IRMPD spectroscopy of metalated flavins: structure and bonding of Mq+-lumichrome complexes (Mq+ = Li+-Cs+, Ag+, Mg2+)

dc.contributor.authorGĂĽnther, Alan
dc.contributor.authorNieto, Pablo
dc.contributor.authorBerden, Giel
dc.contributor.authorOomens, Jos
dc.contributor.authorDopfer, Otto
dc.date.accessioned2016-06-22T08:05:23Z
dc.date.available2016-06-22T08:05:23Z
dc.date.issued2014
dc.descriptionDieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich.de
dc.descriptionThis publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively.en
dc.description.abstractInfrared multiphoton dissociation (IRMPD) spectra of mass selected isolated metal–lumichrome ionic complexes, Mq+LCn with Mq+ = Li+, Na+, K+, Rb+, Cs+, Ag+ (n = 1), and Mg2+ (n = 2), are recorded in the fingerprint range. The complexes are generated in an electrospray ionization source coupled to an ion cyclotron mass spectrometer and the IR free electron laser FELIX. Vibrational and isomer assignments of the IRMPD spectra are accomplished by density functional theory calculations at the B3LYP/cc-pVDZ level, which provide insight into the structure, binding energy, bonding mechanism, and spectral properties of the complexes. The two major binding sites identified involve metal bonding to the oxygen atoms of the two available carbonyl groups of LC (denoted O2 and O4). The more stable O4 isomer benefits from an additional interaction with the lone pair of the nearby N5 atom of LC. While M+LC with alkali metals are mainly stabilized by electrostatic forces, the Ag+LC complex reveals additional stabilization arising from partly covalent contributions. Finally, the interaction of Mg2+ ions with LC is largely enhanced by the doubled positive charge. The frequencies of the C[double bond, length as m-dash]O stretching modes are a sensitive indicator of both the metal binding site and the metal bond strength.en
dc.description.sponsorshipEC/FP7/226716/EU/European Light Sources Activities - Synchrotrons and Free Electron Lasers/ELISAen
dc.identifier.eissn1463-9076
dc.identifier.pmid24905966
dc.identifier.urihttps://depositonce.tu-berlin.de/handle/11303/5581
dc.identifier.urihttp://dx.doi.org/10.14279/depositonce-5210
dc.language.isoen
dc.rights.urihttp://rightsstatements.org/vocab/InC/1.0/en
dc.subject.ddc540 Chemie und zugeordnete Wissenschaftende
dc.titleIRMPD spectroscopy of metalated flavins: structure and bonding of Mq+-lumichrome complexes (Mq+ = Li+-Cs+, Ag+, Mg2+)en
dc.typeArticleen
dc.type.versionpublishedVersionen
dcterms.bibliographicCitation.doi10.1039/c4cp01524j
dcterms.bibliographicCitation.issue27
dcterms.bibliographicCitation.journaltitlePhysical chemistry, chemical physicsen
dcterms.bibliographicCitation.originalpublishernameRoyal Society of Chemistryde
dcterms.bibliographicCitation.originalpublisherplaceCambridgede
dcterms.bibliographicCitation.pageend14171
dcterms.bibliographicCitation.pagestart14161
dcterms.bibliographicCitation.volume16
tub.accessrights.dnbdomain
tub.affiliationFak. 2 Mathematik und Naturwissenschaften::Inst. Optik und Atomare Physikde
tub.affiliation.facultyFak. 2 Mathematik und Naturwissenschaftende
tub.affiliation.instituteInst. Optik und Atomare Physikde
tub.publisher.universityorinstitutionTechnische Universität Berlin

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