title: Cubic smoothing splines background correction in on-line liquid chromatography-Fourier transform infrared spectrometry.
abstract: A background correction method for the on-line coupling of gradient liquid chromatography and Fourier transform infrared spectrometry (LC-FTIR) is proposed. The developed approach applies univariate background correction to each variable (i.e. each wave number) individually. Spectra measured in the region before and after each peak cluster are used as knots to model the variation of the eluent absorption intensity with time using cubic smoothing splines (CSS) functions. The new approach has been successfully tested on simulated as well as on real data sets obtained from injections of standard mixtures of polyethylene glycols with four different molecular weights in methanol:water, 2-propanol:water and ethanol:water gradients ranging from 30 to 90, 10 to 25 and from 10 to 40% (v/v) of organic modifier, respectively. Calibration lines showed high linearity with coefficients of determination higher than 0.98 and limits of detection between 0.4 and 1.4, 0.9 and 1.8, and 1.1 and 2.7 mgmL⁻¹ in methanol:water, 2-propanol:water and ethanol:water, respectively. Furthermore the method performance has been compared with a univariate background correction approach based on the use of a reference spectra matrix (UBC-RSM) to discuss the potential as well as pitfalls and drawbacks of the proposed approach. This method works without previous variable selection and provides minimal user-interaction, thus increasing drastically the feasibility of on-line coupling of gradient LC-FTIR.
authors.affiliation: Department of Analytical Chemistry, Universitat de València, Edificio Jeroni Muñoz, 50th Dr. Moliner, 46100 Burjassot, Spain.
authors.forename: Julia
authors.initials: J
authors.lastname: Kuligowski
authors.forename: David
authors.initials: D
authors.lastname: Carrión
authors.forename: Guillermo
authors.initials: G
authors.lastname: Quintás
authors.forename: Salvador
authors.initials: S
authors.lastname: Garrigues
authors.forename: Miguel
authors.initials: M
authors.lastname: de la Guardia
mesh_terms: D000438:Alcohols / Q000737:chemistry; D000465:Algorithms; D000704:Analysis of Variance; D002853:Chromatography, Liquid / Q000379:methods*; D003198:Computer Simulation; D055772:Green Chemistry Technology; D016014:Linear Models; D011092:Polyethylene Glycols / Q000737:chemistry; D012680:Sensitivity and Specificity; D017550:Spectroscopy, Fourier Transform Infrared / Q000379:methods*
chemical_list: D000438:Alcohols; D011092:Polyethylene Glycols