Coupling of spectrometric, chromatographic, and chemometric analysis in the investigation of the photodegradation of sulfamethoxazole

Abstract

A workflow is proposed for the study of the photodegradation process of the sulfamethoxazole (SMX) based on the combination of different experimental techniques, including liquid chromatography, mass spectrometry, UV-Visible spectrophotometry, and the treatment of all the analytical data with advanced chemometric methods. SMX, which is one of the most widely used antibiotics worldwide and has been found at remarkable concentrations in various rivers and effluents over all Europe, was degraded in the laboratory under a controlled source of UV radiation, which simulates the environmental solar radiation (Suntest). Kinetic monitoring of the photodegradation process was performed using UV-Visible spectrophotometric measurements and by further Liquid Chromatography with Diode Array Detector and Mass Spectrometry analysis (LC-DAD-MS). Additionally, the acid-base properties were also investigated to see how the pH can affect the speciation of this substance during the photodegradation process. Based on the Multivariate Curve Resolution-Alternating Least Squares (MCR-ALS) application, the proposed chemometric method coped with the large amounts of data generated by the different analytical techniques used to monitor the evolution of the photodegradation process. Their simultaneous analysis involved applying a data fusion strategy and an advanced MCR-ALS constrained analysis, which allowed and improved the description of the complete degradation process, detecting the different species of the reaction, and identifying the possible transformation products formed. A total number of six species were resolved in the degradation process of SMX. In addition to the initial SMX, a second species corresponded to a conformational isomer, and the other four species represented different photoproducts, which have also been identified. Furthermore, three different acid-base species of SMX were obtained, and their pK_a values were estimated.

Keywords: Chemometric methods; Data fusion strategy; Drug photostability; Environmental pollutants; Multivariate Curve Resolution–Alternating Least Squares (MCR-ALS); Sulfamethoxazole (SMX); UV–Visible spectrophotometry and LC-DAD-MS; Workflow.