Fast Screening and Identification of Illegal Adulterated Glucocorticoids in Dietary Supplements and Herbal Products Using UHPLC-QTOF-MS With All-Ion Fragmentation Acquisition Combined With Characteristic Fragment Ion List Classification

Ultra-high-performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (UHPLC-QTOF-MS) with all-ion fragmentation (AIF) acquisition was established for an identification and quantification of illegal adulterated glucocorticoids in dietary supplements and herbal products. Next, a novel method called characteristic fragment ion list classification (CFILC) was developed for a fast screening of adulterated compounds. CFILC could provide the characteristic ions comprehensively and completely through direct extract from the MS2 library instead of finding them manually. This is time-saving and provides fast screening results with a high confidence level by filtering of a pre-calculated threshold of similarity scores for illegal adulterants that are not included in the library as well as for new emerging structural analogs. The obtained results demonstrated the great qualitative and quantitative strength of this approach, providing a promising and powerful method for a routine fast screening of illegal adulterated glucocorticoids.

Practical aspect of dimer adduct formation in small-molecule drug analysis with LC-MS/MS

Aim: Since the MS/MS based detection of small-molecule drugs with poor or even no ion fragmentation is a challenge in bioanalysis, alternative MS/MS detection strategies were in focus of this study and applied in the field of forensic toxicology. Material & methods: Analyte quantification with liquid chromatography-tandem mass spectrometry of problematic drugs was studied by the application of dimer adduct formation and valproic acid (VPA) was used as a model drug. VPA adduct ions could be identified during infusion experiments and the VPA dimer adduct ion was optimized for the detection. Conclusion: Dimer adduct ion formation can be used as an effective way of VPA quantification in human serum. Further, the parallel detection of dimer adduct ions with other adduct ion types can be stated as advantage in LC-MS/MS analysis of problematic drugs.

Identification of N-glycans with GalNAc-containing antennae from recombinant HIV trimers by ion mobility and negative ion fragmentation

Negative ion collision-induced dissociation (CID) of underivatized N-glycans has proved to be a simple, yet powerful method for their structural determination. Recently, we have identified a series of such structures with GalNAc rather than the more common galactose capping the antennae of hybrid and complex glycans. As part of a series of publications describing the negative ion fragmentation of different types of N-glycan, this paper describes their CID spectra and estimated nitrogen cross sections recorded by travelling wave ion mobility mass spectrometry (TWIMS). Most of the glycans were derived from the recombinant glycoproteins gp120 and gp41 from the human immunodeficiency virus (HIV), recombinantly derived from human embryonic kidney (HEK 293T) cells. Twenty-six GalNAc-capped hybrid and complex N-glycans were identified by a combination of TWIMS, negative ion CID, and exoglycosidase digestions. They were present as the neutral glycans and their sulfated and α2→3-linked sialylated analogues. Overall, negative ion fragmentation of glycans generates fingerprints that reveal their structural identity.

A simulation study of excitation contour of a linear trap with spatial harmonics

The process of nonlinear resonant excitation of ion oscillations in a linear trap is studied. There is still no detailed simulation of the resonance peak in the literature. We propose to use the excitation contour to describe the collective ion resonance. The excitation contour is a resonant mass peak obtained by the trajectory method with the Gaussian distribution of the initial coordinates and velocities. The following factors are considered: excitation time, low order hexapole and octopole harmonics with amplitudes A3 and A4, the depth of the initial ion cloud position. These multipoles are used for selective ion ejection from linear ion trap. All these factors affect the ion yield and the shape of the contours. Obtained data can be useful for control of such processes as ion fragmentation, ion isolation, ion activation, and ion ejection. Simulated resonance peaks are important for the theoretical description of the ion collective nonlinear resonances.