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dc.contributor.authorJayapaul, Jabadurai
dc.contributor.authorKomulainen, Sanna
dc.contributor.authorZhivonitko, Vladimir V.
dc.contributor.authorMareš, Jiří
dc.contributor.authorGiri, Chandan
dc.contributor.authorRissanen, Kari
dc.contributor.authorLantto, Perttu
dc.contributor.authorTelkki, Ville-Veikko
dc.contributor.authorSchröder, Leif
dc.date.accessioned2022-04-04T08:27:17Z
dc.date.available2022-04-04T08:27:17Z
dc.date.issued2022
dc.identifier.citationJayapaul, J., Komulainen, S., Zhivonitko, V. V., Mareš, J., Giri, C., Rissanen, K., Lantto, P., Telkki, V.-V., & Schröder, L. (2022). Hyper-CEST NMR of metal organic polyhedral cages reveals hidden diastereomers with diverse guest exchange kinetics. <i>Nature Communications</i>, <i>13</i>, Article 1708. <a href="https://doi.org/10.1038/s41467-022-29249-w" target="_blank">https://doi.org/10.1038/s41467-022-29249-w</a>
dc.identifier.otherCONVID_117561698
dc.identifier.urihttps://jyx.jyu.fi/handle/123456789/80456
dc.description.abstractGuest capture and release are important properties of self-assembling nanostructures. Over time, a significant fraction of guests might engage in short-lived states with different symmetry and stereoselectivity and transit frequently between multiple environments, thereby escaping common spectroscopy techniques. Here, we investigate the cavity of an iron-based metal organic polyhedron (Fe-MOP) using spin-hyperpolarized 129Xe Chemical Exchange Saturation Transfer (hyper-CEST) NMR. We report strong signals unknown from previous studies that persist under different perturbations. On-the-fly delivery of hyperpolarized gas yields CEST signatures that reflect different Xe exchange kinetics from multiple environments. Dilute pools with ~ 104-fold lower spin numbers than reported for directly detected hyperpolarized nuclei are readily detected due to efficient guest turnover. The system is further probed by instantaneous and medium timescale perturbations. Computational modeling indicates that these signals originate likely from Xe bound to three Fe-MOP diastereomers (T, C3, S4). The symmetry thus induces steric effects with aperture size changes that tunes selective spin manipulation as it is employed in CEST MRI agents and, potentially, impacts other processes occurring on the millisecond time scale.en
dc.format.mimetypeapplication/pdf
dc.language.isoeng
dc.publisherNature Publishing Group
dc.relation.ispartofseriesNature Communications
dc.rightsCC BY 4.0
dc.subject.otherchemical physics
dc.subject.othermolecular self-assembly
dc.subject.otherorganometallic chemistry
dc.subject.otherself-assembly
dc.subject.othersolution-state NMR
dc.titleHyper-CEST NMR of metal organic polyhedral cages reveals hidden diastereomers with diverse guest exchange kinetics
dc.typearticle
dc.identifier.urnURN:NBN:fi:jyu-202204042135
dc.contributor.laitosKemian laitosfi
dc.contributor.laitosDepartment of Chemistryen
dc.contributor.oppiaineOrgaaninen kemiafi
dc.contributor.oppiaineOrganic Chemistryen
dc.type.urihttp://purl.org/eprint/type/JournalArticle
dc.type.coarhttp://purl.org/coar/resource_type/c_2df8fbb1
dc.description.reviewstatuspeerReviewed
dc.relation.issn2041-1723
dc.relation.volume13
dc.type.versionpublishedVersion
dc.rights.copyright© The Author(s) 2022
dc.rights.accesslevelopenAccessfi
dc.subject.ysoNMR-spektroskopia
dc.subject.ysonanorakenteet
dc.subject.ysosupramolekulaarinen kemia
dc.subject.ysoorganometalliyhdisteet
dc.format.contentfulltext
jyx.subject.urihttp://www.yso.fi/onto/yso/p26254
jyx.subject.urihttp://www.yso.fi/onto/yso/p25315
jyx.subject.urihttp://www.yso.fi/onto/yso/p37759
jyx.subject.urihttp://www.yso.fi/onto/yso/p28123
dc.rights.urlhttps://creativecommons.org/licenses/by/4.0/
dc.relation.doi10.1038/s41467-022-29249-w
jyx.fundinginformationWe acknowledge support provided by the DFG through Koselleck grant no. 316693477 (SCHR 995/5-1) and by the Dieter Morszeck Stiftung to L.S., University of Jyväskylä, the Academy of Finland (projects 285666 (P.L.), 289649 (V.-V.T.), 294027 (V.-V.T.), 319216 (V.-V.T.), 340099 (V.-V.T.) and 323480 (V.V.Z.), University of Oulu (Kvantum Institute) and Horizon 2020 (H2020/2018-2022)/ERC grant agreement no. 772110 to V.-V.T. Computational resources due to CSC (Espoo, Finland) and the Finnish Grid and Cloud Infrastructure project (persistent identifier urn:nbn:fi:research-infras-2016072533), were used. The authors thank Barth van Rossum, FMP Berlin, for support with rendering of graphical illustrations.
dc.type.okmA1


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