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/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 for 1/T2 than 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.

UHF EPR spectrometer operating at frequencies between 400 MHz and 1 GHz

“…The increase in T 1 with increasing frequency is consistent with published results at 250 MHz and 1 GHz . The dependence of T 1 and T 2 for OX063 on frequency, radical concentration, and salt concentration are described in detail in reference …”

“…12 The dependence of T 1 and T 2 for OX063 on frequency, radical concentration, and salt concentration are described in detail in reference. 13…”

Assessment of blood–brain barrier leakage and brain oxygenation in Connexin‐32 knockout mice with systemic neuroinflammation using pulse electron paramagnetic resonance imaging techniques

“…However, in our experiments, trityl showed a limited leakage in the brain for all animals, and that allowed us to quantify the leakage in BBB for experimental and WT animals. The reason for this could be that our scanner operated at 25‐mT field that has a higher SNR than most scanners (9 or 10 mT) used for EPR imaging in the field 70 . This allowed us to acquire images in much finer detail.…”

Tabletop 700 MHz electron paramagnetic resonance imaging spectrometer

“…11 However, the goal usually is to image a constant small volume element (voxel), and for this case the EPR signal increases with increase in frequency. [12][13][14] Depth of penetration is greater at lower frequency. 15 For many animal and eventual human studies the Halpern and Krishna laboratories chose 250 and 300 MHz as a reasonable trade-off of depth of penetration and signal amplitude.…”