Studies of Solution Paramagnetic-Substrate Nuclear and Electron Intermolecular Interactions

Simple item page
dc.contributor.authorRuss, Jennifer Lynnen
dc.contributor.committeechairDorn, Harry C.en
dc.contributor.committeememberMerola, Joseph S.en
dc.contributor.committeememberRitter, Alfred L.en
dc.contributor.committeememberTanko, James M.en
dc.contributor.committeememberCrawford, T. Danielen
dc.contributor.departmentChemistryen
dc.date.accessioned2014-03-14T20:10:12Zen
dc.date.adate2006-04-26en
dc.date.available2014-03-14T20:10:12Zen
dc.date.issued2006-04-17en
dc.date.rdate2007-04-26en
dc.date.sdate2006-04-20en
dc.description.abstractAdvanced nuclear and electron magnetic resonance techniques (i.e. nuclear magnetic resonance (NMR), dynamic nuclear polarization (DNP), and magnetic resonance imaging (MRI)) were used to study the attitude and dynamics of TEMPO (2,2,6,6-tetramethylpiperidinyloxy)-substrate systems and the relaxivity properties of water-soluble trimetallic nitride template functionalized endohedral metallofullerenes (TNT-fMF). The attitude and average distance of interaction for each TEMPO-substrate system was determined from comparing density functional theory (DFT) calculation results with experimental hyperfine coupling constants leading to an improved understanding of solution dynamics. The short-lived solvent-solute interactions of the TEMPO-substrate molecules, such as transient complex formation, are governed by weak hydrogen-bonding interactions. The collisions in solution were explained by determining the favored orientations of the two molecules interacting using calculated relative energy minima and reproducibility of the experimental results by the calculated coupling constants. Water-soluble TNT-fMFs are studied as candidates for the next generation MRI contrast agents as diagnostic agents and also as possible therapeutic agents to kill cancer cells and decrease tumors. The TNT-fMFs are being studied as part of a multi-modal platform dependent upon which metal atoms are encapsulated inside: Gd — MRI contrast agent (diagnostic), Lu and Ho — radio labeled for use as a therapeutic agent, Tb – fluorescence, and Lu – x-ray contrast. The current commercial MRI contrast agent, OmniscanTM, contains one gadolinium atom; however, the metal is complexed to, not encapsulated in, the molecule. TNT-fMFs fully encapsulate three metal atoms to ensure the patient does not run the risk of metal poisoning. The r1 and r2 relaxivities of TNT-fMFs containing either Gd, Lu, Ho, or Sc metals were measured at 0.35T. The data for the Gd containing TNT-fMFs indicated the metallofullerene has significantly higher relaxivities than OmniscanTM, and can be the next generation MRI contrast agent. The Ho containing species has a high r2/r1 ratio compared to the other samples showing it is a potential T2 agent, and has therapeutic capabilities.en
dc.description.degreePh. D.en
dc.identifier.otheretd-04202006-115256en
dc.identifier.sourceurlhttp://scholar.lib.vt.edu/theses/available/etd-04202006-115256/en
dc.identifier.urihttp://hdl.handle.net/10919/27050en
dc.publisherVirginia Techen
dc.relation.haspartTable_of_Contents.pdfen
dc.relation.haspartDissertation_v2.pdfen
dc.rightsIn Copyrighten
dc.rights.urihttp://rightsstatements.org/vocab/InC/1.0/en
dc.subjectRelaxivityen
dc.subjectTEMPOen
dc.subjectHyperfine Coupling Constanten
dc.subjectMagnetic Resonance Imagingen
dc.subjectEndohedral Metallofullereneen
dc.subjectContrast Agenten
dc.titleStudies of Solution Paramagnetic-Substrate Nuclear and Electron Intermolecular Interactionsen
dc.typeDissertationen
thesis.degree.disciplineChemistryen
thesis.degree.grantorVirginia Polytechnic Institute and State Universityen
thesis.degree.leveldoctoralen
thesis.degree.namePh. D.en

Files

Original bundle
Now showing 1 - 2 of 2
Thumbnail Image
Name:
Table_of_Contents.pdf
Size:
49.24 KB
Format:
Adobe Portable Document Format
Download
Thumbnail Image
Name:
Dissertation_v2.pdf
Size:
2.26 MB
Format:
Adobe Portable Document Format
Download

Collections

Doctoral Dissertations