An improved external loop resonator for in vivo L-band EPR spectroscopy

An improved external loop resonator (ELR) used for L-band electron paramagnetic resonance (EPR) spectroscopy is reported. This improvement is achieved by shortening the parallel coaxial line. The resonant structure is formed by two single turn coils (10mm in diameter) that are connected to a parallel coaxial line. A resonance frequency of 1197 MHz and a quality factor of 466 were obtained in the absence of biological tissue and were approximately 1130 MHz and approximately 50 with a living animal, respectively. The sensitivity of the new ELR was compared to the previously developed ELR using three types of EPR samples: (1) paramagnetic material with no biological tissue, (2) paramagnetic material in a leg and in the peritoneal cavity of a dead rat, and (3) paramagnetic material in the back of an anesthetized rat. The sensitivity was 1.2-1.6 times greater in the rat and 4.2 times without tissue.     

An L-band crossed-loop (Bimodal) EPR resonator

Our crossed-loop resonator design has been enhanced to increase the filling factor and has been extended from S-band to L-band. High isolation between the two modes results in shorter dead time in pulsed EPR experiments than would occur with a reflection resonator of the same Q.     

A tunable reentrant resonator with transverse orientation of electric field for in vivo EPR spectroscopy

There has been a need for development of microwave resonator designs optimized to provide high sensitivity and high stability for EPR spectroscopy and imaging measurements of in vivo systems. The design and construction of a novel reentrant resonator with transversely oriented electric field (TERR) and rectangular sample opening cross section for EPR spectroscopy and imaging of in vivo biological samples, such as the whole body of mice and rats, is described. This design with its transversely oriented capacitive element enables wide and simple setting of the center frequency by trimming the dimensions of the capacitive plate over the range 100-900 MHz with unloaded Q values of approximately 1100 at 750 MHz, while the mechanical adjustment mechanism allows smooth continuous frequency tuning in the range +/-50 MHz. This orientation of the capacitive element limits the electric field based loss of resonator Q observed with large lossy samples, and it facilitates the use of capacitive coupling. Both microwave performance data and EPR measurements of aqueous samples demonstrate high sensitivity and stability of the design, which make it well suited for in vivo applications.     

A bridged loop-gap S-band surface resonator for topical EPR spectroscopy.

The design and structure of a bridged loop-gap surface resonator developed for topical EPR spectroscopy and imaging of the distribution and metabolism of spin labels in in vivo skin is reported. The resonator is a one-loop, one-gap bridged structure. A pivoting single loop-coupling coil was used to couple the microwave power to the loop-gap resonant structure. A symmetric coupling circuit was used to achieve better shielding and minimize radiation. The frequency of the resonator can be easily adjusted by trimming the area of the capacitive foil bridge, which overlaps the gap in the cylindrical loop. The working frequency set was 2.2 GHz and the unloaded Q was 720. The B1 field of this resonator was measured and spatially mapped by three-dimensional EPR imaging. The resonator is well suited to topical measurements of large biological subjects and is readily applicable for in vivo measurements of free radicals in human skin.     

Modified surface-coil-type resonators for EPR measurements of a thin membranelike sample

Surface-coil-type resonators (SCRs) equipped with a circular single-tum coil (conventional SCR), a circular spiral coil (spiral SCR), and a plate-type single-turn coil (plate-type SCR) were fabricated. By using these SCRs, the electron paramagnetic resonance (EPR) sensitivities of thin membranelike samples were investigated. For a non-dielectric-loss phantom, filter paper containing 1,1-diphenyl-2-picrylhydrazyl was used. For a high-dielectric-loss phantom, gauze containing an aqueous solution of 3-carbamoyl-2,2,5,5-tetramethylpyrrolidine-1-oxyl (carbamoyl-PROXYL) was used. For a biological sample, a pea leaf impregnated with the carbamoyl-PROXYL solution was used. The sensitivity (signal-to-noise ratio) of the spiral and plate-type SCRs for the non-dielectric-loss phantom was significantly greater than that of the conventional SCR. Under these conditions, the sensitivity of the spiral SCR was relatively higher than that of the plate-type SCR. For the high-dielectric-loss phantom, the sensitivity of the plate-type SCRs was significantly greater than that of the conventional SCR, but there were no differences in sensitivity between the spiral and conventional SCRs. The sensitivity of the plate-type SCR in the EPR measurement of a pea leaf was significantly greater than that of the conventional SCR. These findings show that the spiral and plate-type SCRs are suitable for measuring EPR of thin membranelike samples, especially when the former is used for the non-dielectric-loss sample and the latter for high-dielectric-loss sample, including the leaf.     

Coupling of waveguide and resonator by inductive and capacitive irises for EPR spectroscopy

An analytic circuit model for slot coupling from a waveguide to a loop-gap resonator (LGR) in a context of electron paramagnetic resonance (EPR) spectroscopy is presented. The physical dimensions of the waveguide, iris, LGR, and aqueous sample are transformed into circuit values of inductance, capacitance, and resistance. These values are used in a solution of circuit equations that results in a prediction of the radio frequency (rf) currents, magnitude and phase, frequency, and magnetic and electric stored energies near the critical coupling. The circuit geometry reflects magnetic flux conservation between the iris and LGR as well as modification of the outer loop LGR currents by the iris. Unlike conventional models, coupling is not explicitly based on a mutual inductance between the iris and LGR. Instead, the conducting wall high-frequency rf boundary condition is used to define surface currents, regions, and circuit topology with lumped-circuit values of self-inductance, capacitance, and resistance. Match is produced by a combination of self-inductive and capacitive circuit coupling. Two conditions must be met to achieve match. First, the equivalent resistance of the LGR as seen by the iris must be transformed into the waveguide characteristic impedance. This transformation is met at a particular frequency relative to the natural LGR resonance frequency. The frequency shift magnitude is largely determined by the LGR properties, weakly dependent on the iris length and placement, and independent of other iris dimensions. The second condition for match is that the iris reactance at this frequency shift must cancel the residual reactance of the LGR. This second condition is sensitive to the iris dimensions. If both conditions are not simultaneously satisfied, overcoupling or undercoupling results. A slotted iris with a length equal to the size of the large dimension of the waveguide is found to have many properties opposite to a conventional iris with shorter length. Notably, the magnetic field near the iris tends to reinforce rather than oppose the magnetic field in the resonator. The long iris improves the LGR EPR performance by providing increased rf magnetic field homogeneity at the sample, higher signal, and reduced total frequency shift since the shifts due to sample and iris tend to cancel. Investigations reveal that the first match condition can be adjusted by LGR dimensional changes and such adjustment can eliminate the frequency shift. Results are consistent with Ansoft High Frequency Structure Simulator (Version 10.1, Ansoft Corporation, Pittsburgh, PA) simulations and can be extended to cavity resonators.     

Electronically tunable external-cavity laser diode

We present a new concept for an electronically tunable diode laser. It is based on an external-cavity configuration with simultaneous feedback and intracavity spatial separation of the laser's spectral components. The electronical tunability is achieved by insertion of a liquid-crystal array as an electronically controlled aperture into the region of spatial separation of the spectral components. Wavelength tunability without mechanical movement over a range of 10 nm and two-color operation are demonstrated with a 670-nm laser diode.     

High-frequency tunable EPR spectroscopy of Cr3+ in synthetic forsterite

The electron paramagnetic resonance spectra of isolated and dimer impurity centers of trivalent chromium ions in the octahedral Ml sites in synthetic forsterite are studied in the frequency range of 65–90 GHz. The measurements are performed at 4.2 K in magnetic field from ?0.04 to 0.3 T. The zero-field splitting between spin doublets of the isolated Cr³⁺ ion Δ_s = 66.7 GHz and between spin sublevels of the Cr³⁺-Cr³⁺ dimer Δ_d1 = 71.5 GHz and Δ_d2 = 73.0 GHz is measured directly at zero field. The analysis of the spin Hamiltonian parameters shows that the dimer center consists of a pair of Cr³⁺ ions with an Mg²⁺ vacancy between them replacing three Mg²⁺ ions situated in a quasi-one-dimensional chain aligned parallel to the crystal c-axis. It is found that the exchange interaction in the dimer is ferromagnetic with parameters J_z = 0.47 GHz and J_t = 0.79 GHz.     

High-frequency tunable EPR spectroscopy of Tm3+ ions in synthetic forsterite

Paramagnetic centers formed by impurity Tm³⁺ ions in synthetic forsterite Mg₂SiO₄ were studied by high-frequency tunable electron paramagnetic resonance spectroscopy in the frequency range of 150–315 GHz. Crystals were grown from the melt by the Czochralski technique in slightly oxidizing atmosphere. Several centers distinguished by different zero-field splitting between the ground and first excited singlets were found and investigated. Parameters of the effective spin Hamiltonian for these centers describing the dependence of electron-nuclear sublevels on magnetic field were determined.     

Sensitivity of whole human teeth to fast neutrons and gamma-rays estimated by L-band EPR spectroscopy

This paper reports the first attempt to use L-band spectroscopy for estimating the sensitivity of whole teeth to fast neutrons and gamma-rays. Three teeth were successively irradiated first with fast neutrons with a wide energy spectrum (mean energy around 30 MeV) up to 160 Gy and then with gamma-rays up to 14 Gy. After each irradiation, L-band (1 GHz) EPR spectra of each whole tooth surrounded by the surface–coil resonator were recorded, yielding a single composite line principally due to CO₂⁻ and native radicals. The sensitivities are estimated by the slopes of the linear dose response curves of the dosimetric CO₂⁻ radicals. The ratios of the gamma/neutron sensitivities were found to be in the range 8–9 (±2) for the three teeth.     

Radiation dose reconstruction from L-band in vivo EPR spectroscopy of intact teeth: Comparison of methods

In vivo EPR tooth dosimetry is a more challenging problem than in vitro EPR dosimetry because of several potential additional sources of variation associated with measurements that are made in the mouth of a living subject. For in vivo measurement a lower RF frequency is used and, unlike in the in vitro studies, the tooth cannot be processed to optimize the amount and configuration of the enamel that is measured. Additional factors involved with in vivo measurements include the reproducibility of positioning the resonator on the surface of the tooth in the mouth, irregular tooth geometry, and the possible influence of environmental noise. Consequently, in addition to using the theoretical and empirical models developed for analyzing data from measurements of teeth in vitro, other unconventional and more robust methods of dose reconstruction may be needed. The experimental parameter of interest is the peak-to-peak amplitude of the spectrum, which is correlated to the radiation dose through a calibration curve to derive the reconstructed dose. In this study we describe and compare the results from seven types of computations to measure the peak-to-peak amplitude for estimation of the radiation induced signal. The data utilized were from three sets of in vivo measurements of irradiated teeth. Six different teeth with different doses were placed in the mouth of a volunteer in situ and measurements of each tooth were carried out on three different days. The standard error of dose prediction (SEP) is used as a figure of merit for quantifying precision of the reconstruction. We found that many of the methods gave fairly similar results, with the best error of prediction resulting from a computation based on a Lorentzian line model whose center field corresponds to the known parameter of the radiation-induced EPR spectra of teeth, with corrections from a standard sample that was measured as part of the data acquisition scheme. When the results from the three days of measurement were pooled, the SEP decreased dramatically, which suggests that one of the principal sources of variation in the data is the ability to precisely standardize the measurements conditions within the mouth. There are very plausible ways to accomplish improvements in the existing procedures.     

Wavelength tunable erbium-doped fiber ring laser operating in L-band

We describe a novel erbium-doped fiber ring laser utilizing the backward amplified spontaneous emission (ASE) power as a secondary pump source so that it can operate in L-band stably. The output wavelength can be tuned in a wide range of 45 nm, from 1560 to 1605 nm. We also compared this scheme with the condition of not using the ASE as secondary pump source, and found this scheme could improve the performance of the laser when using the same components.     

A tunable general purpose Q-band resonator for CW and pulse EPR/ENDOR experiments with large sample access and optical excitation

We describe a frequency tunable Q-band cavity (34 GHz) designed for CW and pulse Electron Paramagnetic Resonance (EPR) as well as Electron Nuclear Double Resonance (ENDOR) and Electron Electron Double Resonance (ELDOR) experiments. The TE(011) cylindrical resonator is machined either from brass or from graphite (which is subsequently gold plated), to improve the penetration of the 100 kHz field modulation signal. The (self-supporting) ENDOR coil consists of four 0.8mm silver posts at 2.67 mm distance from the cavity center axis, penetrating through the plunger heads. It is very robust and immune to mechanical vibrations. The coil is electrically shielded to enable CW ENDOR experiments with high RF power (500 W). The top plunger of the cavity is movable and allows a frequency tuning of ±2 GHz. In our setup the standard operation frequency is 34.0 GHz. The microwaves are coupled into the resonator through an iris in the cylinder wall and matching is accomplished by a sliding short in the coupling waveguide. Optical excitation of the sample is enabled through slits in the cavity wall (transmission ～60%). The resonator accepts 3mm o.d. sample tubes. This leads to a favorable sensitivity especially for pulse EPR experiments of low concentration biological samples. The probehead dimensions are compatible with that of Bruker flexline Q-band resonators and it fits perfectly into an Oxford CF935 Helium flow cryostat (4-300 K). It is demonstrated that, due to the relatively large active sample volume (20-30 μl), the described resonator has superior concentration sensitivity as compared to commercial pulse Q-band resonators. The quality factor (Q(L)) of the resonator can be varied between 2600 (critical coupling) and 1300 (over-coupling). The shortest achieved π/2-pulse durations are 20 ns using a 3 W microwave amplifier. ENDOR (RF) π-pulses of 20 μs ((1)H @ 51 MHz) were obtained for a 300 W amplifier and 7 μs using a 2500 W amplifier. Selected applications of the resonator are presented.     

Development of surface-coil-type resonators consisting of an irradiation and receiver coil system for EPR measurements at 700 MHz

Surface-coil-type resonators (SCRs) consisting of irradiation and receiver coils that are highly isolated from each other were developed for electron paramagnetic resonance (EPR) measurements. Their sample space was open to free space. For these coils, a circular single-turn one-loop receiver coil and a square single-turn twin-loop irradiation coil were fabricated. The transmission lines were set to resonate at about 700 MHz. A phantom (agar, including a nitroxide radical and physiological saline solution) is located on the receiver coil, and the irradiation coil is under the receiver coil. In this condition, the isolation between the receiver and irradiation SCRs was about 40 dB at the resonant frequency. When radiowaves that were divided from the line to the irradiation SCR were applied to the line from the receiver SCR at the appropriate phase and power to cancel the direct coupling between both SCRs, the isolation increased to more than 70 dB. In the conventional SCR, the noise level increased at high incident power. Because such an increase in the noise was not observed in the irradiation-receiver SCR system, high sensitivity at high incident power was obtained.     

Development of a resonator with automatic tuning and coupling capability to minimize sample motion noise for in vivo EPR spectroscopy

EPR spectroscopy has been applied to measure free radicals in vivo; however, respiratory, cardiac, and other movements of living animals are a major source of noise and spectral distortion. Sample motions result in changes in resonator frequency, Q, and coupling. These instabilities limit the applications that can be performed and the quality of data that can be obtained. Therefore, it is of great importance to develop resonators with automatic tuning and automatic coupling capability. We report the development of automatic tuning and automatic coupling provisions for a 750-MHz transversely oriented electric field reentrant resonator using two electronically tunable high Q hyperabrupt varactor diodes and feedback loops. In both moving phantoms and living mice, these automatic coupling control and automatic tuning control provisions resulted in an 8- to 10-fold increase in signal-to-noise ratio.     

A novel loop-gap resonator probehead for EPR and ENDOR at X-band

An EPR and ENDOR probehead with a loop-gap resonator for X-band is described. The novel feature of the construction is that an iris-type coupling of the resonator is used instead of the conventional antenna coupling. The ENDOR coil combines the role of creating the radio frequency field and that of a shield for the microwave loop-gap structure. Hence, in order to accommodate the iris and waveguide, a pair of RF coils is used in conjunction with a reduced waveguide with dielectric filling. This arrangement simplifies matching the resonator to the microwave bridge, and standard EPR cryostats can be used making sample manipulation more convenient.     

A loop resonator for slice-selective in vivo EPR imaging in rats

A loop resonator was developed for 300 MHz continuous-wave electron paramagnetic resonance (CW-EPR) spectroscopy and imaging in live rats. A single-turn loop (55 mm in diameter) was used to provide sufficient space for the rat body. Efficiency for generating a radiofrequency magnetic field of 38 microT/W(1/2) was achieved at the center of the loop. For the resonator itself, an unloaded quality factor of 430 was obtained. When a 350 g rat was placed in the resonator at the level of the lower abdomen, the quality factor decreased to 18. The sensitive volume in the loop was visualized with a bottle filled with an aqueous solution of the nitroxide spin probe 3-carbamoyl-2,2,5,5-tetramethyl-3-pyrrolin-1-yloxy (3-CP). The resonator was shown to enable EPR imaging in live rats. Imaging was performed for 3-CP that had been infused intravenously into the rat and its distribution was visualized within the lower abdomen.     

Low-noise, tunable diode laser for ultra-high-resolution spectroscopy

We demonstrate the excellent spectral properties of a diode laser setup that combines good tunability with superb short-term frequency stability and controllability. It is based on merging two concepts, the diode laser with resonant optical feedback and the grating stabilized diode laser. To characterize the short-term performance we beat two essentially identical diode lasers and find a short-term linewidth of ~11 kHz. Phase locking between these lasers is achieved with a servo bandwidth as small as 46 kHz, although an analog phase detector is used that requires subradian residual phase error. Despite small phase error detection range and small servo bandwidth, cycle-slip-free phase locking is accomplished for typically many 10 min, and the optical power is essentially contained in a spectral window of less than 20 mHz relative to the optical reference. Due to the excellent performance this laser concept is well suited for atomic or molecular coherence experiments, which require phase locking of different lasers to each other, and as part of a flywheel for optical clocks.