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A Toroidal Zr₇₀ Oxysulfate Cluster and Its Diverse Packing Structures.

ABSTRACT: Herein, we report the discovery of a toroidal inorganic cluster of zirconium(IV) oxysulfate of unprecedented size with the formula Zr₇₀ (SO₄ )₅₈ (O/OH)₁₄₆ ⋅x(H₂ O) (Zr₇₀ ), which displays different packing of ring units and thus several polymorphic crystal structures. The ring measures over 3 nm across, has an inner cavity of 1 nm and displays a pseudo-10-fold rotational symmetry of Zr₆ octahedra bridged by an additional Zr in the outer rim of the ring. Depending on the co-crystallizing species, the rings form various crystalline phases in which the torus units are connected in extended chain and network structures. One phase, in which the ring units are arranged in layers and form one-dimensional channels, displays high permanent porosity (BET surface area: 241 m² g^-1 ), and thus demonstrates a functional property for potential use in, for example, adsorption or heterogeneous catalysis.

SUBMITTER: Oien-Odegaard S

PROVIDER: S-EPMC7756470 | biostudies-literature | 2020 Nov

REPOSITORIES: biostudies-literature

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A Toroidal Zr70 Oxysulfate Cluster and Its Diverse Packing Structures.

Øien-Ødegaard Sigurd S Bazioti Calliope C Redekop Evgeniy A EA Prytz Øystein Ø Lillerud Karl Petter KP Olsbye Unni U

Angewandte Chemie (International ed. in English) 20201111 48

Herein, we report the discovery of a toroidal inorganic cluster of zirconium(IV) oxysulfate of unprecedented size with the formula Zr70 (SO4 )58 (O/OH)146 ⋅x(H2 O) (Zr70 ), which displays different packing of ring units and thus several polymorphic crystal structures. The ring measures over 3 nm across, has an inner cavity of 1 nm and displays a pseudo-10-fold rotational symmetry of Zr6 octahedra bridged by an additiona ...[more]

PMID: 32902113

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Project description:The kinetics and mechanism of the acetate ligand exchange with free acetic acid in [Zr6O4(OH)4(O2CCH3)12]2, used as a molecular model of crosslink migration in [Zr6O4(OH)4(carboxylate)12-n(OH)n]-based coordination adaptable networks with vitrimer-like properties, has been thoroughly investigated by dynamic 1H NMR and DFT calculations. The compound maintains its C2h-symmetric Zr12 structure in CD2Cl2 and C6D6, while it splits into its Zr6 subunits in CD3OD and D2O. In the Zr12 structure, the topologically different acetates (3 chelating, 6 belt-bridging, 2 intercluster-bridging and 1 inner-face-bridging) of the Zr6 subunits behave differently in the presence of free CH3COOH: very fast exchange for the chelating (coalesced resonance at room temperature), slower exchange for the belt-bridging (line broadening upon warming), no observable exchange up to 65 °C (by EXSY NMR) for the intercluster- and inner-face-bridging. The rates of the first two exchange processes have zero-order dependence on [CH3COOH]. Variable-temperature line broadening studies yielded ΔH‡ = 15.0 ± 0.4 kcal mol-1, ΔS‡ = 8 ± 1 cal mol-1 K-1 (-30 to +25 °C range in CD2Cl2) for the chelating acetates and ΔH‡ = 22.7 ± 1.6, 22.9 ± 2.1 and 20.6 ± 1.0 kcal mol-1 and ΔS‡ = 13 ± 5, 14 ± 6 and 9 ± 3 cal mol-1 K-1, respectively (+25 to +70 °C range in C6D6), for three distinct resonances of magnetically inequivalent belt-bridging acetates. With support of DFT calculations, these results point to an operationally associative mechanism involving a rate-determining partial dissociation to monodentate acetate, followed by rapid acid coordination and proton transfer. The cluster μ3-OH ligands accelerate the exchange processes through H-bonding stabilization of the coordinatively unsaturated intermediate. The lower exchange barrier for the chelated vs. bridging acetates is associated to the release of ring strain. The results presented in this investigation may help the interpretation of carboxylate exchange phenomena in other systems and the design of new carboxylate-based materials.

Project description:BackgroundIn vivo monitoring of cell biodistribution using positron emission tomography (PET) provides a quantitative non-invasive method to further optimize cell therapies and related new developments in the field. Our group has earlier optimized and evaluated the in vitro properties of two radiotracers,[89Zr]Zr-(oxinate)4 and [89Zr]Zr-DFO-NCS, for the radiolabelling of different cell types. Here, we performed a microPET study to assess the in vivo biodistribution of cells in rats using these two radiotracers. Human decidual stromal cells (hDSC) and rat macrophages (rMac) were radiolabelled with [89Zr]Zr-(oxinate)4 or [89Zr]Zr-DFO-NCS. Rats were intravenously injected with radiolabelled cells, and the in vivo biodistribution was monitored with microPET/CT imaging for up to day 7. Organ uptake was evaluated and presented as a percentage of injected activity per gram tissue (%IA/g) and total absorbed organ doses (mSv/MBq).ResultsThe biodistribution in vivo showed an immediate uptake in the lungs. Thereafter, [89Zr]Zr-(oxinate)4 labelled cells migrated to the liver, while the signal from [89Zr]Zr-DFO-NCS labelled cells lingered in the lungs. The differences in the in vivo behaviour for the same cell type appeared related to the radiotracer labelling. After 24 h, [89Zr]Zr-(oxinate)4 labelled cells had over 70% higher liver uptake for both hDSC and rMac compared to [89Zr]Zr-DFO-NCS labelled cells, whereas [89Zr]Zr-DFO-NCS labelled cells showed over 60% higher uptake in the lungs compared to [89Zr]Zr-(oxinate)4 labelled cells. This difference in both lung and liver uptake continued until day 7. Dosimetry calculations showed a higher effective dose (mSv/MBq) for [89Zr]Zr-DFO-NCS compared to [89Zr]Zr-(oxinate)4, for both cell types. Although the bone uptake was higher for [89Zr]Zr-(oxinate)4 labelled cells, the prolonged uptake in the lungs contributed to a significant crossfire to bone marrow resulting in a higher bone dose.ConclusionThe [89Zr]Zr-DFO-NCS labelled cells suggest a prolonged accumulation in the lungs, while [89Zr]Zr-(oxinate)4 suggests quicker clearance of the lungs followed by accumulation in the liver. Accumulation of radiolabelled cells in the liver corresponds to other cell-tracking methods. Further studies are required to determine the actual location of the [89Zr]Zr-DFO-NCS labelled cell.

Dataset Information

A Toroidal Zr₇₀ Oxysulfate Cluster and Its Diverse Packing Structures.

Publications

A Toroidal Zr<sub>70</sub> Oxysulfate Cluster and Its Diverse Packing Structures.

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