Mateusz Marianski
Max Planck Society
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Featured researches published by Mateusz Marianski.
Angewandte Chemie | 2017
Eike Mucha; Ana Isabel González Flórez; Mateusz Marianski; Daniel Thomas; Waldemar Hoffmann; Weston B. Struwe; Heung Sik Hahm; Sandy Gewinner; Wieland Schöllkopf; Peter H. Seeberger; Gert von Helden; Kevin Pagel
The diversity of stereochemical isomers present in glycans and glycoconjugates poses a formidable challenge for comprehensive structural analysis. Typically, sophisticated mass spectrometry (MS)-based techniques are used in combination with chromatography or ion-mobility separation. However, coexisting structurally similar isomers often render an unambiguous identification impossible. Other powerful techniques such as gas-phase infrared (IR) spectroscopy have been limited to smaller glycans, since conformational flexibility and thermal activation during the measurement result in poor spectral resolution. This limitation can be overcome by using cold-ion spectroscopy. The vibrational fingerprints of cold oligosaccharide ions exhibit a wealth of well-resolved absorption features that are diagnostic for minute structural variations. The unprecedented resolution of cold-ion spectroscopy coupled with tandem MS may render this the key technology to unravel complex glycomes.
Journal of Chemical Physics | 2012
Mateusz Marianski; Amparo Asensio; J. J. Dannenberg
We compare the energetic and structural properties of fully optimized α-helical and antiparallel β-sheet polyalanines and the energetic differences between axial and equatorial conformations of three cyclohexane derivatives (methyl, fluoro, and chloro) as calculated using several functionals designed to treat dispersion (B97-D, ωB97x-D, M06, M06L, and M06-2X) with other traditional functionals not specifically parametrized to treat dispersion (B3LYP, X3LYP, and PBE1PBE) and with experimental results. Those functionals developed to treat dispersion significantly overestimate interaction enthalpies of folding for the α-helix and predict unreasonable structures that contain Ramachandran φ and ψ and C = O...N H-bonding angles that are out of the bounds of databases compiled the β-sheets. These structures are consistent with overestimation of the interaction energies. For the cyclohexanes, these functionals overestimate the stabilities of the axial conformation, especially when used with smaller basis sets. Their performance improves when the basis set is improved from D95∗∗ to aug-cc-pVTZ (which would not be possible with systems as large as the peptides).
Journal of Physical Chemistry A | 2012
Mateusz Marianski; Antoni Oliva; J. J. Dannenberg
We reevaluate the interaction of pyridine and p-benzoquinone using functionals designed to treat dispersion. We compare the relative energies of four different structures: stacked, T-shaped (identified for the first time), and two planar H-bonded geometries using these functionals (B97-D, ωB97x-D, M05, M05-2X, M06, M06L, and M06-2X), other functionals (PBE1PBE, B3LYP, X3LYP), MP2, and CCSD(T) using basis sets as large as cc-pVTZ. The functionals designed to treat dispersion behave erratically as the predictions of the most stable structure vary considerably. MP2 predicts the experimentally observed structure (H-bonded) to be the least stable, while single-point CCSD(T) at the MP2 optimized geometry correctly predicts the observed structure to be the most stable. We have confirmed the assignment of the experimental structure using new calculations of the vibrational frequency shifts previously used to identify the structure. The MP2/cc-pVTZ vibrational calculations are in excellent agreement with the observations. All methods used to calculate the energies provide vibrational shifts that agree with the observed structure even though most do not predict this structure to be most stable. The implications for evaluating possible π-stacking in biologically important systems are discussed.
Angewandte Chemie | 2018
Daniel A. Thomas; Mateusz Marianski; Eike Mucha; Gerard Meijer; Mark A. Johnson; Gert von Helden
The proton-bound dicarboxylate motif, RCOO- ⋅H+ ⋅- OOCR, is a prevalent chemical configuration found in many condensed-phase systems. The proton-bound formate dimer HCOO- ⋅H+ ⋅- OOCH was studied utilizing cold-ion IR action spectroscopy in the range 400-1800 cm-1 . The spectrum obtained at ca. 0.4 K of ions captured in He nanodroplets was compared to that measured at ca. 10 K by photodissociation of Ar-ion complexes. Similar band patterns are obtained by the two techniques that are consistent with calculations for a C2 symmetry structure with a proton shared equally between the two formate moieties. Isotopic substitution experiments point to the nominal parallel stretch of the bridging proton appearing as a sharp, dominant feature near 600 cm-1 . Multidimensional anharmonic calculations reveal that the bridging proton motion is strongly coupled to the flanking -COO- framework, an effect that is in line with the expected change in -C=O bond rehybridization upon protonation.
Angewandte Chemie | 2018
Eike Mucha; Maike Lettow; Mateusz Marianski; Daniel A. Thomas; Weston B. Struwe; David J. Harvey; Gerard Meijer; Peter H. Seeberger; Gert von Helden; Kevin Pagel
Fucose is an essential deoxysugar that is found in a wide range of biologically relevant glycans and glycoconjugates. A recurring problem in mass spectrometric analyses of fucosylated glycans is the intramolecular migration of fucose units, which can lead to erroneous sequence assignments. This migration reaction is typically assigned to activation during collision-induced dissociation (CID) in tandem mass spectrometry (MS). In this work, we utilized cold-ion spectroscopy and show for the first time that fucose migration is not limited to fragments obtained in tandem MS and can also be observed in intact glycan ions. This observation suggests a possible low-energy barrier for this transfer reaction and generalizes fucose migration to an issue that may universally occur in any type of mass spectrometry experiment.
Nature Communications | 2018
Eike Mucha; Mateusz Marianski; Fei-Fei Xu; Daniel A. Thomas; Gerard Meijer; Gert von Helden; Peter H. Seeberger; Kevin Pagel
Glycosyl cations are the key intermediates during the glycosylation reaction that covalently links building blocks during the synthetic assembly of carbohydrates. The exact structure of these ions remained elusive due to their transient and short-lived nature. Structural insights into the intermediate would improve our understanding of the reaction mechanism of glycosidic bond formation. Here, we report an in-depth structural analysis of glycosyl cations using a combination of cold-ion infrared spectroscopy and first-principles theory. Participating C2 protective groups form indeed a covalent bond with the anomeric carbon that leads to C1-bridged acetoxonium-type structures. The resulting bicyclic structure strongly distorts the ring, which leads to a unique conformation for each individual monosaccharide. This gain in mechanistic understanding fundamentally impacts glycosynthesis and will allow to tailor building blocks and reaction conditions in the future.Glycosyl cations are key intermediates in glycosylation reactions, but their structure has remained elusive due to their transient nature. Here, the authors perform an in-depth structural analysis and report that C2-participating protective groups induce acetoxonium cations with distinct ring conformations.
Journal of Chemical Theory and Computation | 2016
Mateusz Marianski; Adriana Supady; Teresa Ingram; Markus Schneider; Carsten Baldauf
Physical Chemistry Chemical Physics | 2016
Waldemar Hoffmann; Mateusz Marianski; Stephan Warnke; Jongcheol Seo; Carsten Baldauf; Gert von Helden; Kevin Pagel
Computational and Theoretical Chemistry | 2012
Nadya Kobko; Mateusz Marianski; Amparo Asensio; Robert Wieczorek; J. J. Dannenberg
Angewandte Chemie | 2017
Eike Mucha; Ana Isabel González Flórez; Mateusz Marianski; Daniel Thomas; Waldemar Hoffmann; Weston B. Struwe; Heung Sik Hahm; Sandy Gewinner; Wieland Schöllkopf; Peter H. Seeberger; Gert von Helden; Kevin Pagel