dc.contributor.author | Jayapaul, Jabadurai | |
dc.contributor.author | Komulainen, Sanna | |
dc.contributor.author | Zhivonitko, Vladimir V. | |
dc.contributor.author | Mareš, Jiří | |
dc.contributor.author | Giri, Chandan | |
dc.contributor.author | Rissanen, Kari | |
dc.contributor.author | Lantto, Perttu | |
dc.contributor.author | Telkki, Ville-Veikko | |
dc.contributor.author | Schröder, Leif | |
dc.date.accessioned | 2022-04-04T08:27:17Z | |
dc.date.available | 2022-04-04T08:27:17Z | |
dc.date.issued | 2022 | |
dc.identifier.citation | Jayapaul, 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.other | CONVID_117561698 | |
dc.identifier.uri | https://jyx.jyu.fi/handle/123456789/80456 | |
dc.description.abstract | Guest 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.mimetype | application/pdf | |
dc.language.iso | eng | |
dc.publisher | Nature Publishing Group | |
dc.relation.ispartofseries | Nature Communications | |
dc.rights | CC BY 4.0 | |
dc.subject.other | chemical physics | |
dc.subject.other | molecular self-assembly | |
dc.subject.other | organometallic chemistry | |
dc.subject.other | self-assembly | |
dc.subject.other | solution-state NMR | |
dc.title | Hyper-CEST NMR of metal organic polyhedral cages reveals hidden diastereomers with diverse guest exchange kinetics | |
dc.type | article | |
dc.identifier.urn | URN:NBN:fi:jyu-202204042135 | |
dc.contributor.laitos | Kemian laitos | fi |
dc.contributor.laitos | Department of Chemistry | en |
dc.contributor.oppiaine | Orgaaninen kemia | fi |
dc.contributor.oppiaine | Organic Chemistry | en |
dc.type.uri | http://purl.org/eprint/type/JournalArticle | |
dc.type.coar | http://purl.org/coar/resource_type/c_2df8fbb1 | |
dc.description.reviewstatus | peerReviewed | |
dc.relation.issn | 2041-1723 | |
dc.relation.volume | 13 | |
dc.type.version | publishedVersion | |
dc.rights.copyright | © The Author(s) 2022 | |
dc.rights.accesslevel | openAccess | fi |
dc.subject.yso | NMR-spektroskopia | |
dc.subject.yso | nanorakenteet | |
dc.subject.yso | supramolekulaarinen kemia | |
dc.subject.yso | organometalliyhdisteet | |
dc.format.content | fulltext | |
jyx.subject.uri | http://www.yso.fi/onto/yso/p26254 | |
jyx.subject.uri | http://www.yso.fi/onto/yso/p25315 | |
jyx.subject.uri | http://www.yso.fi/onto/yso/p37759 | |
jyx.subject.uri | http://www.yso.fi/onto/yso/p28123 | |
dc.rights.url | https://creativecommons.org/licenses/by/4.0/ | |
dc.relation.doi | 10.1038/s41467-022-29249-w | |
jyx.fundinginformation | We 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.okm | A1 | |