A1 Journal article (refereed)
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 authors or editors

Publication details

All authors or editorsJayapaul, Jabadurai; Komulainen, Sanna; Zhivonitko, Vladimir V.; Mareš, Jiří; Giri, Chandan; Rissanen, Kari; Lantto, Perttu; Telkki, Ville-Veikko; Schröder, Leif

Journal or seriesNature Communications


Publication year2022

Publication date31/03/2022


Article number1708

PublisherNature Publishing Group

Publication countryUnited Kingdom

Publication languageEnglish


Publication open accessOpenly available

Publication channel open accessOpen Access channel

Publication is parallel published (JYX)https://jyx.jyu.fi/handle/123456789/80456


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.

Keywordssupramolecular chemistrynanostructuresorganometallic compoundsNMR spectroscopy

Free keywordschemical physics; molecular self-assembly; organometallic chemistry; self-assembly; solution-state NMR

Contributing organizations

Ministry reportingYes

Reporting Year2022

JUFO rating3

Last updated on 2024-15-06 at 20:26