and RON (Research Octane Number) in gasoline. Seven transfer methods are compared: direct standardization (DS), piecewise direct standardization (PDS), orthogonal signal correction (OSC), reverse standardization (RS), piecewise reverse standardization (PRS), slope and bias correction (SBC) and model updating (MU). Two pre-treatment procedures, namely standard normal variate (SNV) and multiplicative scatter correction (MSC), are also investigated. The choice of an appropriate number of transfer samples for each technique, as well as the effect of window size in PDS/PRS and OSC components, are discussed. A broad set of gasoline samples representative of the Northeastern states of Brazil is employed in the investigation. The results show that the use of calibration transfer yields prediction errors comparable to those obtained with complete recalibration of the secondary instrument. Overall, the results point to RS as the best method for the analytical problem under consideration. When storage and/or physical transportation of transfer samples are impractical, MU is more appropriate. The comprehensive investigation carried out in the present work will be of value for practitioners involved in networks of fuel monitoring.     

小波变换-分段直接校正法用于近红外光谱模型传递研究

提出了一种新的传递算法(WT-PDS)———小波变换-分段直接校正法,并详细讨论了模型传递参数和传递结果。首先利用小波变换对光谱进行压缩处理,采用PDS算法消除不同仪器之间压缩数据的差异,最后利用经校正的压缩数据进行分析,实现模型传递。本方法能够扣除不同仪器之间的大部分差异,大幅度改善分析精度。传递后模型分析精度与源机模型稳健性紧密相关。如果源机模型稳健性强,则能够实现不同仪器之间的共享。本方法能够实现源机的0#轻柴十六烷值、凝点、馏出温度;-10#轻柴十六烷值、凝点以及-10#军柴凝点和馏出温度共10个模型在5台仪器之间共享,简化了建模的成本。与传统的PDS相比,WT-PDS方法具有传递和建模变量少、速度快、光谱校正性能高等优点,而其模型分析精度与传统PDS基本一致。     

The absolute calibration of mid-infrared transmittance standards

The National Physical Laboratory (NPL) uniquely has 40 years’ experience in pioneering, developing instruments and exploiting the spectroscopic advantages of the Fourier transform technique. This has allowed an objective and knowledgeable appraisal of the Fourier transform technique for ordinate standards work. At present not enough is known of the ways in which the many and complicated categories of systematic error in such instruments can be identified, separated, evaluated and corrected for. Thus at NPL grating spectrophotometers are still used to determine, maintain and disseminate transmittance standards for the mid-infrared spectral region. This allows well-established methods developed in UV/visible region work to be adapted and used to minimise and where necessary correct for the residual systematic errors.

The paper expands on the above considerations, and goes on to describe the techniques used to explore possible systematic errors and to give an absolute regular transmittance calibration to a suitable secondary and transfer standard. This last was designed at NPL and consists of a Schott NG11 optical glass filter mounted in a protective milled frame that allows for reproducible alignment in the spectrophotometer, and this is described, together with the particular properties that were required of it. Seven levels of transmittance are provided, ranging from about 73% down to just above zero. The uncertainties of calibration are of order ±0.1%, varying with transmittance level. The pros and cons of highly reflecting filters are also discussed, and it is concluded that these last should be used initially to explore and minimise the interreflection errors in an instrument by adding stops, etc. and then the NPL-certified NG11 filter should be used to actually calibrate the ordinate scale.