title: Pure component selectivity analysis of multivariate calibration models from near-infrared spectra.
abstract: A novel procedure is proposed as a method to characterize the chemical basis of selectivity for multivariate calibration models. This procedure involves submitting pure component spectra of both the target analyte and suspected interferences to the calibration model in question. The resulting model output is analyzed and interpreted in terms of the relative contribution of each component to the predicted analyte concentration. The utility of this method is illustrated by an analysis of calibration models for glucose, sucrose, and maltose. Near-infrared spectra are collected over the 5000-4000-cm(-)(1) spectral range for a set of ternary mixtures of these sugars. Partial least-squares (PLS) calibration models are generated for each component, and these models provide selective responses for the targeted analytes with standard errors of prediction ranging from 0.2 to 0.7 mM over the concentration range of 0.5-50 mM. The concept of the proposed pure component selectivity analysis is illustrated with these models. Results indicate that the net analyte signal is solely responsible for the selectivity of each individual model. Despite strong spectral overlap for these simple carbohydrates, calibration models based on the PLS algorithm provide sufficient selectivity to distinguish these commonly used sugars. The proposed procedure demonstrates conclusively that no component of the sucrose or maltose spectrum contributes to the selective measurement of glucose. Analogous conclusions are possible for the sucrose and maltose calibration models.
authors.affiliation: Department of Chemistry, University of Iowa, Iowa City, Iowa 52242, USA. mark-arnold@uiowa.edu
authors.forename: Mark A
authors.initials: MA
authors.lastname: Arnold
authors.forename: Gary W
authors.initials: GW
authors.lastname: Small
authors.forename: Dong
authors.initials: D
authors.lastname: Xiang
authors.forename: Jiang
authors.initials: J
authors.lastname: Qui
authors.forename: David W
authors.initials: DW
authors.lastname: Murhammer
mesh_terms: D002138:Calibration; D002241:Carbohydrates / Q000032:analysis* / Q000737:chemistry; D005947:Glucose / Q000032:analysis / Q000737:chemistry; D016018:Least-Squares Analysis; D016014:Linear Models; D008320:Maltose / Q000032:analysis / Q000737:chemistry; D015233:Models, Statistical; D015999:Multivariate Analysis; D015203:Reproducibility of Results; D012680:Sensitivity and Specificity; D019265:Spectroscopy, Near-Infrared / Q000379:methods* / Q000706:statistics & numerical data; D013395:Sucrose / Q000032:analysis / Q000737:chemistry
chemical_list: D002241:Carbohydrates; D013395:Sucrose; D008320:Maltose; D005947:Glucose