id,collection,dc.contributor.author,dc.contributor.firstReferee,dc.contributor.furtherReferee,dc.contributor.gender,dc.date.accepted,dc.date.accessioned,dc.date.available,dc.date.issued,dc.description.abstract[en],dc.format.extent,dc.identifier.uri,dc.identifier.urn,dc.language,dc.rights.uri,dc.subject.ddc,dc.subject[en],dc.title,dc.type,dcterms.accessRights.dnb,dcterms.accessRights.openaire,dcterms.format,refubium.affiliation "e2afbdfc-2e5c-4acd-a3f3-84f24074f552","fub188/14","Wollschläger, Jan-Marwin","Schalley, Christoph","Paulus, Beate","male","2019-07-02","2019-08-09T09:48:11Z","2019-08-09T09:48:11Z","2019","Synthetic supramolecular systems share many similarities with natural biological assemblies, especially when considering that the structure and guest binding are typically governed by non-covalent interactions. As such, the defining characteristic is that only comparably weak forces define the shape of a synthetic supramolecule or the tertiary structure of a protein, so that the resulting dynamic binding mode makes structure elucidation challenging. One of the major advances in recent analytical chemistry has been the development of ion mobility-mass spectrometry (IM-MS) to tackle the challenging problems faced in proteomics, glycomics, metabolomics, and lipidomics. By analogy, the prospects of applying IM-MS to supramolecules are bright and it is to be expected that unprecedented analytical insights into diverse systems such as host-guest complexes, molecular devices, self-assemblies and metallosupramolecular complexes will be obtained. The recurrent theme throughout this dissertation is that both structure (differentiation of diastereomers, photoisomers, mechanoisomers) and non-covalent interactions (hydrogen bonding, $TTF^{n+}/TTF^{n+}$-charge repulsion, dispersive interactions) can be investigated by a combination of the three methods of ion-mobility mass spectrometry (IM-MS), collision-induced dissociation (CID) and gas-phase H/D-exchange (GP-HDX). In the study of the gas-phase chiral recognition of crown-ether ammonium complexes, the importance of a single hydrogen bond for the enantiodifferentiation was revealed. Similarly, in an azobenzene model a hydrogen bonding interaction led to an increased stability of the (Z)-photoisomer. This surprising observation illustrates an important aspect, namely that there can be significant differences between the gas-phase and the solution environment. In the absence of solvent, both the stabilization of charged sites and the Coulomb repulsion of nearby charges are accentuated. In a way, the conundrum of supramolecular mass spectrometry revolves around the problem that ions are easily manipulated in the gas-phase where a high analytic resolution power is available, to then face the question if the obtained results still reflect the solution environment. Therefore, it is very convincing to see that in three of the five presented studies, the solution environment is reflected in a quantitative fashion: In the quantification of the enantiomeric excess (first study), the quantification of photoisomer content (second study), and the quantitative determination of equilibrium constants for redox-controlled dethreading (third study). Together with these five studies, and the detailed description in the subsequent chapters, I expect the treatment to be useful also from the practitioner's point of view. It is my hope that the performance, speed, and reliability with which measurements can be performed with modern instrumentation will make IM-MS a routine analytical tool in the repertoire of the working supramolecular chemist.","242 Seiten","https://refubium.fu-berlin.de/handle/fub188/25249||http://dx.doi.org/10.17169/refubium-3954","urn:nbn:de:kobv:188-refubium-25249-5","eng","http://www.fu-berlin.de/sites/refubium/rechtliches/Nutzungsbedingungen","500 Naturwissenschaften und Mathematik::540 Chemie::543 Analytische Chemie","ion mobility||mass spectrometry||analytical chemistry||supramolecular complexes||hydrogen bonding","Tandem Mass Spectrometric and Ion Mobility Studies of Supramolecular Complexes","Dissertation","free","open access","Bild||Text","Biologie, Chemie, Pharmazie"