Protocols are established for coupling digital filtering techniques with partial least-squares (PLS) regression for use in constructing multivariate calibration models from Fourier transform near-infrared absorbance spectra. Calibration models are developed to predict glucose concentrations in bovine plasma samples. Employing a calibration data set of 300 spectra collected from 55 plasma samples and 3 plasma lots, individual calibration models are developed based on four spectral ranges selected from the region 5000-4000 cm-1. A separate test set of 69 spectra collected from 14 plasma samples is used to evaluate the computed models. Gaussian-shaped bandpass digital filters are implemented by use of Fourier filtering techniques and employed to preprocess spectra to remove variation due to the background absorbance of the plasma matrix. PLS regression is used with the filtered spectra to compute calibration models for glucose. The optimization of the filter bandpass parameters is explored through the use of response surface methods. Through these optimization studies, calibration models are developed that achieve standard errors of estimate and standard errors of prediction in the range 0.4-0.5 mM across the concentration range of 2.5-25.5 mM. It is determined that the use of digital filtering as a preprocessing step significantly improves the performance of the resulting calibration models, minimizes the importance of spectral range in the calibration model development, and reduces the required number of PLS factors in each model.
[1]
H. Mantsch,et al.
Noise in Fourier self-deconvolution.
,
1981,
Applied optics.
[2]
Harald Martens,et al.
A multivariate calibration problem in analytical chemistry solved by partial least-squares models in latent variables
,
1983
.
[3]
C. Bush,et al.
Fourier method for digital data smoothing in circular dichroism spectrometry
,
1974
.
[4]
M A Arnold,et al.
Determination of physiological levels of glucose in an aqueous matrix with digitally filtered Fourier transform near-infrared spectra.
,
1990,
Analytical chemistry.
[5]
Gary Horlick,et al.
Digital data handling of spectra utilizing Fourier transformations
,
1972
.
[6]
John H. Kalivas,et al.
Convergence of generalized simulated annealing with variable step size with application towards parameter estimations of linear and nonlinear models
,
1991
.
[7]
A. Savitzky,et al.
Smoothing and Differentiation of Data by Simplified Least Squares Procedures.
,
1964
.
[8]
W. F. McClure,et al.
Fourier Analysis Enhances NIR Diffuse Reflectance Spectroscopy
,
1984
.
[9]
I. Warner,et al.
Fourier Transform Filtering of Two-Dimensional Fluorescence Data
,
1984
.