Sponsor
Portland State University. Department of Chemistry
First Advisor
Theresa McCormick
Term of Graduation
Spring 2024
Date of Publication
7-17-2024
Document Type
Thesis
Degree Name
Master of Science (M.S.) in Chemistry
Department
Chemistry
Language
English
Subjects
CEST, DFT, Macrocyclic Lanthanide Complex, paraCEST
Physical Description
1 online resource (xiii, 136 pages)
Abstract
The uses of macrocyclic lanthanide complexes are vast, with many targeted MRI contrast agents at the forefront of the field. Many of these are ParaCEST agents, which require exchangeable protons accessible on the macrocycle and the slow exchange of coordinated water molecules. The substitution at both the α- and δ-carbon on the amide pendant arm of these macrocyclic lanthanide complexes can lock bulky groups on the δ-carbon to a pseudo-axial position. When the α- and δ-carbons have the same chirality, the bulky group will be pseudo-equatorial, and when the chirality is opposed, the bulky group will be pseudo-axial. By performing DFT studies of the total free energies of these isomers, it was shown that the TSAP isomer is lower in energy for both structural isomers. These findings were seen in the NMR spectra of the hetero-chiral complexes. However, the homo-chiral complexes favored the SAP isomer in solution. The effect of the structural differences on water binding and exchange rates is yet to be determined. Still, these structures could pose a new way to vastly slow water exchange and thus improve the ParaCEST capability of newly designed targeted MRI contrast agents.
Rights
© 2024 Delainey Amara Winder
In Copyright. URI: http://rightsstatements.org/vocab/InC/1.0/ This Item is protected by copyright and/or related rights. You are free to use this Item in any way that is permitted by the copyright and related rights legislation that applies to your use. For other uses you need to obtain permission from the rights-holder(s).
Persistent Identifier
https://archives.pdx.edu/ds/psu/42430
Recommended Citation
Winder, Delainey Amara, "Synthesis and Computational Studies of α- and δ-Substituted Macrocyclic Europium and Ytterbium Complexes" (2024). Dissertations and Theses. Paper 6677.