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Ion mobility-mass spectrometry (IM-MS) is a useful technique for determining information about analyte ion conformation in addition to mass/charge ratio. The physical principles that govern the mobility of an ion through a gas in the presence of a uniform electric field are well understood, enabling rotationally averaged collision cross sections (Ω) to be directly calculated from measured drift times under well-defined experimental conditions. However, such "first principle" calculations are not straightforward for Traveling Wave (T-Wave) mobility separations due to the range of factors that influence ion motion through the mobility cell. If collision cross section information is required from T-Wave mobility separations, then calibration of the instruments using known standards is essential for each set of experimental conditions. To facilitate such calibration, we have designed and generated an artificial protein based on the QconCAT technology, QCAL-IM, which upon proteolysis can be used as a universal ion mobility calibration standard. This single unique standard enables empirical calculation of peptide ion collision cross sections from the drift time on a T-Wave mobility instrument.
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http://dx.doi.org/10.1021/pr3005327 | DOI Listing |
J Am Chem Soc
December 2024
School of Chemistry, University of New South Wales, Kensington, NSW 2052, Australia.
Hydrofluoroolefins (HFOs) and hydrochlorofluoroolefins (HCFOs) are the leading synthetic replacements for compounds successively banned by the Montreal Protocol and amendments. HFOs and HCFOs readily decompose in the atmosphere to form fluorinated carbonyls, including CFCHO in yields of up to 100%, which are then photolyzed. A long-standing issue, critical for the transition to safe industrial gases, is whether atmospheric decomposition of CFCHO yields any quantity of CHF (HFC-23), which is one of the most environmentally hazardous greenhouse gases.
View Article and Find Full Text PDFPhys Sportsmed
December 2024
Department of Kinesiology and Applied Physiology, University of Delaware, Newark, DE, USA.
Objectives: To cross-sectionally determine 1) the association between lifetime diagnosed concussion and upper extremity musculoskeletal injury (UE-MSI) amongst a novel cohort of community rugby union players and 2) the sex specific risk of UE-MSI given concussion history among these rugby players.
Methods: 1,037 (31.0% female, 31.
J Phys Chem A
December 2024
Division of Electron Collisions Physics, Institute of Physics and Applied Computer Science, Faculty of Applied Physics and Mathematics, Gdańsk University of Technology, ul. Gabriela Narutowicza 11/12, 80-233 Gdańsk, Poland.
The absolute total cross section for electron collisions with acetic acid has been measured using an electrostatic electron spectrometer and linear transmission method for collision energies ranging from 0.4 to 300 eV. Elastic electron scattering from acetic acid within a low-energy range has also been studied theoretically using the Schwinger multichannel and R-matrix methods, in the static-exchange and static-exchange plus polarization levels of approximation for energies up to 15 eV.
View Article and Find Full Text PDFAnal Chem
December 2024
SCIEX, Concord, Ontario L4K 4V8, Canada.
We report the first implementation of ion mobility mass spectrometry combined with an ultrahigh throughput sample introduction technology for high-throughput screening (HTS). The system integrates differential mobility spectrometry (DMS) with acoustic ejection mass spectrometry (AEMS), termed DAEMS, enabling the simultaneous quantitation of structural isomers that are the substrates and products of isomerase-mediated reactions in intermediary metabolism. We demonstrate this potential by comparing DAEMS to a luminescence assay for the isoform of phosphoglycerate mutase (iPGM) distinctively present in pathogens, offering an opportunity as a drug target for a variety of microbial and parasite borne diseases.
View Article and Find Full Text PDFJ Am Soc Mass Spectrom
December 2024
Department of Chemistry, Bagley Hall, Box 351700, University of Washington, Seattle, Washington 98195-1700, United States.
We report a study of internal covalent cross-linking with photolytically generated diarylnitrile imines of N-terminal arginine, lysine, and histidine residues in peptide conjugates. Conjugates in which a 4-(2-phenyltetrazol-5-yl)benzoyl group was attached to C-terminal lysine, that we call RAAA--K, KAAA--K, and HAAA--K, were ionized by electrospray and subjected to UV photodissociation (UVPD) at 213 nm. UVPD triggered loss of N and proceeded by covalent cross-linking to nitrile imine intermediates that involved the side chains of N-terminal arginine, lysine, and histidine, as well as the peptide amide groups.
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