Using Chiral Auxiliaries to Mimic the Effect of Chiral Media on the Structure of Lanthanide(III) Complexes Common in Bioimaging and Diagnostic MRI.

Nielsen, Lea Gundorff; Andersen, Helene O B; Kenwright, Alan M; Platas-Iglesias, Carlos; So Rensen, Thomas Just

Abstract

[Ln·DOTA] complexes and systems derived therefrom are commonly used in MRI and optical bioimaging. These lanthanide(III) complexes are chiral, and, in solution, they are present in four forms, with two sets of enantiomers, with the ligand donors arranged in either a square antiprismatic, SAP, or twisted square antiprismatic geometry, TSAP. This complicated speciation is found in laboratory samples. To investigate speciation in biological media, when Ln·DOTA-like complexes interact with chiral biomolecules, six Eu·DOTA-monoamide complexes were prepared and investigated by using 1D and 2D H NMR. To emulate the chirality of biological media, the amide pendant arm was modified with one or two chiral centers. It is known that a chiral center on the DOTA scaffold significantly influences the properties of the system. Here, it was found that chirality much further away from the metal center changes the available conformational space and that both chiral centers and amide / isomerism may need to be considered─a fact that, for the optically enriched materials, led to the conclusion that eight chemically different forms may need to be considered, instead of the four forms necessary for DOTA. The results reported here clearly demonstrate the diverse speciation that must be considered when correlating an observation to a structure of a lanthanide(III) complex.

Citation

Nielsen, L. G., Andersen, H. O. B., Kenwright, A. M., Platas-Iglesias, C., & So Rensen, T. J. (2024). Using Chiral Auxiliaries to Mimic the Effect of Chiral Media on the Structure of Lanthanide(III) Complexes Common in Bioimaging and Diagnostic MRI. Inorganic Chemistry, 63(17), 7560 - 7570. https://doi.org/10.1021/acs.inorgchem.3c01589

• Journal Article Type: Article
• Acceptance Date: Apr 3, 2024
• Online Publication Date: Apr 12, 2024
• Publication Date: Apr 12, 2024
• Deposit Date: May 22, 2024
• Journal: Inorganic Chemistry
• Print ISSN: 0020-1669
• Electronic ISSN: 1520-510X
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 63
• Issue: 17
• Pages: 7560 - 7570
• DOI: https://doi.org/10.1021/acs.inorgchem.3c01589
• Public URL: https://durham-repository.worktribe.com/output/2407255