University of Oulu

Jayapaul, J., Komulainen, S., Zhivonitko, V.V. et al. Hyper-CEST NMR of metal organic polyhedral cages reveals hidden diastereomers with diverse guest exchange kinetics. Nat Commun 13, 1708 (2022).

Hyper-CEST NMR of metal organic polyhedral cages reveals hidden diastereomers with diverse guest exchange kinetics

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Author: Jayapaul, Jabadurai1,2; Komulainen, Sanna3; Zhivonitko, Vladimir V.3;
Organizations: 1Molecular Imaging, Department of Structural Biology, Leibniz-Forschungsinstitut für Molekulare Pharmakologie (FMP), 13125, Berlin, Germany
2Division of Translational Molecular Imaging, Deutsches Krebsforschungszentrum (DKFZ), 69120, Heidelberg, Germany
3NMR Research Unit, University of Oulu, 90014, Oulu, Finland
4Research Unit of Medical Imaging, Physics and Technology (MIPT), University of Oulu, 90014, Oulu, Finland
5University of Jyvaskyla, Department of Chemistry, 40014, Jyväskylä, Finland
Format: article
Version: published version
Access: open
Online Access: PDF Full Text (PDF, 1.2 MB)
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Language: English
Published: Springer Nature, 2022
Publish Date: 2022-10-21


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.

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Series: Nature communications
ISSN: 2041-1723
ISSN-E: 2041-1723
ISSN-L: 2041-1723
Volume: 13
Issue: 1
Article number: 1708
DOI: 10.1038/s41467-022-29249-w
Type of Publication: A1 Journal article – refereed
Field of Science: 116 Chemical sciences
114 Physical sciences
Funding: 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. Open Access funding enabled and organized by Projekt DEAL.
EU Grant Number: (772110) UFLNMR - Ultrafast Laplace NMR
Academy of Finland Grant Number: 285666
Detailed Information: 285666 (Academy of Finland Funding decision)
289649 (Academy of Finland Funding decision)
294027 (Academy of Finland Funding decision)
319216 (Academy of Finland Funding decision)
340099 (Academy of Finland Funding decision)
323480 (Academy of Finland Funding decision)
Dataset Reference: All data generated and analysed during this study are included in this article and its Supplementary Information, and are also available from the authors upon request. The details about synthesis, structural characterization, hyper-CEST spectra under different perturbation conditions, inversion recovery measurements, 2D CEST (short saturation) experiment and computational methods are available as supplementary information. The code used for computational methods, including in-house MC-NVT python code, is also available from the authors upon request. The semiempirical extended tight binding program package xtb can be assessed using the following link The xTB standalone code, Version 6.2. from the above link was utilized for the semiempirical calculations. The online version contains supplementary material available at
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