Compact electron spin resonance skin oximeter: Properties and initial clinical results.

PURPOSE: Skin oxygen level is of significance for the diagnosis and treatment of many clinical problems, such as chronic wounds and diabetic foot ulcers. Furthermore, skin oxygen levels can be correlated to arterial oxygen partial pressure, thereby revealing potentially dangerous conditions such as hyperoxia (too much oxygen), which may occur in ventilated neonates. Traditionally, skin oxygen levels are measured using electrochemical methods and, more recently, also by fluorescence lifetime techniques. These approaches suffer from several drawbacks, rendering them suboptimal. The purpose of this work is to develop an electron spin resonance (ESR) -based method for monitoring oxygen partial pressure (pO2 ) in skin tissue. METHODS: A compact sensor for pulsed ESR is designed and constructed. Our ESR-based method makes use of a unique exogenous paramagnetic spin probe that is placed on the skin in a special partially sealed sticker, and subsequently measuring its signal with the compact pulsed ESR sensor that includes a miniature magnet and a small S-band (~2.3 GHz) microwave resonator. The inverse of the spin-spin relaxation time (1/T2 ) measured by ESR is shown to be linearly correlated with pO2 levels. RESULTS: The sensor and its matching sticker were tested both in vitro and in vivo (with human subjects). Measured skin pO2 levels reached equilibrium after ~2-3 h and were found to be comparable to those measured by continuous-wave (CW) ESR using a large electromagnet. CONCLUSIONS: A compact pulsed ESR sensor with a matching paramagnetic sticker can be used for pO2 monitoring of the skin tissue, similar to large bulky CW ESR systems.

Electron-Spin-Resonance Dipstick.

Electron spin resonance (ESR) is a powerful analytical technique used for the detection, quantification, and characterization of paramagnetic species ranging from stable organic free radicals and defects in crystals to gaseous oxygen. Traditionally, ESR requires the use of complex instrumentation, including a large magnet and a microwave resonator in which the sample is placed. Here, we present an alternative to the existing approach by inverting the typical measurement topology, namely placing the ESR magnet and resonator inside the sample rather than the other way around. This new development relies on a novel self-contained ESR sensor with a diameter of just 2 mm and length of 3.6 mm, which includes both a small permanent magnet assembly and a tiny (∼1 mm in size) resonator for spin excitation and detection at a frequency of ∼2.6 GHz. The spin sensitivity of the sensor has been measured to be ∼1011 spins/√Hz, and its concentration sensitivity is ∼0.1 mM, using reference samples with a measured volume of just ∼10 nL. Our new approach can be applied for monitoring the partial pressure of oxygen in vitro and in vivo through its paramagnetic interaction with another stable radical, as well as for simple online quantitative inspection of free radicals generated in reaction vessels and electrochemical cells via chemical processes.

Recent trends in high spin sensitivity magnetic resonance.

Magnetic resonance is a very powerful methodology that has been employed successfully in many applications for about 70years now, resulting in a wealth of scientific, technological, and diagnostic data. Despite its many advantages, one major drawback of magnetic resonance is its relatively poor sensitivity and, as a consequence, its bad spatial resolution when examining heterogeneous samples. Contemporary science and technology often make use of very small amounts of material and examine heterogeneity on a very small length scale, both of which are well beyond the current capabilities of conventional magnetic resonance. It is therefore very important to significantly improve both the sensitivity and the spatial resolution of magnetic resonance techniques. The quest for higher sensitivity led in recent years to the development of many alternative detection techniques that seem to rival and challenge the conventional "old-fashioned" induction-detection approach. The aim of this manuscript is to briefly review recent advances in the field, and to provide a quantitative as well as qualitative comparison between various detection methods with an eye to future potential advances and developments. We first offer a common definition of sensitivity in magnetic resonance to enable proper quantitative comparisons between various detection methods. Following that, up-to-date information about the sensitivity capabilities of the leading recently-developed detection approaches in magnetic resonance is provided, accompanied by a critical comparison between them and induction detection. Our conclusion from this comparison is that induction detection is still indispensable, and as such, it is very important to look for ways to significantly improve it. To do so, we provide expressions for the sensitivity of induction-detection, derived from both classical and quantum mechanics, that identify its main limiting factors. Examples from current literature, as well as a description of new ideas, show how these limiting factors can be mitigated to significantly improve the sensitivity of induction detection. Finally, we outline some directions for the possible applications of high-sensitivity induction detection in the field of electron spin resonance.

Surface loop-gap resonators for electron spin resonance at W-band.

Electron spin resonance (ESR) is a spectroscopic method used to detect paramagnetic materials, reveal their structure, and also image their position in a sample. ESR makes use of a large static magnetic field to split the energy levels of the electron magnetic moment of the paramagnetic species. A strong microwave magnetic field is applied to excite the spins, and subsequently the ESR system detects their faint microwave signal response. The sensitivity of an ESR system is greatly influenced by the magnitude of the static field and the properties of the microwave resonator used to detect the spin signal. In general terms, the higher the static field (microwave frequency) and the smaller the resonator, the more sensitive the system will be. Previous work aimed at high-sensitivity ESR was focused on the development and testing of very small resonators operating at moderate magnetic fields in the range of ∼0.1-1.2 T (maximum frequency of ∼35 GHz). Here, we describe the design, construction, and testing of recently developed miniature surface loop-gap resonators used in ESR and operating at a much higher frequency of ∼95 GHz (W-band, corresponding to a field of ∼3.4 T). Such resonators can greatly enhance the sensitivity of ESR and also improve the resulting spectral resolution due to the higher static field employed. A detailed description of the resonator's design and coupling mechanism, as well as the supporting probe head, is provided. We also discuss the production method of the resonators and probe head and, in the end, provide preliminary experimental results that show the setup's high spin sensitivity and compare it to theoretical predictions.

A magnetic resonance probehead for evaluating the level of ionizing radiation absorbed in human teeth.

A miniature electron spin resonance (ESR) probehead that includes a static field source and a microwave resonator for in vivo measurement of paramagnetic defects in tooth enamel was developed. These defects are known to be a good marker for quantifying the ionizing radiation dose absorbed in teeth. The probehead has a typical length of just 30 mm and total weight of 220 g. The patient "bites" into the probehead while the measurement procedure is being carried out. The probehead operates in pulsed mode at a frequency of ∼ 11.2 GHz and supplies a static magnetic field of ∼ 400 mT. A detailed design of the probehead is provided together with its specifications in terms of measurement volume and signal-to-noise ratio for a typical sample. A specially developed simulation program was used to predict the spatial distribution of the acquired signal under conditions of grossly inhomogeneous static and RF fields. Experimental results with irradiated incisor teeth validated the probehead's sensitivity, being able to detect signals in tooth irradiated by only 2 Gy. Subject to additional improvements and tests, this type of probehead can potentially have significant clinical applications ranging from mass triage following major nuclear events to routine occupational evaluation of ionizing radiation absorbed over long periods of time.

Cryogenic electron spin resonance microimaging probe.

A new probe for acquiring ESR images with microscopic resolution and high spin sensitivity, at a temperature range of ~4.2-300 K, is presented. Details of the probe design, as well as its principle of operation, are provided. The probe incorporates a unique surface loop-gap microresonator. Experimental results demonstrate the system's capability to acquire two - as well as three-dimensional images with a flat test sample of phosphorus-doped silicon. The imaging results also allow verifying the resonator's resonance mode - they show its B(1) distribution, which also makes it possible to estimate the number of spins measured in the sample.

Note: High sensitivity pulsed electron spin resonance spectroscopy with induction detection.

Commercial electron spin resonance spectroscopy and imaging systems make use of the so-called "induction" or "Faraday" detection, which is based on a radio frequency coil or a microwave resonator. The sensitivity of induction detection does not exceed ~3 × 10(8) spins/√Hz. Here we show that through the use of a new type of surface loop-gap microresonators (inner size of 20 µm), operating at cryogenic temperatures at a field of 0.5 T, one can improve upon this sensitivity barrier by more than 2 orders of magnitude and reach spin sensitivities of ~1.5 × 10(6) spins/√Hz or ~2.5 × 10(4) spins for 1 h.

High-sensitivity Q-band electron spin resonance imaging system with submicron resolution.

A pulsed electron spin resonance (ESR) microimaging system operating at the Q-band frequency range is presented. The system includes a pulsed ESR spectrometer, gradient drivers, and a unique high-sensitivity imaging probe. The pulsed gradient drivers are capable of producing peak currents ranging from ∼9 A for short 150 ns pulses up to more than 94 A for long 1400 ns gradient pulses. Under optimal conditions, the imaging probe provides spin sensitivity of ∼1.6 × 10(8) spins∕√Hz or ∼2.7 × 10(6) spins for 1 h of acquisition. This combination of high gradients and high spin sensitivity enables the acquisition of ESR images with a resolution down to ∼440 nm for a high spin concentration solid sample (∼10(8) spins∕µm(3)) and ∼6.7 µm for a low spin concentration liquid sample (∼6 × 10(5) spins/µm(3)). Potential applications of this system range from the imaging of point defects in crystals and semiconductors to measurements of oxygen concentration in biological samples.

Sensitive surface loop-gap microresonators for electron spin resonance.

This work presents the design, construction, and experimental testing of unique sensitive surface loop-gap microresonators for electron spin resonance (ESR) measurements. These resonators are made of "U"-shaped gold structures with typical sizes of 50 and 150 µm that are deposited on a thin (220 µm) rutile substrate and fed from the rear by a microstrip line. This allows accommodating a large flat sample above the resonator in addition to having variable coupling properties. Such resonators have a very small volume which, compared to previous designs, improves their absolute spin sensitivity by a factor of more than 2 (based on experimental results). They also have a very high microwave field-power conversion ratio of up to 86 gauss/√Hz. This could facilitate the use of very short excitation pulses with relatively low microwave power. Following the presentation and the discussion of the experimental results, ways to further increase sensitivity significantly are outlined.