Ultra high performance supercritical fluid chromatography coupled with tandem mass spectrometry for screening of doping agents. II: Analysis of biological samples

Systematic evaluation of matrix effects in hydrophilic interaction chromatography versus reversed phase liquid chromatography coupled to mass spectrometry

“…Such differences of the occurrence and the extent of ME between HILIC and RPLC conditions may be explained by the high HILIC retention of salts and polar compounds including urea, creatinine, glucuronic acids, phenol, uric acid, hippuric acid and urobilin present in urine and probably responsible for ME. These polar endogenous compounds were certainly poorly retained in RPLC mode and, thus, did not co-elute with the analytes of interest [24,42].…”

“…Spiked urine samples were prepared by evaporating 100 L of solution containing all compounds at a concentration of 1 g/mL in MeOH to dryness under nitrogen at 40 • C before reconstitution in 100 L of filtered urine. Urine samples were 10-fold diluted with H 2 O or a solution of H 2 O/ACN 25:75 (v/v) for RPLC or HILIC analysis, respectively, to avoid any salts precipitation observed at higher amount of ACN [24]. This approach was referred to as "dilute and shoot approach" (DS) hereafter.…”

Quantitative mass spectrometry methods for pharmaceutical analysis

“…The gain in sensitivity related to mobile phase evaporation and the impact of new-generation ionization sources have also been confirmed by Grand-Guillaume Perrenoud and Novakova et al by comparing the sensitivity of UHPLC with ultra-high-performance supercritical fluid chromatography (UHPSFC). Owing to the higher desolvation efficiency of the MeOH surrounded with compressed CO 2 in the UHPSFC mobile phase, a gain in sensitivity was observed for the less retained drugs which elute under aqueous conditions in UHPLC [36,43]. Besides sensitivity issues, source design modifications can also result in more robust, repeatable and therefore more reliable data.…”

“…Acidic functional groups easily lose a proton and are thus more likely ionized in negative mode. However, pharmaceutical analyses are generally performed in positive mode, because most drugs are weak bases and thus easily protonated [35,36].…”

“…Owing to the more volatile mobile phases in comparison with those in UHPLC, UHPSFC-MS can moreover be more sensitive and less prone to MEs, especially for polar analytes. Because of the different selectivities and retention mechanisms, UHPSCF-MS is considered as an alternative or complementary approach to UHPLC-MS. Owing to its high potential applicability in the field of bioanalysis and enantioselective separations, SFC-MS is increasingly used to analyse pharmaceuticals in biological samples [36,[76][77][78][79].…”