Triarylmethyl Radical: EPR Signal to Noise at Frequencies between 250MHz and 1.5 GHz and Dependence of Relaxation on Radical and Salt Concentrationand on Frequency

摘要

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/T1 decreases with increasing frequency because the tumbling dependent processes that dominate relaxation at 250 MHz are less effective at higher frequency. 1/T2 also decreases with increasing frequency because 1/T1 is a significant contribution to 1/T2 for 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 for1/T2 than 1/T1. The collisional contribution torelaxation increases as the concentration of counter-ions in solution increases,which is attributed to interactions of cations with the negatively chargedradicals that decrease repulsion between trityl radicals. The Signal-to-Noiseratio (S/N) of field-swept echo-detected spectra of OX063 were measured in thefrequency range of 400 MHz–1 GHz. S/N values, normalized by √Q,increase as frequency increases. Adding salt to the radical solution decreasedS/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 ratesand higher S/N at higher frequencies are advantageous for oximetry. Thepotential disadvantage of higher frequencies is the decreased depth ofpenetration into tissue.