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Modelado quimiométrico de datos espectroscópicos multivariados

Resumen

Se propone la investigación de técnicas quimiométricas avanzadas de procesamiento de datos espectroscópicos (luminiscentes y absortivos), con el objetivo de desarrollar métodos analíticos aplicables a mezclas de composición compleja. Los analitos de interés serán fármacos con diferente actividad biológica y sus metabolitos en muestras biomédicas, aditivos en alimentos y componentes de muestras industriales. Se pondrá énfasis en las nuevas herramientas quimiométricas basadas en datos de orden superior, que exhiben la llamada "ventaja de segundo orden" (es decir, el análisis de componentes calibrados en presencia de interferentes no calibrados), contribuyendo al desarrollo y análisis de la estructura de nuevos algoritmos. Se emplearán especialmente datos multidimensionales tales como matrices de excitación-emisión de luminiscencia (eventualmente acopladas a una reacción química que produzca variaciones temporales de la señal), o espectros de absorción en los que se introducirá una nueva dimensión a través de un gradiente de pH o la cinética de una reacción, y también datos espectroscópicos unidimensionales tales como espectros luminiscentes y de absorción UV-visible, infrarroja o infrarroja cercana. Las nuevas metodologías se validarán frente a técnicas cromatográficas de referencia, con el propósito de evaluar su calidad y cifras de mérito comparativas.

Grupo de Investigación

Director:

Dr. Olivieri, Alejandro C.

Investigador Superior
Profesor Titular, Dedicación Exclusiva

Investigadores:

Dra. Damiani, Patricia C.

Jefe de Trabajos Prácticos, Dedicación Exclusiva

Dr. García Reiriz, Alejandro G.

Investigador Adjunto
Auxiliar de Primera Categoría, Dedicación Simple

Publicaciones seleccionadas

Four-way data coupled to parallel factor model applied to environmental analysis: determination of 2,3,7,8-tetrachloro-dibenzo-para-dioxin in highly contaminated waters by solid-liquid extraction laser-excited time-resolved Shpol’skii spectroscopy. Goicoechea, HC, Yu, S, Olivieri, AC, Campiglia, AD, Anal. Chem. 77, 2608-2616 (2005).

 

Computing sensitivity and selectivity in parallel factor analysis and related multi-way techniques: the need for further developments in net analyte signal theory. Olivieri, AC, Anal. Chem. 77 (2005) 4936-4946.

 

Evaluation of complex spectral-pH three-way arrays by modified bilinear least-squares: determination of four different dyes in interfering systems. Marsili, NR, Lista, A, Fernandez Band, BS, Goicoechea, HC, Olivieri, AC, Analyst 130 (2005) 1291-1298.

 

Application of partial least-squares spectrophotometric multivariate calibration to the determination of 2-sec-butyl-4,6-dinitrophenol (dinoseb) and 2,6-dinitro-p-cresol in industrial and water samples containing hydrocarbons. Arancibia, JA, Martínez Delfa, G, Boschetti, CE, Escandar, GM, Olivieri, AC, Anal. Chim. Acta 553 (2005) 141-147.

 

Simultaneous determination of flufenamic and meclofenamic acids in human urine samples by second-order multivariate calibration of micellar-enhanced excitation-emission fluorescence data. Muñoz de la Peña, A, Mora Díez, N, Bohoyo Gil, D, Olivieri, AC, Escandar, GM, Anal. Chim. Acta 569 (2006) 250-259.

 

Evaluation of partial least-squares with second-order advantage for the multi-way spectroscopic analysis of complex biological samples in the presence of analyte-background interactions.Culzoni, MJ, Goicoechea, HC, Pagani, AP, Cabezón, MA, Olivieri, AC, Analyst 131 (2006) 718-723.

 

Second-order advantage achieved by unfolded-partial least-squares/residual bilinearization modelling of excitation-emission fluorescence data presenting inner filter effects. Bohoyo Gil, D, Muñoz de la Peña, A, Arancibia, JA, Escandar, GM, Olivieri, AC, Anal. Chem. 78 (2006)8051-8058.

 

Different strategies for the direct determination of amoxicillin in human urine by second-order multivariate analysis of kinetic-spectrophotometric data. García-Reiriz, A, Damiani, PC, Olivieri, AC, Talanta 71 (2007) 806-815.

 

Analysis of amoxicillin in human urine by photo-activated generation of fluorescence excitation-emission matrices and artificial neural networks combined with residual bilinearization. García-Reiriz, A, Damiani, PC, Olivieri, AC, Anal. Chim. Acta 588 (2007) 192-199.

 

Determination of pesticides and metabolites in wine samples by HPLC-DAD and second-order calibration methods. Braga, JWB, Bottoli, CBG, Jardim, ISCF, Goicoechea, HC, Olivieri, AC, Poppi, RJ, J. Chromatogr. A 1148 (2007) 200-210.

 

Experimental study of non-linear second-order analytical data with focus on the second-order advantage. Culzoni, MJ, Damiani, PC, García-Reiriz, A, Goicoechea, HC, Olivieri, AC, Analyst 132 (2007) 654-663.

 

Multi-way partial least-squares coupled to residual trilinearization: a genuine multi-dimensional tool for the study of third-order data. Simultaneous analysis of procaine and its metabolite p-amino benzoic acid in equine serum. Damiani, PC, Durán-Merás, I, García-Reiriz, A,Jiménez-Girón, A, Muñoz de la Peña, A, Olivieri, AC, Anal. Chem. 79 (2007) 6949-6858.

 

Photoinduced fluorimetric determination of folic acid and 5-methyltetrahydrofolic acid in serum using the kinetic evolution of the emission spectra accomplished with multivariate second-order calibration methods. Jiménez Girón, A, Durán Merás, I, Muñoz de la Peña, A, Espinosa Mansilla, A, Cañada-Cañada, F, Olivieri, AC, Anal. Bioanal. Chem. 391 (2008) 827-835.

 

Three-way partial least-squares/residual bilinearization study of second-order lanthanide-sensitized luminescence excitation-time decay data. Analysis of benzoic acid in beverage samples. Lozano, VA, Ibañez, GA, Olivieri, AC, Anal. Chim. Acta 610 (2008) 186-195.

 

Second-order advantage from kinetic-spectroscopic data matrices in the presence of extreme spectral overlapping. A multivariate curve resolution - alternating least-squares approach. Culzoni, MJ, Goicoechea, HC, Ibañez, GA, Lozano, VA, Marsili, NR, Olivieri, AC, Pagani, AP, Anal. Chim. Acta 614 (2008) 46-57.

 

Screening of oil samples on the basis of excitation-emission room-temperature phosphorescence data and multi-way chemometric techniques. Introducing the second-order advantage in a classification study. Arancibia, JA, Boschetti, CE, Olivieri, AC, Escandar, GM, Anal. Chem. 80 (2008) 2789-2798.

 

Determination of folic acid and its two main metabolites in serum by on line photochemically induced excitation-emission-kinetic four-way data. Jiménez Girón, A, Durán-Merás, I, Espinosa-Mansilla, A, Muñoz de la Peña, A, Cañada-Cañada, F, Olivieri, AC, Anal. Chim. Acta 622 (2008) 94-103.

 

Non-linear four-way kinetic-excitation-emission fluorescence data processed by a variant of parallel factor analysis and by a neural network model achieving the second-order advantage: malonaldehyde determination in olive oil samples. García-Reiriz, A, Damiani, PC, Olivieri, AC, Cañada-Cañada, F, Muñoz de la Peña, A, Anal. Chem. 80 (2008) 7248-7256.

 

Standard addition analysis of fluoroquinolones in human serum in the presence of the interferent salicylate using lanthanide-sensitized excitation-time decay luminescence data and multivariate curve resolution. Lozano, VA, Tauler, R, Ibañez, GA, Olivieri, AC, Talanta 77 (2009) 1715-1723.

 

Second-order multivariate calibration procedures applied to high-performance liquid chromatography coupled to fast-scanning fluorescence detection for the determination of fluoroquinolones. Cañada-Cañada, F, Arancibia, JA,Escandar, GM, Ibañez, GA, Espinosa Mansilla, A, Muñoz de la Peña, A, Olivieri, AC, J. Chromatogr. A 1219 (2009) 4868-4876.

 

When unfolding is better: unique success of unfolded partial least-squares regression with residual bilinearization for the processing of spectral-pH data with strong spectral overlapping. Analysis of fluoroquinolones in human urine based on flow-injection pH-modulated synchronous fluorescence data matrices. Borraccetti, MD, Damiani, PC, Olivieri, AC, Analyst 134 (2009) 1682-1691.

 

A novel second-order standard addition analytical method based on data processing with multidimensional partial least-squares and residual bilinearization. Lozano, VA, Ibañez, GA, Olivieri, AC, Anal. Chim. Acta 651 (2009) 165-172.

 

Application of the correlation constrained multivariate curve resolution alternating least-squares method for analyte quantitation in the presence of unexpected interferences using first-order instrumental data. Goicoechea, HC, Olivieri, AC,Tauler, R, Analyst 135 (2010) 636-642.

 

Second-order analyte quantitation under identical profiles in one data dimension. A dependency-adapted partial least-squares/residual bilinearization method. Olivieri, AC, Ibañez, GA, Lozano, VA, Anal. Chem. 82 (2010) 4510-4519.

 

Simultaneous voltammetric determination of levodopa, carbidopa and benserazide in pharmaceuticals using multivariate calibration. Zapata-Urzúa, C, Pérez-Ortiz, M, Bravo, M, Olivieri, AC, Álvarez-Lueje, A, Talanta 82 (2010) 962-968.

 

Four-way kinetic-excitation-emission fluorescence data processed by multi-way algorithms. Determination of carbaryl and 1-naphthol in water samples in the presence of fluorescent interferents. Maggio, RM, Damiani, PC, Olivieri, AC, Anal. Chim. Acta 677 (2010) 97-107.

 

Multivariate curve resolution analysis of pesticides in water samples from liquid chromatographic - diode array data. Maggio, RM, Damiani, PC, Olivieri, AC, Talanta 80 (2011) 1173-1180.

 

A new and efficient variable selection algorithm based on ant colony optimization. Applications to near infrared spectroscopy / partial least-squares analysis. Allegrini, F, Olivieri, AC, Anal. Chim. Acta 699 (2011) 18-25.

 

Comparison of the predictive ability of several second-order multivariate methods in the simultaneous determination of two therapeutic drugs in human urine. Hurtado Sánchez, MC, Durán Merás, I, Rodríguez Cáceres, MI, Jiménez Girón, A, Olivieri, AC, Talanta 88 (2012) 609-616.

 

New developments for the sensitivity estimation in four-way calibration with the quadri-linear parallel factor model. Olivieri, AC, Faber, K, Anal. Chem. 84 (2012) 186-193.

  Unidades

Suipacha 531 - Rosario, Santa Fe.- Te: 54-341-4370477