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

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          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 ~ 10 4-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,  C 3,  S 4). 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.

          Abstract

          Self-assembling nanostructures that trap guest molecules find applications in materials research and the life sciences. Here, authors describe how ultra-sensitive NMR reveals sub-types with broken symmetry that significantly impacts guest exchange.

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          Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density

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            A new mixing of Hartree–Fock and local density-functional theories

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              • Abstract: not found
              • Article: not found

              GFN2-xTB—An Accurate and Broadly Parametrized Self-Consistent Tight-Binding Quantum Chemical Method with Multipole Electrostatics and Density-Dependent Dispersion Contributions

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                Author and article information

                Contributors
                perttu.lantto@oulu.fi
                leif.schroeder@dkfz.de
                Journal
                Nat Commun
                Nat Commun
                Nature Communications
                Nature Publishing Group UK (London )
                2041-1723
                31 March 2022
                31 March 2022
                2022
                : 13
                : 1708
                Affiliations
                [1 ]GRID grid.418832.4, ISNI 0000 0001 0610 524X, Molecular Imaging, Department of Structural Biology, , Leibniz-Forschungsinstitut für Molekulare Pharmakologie (FMP), ; 13125 Berlin, Germany
                [2 ]GRID grid.7497.d, ISNI 0000 0004 0492 0584, Division of Translational Molecular Imaging, , Deutsches Krebsforschungszentrum (DKFZ), ; 69120 Heidelberg, Germany
                [3 ]GRID grid.10858.34, ISNI 0000 0001 0941 4873, NMR Research Unit, University of Oulu, ; 90014 Oulu, Finland
                [4 ]GRID grid.10858.34, ISNI 0000 0001 0941 4873, Research Unit of Medical Imaging, Physics and Technology (MIPT), University of Oulu, ; 90014 Oulu, Finland
                [5 ]GRID grid.9681.6, ISNI 0000 0001 1013 7965, University of Jyvaskyla, Department of Chemistry, ; 40014 Jyväskylä, Finland
                Author information
                http://orcid.org/0000-0001-5141-1166
                http://orcid.org/0000-0002-1634-5359
                http://orcid.org/0000-0003-2919-8690
                http://orcid.org/0000-0001-6107-3199
                http://orcid.org/0000-0001-7026-6320
                http://orcid.org/0000-0002-7282-8419
                http://orcid.org/0000-0003-0685-7657
                http://orcid.org/0000-0003-0846-6852
                http://orcid.org/0000-0003-4901-0325
                Article
                29249
                10.1038/s41467-022-29249-w
                8971460
                35361759
                eda8e7a8-c0dd-4db3-aae7-577c123bda4c
                © The Author(s) 2022

                Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.

                History
                : 26 May 2021
                : 3 March 2022
                Funding
                Funded by: FundRef https://doi.org/10.13039/501100002341, Academy of Finland (Suomen Akatemia);
                Award ID: 323480
                Award ID: 285666
                Award ID: 289649
                Award ID: 294027
                Award ID: 319216
                Award Recipient :
                Funded by: FundRef https://doi.org/10.13039/100010663, EC | EU Framework Programme for Research and Innovation H2020 | H2020 Priority Excellent Science | H2020 European Research Council (H2020 Excellent Science - European Research Council);
                Award ID: 772110
                Award Recipient :
                Funded by: FundRef https://doi.org/10.13039/501100001659, Deutsche Forschungsgemeinschaft (German Research Foundation);
                Award ID: 316693477
                Award Recipient :
                Funded by: Dieter Morszeck Stiftung
                Categories
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                © The Author(s) 2022

                Uncategorized
                organometallic chemistry,self-assembly,molecular self-assembly,chemical physics,solution-state nmr

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