Multi-way partial least-squares and residual bi-linearization for the direct determination of monohydroxy-polycyclic aromatic hydrocarbons on octadecyl membranes via room-temperature fluorescence excitation emission matrices.
Multi-way partial least-squares (N-PLS) is combined to the residual bi-linearization procedure (RBL) for the direct analysis of metabolites of polycyclic aromatic hydrocarbons in urine samples. Metabolite analysis is carried out via a two-step experimental procedure based on solid-phase extraction and room temperature fluorescence spectroscopy. Excitation-emission matrices are recorded from octadecyl (C18) membranes that serve as solid substrates for sample extraction and spectroscopic measurements. Excellent metabolite recoveries were obtained in all cases, which varied from 96.2±1.35% (9-hydroxyphenanthrene) to 99.7±0.49% (3-hydroxybenzo[a]pyrene). Background correction of extraction membranes is carried out with a new alternating least-squares (ALS) procedure adapted to second order data. The performance of N-PLS/RBL is compared to the well-established multivariate curve resolution-alternating least-squares (MCR-ALS) algorithm. Both algorithms provided similar analytical figures of merit, including their ability to handle unknown interference in urine samples. With only 10 mL of sample, the limits of detection varied between 0.06-0.08 ng mL(-1) (1-hydroxypyrene) and 0.016-0.018 ng mL(-1) (2-hydroxyfluorene). When compared to previously reported univariate calibration data, the limits of detection via N-PLS/RBL and MCR-ALS are approximately one order of magnitude higher. This was somehow expected due to the effect of unexpected components in multivariate figures of merit, i.e. a more realistic approach to the analysis of metabolites in human urine samples.
Department of Chemistry, 4000 Central Florida Blvd, Physical Sciences Room 255, University of Central Florida, Orlando, FL 32816-2366, United States.
Hector C
HC
Goicoechea
Korina
K
Calimag-Williams
Andres D
AD
Campiglia
D000465:Algorithms; D002138:Calibration; D006801:Humans; D016018:Least-Squares Analysis; D016014:Linear Models; D015999:Multivariate Analysis; D011084:Polycyclic Aromatic Hydrocarbons / Q000378:metabolism* / Q000652:urine*; D012680:Sensitivity and Specificity; D052616:Solid Phase Extraction / Q000379:methods*; D013050:Spectrometry, Fluorescence / Q000379:methods*
D011084:Polycyclic Aromatic Hydrocarbons