Microhydration of substituted diamondoid radical cations of biological relevance: infrared spectra of amantadine+-(H2O)n = 1–3 clusters

dc.contributor.authorGeorge, Martin Andreas Robert
dc.contributor.authorButtenberg, Friedrich
dc.contributor.authorFörstel, Marko
dc.contributor.authorDopfer, Otto
dc.date.accessioned2021-01-07T09:40:44Z
dc.date.available2021-01-07T09:40:44Z
dc.date.issued2020-11-18
dc.description.abstractHydration of biomolecules and pharmaceutical compounds has a strong impact on their structure, reactivity, and function. Herein, we explore the microhydration structure around the radical cation of the widespread pharmaceutical drug amantadine (C16H15NH2, Ama) by infrared photodissociation (IRPD) spectroscopy of mass-selected Ama+Wn = 1–3 clusters (W = H2O) recorded in the NH, CH, and OH stretch range of the cation ground electronic state. Analysis of the size-dependent frequency shifts by dispersion-corrected density functional theory calculations (B3LYP-D3/cc-pVTZ) provides detailed information about the acidity of the protons of the NH2 group of Ama+ and the structure and strength of the NH⋯O and OH⋯O hydrogen bonds (H-bonds) of the hydration network. The preferred sequential cluster growth begins with hydration of the two acidic NH protons of the NH2 group (n = 1–2) and continues with an extension of the H-bonded hydration network by forming an OH⋯O H-bond of the third W to one ligand in the first hydration subshell (n = 3), like in the W2 dimer. For n = 2, a minor population corresponds to Ama+W2 structures with a W2 unit attached to Ama+via a NH⋯W2 H-bond. Although the N–H proton donor bonds are progressively destabilized by gradual microhydration, no proton transfer to the Wn solvent cluster is observed in the investigated size range (n ≤ 3). Besides the microhydration structure, we also obtain a first impression of the structure and IR spectrum of bare Ama+, as well as the effects of both ionization and hydration on the structure of the adamantyl cage. Comparison of Ama+ with aliphatic and aromatic primary amine radical cations reveals differences in the acidity of the NH2 group and the resulting interaction with W caused by substitution of the cycloalkyl cage.en
dc.description.sponsorshipTU Berlin, Open-Access-Mittel – 2020en
dc.identifier.eissn1463-9084
dc.identifier.issn1463-9076
dc.identifier.urihttps://depositonce.tu-berlin.de/handle/11303/12360
dc.identifier.urihttp://dx.doi.org/10.14279/depositonce-11200
dc.language.isoenen
dc.relation.ispartof10.14279/depositonce-18298
dc.rights.urihttps://creativecommons.org/licenses/by/3.0/en
dc.subject.ddc540 Chemie und zugeordnete Wissenschaftende
dc.subject.otheramantadine+-(H2O)n = 1–3en
dc.subject.othermicrohydrationen
dc.subject.othersubstituted diamondoid radical cationsen
dc.titleMicrohydration of substituted diamondoid radical cations of biological relevance: infrared spectra of amantadine+-(H2O)n = 1–3 clustersen
dc.typeArticleen
dc.type.versionpublishedVersionen
dcterms.bibliographicCitation.doi10.1039/D0CP05299Jen
dcterms.bibliographicCitation.issue48en
dcterms.bibliographicCitation.journaltitlePhysical Chemistry, Chemical Physicsen
dcterms.bibliographicCitation.originalpublishernameRoyal Society of Chemistryen
dcterms.bibliographicCitation.originalpublisherplaceCambridgeen
dcterms.bibliographicCitation.pageend28139en
dcterms.bibliographicCitation.pagestart28123en
dcterms.bibliographicCitation.volume22en
tub.accessrights.dnbfreeen
tub.affiliationFak. 2 Mathematik und Naturwissenschaften::Inst. Optik und Atomare Physik::FG Lasermolekülspektroskopie und Umweltphysikde
tub.affiliation.facultyFak. 2 Mathematik und Naturwissenschaftende
tub.affiliation.groupFG Lasermolekülspektroskopie und Umweltphysikde
tub.affiliation.instituteInst. Optik und Atomare Physikde
tub.publisher.universityorinstitutionTechnische Universität Berlinen

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