New second-order luminescent signals for analyte quantitation in the presence of interferents: time-decay sensitized lanthanide excitation and time-evolving chemiluminescence

OLIVIERI, A. C.; MUÑOZ DE LA PEÑA, A.; LOZANO, V. A.; IBAÑEZ, G. A.

Praga

Congreso; XIV International Symposium on Luminescence Spectrometry; 2010

Charles University in Prague. Faculty of Pharmacy in Hradec Králové

The determination of the antibiotic ciprofloxacin in urine and serum samples hasbeen carried out in the presence of uncalibrated interferences, by processing newsecond-order signals, achieving the so-called second-order advantage. These are,respectively, lanthanide sensitized excitation-time decay matrices and the time evolutionof chemiluminescence emission. Due to significant interactions between analyte andbiological background, quantitation was performed in the standard addition mode,using a new processing method involving subtraction of the unknown data matrix fromthe standard addition matrices. In both cases, complete spectral overlapping betweeninterferents and calibrated components occurs in one of the data dimensions, and thusonly multivariate curve resolution-alternating least squares (MCR-ALS) and parallelfactor analysis adapted for linear dependency (PARALIND) could be successfullyapplied to the studied data. The results indicate good analytical performance towardsthe analyte, with root mean square errors of ca. 10 and 0.4 mglL in urine and serumrespectively.