Instrument and Application Development in Saturation Recovery and Rapid Scan Electron Paramagnetic Resonance
Date of Award
Chemistry and Biochemistry
Gareth R. Eaton
Sandra S. Eaton
Bryan J. Cowen
Brian J. Majestic
Electron paramagnetic resonance, Instrumentation, Magnetic resonance, Physical chemistry, Rapid scan, Saturation recovery
Enhanced signal sensitivity by the use of Rapid Scan (RS) electron paramagnetic resonance (EPR), a technique that allows for much faster magnetic field scans than traditional field-swept techniques, has facilitated improved data acquisition for many types of samples. For example, irradiated fingernails for radiation dosimetry have been studied using RS-EPR, which resulted in substantial decreases in detection limits. Samarium-mediated reduction mechanisms in organic synthesis have been investigated by RS-EPR providing evidence for a radical intermediate. Spectra of organic radicals exhibiting both narrow lines and closely spaced hyperfine interactions have been recorded via RS-EPR. Well-resolved spectra can be recorded at a rate of 40 spectra/minute to gain insight into molecular changes on this timescale. RS-EPR performed at low temperatures using a closed cycle helium system and a cryostat containing a region with low electrical conductivity provides very wide (>9000 G) spectra free of passage effects near 5 K, expanding the capabilities of RS-EPR.
Recent developments in arbitrary wave form generators (AWGs) provide digital waveform synthesis at high enough frequencies to be used in EPR experiments at ca. 9 GHz (X-band). A new saturation recovery (SR) EPR spectrometer has been constructed with an AWG as the microwave source. Circuit design focuses on implementation of an X-band crossed-loop resonator with a reduced quality factor (Q) to minimize dead time due to resonator ring down processes. Increased accuracy of the AWG instrument relative to conventional sources has made nitroxide spin-lattice relaxation time measurements possible via SR-EPR with S/N high enough to permit separation of electron and nuclear spin-lattice relaxation contributions. These results enabled more accurate estimation of the saturation factor in dynamic nuclear polarization (DNP) experiments.
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McPeak, Joseph E., "Instrument and Application Development in Saturation Recovery and Rapid Scan Electron Paramagnetic Resonance" (2020). Electronic Theses and Dissertations. 1808.
Received from ProQuest
Joseph E. McPeak
Chemistry, Physical chemistry, Electrical engineering
Electrical and Computer Engineering Commons, Other Chemistry Commons, Physical Chemistry Commons