LC-MS/MS and LC-UV Determination of Moniliformin by Adding Lanthanide Ions to the Mobile Phase

Abstract

An innovative chromatographic analysis was developed for the determination of moniliformin (MON). Because of its ionic nature, MON is weakly retained in reversed-phase chromatography and the separation may be tricky. Nevertheless, this technique is normally used either with the formation of ion pairs or employing specific RP columns for polar compounds, or combining anion exchange and hydrophobic interactions. Hydrophilic interaction chromatography (HILIC) was also used, but a non-negligible peak tailing was observed. Besides its ionic nature, MON is a di-ketone and di-ketones, mainly β-di-ketones, can easily form complexes with lanthanide ions. Then, in this work the addition of lanthanide ions to the mobile phase was investigated, aiming at improving peak shape and MON separation. La3+, Tb3+ or Eu3+ aqueous solutions were used as mobile phase and MON was chromatographed using a LC-NH2 column. The probable formation of coordination complexes lanthanide-MON in the HPLC mobile phase allowed to obtain a symmetrical peak shape and a satisfactory chromatographic separation by both mass spectrometry (MS/MS) and UV detection. Finally, a suitable extraction and purification method for MON determination in cereal samples was developed.

Development and validation of an HPLC–DAD method for the determination of moniliformin in maize

“…Therefore, clean‐up step with MycoSep ® 240 MON column was discarded. Similarly, other authors did not obtain satisfactory recoveries using these columns and consequently clean‐up step was modified or not carried out in their method (Bertuzzi et al., 2019; Scarpino et al., 2013). They reported that the evaporation under N 2 flow decreased the recovery.…”

“…An analytical principle common for HPLC–DAD analysis of MON is the application of ion‐pair reagents to achieve good chromatographic separation (Bertuzzi et al., 2019; Parich et al., 2003). Therefore, the method development for estimation of MON was carried out using various mobile phases, with and without the addition of an ion‐pair reagent in order to examine its effect on separation and peak shape.…”

“…Purification steps mainly include the usage of strong anion exchange columns or other solid‐phase extraction columns such as MycoSep columns (EFSA, 2018). Several analytical methods for the quantification of MON have been published so far: high‐performance liquid chromatography (HPLC) with ultraviolet (UV) detection (Bertuzzi et al., 2019; Pena et al., 2019), fluorescence (FLD) detection (Filek & Lindner, 1996), diode array detection (DAD; Parich et al., 2003), thin‐layer chromatography (TLC; Kostecki et al., 1997), capillary zone electrophoresis coupled with diode array detector (CZE–DAD; Maragos, 2004), gas chromatography–mass spectrometry (GC–MS; Gilbert et al., 1986), and liquid chromatography coupled with tandem mass spectrometry (LC–MS/MS;Nazari et al., 2015; Scarpino et al., 2013).…”

Application of LC–MS/MS in the Mycotoxins Studies

“…In this sense, liquid chromatography tandem mass spectrometry (LC-MS/MS) is a powerful tool for the unique identification and quantification of analytes. Moreover, the use of high-resolution mass spectrometry (HRMS) allows the identification of novel mycotoxins and targeted/untargeted approaches for their study.This Special Issue is dedicated to recent applications of LC-MS/MS in mycotoxin studies, including the development and validation of new analytical methods for their identification and quantification in different food matrices and feed, occurrence studies and biomonitoring of mycotoxins, and their metabolites in biological fluids.Although most of the papers propose methods for the simultaneous determination of several mycotoxins, Bertuzzi et al focus their work on the improvement of determination of moniliformin (MON) by adding lanthanide ions to the mobile phase during chromatographic separation [5]. MON is weakly retained in reversed-phase chromatography, making the separation difficult.…”

“…Although most of the papers propose methods for the simultaneous determination of several mycotoxins, Bertuzzi et al focus their work on the improvement of determination of moniliformin (MON) by adding lanthanide ions to the mobile phase during chromatographic separation [5]. MON is weakly retained in reversed-phase chromatography, making the separation difficult.…”