Conventional Electron Paramagnetic Resonance Research Articles

19F Paramagnetic Relaxation-Based NMR for Quaternary Structural Restraints of Ion Channels.

Quaternary distance restraints are essential to define the three-dimensional structures of protein assemblies. These distances often fall within a range of 10-18 Å, which challenges the high and low measurement limits of conventional nuclear magnetic resonance (NMR) and double electron-electron resonance electron spin resonance spectroscopies. Here, we report the use of 19F paramagnetic relaxation enhancement (PRE) NMR in combination with 19F/paramagnetic labeling to equivalent sites in different subunits of a protein complex in micelles to determine intersubunit distances. The feasibility of this strategy was evaluated on a pentameric ligand-gated ion channel, for which we found excellent agreement of the 19F PRE NMR results with previous structural information. The study suggests that 19F PRE NMR is a viable tool in extracting distance restraints to define quaternary structures.

Broadband Tunable Electron Paramagnetic Resonance Spectroscopy of Dilute Metal Complexes.

Analysis of the electron paramagnetic resonance (EPR) of transition ion complexes requires data taken at different microwave frequencies because the spin Hamiltonian contains operators linear in the frequency as well as operators independent of the frequency. In practice, data collection is hampered by the fact that conventional EPR spectrometers have always been designed to operate at a single frequency. Here, a broadband instrument is described and tested that operates from 0.5 to 12 GHz and whose sensitivity approaches that of single-frequency spectrometers. Multifrequency EPR from triclinic substitutional (0.5%) Cu(II) in ZnSO4 is globally analyzed to illustrate a novel approach to reliable determination of the molecular electronic structure of transition ion complexes from field-frequency 2D data sets.

Multifrequency (9 and 95 GHz) EPR study of stable radicals in asphaltenes fractions of oils and bitumen

Structural characterization of asphaltenes in complex systems such as native hydrocarbons is in the focus of scientific and industrial interests since many years. Various analytical tools and approaches are used for that. We present the results of our study of asphaltene fractions A1 and A2 with the predominantly “island” type and “archipelago” type asphaltene molecules by conventional and pulsed electron paramagnetic resonance (EPR) at X-band (9 GHz) and W-band (95 GHz) with aim to expand the abilities of EPR technique for asphaltene characterization. Shift to the higher frequencies allows to separate spectrally the contributions from paramagnetic complexes of different origin, define the EPR parameters more accurately comparing to the conventional X-band EPR. Application of pulsed techniques allows (at least partially) to separate the radicals in time domain. Features of the obtained spectra are described. Electronic relaxation times are found to be different for stable “free” radical for A1 and A2 fractions. We suggest that the obtained results can be used for investigation of various petroleum systems.

95 GHz electron paramagnetic resonance of LiYF4: Nd3+ crystal in parallel orientation

We report the observation of the conventional and pulsed electron paramagnetic resonance (EPR), electron-nuclear double resonance (ENDOR) spectra from 19F and 7Li nuclei on impurity Nd3+ ions in LiYF4 crystal doped with Nd3+ ions in parallel orientation at microwave frequency of ν ≈ 95 GHz (W-band). The resolved structure from the nearby and remote nuclei in spectra is observed. The outcome shows that LiYF4:Nd3+ system can be exploited as a convenient matrix for performing spin manipulations and adjusting quantum computation protocols while ENDOR technique is usable for the investigation of electron-nuclear interaction with the nuclei of the system.

Electron Spin Resonance of P Donors in Isotopically PurifiedSiDetected by Contactless Photoconductivity

Coherence times of electron spins bound to phosphorus donors have been measured, using a standard Hahn echo technique, to be up to 20 ms in isotopically pure silicon with [P]$ = 10^{14}$ cm$^{-3}$ and at temperatures $\leq 4 $K. Although such times are exceptionally long for electron spins in the solid state, they are nevertheless limited by donor electron spin-spin interactions. Suppressing such interactions requires even lower donor concentrations, which lie below the detection limit for typical electron spin resonance (ESR) spectrometers. Here we describe an alternative method for phosphorus donor ESR detection, exploiting the spin-to-charge conversion provided by the optical donor bound exciton transition. We characterise the method and its dependence on laser power and use it to measure a coherence time of $T_2 = 130 $ms for one of the purest silicon samples grown to-date ([P]$ = 5\times 10^{11} $cm$^{-3}$). We then benchmark this result using an alternative application of the donor bound exciton transition: optically polarising the donor spins before using conventional ESR detection at 1.7~K for a sample with [P]$ = 4\times10^{12} $cm$^{-3}$, and measuring in this case a $T_2$ of 350 ms.

Solvent accessibility in interdigitated and micellar phases formed by DPPC/Lyso-PPC mixtures: D2O-ESEEM of chain labeled lipids.

Electron spin echo envelope modulation (ESEEM) spectroscopy was used to investigate binary mixtures of single-chain micelle-forming lipids and diacyl bilayer-forming lipids dispersed in D2O at 77 K. Mixtures of dipalmitoylphosphatidylcholine (DPPC) and lyso-palmitoylphosphatidylcholine (Lyso-PPC) over the entire composition range (0-100 mol%) and phosphatidylcholine spin-labeled at selected carbon atom position along the sn-2 chain (n-PCSL) were considered. On increasing the content of the lysolipids incorporated in DPPC, the lipid bilayers are first transformed in interdigitated lamellae and then converted in micelles of Lyso-PPC. In the interdigitated phase, the profile of translamellae water accessibility is rather uniform as all the hydrocarbon segments are equally exposed to the solvent. In Lyso-PPC micelle, water penetrates at any depth of the hydrocarbon region with a tendency to increase toward the chain termini. The extent of water penetration is higher in the interdigitated DPPC/Lyso-PPC dispersions than in Lyso-PPC micelles. The profiles of water permeation revealed directly by D2O-ESEEM are also confirmed by more indirect evaluation of the polarity profiles based on the 14N-hyperfine splitting in the conventional electron paramagnetic resonance spectra of n-PCSL in frozen DPPC/Lyso-PPC mixtures at 77 K. The ESEEM data reveal that H-bonding formation between the -NO group of the spin-label and the D2O molecules is favored in the intergitated phase with respect to the micellar phase and, in any lipid dispersion, the fraction of nitroxides that are singly H-bonded to deuterons is higher than the fraction that are doubly H-bonded. The overall results highlight the differences in the accessibility and properties of the solvent in the hydrocarbon region of lipid bilayers, interdigitated bilayers and micelles.

Slow- and rapid-scan frequency-swept electrically detected magnetic resonance of MOSFETs with a non-resonant microwave probe within a semiconductor wafer-probing station.

We report on a novel electron paramagnetic resonance (EPR) technique that merges electrically detected magnetic resonance (EDMR) with a conventional semiconductor wafer probing station. This union, which we refer to as wafer-level EDMR (WL-EDMR), allows EDMR measurements to be performed on an unaltered, fully processed semiconductor wafer. Our measurements replace the conventional EPR microwave cavity or resonator with a very small non-resonant near-field microwave probe. Bipolar amplification effect, spin dependent charge pumping, and spatially resolved EDMR are demonstrated on various planar 4H-silicon carbide metal-oxide-semiconductor field-effect transistor (4H-SiC MOSFET) structures. 4H-SiC is a wide bandgap semiconductor and the leading polytype for high-temperature and high-power MOSFET applications. These measurements are made via both "rapid scan" frequency-swept EDMR and "slow scan" frequency swept EDMR. The elimination of the resonance cavity and incorporation with a wafer probing station greatly simplifies the EDMR detection scheme and offers promise for widespread EDMR adoption in semiconductor reliability laboratories.

Advanced surface resonators for electron spin resonance of single microcrystals.

Electron spin resonance (ESR) spectroscopy of paramagnetic species in single crystals is a powerful tool for characterizing the latter's magnetic interaction parameters in detail. Conventional ESR systems are optimized for millimeter-size samples and make use of cavities and resonators that accommodate tubes and capillaries in the range 1-5 mm. Unfortunately, in the case of many interesting materials such as enzymes and inorganic catalytic materials (e.g., zeolites), single crystals can only be obtained in micron-scale sizes (1-200 µm). To boost ESR sensitivity and to enable experiments on microcrystals, the ESR resonator needs to be adapted to the size and shape of these specific samples. Here, we present a unique family of miniature surface resonators, known as "ParPar" resonators, whose mode volume and shape are optimized for such micron-scale single crystals. This approach significantly improves upon the samples' filling factor and thus enables the measurement of much smaller crystals than was previously possible. We present here the design of such resonators with a typical mode dimension of 20-50 µm, as well as details about their fabrication and testing methods. The devices' resonant mode(s) are characterized by ESR microimaging and compared to the theoretical calculations. Moreover, experimental ESR spectra of single microcrystals with typical sizes of ∼25-50 µm are presented. The measured spin sensitivity for the 50-µm resonator at cryogenic temperatures of 50 K is found to be ∼1.8 × 106 spins/G √Hz for a Cu-doped single crystal sample that is representative of many biological samples of relevance.

Rectal Cancer: Redox State of Venous Blood and Tissues of Blood Vessels from Electron Paramagnetic Resonance and Its Correlation with the Five-Year Survival.

A role of pro- and antioxidants for reducing rectal cancer (RC) incidence in operative, preoperative, and postoperative treatments is still disputable and controversial. The redox state of venous blood and tissues of blood vessels of 60 patients with RC (T2-4N0-2M0G2) and 20 donors is studied by means of the conventional and spin-trapping electron paramagnetic resonance (EPR). The intensity of the signals from ceruloplasmin (CP), transferrin (TF), and labile iron pool (LIP) at temperature T = 77 K as well as superoxide generation rate and nitric oxide (NO) levels at T = 300 K is measured. The reduced CP and TF activity and decreased NO levels increased LIP levels and superoxide-generating rates are detected in blood species. Correlation analysis for the five-year survival rate as a function of the extracted values is done. The results show that the intensities of the corresponding EPR signals from the “native” and “trapped” paramagnetic centers can be potentially used for the understanding of the molecular mechanisms underlying the RC progression and treatment.

Electron spin resonance characterisation of sedimentary quartz of different grain sizes

Different optically stimulated luminescence (OSL) single aliquot regenerative (SAR) saturation characteristics have been previously reported for quartz of diverse grain sizes. This preliminary electron spin resonance (ESR) study documents on paramagnetic signals in natural sedimentary quartz extracts of different grain sizes (4–11 μm, 63–90 μm, 90–125 μm, 125–180 μm, 180–250 μm) extracted from loess and sand samples that are amendable to OSL and ESR dating. Spectra recorded at room temperature and low power (<1 mW) are dominated by the E1’ centre, whose intensity in natural samples was found to decreases with increasing grain size. The signature of titanium centre could not be detected in fine (4–11 μm) quartz. For coarse fractions (>63 μm) titanium-lithium [TiO4/Li+]0 signals increase with increasing grain size. Aluminium-hole ([AlO4]0) signals are observed in all natural and laboratory irradiated investigated samples when spectra are recorded at low temperature (90 K). The intensity of these signals appears to decrease with increasing grain size, however, room temperature measurements show that these signals are highly interfered by a variety of signals tentatively attributed to peroxy (g ≈ 2.007 and g ≈ 2.004) with significantly higher intensities in fine grains (4–11 μm). A decrease of their intensity is reported when grain size increases and partial evidence that these defects are preferentially located in damaged regions of the grains is presented. A dose dependent paramagnetic signal at g ≈ 2.011 was detected only in 4–11 μm quartz. The stronger signature of the [TiO4/Li+]0 signals in larger grains coupled with the weaker signals of peroxy signals interfering with [AlO4]0 signal measurement is suggesting that coarser fractions should be preferred for conventional ESR dating using aluminium-hole and titanium signals. The understanding of the implication of these defects in OSL dating alongside with their concentration dependency on grain size requires further investigations.

Conventional electron paramagnetic resonance of Mn2+ in synthetic hydroxyapatite at different concentrations of the doped manganese

Powders of synthetic hydroxyapatite doped with Mn2+ ions in concentrations from 0.05 till 5 wt. % were investigated by conventional electron paramagnetic resonance (EPR). The parameters of the spin-Hamiltonian are derived. Partially resolved hyperfine structure in the magnetic fields corresponding to g ≈ 4.3 and g ≈ 9.4 is observed. The narrowing of the central peak with concentration is reported. A possibility to use the linewidth and intensity of the central peak for concentration measurements are discussed. The results could be used for the identification and qualification of Mn2+ in oil, mining and ore formations.

Synthesis and study of the synthetic hydroxyapatite doped with aluminum

Powders of synthetic hydroxyapatite doped with aluminium (Al) ions in concentrations 0 and 20 mol. % were synthesized by the precipitation method from the nitrate solutions and investigated by atomic emission spectrometry with inductively coupled plasma (AES-ICP), X-ray diffraction (XRD), scanning electron microscopy (SEM), gas absorption and conventional electron paramagnetic resonance (EPR). It is shown that for the chosen synthesis route an introduction of Al provokes formation of highly anisotropic phase, leads to the decrease in the crystallinity while no significant changes in the EPR spectra of the radiation-induced defects is observed. The results could be used for understanding the structural transformations with Al doping of the mineralized materials for geological and biomedical applications.

Radiation induced paramagnetic radicals in synthetic octacalcium phosphate

Created at room temperature by X-ray irradiation at the dose of about 5 kGy radiation induced centres in stable octacalcium phosphate (OCP) obtained by double transformation of α-tricalcium phosphate (α-TCP) are studied by means of the conventional and pulsed electron paramagnetic resonance (EPR). No EPR signals within the sensitivity of the used equipment in the non-irradiated samples were detected. In the irradiated species complex EPR spectrum signals due to H0 and CO-like radicals appear. The obtained results could be used for the tracing of the mineralization processes from its initiation to the completion of the final product and for the in situ identification of the OCP phase.

Nanoscale zero-field electron spin resonance spectroscopy

Electron spin resonance (ESR) spectroscopy has broad applications in physics, chemistry, and biology. As a complementary tool, zero-field ESR (ZF-ESR) spectroscopy has been proposed for decades and shown its own benefits for investigating the electron fine and hyperfine interaction. However, the ZF-ESR method has been rarely used due to the low sensitivity and the requirement of much larger samples than conventional ESR. In this work, we present a method for deploying ZF-ESR spectroscopy at the nanoscale by using a highly sensitive quantum sensor, the nitrogen vacancy center in diamond. We also measure the nanoscale ZF-ESR spectrum of a few P1 centers in diamond, and show that the hyperfine coupling constant can be directly extracted from the spectrum. This method opens the door to practical applications of ZF-ESR spectroscopy, such as investigation of the structure and polarity information in spin-modified organic and biological systems.

Conventional, pulsed and high-field electron paramagnetic resonance for studying metal impurities in calcium phosphates of biogenic and synthetic origins

Calcium phosphates (CaP) based materials are widely recognized as the most suitable matrix for bone tissue engineering. The cationic and anionic substitutions of CaP structure by the elements and groups of biological importance seem to be the effective ways to improve the properties of CaP-based substances to achieve the material’s desired parameters. Various analytical and biochemical methods are used for controlling their chemical content, structure, morphology, etc. Unfortunately, magnetic resonance techniques are usually not even considered as necessary tools for CaP inspection.Some aspects of application of the commercially realized electron paramagnetic resonance (EPR) approaches for characterization of CaP powders and ceramics (including the nanosized materials) such as hydroxyapatite and tricalcium phosphates of biogenic and synthetic origins containing intrinsic impurities or intentional dopants are demonstrated. Among them (1) conventional approaches; (2) high-frequency approaches – for measuring small amount of material; (3) pulsed methods – to study size effects, effects of the co-doping by different sorts of ions, to determine the location of paramagnetic centers, etc. The key features and advantages of the EPR techniques for CaP based materials characterization that could complement the data obtained with the recognized analytical methods are stressed.

Ether-linked lipids: Spin-label EPR and spin echoes

Electron spin echo envelope modulation (ESEEM) and conventional electron paramagnetic resonance (EPR) of site-specifically spin-labelled phospholipids are used to investigate the effect of ether-linked chains on the water-penetration and polarity profiles, as well as the phase behaviour and chain flexibility profiles, of phospholipid membranes. D2O-ESEEM reveals that water exposure of the terminal methyl groups in the interdigitated phase of dihexadecyl phosphatidylcholine (DHPC) is comparable to that of the methylene groups at the polar head-group end of the chains. Similarly, an uniform transmembrane polarity profile is obtained from the dependence of the outer 14N-hyperfine splitting on the spin-label position along the chain in frozen interdigitated DHPC dispersions. Two-component conventional EPR spectra of spin labels at the terminal methyl end of the chain reveal that the intermediate gel phase above the pretransition of DHPC contains components in which the lipid chains are interdigitated. The polarity and chain-flexibility profiles in the fluid Lα-phase of DHPC with ether-linked chains are shifted outwards, towards the polar-apolar interface, as compared with that of dihexadecanoyl phosphatidylcholine (DPPC) with ester-linked chains. Also, the polarity profile of DHPC is shifted upwards, to higher polarities. These differences reflect those in hydrocarbon thickness and area/lipid molecule reported by x-ray diffraction for the Lα-phases of the two lipids.

Enhanced accuracy of the microwave field strength measurement in a CW-EPR by pulsed modulation technique

The microwave magnetic field strength, B1, in the cavity of a conventional continuous wave electron paramagnetic resonance, CW-EPR, spectrometer was measured by employing modulation sidebands, MS, in the EPR spectrum. MS spectrum in CW-EPR is produced by applying the modulation frequency, ωrf, which exceeds the linewidth, δB, given in frequency units. An amplitude-modulated CW-EPR, AM-CW-EPR, was selected as detection method. Theoretical description of AM-CW-EPR spectrum was modified by adding Bloch-Siegert-like shift obtained by taking into account the cumulative effect of the non-resonant interactions between the driving fields and the spin system. This approach enables to enhance the precision of B1 measurement. In order to increase the sensitivity of the method when saturation effects, due to higher intensity of B1, decrease the resolution of AM-CW-EPR spectrum, detection at the second harmonic of CW-EPR has been employed.

Angle-dependent electron spin resonance of [formula omitted] measured with planar microwave resonators and in-situ rotation

We present a new experimental approach to investigate the magnetic properties of the anisotropic heavy-fermion system YbRh2Si2 as a function of crystallographic orientation. Angle-dependent electron spin resonance (ESR) measurements are performed at a low temperature of 1.6K and at an ESR frequency of 4.4GHz utilizing a superconducting planar microwave resonator in a 4He-cryostat in combination with in-situ sample rotation. The obtained ESR g-factor of YbRh2Si2 as a function of the crystallographic angle is consistent with results of previous measurements using conventional ESR spectrometers at higher frequencies and fields. Perspectives to implement this experimental approach into a dilution refrigerator and to reach the magnetically ordered phase of YbRh2Si2 are discussed.

Characterization of lipid oxidation process of beef during repeated freeze-thaw by electron spin resonance technology and Raman spectroscopy

In this study, electron spin resonance (ESR) and Raman spectroscopy were applied to characterize lipid oxidation of beef during repeated freeze–thaw (RFT). Besides the conventional indexes including peroxide values (PV), thiobarbituric acid-reactive substances (TBARS) and acid values (AV) were evaluated, the radical and molecular structure changes were also measured by ESR and Raman spectroscopy. The results showed that PV, TBARS and AV were increased (P<0.05) after RFT. This suggested that lipid oxidation was occurred during RFT. With the increase of radical signal intensity, lower oxidation stability was presented by ESR. Raman intensity of ν(CC) stretching region (1655cm−1) was decreased during RFT. Furthermore, lower Raman intensity ratio of I1655/I1442, I1655/I1745 that determine total unsaturation was also observed. Significant correlations (p<0.01) were obtained among conventional methods, ESR and Raman spectroscopy. Our result has proved that ESR and Raman spectroscopy showed great potential in characterizing lipid oxidation process of beef during RFT.

Optimization Methods for the Design of Sensitive Surface ESR Resonators

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.