Design and synthesis of macrocyclic ligands for specific interaction with crystalline ettringite and demonstration of a viable mechanism for the setting of cement

Griffin, Jonathan L. W.; Coveney, Peter V.; Whiting, Andrew; Davey, Roger J.

doi:10.1039/a902760b

Cited by 20 publications

(15 citation statements)

References 17 publications

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“…The identity and purity of the intermediates and final product were ascertained by NMR spectroscopy, mass spectrometry, and analytical HPLC (Figures S1–S9). The macrodipa ligand was obtained via published procedures. ,, …”

Section: Results and Discussionmentioning

confidence: 99%

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Py-Macrodipa: A Janus Chelator Capable of Binding Medicinally Relevant Rare-Earth Radiometals of Disparate Sizes

Aluicio‐Sarduy

Brown

et al. 2021

J. Am. Chem. Soc.

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Supporting InformationThe Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.1c05339. Experimental procedures and supplementary data for syntheses, potentiometric titrations, UV−Vis spectrophotometric titrations, NMR spectroscopy studies, X-ray crystallography studies, DFT calculations, photophysical studies, DTPA transchelation challenges, radiolabeling studies, and human serum challenges (PDF) Crystallographic data for La 3+ −, Lu 3+ −, and Sc 3+ −py-macrodipa complexes (CIF) Geometry outputs for all DFT-optimized structures (ZIP) Accession Codes CCDC 2085495-2085497 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk

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Section: Results and Discussionmentioning

confidence: 99%

“…The macrodipa ligand was obtained via published procedures. 16,25,26 Ln 3+ Complex Stability Constants. Metal complex stability constants provide a quantitative measure of the thermodynamic affinity of ligands for metal ions.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Py-Macrodipa: A Janus Chelator Capable of Binding Medicinally Relevant Rare-Earth Radiometals of Disparate Sizes

Aluicio‐Sarduy

Brown

et al. 2021

J. Am. Chem. Soc.

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“…Starting material 2,2′-oxybis(Ntosylethan-1-amine) (1) and 6-chloromethylpyridine-2-carboxylic methyl ester were prepared as described in the literature. 30,31 Deionized H 2 O (≥18 MΩ•cm) was obtained from an Elga Purelab Flex 2 water purification system. Organic solvents were of ACS grade or higher.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Oxyaapa: A Picolinate-Based Ligand with Five Oxygen Donors that Strongly Chelates Lanthanides

Keresztes

MacMillan

et al. 2020

Inorg. Chem.

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Coordination compounds of the lanthanide ions (Ln3+) have important applications in medicine due to their photophysical, magnetic, and nuclear properties. To effectively use the Ln3+ ions for these applications, chelators that stably bind them in vivo are required to prevent toxic side effects that arise from localization of these ions in off-target tissue. In this study, two new picolinate-containing chelators, a heptadentate ligand OxyMepa and a nonadentate ligand Oxyaapa, were prepared, and their coordination chemistries with Ln3+ ions were thoroughly investigated to evaluate their suitability for use in medicine. Protonation constants of these chelators and stability constants for their Ln3+ complexes were evaluated. Both ligands exhibit a thermodynamic preference for small Ln3+ ions. The log K LuL = 12.21 and 21.49 for OxyMepa and Oxyaapa, respectively, indicating that the nonadentate Oxyaapa forms complexes of significantly higher stability than the heptadentate OxyMepa. X-ray crystal structures of the Lu3+ complexes were obtained, revealing that Oxyaapa saturates the coordination sphere of Lu3+, whereas OxyMepa leaves an additional open coordination site for a bound water ligand. Solution structural studies carried out with NMR spectroscopy revealed the presence of two possible conformations for these ligands upon Ln3+ binding. Density functional theory (DFT) calculations were applied to probe the geometries and energies of these conformations. Energy differences obtained by DFT are small but consistent with experimental data. The photophysical properties of the Eu3+ and Tb3+ complexes were characterized, revealing modest photoluminescent quantum yields of <2%. Luminescence lifetime measurements were carried out in H2O and D2O, showing that the Eu3+ and Tb3+ complexes of OxyMepa have two inner-sphere water ligands, whereas the Eu3+ and Tb3+ complexes of Oxyaapa have zero. Lastly, variable-temperature 17O NMR spectroscopy was performed for the Gd-OxyMepa complex to determine its water exchange rate constant of k ex 298 = (2.8 ± 0.1) × 106 s–1. Collectively, this comprehensive characterization of these Ln3+ chelators provides valuable insight for their potential use in medicine and garners additional understanding of ligand design strategies.

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“…Again, how the modern super‐plasticizing additives operate to change the kinetics of the reactions is empirically observed but hardly modelled at a molecular level . The organic‐inorganic interaction at the surface of the hydrating particles is a key process that is still poorly investigated, though some modelling at the molecular level has been attempted .…”

Section: Open Problemsmentioning

confidence: 99%

Cement hydration: the role of adsorption and crystal growth

Artioli

Bullard

2013

Crystal Research and Technology

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Design and synthesis of macrocyclic ligands for specific interaction with crystalline ettringite and demonstration of a viable mechanism for the setting of cement

Cited by 20 publications

References 17 publications

Py-Macrodipa: A Janus Chelator Capable of Binding Medicinally Relevant Rare-Earth Radiometals of Disparate Sizes

Py-Macrodipa: A Janus Chelator Capable of Binding Medicinally Relevant Rare-Earth Radiometals of Disparate Sizes

Oxyaapa: A Picolinate-Based Ligand with Five Oxygen Donors that Strongly Chelates Lanthanides

Cement hydration: the role of adsorption and crystal growth

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