ORCID Profile
0000-0003-0564-203X
Current Organisation
Fritz-Haber-Institut der Max-Planck-Gesellschaft
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Publisher: Wiley
Date: 24-03-2022
Abstract: Over the course of the COVID-19 pandemic, mRNA-based vaccines have gained tremendous importance. The development and analysis of modified RNA molecules benefit from advanced mass spectrometry and require sufficient understanding of fragmentation processes. Analogous to the degradation of RNA in solution by autohydrolysis, backbone cleavage of RNA strands was equally observed in the gas phase however, the fragmentation mechanism remained elusive. In this work, autohydrolysis-like intermediates were generated from isolated RNA dinucleotides in the gas phase and investigated using cryogenic infrared spectroscopy in helium nanodroplets. Data from both experiment and density functional theory provide evidence for the formation of a five-membered cyclic phosphate intermediate and rule out linear or six-membered structures. Furthermore, the experiments show that another prominent condensed-phase reaction of RNA nucleotides can be induced in the gas phase: the tautomerization of cytosine. Both observed reactions are therefore highly universal and intrinsic properties of the investigated molecules.
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/D0CP02482A
Abstract: Kinetic trapping in helium nanodroplets enables measurement of conformer thermochemistry via infrared spectroscopy at 0.4 K.
Publisher: Springer Science and Business Media LLC
Date: 11-02-2022
DOI: 10.1007/S00216-022-03927-6
Abstract: Tandem mass spectrometry is arguably the most important analytical tool for structure elucidation of lipids and other metabolites. By fragmenting intact lipid ions, valuable structural information such as the lipid class and fatty acyl composition are readily obtainable. The information content of a fragment spectrum can often be increased by the addition of metal cations. In particular, the use of silver ions is deeply rooted in the history of lipidomics due to their propensity to coordinate both electron-rich heteroatoms and C = C bonds in aliphatic chains. Not surprisingly, coordination of silver ions was found to enable the distinction of sn -isomers in glycerolipids by inducing reproducible intensity differences in the fragment spectra, which could, however, not be rationalized. Here, we investigate the fragmentation behaviors of silver-adducted sn - and double bond glycerophospholipid isomers by probing fragment structures using cryogenic gas-phase infrared (IR) spectroscopy. Our results confirm that neutral headgroup loss from silver-adducted glycerophospholipids leads to dioxolane-type fragments generated by intramolecular cyclization. By combining high-resolution IR spectroscopy and computational modelling of silver-adducted fragments, we offer qualitative explanations for different fragmentation behaviors of glycerophospholipid isomers. Overall, the results demonstrate that gas-phase IR spectroscopy of fragment ions can significantly contribute to our understanding of lipid dissociation mechanisms and the influence of coordinating cations. Graphical abstract
Publisher: Springer Science and Business Media LLC
Date: 22-02-2021
DOI: 10.1038/S41467-021-21480-1
Abstract: Glycolipids are complex glycoconjugates composed of a glycan headgroup and a lipid moiety. Their modular biosynthesis creates a vast amount of erse and often isomeric structures, which fulfill highly specific biological functions. To date, no gold-standard analytical technique can provide a comprehensive structural elucidation of complex glycolipids, and insufficient tools for isomer distinction can lead to wrong assignments. Herein we use cryogenic gas-phase infrared spectroscopy to systematically investigate different kinds of isomerism in immunologically relevant glycolipids. We show that all structural features, including isomeric glycan headgroups, anomeric configurations and different lipid moieties, can be unambiguously resolved by diagnostic spectroscopic fingerprints in a narrow spectral range. The results allow for the characterization of isomeric glycolipid mixtures and biological applications.
Publisher: Wiley
Date: 18-05-2020
Publisher: Wiley
Date: 24-04-2022
Publisher: Wiley
Date: 22-06-2020
Publisher: Wiley
Date: 18-05-2020
Publisher: Wiley
Date: 22-06-2020
Publisher: Wiley
Date: 24-04-2022
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D0CP05195K
Abstract: Infrared multiple-photon dissociation spectroscopy reveals the nature of nitrous oxide binding to metal clusters.
Publisher: American Chemical Society (ACS)
Date: 03-06-2020
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/D0CP02800B
Abstract: Infrared multiple-photon dissociation spectroscopy has been applied to study Pt n (N 2 O) + ( n = 1–8) clusters which represent entrance-channel complexes on the reactive potential energy surface for nitrous oxide decomposition on platinum.
Publisher: American Chemical Society (ACS)
Date: 05-11-2020
Publisher: American Chemical Society (ACS)
Date: 02-09-2021
DOI: 10.1021/JACS.1C06944
Publisher: Wiley
Date: 24-03-2022
Abstract: Im Laufe der COVID‐19 Pandemie haben mRNA‐basierte Impfstoffe an immenser Bedeutung gewonnen. Massenspektrometrie ist für die Entwicklung und Analyse von modifizierten RNA Molekülen unerlässlich, setzt jedoch ein grundlegendes Verständnis über Fragmentierungsprozesse voraus. Analog zu der Zersetzung von RNA in Lösung durch Autohydrolyse, kann die Spaltung des RNA Rückgrats ebenso in der Gasphase stattfinden. Bislang sind die Fragmentierungsmechanismen jedoch unzureichend untersucht. In dieser Arbeit wurden Intermediate aus isolierten RNA Dinukleotiden in der Gasphase generiert und mittels kryogener Infrarotspektroskopie in Helium‐Nanotröpfchen untersucht. Die experimentellen Daten, unterstützt durch Dichtefunktionaltheorie, liefern Hinweise dafür, dass die Bildung eines fünfgliedrigen zyklischen Phosphat‐Intermediats begünstigt ist, während lineare oder sechsgliedrige Strukturen ausgeschlossen werden können. Weiterhin zeigen die Experimente, dass eine zusätzliche, bekannte Reaktion von RNA Nukleotiden in Lösung auch in der Gasphase induziert werden kann: die Tautomerisierung von Cytosin. Die beiden beobachteten Reaktionen spiegeln daher universelle und intrinsische Eigenschaften der untersuchten Moleküle wider.
Publisher: American Physical Society (APS)
Date: 16-07-2021
Publisher: Royal Society of Chemistry (RSC)
Date: 2023
DOI: 10.1039/D2SC06487A
Abstract: 3-Pyridylcarbinol ester derivatization introduces a universal probe for cryogenic gas-phase infrared spectroscopy of fatty acids that enables assignment of the position and configuration of carbon–carbon double bonds even in the presence of isomers.
No related grants have been discovered for Wieland Schöllkopf.