title: Triarylmethyl Radical: EPR Signal to Noise at Frequencies between 250 MHz and 1.5 GHz and Dependence of Relaxation on Radical and Salt Concentration and on Frequency.
abstract: In vivo oximetry by pulsed electron paramagnetic resonance is based on measurements of changes in electron spin relaxation rates of probe molecules, such as the triarylmethyl radicals. A series of experiments was performed at frequencies between 250 MHz and 1.5 GHz to assist in the selection of an optimum frequency for oximetry. Electron spin relaxation rates for the triarylmethyl radical OX063 as a function of radical concentration, salt concentration, and resonance frequency were measured by electron spin echo 2-pulse decay and 3-pulse inversion recovery in the frequency range of 250 MHz-1.5 GHz. At constant OX063 concentration, 1/T1decreases with increasing frequency because the tumbling dependent processes that dominate relaxation at 250 MHz are less effective at higher frequency. 1/T2also decreases with increasing frequency because 1/T1is a significant contribution to 1/T2for trityl radicals in fluid solution. 1/T2-1/T1, the incomplete motional averaging contribution to 1/T2, increases with increasing frequency. At constant frequency, relaxation rates increase with increasing radical concentration due to contributions from collisions that are more effective for 1/T2than 1/T1. The collisional contribution to relaxation increases as the concentration of counter-ions in solution increases, which is attributed to interactions of cations with the negatively charged radicals that decrease repulsion between trityl radicals. The Signal-to-Noise ratio (S/N) of field-swept echo-detected spectra of OX063 were measured in the frequency range of 400 MHz-1 GHz. S/N values, normalized by √Q, increase as frequency increases. Adding salt to the radical solution decreased S/N because salt lowers the resonator Q. Changing the temperature from 19 to 37 °C caused little change in S/N at 700 MHz. Both slower relaxation rates and higher S/N at higher frequencies are advantageous for oximetry. The potential disadvantage of higher frequencies is the decreased depth of penetration into tissue.
authors.affiliation: Department of Chemistry and Biochemistry and Center for EPR Imaging In Vivo Physiology, University of Denver, Denver, CO 80210, USA.
authors.forename: Yilin
authors.initials: Y
authors.lastname: Shi
authors.affiliation: School of Engineering and Computer Science and Center for EPR Imaging In Vivo Physiology, University of Denver, Denver, CO 80210, USA.
authors.forename: Richard W
authors.initials: RW
authors.lastname: Quine
authors.affiliation: School of Engineering and Computer Science and Center for EPR Imaging In Vivo Physiology, University of Denver, Denver, CO 80210, USA.
authors.forename: George A
authors.initials: GA
authors.lastname: Rinard
authors.affiliation: Department of Chemistry and Biochemistry and Center for EPR Imaging In Vivo Physiology, University of Denver, Denver, CO 80210, USA.
authors.forename: Laura
authors.initials: L
authors.lastname: Buchanan
authors.affiliation: Department of Chemistry and Biochemistry and Center for EPR Imaging In Vivo Physiology, University of Denver, Denver, CO 80210, USA.
authors.forename: Sandra S
authors.initials: SS
authors.lastname: Eaton
authors.affiliation: Gareth R. Eaton, Department of Chemistry and Biochemistry and Center for EPR Imaging In Vivo Physiology, University of Denver, Denver, CO 80210, USA.
authors.forename: Gareth R
authors.initials: GR
authors.lastname: Eaton
authors.affiliation: Department of Radiation and Cellular Oncology and Center for EPR Imaging In Vivo Physiology, University of Chicago, Chicago, IL 60637, USA.
authors.forename: Boris
authors.initials: B
authors.lastname: Epel
authors.affiliation: Department of Radiation and Cellular Oncology and Center for EPR Imaging In Vivo Physiology, University of Chicago, Chicago, IL 60637, USA.
authors.forename: Simone Wanless
authors.initials: SW
authors.lastname: Seagle
authors.affiliation: Department of Radiation and Cellular Oncology and Center for EPR Imaging In Vivo Physiology, University of Chicago, Chicago, IL 60637, USA.
authors.forename: Howard J
authors.initials: HJ
authors.lastname: Halpern
keywords: cross loop resonator; electron spin relaxation; in vivo imaging; tumbling