A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä
Hyper-CEST NMR of metal organic polyhedral cages reveals hidden diastereomers with diverse guest exchange kinetics (2022)
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. Nature Communications, 13, Article 1708. https://doi.org/10.1038/s41467-022-29249-w
JYU-tekijät tai -toimittajat
Julkaisun tiedot
Julkaisun kaikki tekijät tai toimittajat: Jayapaul, Jabadurai; Komulainen, Sanna; Zhivonitko, Vladimir V.; Mareš, Jiří; Giri, Chandan; Rissanen, Kari; Lantto, Perttu; Telkki, Ville-Veikko; Schröder, Leif
Lehti tai sarja: Nature Communications
eISSN: 2041-1723
Julkaisuvuosi: 2022
Ilmestymispäivä: 31.03.2022
Volyymi: 13
Artikkelinumero: 1708
Kustantaja: Nature Publishing Group
Julkaisumaa: Britannia
Julkaisun kieli: englanti
DOI: https://doi.org/10.1038/s41467-022-29249-w
Julkaisun avoin saatavuus: Avoimesti saatavilla
Julkaisukanavan avoin saatavuus: Kokonaan avoin julkaisukanava
Julkaisu on rinnakkaistallennettu (JYX): https://jyx.jyu.fi/handle/123456789/80456
Tiivistelmä
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.
YSO-asiasanat: supramolekulaarinen kemia; nanorakenteet; organometalliyhdisteet; NMR-spektroskopia
Vapaat asiasanat: chemical physics; molecular self-assembly; organometallic chemistry; self-assembly; solution-state NMR
Liittyvät organisaatiot
OKM-raportointi: Kyllä
Raportointivuosi: 2022
JUFO-taso: 3
