Relative quantification of polyethylene glycol 400 excreted in the urine of male and female volunteers by direct injection electrospray-selected ion monitoring mass spectrometry

Development and Application of an MSALL-Based Approach for the Quantitative Analysis of Linear Polyethylene Glycols in Rat Plasma by Liquid Chromatography Triple-Quadrupole/Time-of-Flight Mass Spectrometry

“…Following infusion into the Q-TOF MS from a syringe pump, PEG standard solutions were full scanned in the TOF-MS mode with CE set at the minimum value and DP adjusted manually. For low MW PEGs, a normal distribution of singly charged PEG precursor ions was observed (Figure A) with [M + H] + , [M + Na] + , and [M + K] + ions all present in good agreement with a previous report . For medium and high MW PEGs (Figure B and C), irrespective of how DP was adjusted, only ions with m / z in the range 400–1400 were observed and virtually no ions with m / z > 2500.…”

“…In recent years, the rapidly developing technique of LC-MS/MS has raised bioanalysis to a new level. Its first application to PEGs was to measure PEG 400 in urine based on direct injection electrospray ionization (ESI) combined with detection by selected ion monitoring (SIM) . Unfortunately the technique was of limited selectivity and prone to interference from endogenous substances.…”

Development of a stable isotope dilution LC–MS assay for the quantitation of multiple polyethylene glycol (PEG) homologues to be used in permeability studies

“…This is generally the case [23 ,24] when deuterium is used as stable isotope label. In our method half of the labels (4 and 8 labels respectively) were deuterium, but with the high MW of PEG ( below the data found in literature, which ranged from 0.1 to 50 µg/mL for PEG 400 with ELSD and RI detection [3,5,7] and 45 to 800 ng/mL for PEG 300 and PEG 400 with MS detection, respectively [8][9][10]. Data for the larger PEG varied between 0.1 and 5 µg/mL with ELSD and RI [3][4][5]7], but no values for MS detection of PEG with similar MW could be found.…”

“…Examples for overlaps are (1) the ammonium adduct of PEG13 (m/z 608.7 Da) and PEG80 with six ammonium charges (m/z 608.4 Da) or (2) PEG65 with five ammonium charges (m/z 594.3 Da), six fold ammoniated PEG78 (m/z 593.7 Da) and the adduct of PEG91 with seven ammonium (m/z 593.3 Da). This restriction could be circumvented by LC separation, but this clearly extended the measurement time in comparison to other methods [8][9][10][11]. In the chromatograms a shift of retention time between the analyte and the corresponding labelled standard of about 0.1 min was observed.…”

“…Using MS technology, short measurement periods with ultra HPLC (UHPLC) or complete waiving of separation in flow injection analysis (FIA) MS are favored, without loss of accuracy. However, with the latter method only short-chained PEG (PEG 300, PEG 400) [8][9][10] and branched 40 kDa PEG [11] have been examined in biological or pharmaceutical samples. At present, electrospray ionization (ESI) with detection of the protonated molecules or the sodium, ammonium or potassium adducts have been applied most commonly.…”