title: A comparative study between PCR and PLS in simultaneous spectrophotometric determination of diphenylamine, aniline, and phenol: Effect of wavelength selection.
abstract: Partial least squares (PLS) and principal component regression (PCR) have received considerable attention in the chemometrics for multicomponent analysis where superiority of one over another is a challenging problem yet. Considering the effect of wavelength selection, a comparison was made between PCR and PLS methods by application those to simultaneous spectrophotometric determination of diphenylamine (DPA), a compound from the third European Union list of priority pollutants, and its environmentally related products aniline and phenol. The UV absorbance spectra of the methanolic solutions of the analytes were measured in the concentration ranges of 1.0-10.0 microg mL(-1) and then subjected to PCR and PLS. The models refinement procedure and validation was performed by cross-validation. A modified changeable size moving windows strategy, where optimized the intervals between the sensors in a selected windows, was also proposed to select the more informative spectral regions for each of the analytes. It was found that wavelength selection improved the quality of predictions for both regression methods whereas more reliable results were obtained by removing of the highly collinear neighboring wavelengths. The resultant data explained that PLS produced more or less better results when whole spectral data were used but in the case of selected wavelength regions both methods produced similar results and no comments could be given about the superiority of one against another. The major difference was obtaining the higher number of factors for PCR, which is not a significant problem.
authors.affiliation: Chemistry Department, Shiraz University, Shiraz 71454, Iran. hemmatb@sums.ac.ir
authors.forename: Bahram
authors.initials: B
authors.lastname: Hemmateenejad
authors.forename: Morteza
authors.initials: M
authors.lastname: Akhond
authors.forename: Fayezeh
authors.initials: F
authors.lastname: Samari
mesh_terms: D000814:Aniline Compounds / Q000032:analysis* / Q000737:chemistry; D002138:Calibration; D004159:Diphenylamine / Q000032:analysis* / Q000737:chemistry; D004785:Environmental Pollutants / Q000032:analysis* / Q000737:chemistry; D016018:Least-Squares Analysis; D000432:Methanol / Q000737:chemistry; D019800:Phenol / Q000032:analysis* / Q000737:chemistry; D025341:Principal Component Analysis; D012015:Reference Standards; D012044:Regression Analysis; D015203:Reproducibility of Results; D012997:Solvents / Q000737:chemistry; D013056:Spectrophotometry, Ultraviolet
chemical_list: D000814:Aniline Compounds; D004785:Environmental Pollutants; D012997:Solvents; D019800:Phenol; D004159:Diphenylamine; C023650:aniline; D000432:Methanol