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dc.contributor.authorMyers, William
dc.date.accessioned2009-01-30T16:24:24Z
dc.date.available2009-01-30T16:24:24Z
dc.date.issued2009-01-30T16:24:24Z
dc.date.submittedDecember 2008
dc.identifier.urihttp://hdl.handle.net/1928/7652
dc.description.abstractHerein, a systematic frozen solution electron-nuclear double resonance (ENDOR) study of high-spin Co(II) complexes is reported to demonstrate the efficacy of methyl substitutions as a means of separating dipolar and contact coupling, and further, to increase the utility of high-spin Co(II) as a spectroscopic probe for the ubiquitous, but spectroscopically-silent Zn(II) metalloenzymes. High-spin (hs) Co(II) has been subject of paramagnetic resonance studies for over 50 years and has been used as a spectroscopic probe for Zn metalloenzymes for over 35 years. However, as will be seen, the inherent complexity of the electronic properties of the cobaltous ion remains to be exploited to offer a wealth of information on Zn(II) enzymatic environments. Specifically, ENDOR measurements on bistrispyrazolylborate cobalt(II) confirm the utility of the novel method of methyl substitution to differentiate dipolar and Fermi contact couplings. An extensive set of electron paramagnetic resonance (EPR) simulations were performed. Software was developed to implement an ENDOR control interface. Finally, proton relaxation measurements were made in the range of 12-42 MHz, which were accounted for with the large g-value anisotropy of the Co(II) compounds. Taken as a whole, these studies point to the rich complexity of the electronic structure of high-spin cobalt(II) and, when sufficiently well-characterized, the great utility it has as a surrogate of biological Zn(II).en_US
dc.language.isoen_USen_US
dc.subjectCobalten_US
dc.subjectENDORen_US
dc.subjecthigh-spin cobalten_US
dc.subjectBistrispyrazolylborate compounds.en_US
dc.subject.lcshCobalt compounds--Spectra.
dc.subject.lcshPyrazoles--Spectra.
dc.subject.lcshElectron nuclear double resonance spectroscopy.
dc.subject.lcshMetalloenzymes.
dc.titleParamagnetic resonance studies of bistrispyrazolylborate cobalt(II) and related derivativesen_US
dc.typeDissertationen_US
dc.description.degreeDoctor of Chemistryen_US
dc.description.levelDoctoralen_US
dc.description.departmentUniversity of New Mexico. Dept. of Chemistryen_US
dc.description.advisorTierney, David
dc.description.committee-memberKirk, Martin
dc.description.committee-memberGuo, Hua
dc.description.committee-memberFukushima, Eiichi


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