Multifrequency (X-band to W-band) CW EPR of the organic free radical in petroleum asphaltene

Petroleum of Arabian and Colombian origin was studied by electron paramagnetic resonance (EPR) spectroscopy at X- (9 GHz), Q- (34 GHz) and W-bands (94 GHz). The experiments were performed at room temperature (about 300 K) and at 77 K (W-band only). The asymmetry in the lines corresponding to free radicals was observed more intensely in the W-band spectra. The values of the line width ΔH in the spectra increased linearly with the microwave frequency utilized in the EPR experiments. A mathematical simulation of the free radical signal for the EPR spectra in three bands with a set of parameters corresponding to a single species was attempted, but this was not exactly coincident with the experimental signals, suggesting that the hyperfine interaction of the unpaired electron with its neighborhood corresponds to more than one species of radical in the molecular structure of the petroleum asphaltene.     

EPR of Marine Diesel

Marine diesel was studied by electron paramagnetic resonance (EPR) spectroscopy at X-(9 GHz) and W-bands (94 GHz). The experiments were performed at room temperature (about 300 K). X-band spectra exhibited isotropy, resolved lines and negligible noise, whereas the W-band spectra exhibited a poorer signal-to-noise ratio and anisotropy in g and in hyperfine interactions. Viscosity at room temperature (2.5 · 10⁻³ kg/m · s) and the tumbling correlation time for free radicals (about 10⁻⁷ s) justified the high mobility of free radicals in marine diesel and consequently, the septet-quartet EPR spectrum of organic radicals with parameters g = 2.0028 ± 0.0005, proton hyperfine couplings A = 6.31 ± 0.01 G (septet) and A′ = 1.80 ± 0.01 G (quartet) at X-band. The perinaphthenyl radicals are probably responsible for the septet-quartet EPR spectrum of this oil by-product. Authors' address: Eduardo Di Mauro, Laboratório de Fluorescência e Ressonancia Paramagnética Eletr?nica, Centro de Ciências Exatas, Universidade Estadual de Londrina, C.P. 6014, CEP 86051-970 Londrina, Paraná, Brasil     

Continuous-Wave and Time-Resolved Electron Paramagnetic Resonance Study of Dimerized Aza-Crown Copper Porphyrins

The dimerization of 5-(4’-(aza-15-crown-5)-phenyl) copper porphyrin (CuP) upon the addition of the K(SCN) salt to a solution of the CuP monomer has been proven by electron paramagnetic resonance (EPR). The magnetic resonance parameters of the CuP monomer, the exchange interaction parameter, J = +0.25 cm^?1, and the Cu–Cu distance of the CuP dimer have been determined by comparing the experimental continuous-wave EPR spectra with the results of the numerical calculations. The photoexcited states have been studied in the time-resolved EPR experiments. It has been shown that the time-resolved EPR spectra of the dimerized porphyrins can be presented as a sum of two components that represent the spectra derived by integrating the dataset in the time windows of 1.1–1.3 and 2.1–2.3 μs. To describe the spectrum in the time window of 2.1–2.3 μs, it is assumed that there is an essential contribution to the signal from the excited state of the supramolecule, which is formed by the interaction between the photoexcited porphyrin in the quartet state and the neighboring non-excited porphyrin in the ground state.     

Spectroscopic,structural and theoretical studies of 2‐methyl‐4‐nitroaniline (MNA) crystal. Electronic transitions in IR

Polarized FT‐IR, Raman, neutron scattering (IINS), and UV‐Vis‐NIR spectra of 2‐methyl‐4‐nitroaniline (MNA) crystal plates, powder, and solutions were measured in the 10–50 000 cm⁻¹ range. The FT‐IR spectrum of deuterated MNA (DMNA) in KBr pellet, the Raman spectrum of the DMNA powder as well as the EPR spectrum of the MNA powder were also recorded. Complete assignments of bands to normal vibrations have been proposed. Density functional theory (DFT) calculations of wavenumbers and potential energy distribution (PED) have been performed to strengthen the assignments. The analysis of vibrational and electronic spectra has revealed vibronic couplings in MNA molecules in solutions and in crystals. In the polarized FT‐IR spectra of the crystal five unusually large bands are observed in MIR and NIR regions. Their origin is discussed in terms of N H···O, C H···O, C H···H N hydrogen bonds, intermolecular charge transfers, electrostatic interactions, and ion radicals formation in the crystal. The role of a methyl group introduction to 4‐nitroaniline is analyzed. The crystal structure of MNA at the room temperature was re‐investigated. Copyright © 2008 John Wiley & Sons, Ltd.     

Simulation of EPR Spectra as a Tool for Interpreting the Degradation Pathway of Hyaluronan

Electron paramagnetic resonance (EPR) spin trapping is one of the choice techniques for identifying free radicals and is often used in the study of biological systems. However, its sensitivity can result in a typical complicated EPR spectrum. The accurate simulation of these systems is essential for correct identification of the radical species, whenever more than one species contributes to the spectrum. Programs implementing the linear combination of single simulations allow the interpretation of EPR spectra without modifying experimental conditions. In this study, this approach was used to investigate the influence of the ferrous ion and the role of oxygen, as well on the formation of transient radical species, in the whole mechanism of hyaluronan degradation. Degradation was carried out under different environmental conditions (air, O₂, Ar, N₂, N₂ + CO₂) and EPR spin trapping studies were performed. The advantages of the simulation of multiple species EPR spectra were applied to the obtained results and some aspects of hyaluronan degradation mechanism were elucidated. The depolymerization reaction pathway has been defined according to two possible subsequent steps: the first is consistent with formation of an amidyl radical that induces a series of strand scissions, which stabilize at two different levels of molecular weight. The second step occurs when the molecular weight is lower than before and two different adducts are generated.     

ENDOR spectroscopic and molecular orbital study of the dynamical properties of the side chain in radical anions of ubiquinones Q-1, Q-2, Q-6, and Q-10

The dynamics of the side chain of the radical anions of ubiquinones Q-1 (2,3-dimethoxy-5-methyl-6-[3-methyl-2-butenyl]-1,4-benzoquinone), Q-2, Q-6, and Q-10 have been investigated using electron nuclear double-resonance (ENDOR) spectroscopy. When radicals are produced in the liquid phase, secondary radicals are also formed. The EPR spectra of these additional radicals overlap with the radical of interest. ENDOR spectroscopy was found to be capable for studying the dynamical properties of such conditions. The temperature dependence of the isotropic hyperfine coupling constants of the beta- and gamma-protons of the side chain was measured. The activation energy of the rotation and other dynamical properties of the side chain were calculated assuming that rotation can be modeled by the classical two-jump model. The rotation energy barrier for Q-1 was also determined by the hybrid Hartree-Fock/density functional method UB3LYP with the 6-31G(d) basis set. Calculated results were in good agreement with the experimental results. Despite the numerous parameters affecting the ENDOR linewidth ENDOR spectroscopy was shown to be a potential method for studying the dynamical properties of the mixtures of the radicals. Prominent forbidden transitions appear in the ENDOR spectra when alkali ions are present in the sample. From these transitions measured ENDOR-induced EPR spectra showed an additional doublet and phase transition in electron Zeeman frequency.     

Pulse EPR, ENDOR, and ELDOR Study of Anionic Flavin Radicals in Na+-Translocating NADH:Quinone Oxidoreductase

The Na⁺-translocating nicotinamide adenine dinucleotide (NADH):quinine oxidoreductase (Na⁺–NQR) is a component of respiratory chain of various bacteria and it generates a redox-driven transmembrane electrochemical Na⁺ potential. It contains four different flavin prosthetic groups, including two flavin mononucleotide (FMN) residues covalently bound to the subunits NqrB and NqrC. Na⁺–NQR from Vibrio harveyi was poised at different redox potentials to prepare two samples, containing either both FMN_NqrB and FMN_NqrC or only FMN_NqrB in a paramagnetic state. These two samples were comparatively studied using pulse electron paramagnetic resonance (EPR), electron-nuclear double resonance (ENDOR), and electron-electron double resonance (ELDOR) spectroscopy. The echo-detected EPR spectra and electron spin relaxation properties were very similar for flavin radicals in both samples. The splitting of the outer peaks in the proton ENDOR spectra, assigned to the C(8α) methyl protons, allows to identify both radicals as anionic flavosemiquinones. The mean interspin distance of 20.7 Å between these radicals was determined by pulse ELDOR experiment, which allows to estimate the edge-to-edge distance (r _e) between these flavin centers as: 11.7 Å < r _e < 20.7 Å. The direct electron transfer between FMN_NqrB and FMN_NqrC during the physiological turnover of the Na⁺–NQR complex is suggested.     

Hyperfine Interaction Tensors of 13C Nuclei for Ring Carbons of Ubisemiquinone-10 Hydrogen Bonded in Alcohol Solvents

The anion radicals of ubiquinones-10 ¹³C chemically labeled at the C₅ or C₆ ring positions in alcohol have been studied by 1D and 2D ESEEM to define the hyperfine interaction tensors with the ¹³C nuclei. Analysis of the cross-peak line shapes and simulations of the spectra allowed us to conclude that the hyperfine tensors are characterized by an anisotropic component T ~6 MHz and an isotropic coupling a ~?3 MHz with support from DFT calculations. However, these values were found to be inconsistent with the shift of the sum combination harmonic in the four-pulse ESEEM spectra. Simulations resolve this apparent discrepancy by showing that the shift of the sum combination to lower frequency and its broadening can be accounted for by a distribution of the hyperfine couplings. A spread of the methoxy group conformations, as supported by previous experimental observations, is suggested as the mechanism influencing the distribution of the hyperfine couplings for the ring carbons.     

Application of EPR Spectroscopy to Examination of Free Radical Formation in Thermally Sterilized Flumetasone

Thermal formation of free radicals in flumetasone sterilized according to the pharmaceutical norms at 160, 170 and 180 °C was examined by electron paramagnetic resonance (EPR) spectroscopy. The microbiological analysis was done. Similar free radical concentrations were measured for flumetasone sterilized at 160 and 170 °C. The concentration was considerably higher than that for flumetasone sterilized at 180 °C. Fast spin–lattice relaxation processes, homogeneously broadened EPR lines, and complex free radicals system characterize the heated flumetasone. Free radicals were not observed 30 days after thermal sterilization. Optimal temperatures of sterilization of flumetasone are 160 and 170 °C.     

Anomalous Phases in Cavity-Free 240 GHz Pulsed ENDOR Spectra of 1.44 GeV Xe-Irradiated LiF

Paramagnetic centers generated by swift heavy ion irradiation of LiF crystals could be identified as electrons trapped at regular anion vacancy sites (F centers). Well-resolved electron-nuclear double resonance (ENDOR) spectra resulting from the hyperfine interaction with ⁷Li and ¹⁹F nuclei located in six different shells could be recorded. In order to preserve the millimeter-sized crystals, a cavity-free setup was used for the ENDOR experiments at an electronic Larmor frequency of 240 GHz. Apparently even under conditions of extremely high local energy loss in the ion track, the local density of persistent F centers is still sufficiently low to prevent distortions of the ionic crystal. The spread of hyperfine coupling constants was less than 5 %. Neither in electron paramagnetic resonance (EPR) nor in ENDOR spectra there was evidence for different types of paramagnetic centers. When performing ENDOR by applying the radiofrequency pulse directly after the 3-pulse Mims-type microwave sequence, an anomalous ENDOR effect was observed. The observed “positive” and “negative” ENDOR response can be attributed to efficient hole and anti-hole formation in the inhomogeneously broadened EPR spectrum and can be used to determine the sign of hyperfine coupling constants.     

Multifrequency CW EPR spectroscopy of extraterrestrial carbonaceous matter

In this work, the carbonaceous matter of Orgueil, Murchison and Tagish Lake carbonaceous meteorites and a reference coal is studied by multifrequency continuous-wave electron paramagnetic resonance (EPR) spectroscopy from 4 to 285 GHz. It is found that the shape of the EPR line of the radicals in meteoritic carbonaceous matter is Lorentzian in all the frequency range, while the line shape of the coal is Lorentzian only below 95 GHz and becomes inhomogeneously broadened at higher frequency, as previously observed for coals by other authors. This points to strong exchange interactions in meteoritic carbonaceous matter, resulting from a pronounced spin clustering that does not occur in biogenic carbonaceous matter (coals). The temperature dependence of the EPR line width has been studied in detail at X- and W-bands for the Orgueil meteorite. It confirmed our previous model of the presence of radicals with thermally accessible triplet states (TATS) in meteorites. These TATS, which were attributed to diradicaloids moieties on the basis of molecular quantum DFT calculations (L. Binet, D. Gourier, S. Derenne, F. Robert, I. Ciofini: Geochim. Cosmochim. Acta 68, 881–891, 2004) do not exist in biogenic carbonaceous matter. This analysis also precised the strength of the clustering effect in meteorites, yielding an estimated local spin concentrationN=5·10²⁰ spin/g, which is two orders of magnitude higher than the average spin concentration in the Orgueil meteorite. It is important to note that such spin clustering has also been observed by other authors in synthetic hydrogenated amorphous carbon. It seems that the clustering of radicals is a common feature of synthetic and extraterrestrial (abiotic) carbonaceous matters, while radicals are homogeneously distributed in biogenic carbonaceous matter.     

EPR and optical absorption characteristics of sodic plagioclase from granite pegmatite in Kadavur,India

The electron paramagnetic resonance (EPR) spectra of sodic plagioclase from dykes of granitic pegmatite occurring in the Kadavur area, Tamil Nadu, India, were examined at room temperature to identify paramagnetic impurities in a “low plagioclase” using EPR and optical techniques. The EPR spectra showed the presence of Fe(III) and Mn(II) impurities. After heating the plagioclase samples for various durations at 600 °C, it has been observed that the concentration of Mn(II) remained as such in one sample but completely disappeared in another sample, while there was no change in Fe(III) ion concentration after the heat treatment in either sample. Optical absorption spectra also showed Fe(II) and Fe(III) in addition to Ti(III) impurities in sodic plagioclase before heating, while after heating the relative concentration of Fe(II) and Fe(III) changed, accompanied by the disappearance of Ti(III).     

A 236 GHz Fe3+ EPR Study of Nanoparticles of the Ferromagnetic Room-Temperature Semiconductor Sn1−x Fe x O2 (x = 0.005)

High-frequency (236 GHz) electron paramagnetic resonance (EPR) studies of Fe³⁺ ions at 255 K are reported in a Sn_1?x Fe _x O₂ powder with x = 0.005, which is a ferromagnetic semiconductor at room temperature. The observed EPR spectrum can be simulated reasonably well as the overlap of spectra due to four magnetically inequivalent high-spin (HS) Fe³⁺ ions (S = 5/2). The spectrum intensity is calculated, using the overlap I(BL) + (I(HS1) + I(HS2) + I(HS3) + I(HS4)) × exp(?0.00001B), where B is the magnetic field intensity in Gauss, I represents the intensity of an EPR line (HS1, HS2, HS3, HS4), and BL stands for the baseline (the exponential factor, as found by fitting to the experimental spectrum, is related to the Boltzmann population distribution of energy levels at 255 K, which is the temperature of the sample in the spectrometer). These high-frequency EPR results are significantly different from those at X-band. The large values of the zero-field splitting parameter (D) observed here for the four centers at the high frequency of 236 GHz are beyond the capability of X-band, which can only record spectra of ions with much smaller D values than those reported here.     

EPR study of gamma-irradiated 2-Bromo-4′-methoxyacetophenone single crystals

The gamma-irradiated single crystals of 2-Bromo-4′-methoxyaceto-phenone (2B4MA) were investigated using electron paramagnetic resonance (EPR) technique. Density-functional theory calculations were employed to investigate and identify the radicals that have been assumed to be formed upon irradiation of 2B4MA single crystals. The EPR spectra of 2B4MA were recorded at different orientations in the magnetic field at room temperature. Taking into account the chemical structure and experimental spectra of irradiated single crystal of 2B4MA, it was assumed that at least two different radicals were produced in the sample. Following this assumption, six possible radicals were modeled and EPR parameters were calculated by using the DFT, B3LYP/6-311+G(d), for the modeled radicals individually. The calculated hyperfine coupling constants and g-tensors were used as initial values for simulation studies. The three crystallographic axes on the simulated spectra were well matched with experimental spectra for the two modeled radicals. Thus, we identified the R1 type radical and R4 type radical as paramagnetic species produced in gamma-irradiated 2B4MA.     

A DFT,X- and W-band EPR and ENDOR Study of Nitrogen-Centered Species in (Nano)Hydroxyapatite

Incorporation of the nitrogen-containing impurities in hydroxyapatite (HAp) powders with the sizes of the crystallites of (20–50) nm was studied using first-principles modeling combined with the multi-frequency (9 and 94 GHz) electron paramagnetic resonance (EPR) methods. It is shown that the observed EPR spectra are undoubtedly due to the presence of the bulk radiation-induced NO₃ ^2? radicals. This conclusion is based on spin-polarized density functional theory calculations of spectroscopic parameters within gauge-including projector augmented wave framework followed by the exact comparison of the simulated EPR and electron–nuclear double resonance spectra with the experimental findings. In addition, a comprehensive analysis of the simulated properties allows us to suggest that the paramagnetic centers preferably occupy PO₄ ^3? sites in the HAp structure.     

EPR and density functional studies on 3-pyridylmethaniminoxy radical:1H hyperfine couplings as a structural criterion for iminoxyls derived from pyridinealdoximes

3-pyridylmethaniminoxyl has been generated by γ-irradiation of the parent oxime in the solid state and by incorporation of 3-pyridinealdoxime into the channels of thermally activated pentasil zeolite ZSM-5. The radical formed by both methods exhibits an electron paramagnetic resonance (EPR) spectrum with a characteristic powder pattern. The assignment of the hyperfine structure of the anisotropic spectra to the couplings with¹⁴N and¹H nuclei of Z geometrical isomer of 3-pyridylmethaniminoxy radical has been aided significantly by comparison with the coupling parameters calculated with the density functional theory (DFT). It has been found that 3- and 4-pyridylmethaniminoxyls generated in the oxime matrices, in contrast to the radicals derived from 2-pyridinealdoxime, have a possibility to isomerize. The EPR spectra of γ-irradiated 3- and 4-pyridinealdoximes show a distinct temperature dependence of particular isomer contributions which have been correlated with the relative energies of the isomers derived from DFT calculations. Hybrid density functional methods have been also used to determine the structure of transition states for isomerization (via inversion at nitrogen) and rotation (of pyridyl ring) as well as to predict the appropriate energy barriers.     

Spectroscopic Studies on Threonine Doped Polyaniline Composites

The structural and magnetic properties of polyaniline (PANI)- and threonine (T)-doped polyaniline composites were characterized by using FTIR, UV-Vis, and electron paramagnetic resonance (EPR) spectroscopic techniques. The FTIR, UV-Vis, and X-band EPR spectra were recorded for PANI- and threonine-doped polyaniline (PANI-T) composites. The increased intensity of the IR bands in PANI-T composites is due to the increasing dopant concentration. The observed red shift corresponding to the N-H ··· N mode indicates the hydrogen bond formation in between the PANI and threonine molecule. The observed decrease in spectral intensity of the UV-Vis spectrum of the PANI-T composite confirms the occurrence of the protonation at the imine nitrogen sites. The EPR parameters such as line width, g factor, line asymmetry parameter, signal intensity, and spin concentration values were estimated. The EPR spectrum of PANI clearly indicates the presence of unpaired polaron. The EPR signal intensity and spin concentration values decrease with increasing dopant concentration, which reveals the polaron to bipolaron formation in PANI-T composites. EPR lineshape analysis showed that the absorption profile was Gaussian shape. The Gaussian-shaped line is generally due to the dipole–dipole interactions in the PANI and PANI-T composites. The line asymmetry parameter and g values indicated the isotropic nature of PANI and PANI-T composites.     

Ion track effect on point defect production in SiC

Low-temperature (40 K) photoluminescence (PL) measurements were used to follow the defect formation induced in the 4H-SiC epitaxial layer by irradiation with 200 keV H⁺ and 800 keV C⁺ in the fluence range of 5×10⁹–3.5×10¹² ions/cm². After irradiation, the PL spectra show the formation of some sharp lines, called “alphabet lines”, located in the wavelength range of 425–443 nm, due to the recombination of excitons at structural defects induced by ion beams. The analysis of luminescence line intensity versus ion fluence allows us to mark two different groups of peaks, namely the P1 group (e, f and g lines) and the P2 group (a, b, c and d lines). The normalised yield of P1 group lines increases with ion fluence and reaches a maximum value, while the normalised yield of P2 group lines exhibits a threshold fluence and then increases until a saturation value is reached. These different trends indicate that, while the P1 group lines are related to the primary defects created by ion beams (interstitial defects, vacancies), the P2 group lines can be associated with some complex defects (divacancy, antisites). The trends are similar for irradiation with H⁺ and C⁺ ions; however, the defect formation occurs in the fluence range of 5×10⁹–10¹¹ ions/cm² for C⁺ irradiation and 10¹¹–4×10¹² ions/cm² for H⁺ irradiation. Taking into account the different values of energy deposited in elastic collision, a dependence on the ion type was found: the C⁺ ion results in being less effective in defect production as a higher defect recombination occurs inside its dense cascade.