Vol 48, No 11-12 (2017)

In recent years, electron–electron double resonance detected nuclear magnetic resonance (EDNMR) has gained considerable attention as a pulsed electron paramagnetic resonance technique to probe hyperfine interactions. Most experiments published so far were performed at W-band frequencies or higher, as at lower frequencies detection of weakly coupled low-γ nuclei is hampered by the presence of a central blind spot, which occurs at zero frequency. In this article we show that EDNMR measurements and a meaningful data analysis is indeed possible at intermediate microwave frequencies (Q-band, 34 GHz), once experimental parameters have been optimized. With highly selective detection pulses and Gaussian shaped electron–electron double resonance (ELDOR) pulses it is possible to detect low-γ nuclei coupled to paramagnetic Mn²⁺. Weakly coupled ¹⁴N resonances, which are separated from the zero frequency by only 2.8 MHz, were readily detected. In systems where different spin active nuclei are coupled to the electron spin, particular care has to be taken when using higher powered ELDOR pulses, as combination frequencies from the two nuclei (∆m_S = ±1, ∆m_I,1 = ±1, ∆m_I,2 = ±1) can lead to severe line broadening and complicated EDNMR spectra. We also compare the EDNMR spectra of ¹³C-labeled Mn–DOTA to ¹³C-Mims electron–nuclear double resonance to get a better insight into the similarities and differences in the results of the two techniques for ¹³C hyperfine coupling.

An electron paramagnetic resonance (EPR) probe consisting of two dielectric resonators (DRs) and a cavity (CV) is ideal for EPR experiments where both signal enhancement and tuning capabilities are required. The coupling of two DRs, resonating in their \({\text{TE}}_{01\delta }\) mode and a CV resonating in its \({\text{TE}}_{011}\) mode, is studied using energy-coupled mode theory (ECMT). The frequencies and eigenvectors of the three coupled modes are analytically derived. As predicted numerically, ECMT confirms that the \({\text{TE}}^{ + + - }\) and \({\text{TE}}^{ + - - }\) modes are indeed found to be degenerate at a specific distance between the two DRs \(d_{12}\). Additionally, the condition at which degeneracy occurs is specified. For a considerable range, the calculated frequency of the \({\text{TE}}^{ + + + }\) mode changes linearly with respect to \(d_{12}\). The \({\text{TE}}^{ + + + }\) mode showed a 500 MHz frequency change over a distance of 2 cm, when the resonance frequency is around 9.7 GHz. This enables the experimentalist to linearly tune the probe over this large frequency range. Finally the asymmetric configuration, where one of the resonators (DR2) is kept at the cavity center and the other one is allowed to move along the cavity axis, is studied. It is estimated that the frequency changes by 600 MHz over a distance of 1.5 cm. A formula for the magnitude of the magnetic field along the cavity axis, where the EPR samples are usually placed, is developed. This is crucial in determining the magnetic field in the vicinity of the sample and the probe’s filling factor.

The dielectric tube resonator (DTR) for electron paramagnetic resonance spectroscopy is introduced. It is defined as a metallic cylindrical TE₀₁₁ microwave cavity that contains a dielectric tube centered on the axis of the cylinder. Contour plots of dimensions of the metallic cylinder to achieve resonance at 9.5 GHz are shown for quartz, sapphire, and rutile tubes as a function of wall thickness and average radius. These contour plots were developed using analytical equations and confirmed by finite-element modeling. They can be used in two ways: design of the metallic cylinder for use at 9.5 GHz that incorporates a readily available tube such as a sapphire tube intended for NMR and design of a custom procured tube for optimized performance for specific sample-size constraints. The charts extend to the limiting condition where the dielectric fills the tube. However, the structure at this limit is not a dielectric resonator due to the metal wall and does not radiate. In addition, the uniform field (UF) DTR is introduced. Development of the UF resonator starting with a DTR is shown. The diameter of the tube remains constant along the cavity axis, and the diameter of the cylindrical metallic enclosure increases at the ends of the cavity to satisfy the uniform field condition. This structure has advantages over the previously developed UF TE₀₁₁ resonators: higher resonator efficiency parameter Λ, convenient overall size when using sapphire tubes, and higher quality data for small samples. The DTR and UF DTR structures fill the gap between free space and dielectric resonator limits in a continuous manner.

Electron spin resonance (ESR) is a powerful spectroscopic technique that has many applications in a wide variety of scientific fields, including chemistry, biology, materials science, and physics. One significant drawback of conventional ESR, however, is its relatively low sensitivity compared to other spectroscopic techniques. Arguably, the most dominant element affecting ESR sensitivity is the microwave resonator used to pick up the ESR signal of the spins. Traditionally, ESR mostly employs a limited set of resonator configurations (e.g., rectangular cavity, dielectric, or loop-gap resonator) that are suboptimal with respect to a wide range of samples. In principle, a smart resonator design can be used to optimize spin sensitivity for a given sample’s properties. In this work, we make use of an efficient Genetic Algorithm (GA) approach to numerically solve, analyze, and optimize a unique class of surface microresonators. The GA is based on a method of moments code, customized directly to render the complexity of a particular resonator’s geometries in our search. The main purposes of the algorithm are to routinely generate more sensitive microresonators, optimized for a predefined sample’s dimensions, and to study the functional relations between the devices’ resonance frequency, quality, and filling factors and their topology, in order to reach a rational optimal design. Preliminary results associated with new, unique, and sensitive surface microresonators are shown and analyzed. Such resonators are cheap and easy to produce on a mass scale with an arbitrary surface geometry.

Resonators for preclinical electron paramagnetic resonance imaging have been designed primarily for rodents and rabbits and have internal diameters between 16 and 51 mm. Lumped-circuit resonators include loop-gap, Alderman–Grant, and saddle coil topologies and surface coils. Bimodal resonators are useful for isolating the detected signal from incident power and reducing dead time in pulse experiments. Resonators for continuous wave, rapid scan, and pulse experiments are described. Experience at the University of Chicago and University of Denver in design of resonators for in vivo imaging is summarized.

Forbidden transitions are not observed in the continuous-wave electron paramagnetic resonance (EPR) spectrum nor in the free induction decay because, unlike allowed transitions, their coherences have no observable magnetic moment and are spectroscopically silent. Yet, the paramagnetic relaxation described by Redfield theory can cause coherence transfer between any types of transitions. Coherence transfer between allowed transitions is now known to cause noticeable changes in EPR spectra, but coherence transfer involving forbidden transitions has long been considered to be negligible because those coherences are silent and unseen. However, our simulations of a simple model system indicate that coherence transfer with silent transitions can introduce new features into EPR spectra. The EPR-silent coherence of a forbidden transition can be transferred to an allowed transition by paramagnetic relaxation. A silent coherence can have consequences felt in the EPR spectrum.

The development of electron paramagnetic resonance (EPR) and magnetic resonance imaging (MRI) over six decades is sketched with an emphasis on the contributions of James S. Hyde. For twenty years starting three years after the first commercial EPR spectrometer was shipped by Varian, he led commercial EPR developments, and then for more than forty years, he led development of instrumentation and biomedical applications of EPR at the Medical College of Wisconsin. It was there that he also made major contributions to MRI, and especially functional MRI.

Experimental studies of 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (Tempol) in 60 wt% aqueous glycerol were carried out for temperatures from 273 to 340 K. Selective isotope substitution allowed comparisons between the experimental spectral manifestations of spin exchange and dipole–dipole interactions for protonated, deuterated, ¹⁵N, and ¹⁴N Tempol. Theoretical spectra were computed from a rigorous theory specifically formulated to include proton hyperfine interactions over a wide range of spin exchange and dipole–dipole interactions to compare with the experimental data. For spin exchange and dipole–dipole interactions small compared with the proton hyperfine coupling constant, spectra were calculated with perturbation theory to gain insight into the behavior of individual proton lines. The theoretical and experimental spectra were analyzed by least-squares fitting to Voigt shapes or by a new two-point method. For most accessible experimental designs, the comparisons are rather good; however, for an experiment constrained to low concentrations and high viscosities, the methods are less accurate.