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Suppression of Collision-Induced Dissociation in a Supersonically Expanding Gas.
Anal Chem
January 2025
Department of Physics & CAMOST, IISER Tirupati, Tirupati 517619, Andhra Pradesh, India.
In high-resolution mass spectrometry, an electrospray ionization source is often paired with an ion-funnel to enhance ion transmission. Although it is established that ions experience collision-induced dissociation as they pass through this device, the impact of gas-flow dynamics on ion fragmentation remains unexplored. The present work demonstrates that the gas-flow dynamics from the capillary interface of an electrospray ionization source into an ion-funnel significantly reduces ion fragmentation.
View Article and Find Full Text PDF[Vacuum ultraviolet laser dissociation and proteomic analysis of halogenated peptides].
Se Pu
February 2025
CAS Key Laboratory of Separation Sciences for Analytical Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
Chemical modifications are widely used in research fields such as quantitative proteomics and interaction analyses. Chemical-modification targets can be roughly divided into four categories, including those that integrate isotope labels for quantification purposes, probe the structures of proteins through covalent labeling or cross-linking, incorporate labels to improve the ionization or dissociation of characteristic peptides in complex mixtures, and affinity-enrich various poorly abundant protein translational modifications (PTMs). A chemical modification reaction needs to be simple and efficient for use in proteomics analysis, and should be performed without any complicated process for preparing the labeling reagent.
View Article and Find Full Text PDFA Unique Intramolecular Redox Reaction by Unidirectional Migration of Three Hydrogen Atoms: Theoretical Elucidation of the 3H-Transfer Sequence.
Chemistry
January 2025
TU Chemnitz: Technische Universitat Chemnitz, Insitut für Chemie, Straße der Nationen 62, 09111, Chemnitz, GERMANY.
The intramolecular migration of three hydrogen atoms from one moiety of a gaseous radical cation to the other prior to fragmentation is an extremely rare type of redox reaction. Within the scope of this investigation, this scenario requires an ionized but electron-rich arene acceptor bearing a para-(3-hydroxyalkyl) residue. The precise mechanism of such unidirectional 3H transfer processes, including the order of the individual H transfer steps, has remained unclear in spite of previous isotope labelling and recent infrared ion spectroscopy (IRIS) studies.
View Article and Find Full Text PDFGas-Phase Fragmentation of Coenzyme Q Radical Anion Generated by APCI: A Study by High/Low-Resolution Tandem/Sequential Mass Spectrometry.
J Am Soc Mass Spectrom
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Dipartimento di Scienze del Suolo, della Pianta e degli Alimenti, Università degli Studi di Bari Aldo Moro, Via G. Amendola 165/a, 70126 Bari, Italy.
Coenzyme Q (CoQ) and closely related compounds with varying isoprenoid tail lengths (CoQ, = 6-9) are biochemical cofactors involved in many physiological processes, playing important roles in cellular respiration and energy production. Liquid chromatography (LC) coupled with single or tandem mass spectrometry (MS) using electrospray (ESI) or atmospheric pressure chemical ionization (APCI) is considered the gold standard for the identification and quantification of CoQ in food and biological samples. However, the characteristic fragmentation exhibited by the CoQ radical anion ([M], / 862.
View Article and Find Full Text PDFSelected Ion Extraction of Peptides with Heavy Isotopes and Hydrogen Loss Reduces the Type II Error in Plasma Proteomics.
ACS Omega
January 2025
Department of Chemistry and Biology, Faculty of Science, Toronto Metropolitan University, 350 Victoria Street, Toronto, Ontario M5B 2K3, Canada.
Naturally occurring peptides display a wide mass distribution after ionization due to the presence of heavy isotopes of C, H, N, O, and S and hydrogen loss. There is a crucial need for sensitive methods that collect as much information as possible about all plasma peptide forms. Statistical analysis of the delta mass distribution of peptide precursors from MS/MS spectra that were matched to 63,077 peptide sequences by X!TANDEM revealed Gaussian peaks representing heavy isotopes and hydrogen loss at integer delta mass values of -3, -2, -1, 0, +1, +2, +3, +4, and +5 Da.
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