CW EPR, echo-detected EPR, and field-step ELDOR study of molecular motions of nitroxides ino-terphenyl glass: Dynamical transition, dynamical heterogeneity and β-relaxation

Continuous-wave electron paramagnetic resonance (CW EPR), echo-detected (ED) EPR, and field-step electron-electron double resonance (FS ELDOR) were simultaneously applied to study molecular motions of nitroxide spin probes of two different types in glassyo-terphenyl. A strong linear temperature dependence of the overall splitting of the CW EPR lineshape was found for nitroxide Tempone and only a weak one for a phenyl-ring-containing imidasoline nitroxide. The linear temperature dependence of the splitting is explained within the model of harmonic librations. The assessed libration frequency for Tempone is of the order of 3·10¹² rad/s. The observed remarkable difference between the two nitroxides is explained by the different strength of interactions between guest and host molecules and by dynamical heterogeneity of the glass. The nonlinear temperature dependence above 250 K is attributed to the onset of anharmonic motion that is postulated in a number of neutron scattering and Mössbauer spectroscopy studies for molecular glasses and proteins (the so-called dynamical transition). Above 245 K also ED EPR spectra change drastically, which may be explained on the same ground. Magnetization transfer was observed in FS ELDOR for nitroxide Tempone, with a time constant around 10^?5 s. It was found to be almost temperature-independent between 160 K and 265 K and was attributed to the Johari-Goldstein β-relaxation process. For the phenyl-ring-containing imidasoline nitroxide this transfer was not observed, which may be explained again by the dynamical heterogeneity of the glass and by small effectivity of the β-relaxation process in this case.     

Librational dynamics of nitroxide molecules in a molecular glass studied by echo-detected EPR

Nitroxides 2,2,6,6-tetramethyl-4-piperidone N-oxide (tempone), 3-carboxy-proxyl and potassium peroxylamine disulfonate (Fremy salt) in glycerol solution were studied in a wide temperature range near the glass transition temperatureT _g. The echo-detected (ED) electron paramagnetic resonance (EPR) lineshape reveals strong dependence on the time interval τ between the echo-forming microwave pulses which is readily explained by anisotropic phase relaxation. Employing a librational model of molecular motion and the Redfield relaxation theory, spectra were simulated for the τ’s varying in a large interval. The anisotropic relaxation rate increases with temperature increase and it is larger for nitroxide with a larger molecular size. The mean-squared amplitude of motion, obtained from reduced hyperfine splitting in continuous-wave EPR, near T_g linearly depends on temperature which is characteristic of harmonic solids. For tempone in a host crystal 2,2,4,4-tetramethyl-cyclobutan-1, 3-dione the anisotropic spin relaxation rate decreases with temperature increase so the found feature solely belongs to a glassy state. A new approach is proposed for modeling slow wobbling motion in a restricted angular space.     

Pulsed EPR spin-probe study of intracellular glasses in seed and pollen

EPR spectra of 3-carboxy-proxyl (CP) in dry biological tissues exhibited a temperature-dependent change in the principal value A'(zz) of the hyperfine interaction tensor. The A'(zz) value changed sharply at a particular temperature that was dependent on water content. At elevated water contents, the break occurred at lower temperatures and appeared to be associated with the melting of the cytoplasmic glassy state. To investigate the reason for the change in A'(zz), we employed echo-detected EPR (ED EPR) spectroscopy. The shape of the ED EPR spectrum revealed the presence of librational motion of the spin probe, a motion typically present in glassy materials. The similarities in temperature dependency of A'(zz) and librational motion of CP in pea seed axes indicated that the change in A'(zz) arose from librational motion. ED EPR measurements of CP as a function of water content in Typha latifolia pollen showed that librational motion decreased with decreasing water contents until a plateau or minimum was reached. ED EPR spectroscopy is a valuable technique for characterizing the relation between molecular motion and storage kinetics of dry seed and pollen.     

Influence of neutron and heavy-ion irradiation on EPR spectra of CuGeO3

The influence of neutron and heavy-ion irradiation on the electron paramagnetic resonance (EPR) spectra of the spin-Peierls compound CuGeO₃ has been investigated in the wide temperature range of 2–300 K. It is found that the neutron irradiation leads to a decrease of the spin-Peierls transition temperature and induces appreciable changes in the EPR signal intensity, resonance line width andg-factor of this material. These changes may be associated with a partial suppression of both the energy gap and dimerization within the Cu chains due to the irradiation-induced changes in the topological and chemical short-range order. In contrast to this, the heavy-ion irradiation induces only an increase in the intensity of the EPR signal and does not produce appreciable changes in the resonance line width,g-factor and spin-Peierls transition temperature. The experimental results show a large increase in the Curie-Weiss component and complete suppression of the spin-Peierls transition for higher irradiation doses.     

Molecular dynamics and spatial distribution of TOAC spin-labelled peptaibols studied in glassy liquid by echo-detected EPR spectroscopy

2,2,6,6-tetramethylpiperidine-l-oxyl-4-carboxylic acid (TOAC) spin-labelled analogues of the Aib-rich peptide (peptaibol) Trichogin GA IV are investigated in a glassy methanol/glycerol (70/30 v/v%) system, using conventional CW EPR and electron spin echo spectroscopy. Echo-detected (ED) EPR spectra indicate that the labels undergo restricted orientational motion (libration). Comparison with the small molecular spin probe Tempone shows that the dynamics of peptide molecules is determined by their structure and not by the surrounding medium. At the terminal positions (position 1 and 8) TOAC residues were found to be more flexible than at the central 4th position. Instantaneous diffusion mechanism in electron spin echo, which also contributes to the ED EPR spectra, was employed for deriving the local concentration of peptaibols. This approach may serve as a tool for investigation of peptide aggregation. In the studied model glassy solution the peptaibols were found to be randomly distributed.     

Motional effects on the epr spectrum of a perturbed H centre in neutron irradiated LiF

The electron paramagnetic resonance (EPR) spectrum of an asymmetric interstitial H centre in LiF has been studied as a function of temperature. The shifts with temperature of the EPR lines have been measured from 7 to 150 K. They are interpreted by a libration process of the molecule ion around its mean orientation. Near 180 K, the EPR lines broaden. The thermally activated broadening arises out from reorientational motions of the molecule ion. The reorientation rates show that there are two distinct jumping motions between 180 and 230 K; one of them implies rotations of the molecule ion around the average 〈111〉 orientation and is assumed to be induced by the same librations modes as those which produce the line-shifts. The other one is the pyramidal jumping motion between the four equivalent 〈111〉 orientations.     

An Electron Paramagnetic Resonance Study of the Orbital Ordering Compound MgTi<Subscript>2</Subscript>O<Subscript>4</Subscript>

We report the electron paramagnetic resonance (EPR) studies of MgTi₂O₄ in the 300–140 K range. Above the transition temperature T _t (~258 K), the EPR results indicate that MgTi₂O₄ is paramagnetic. The parameters of the EPR spectra show an anomalous change at T _t. The clear EPR lines can be observed in temperature between T _t and 220 K. Besides that the EPR intensity, g value, and EPR linewidth increase with decreasing temperature; in temperature range below 220 K, no clear EPR line can be detected. The EPR spectra results demonstrate that magnetic spin-singlet state and the orbital density wave of MgTi₂O₄ system are formed gradually with decreasing temperature at low temperature range.     

The Temperature Dependence of Nitroxide Spin–Label Interaction Parameters: a High-Field EPR Study of Intramolecular Motional Contributions

High-field W-band electron paramagnetic resonance (EPR) spectroscopy was utilized to study the temperature dependence of the magnetic interaction parameters (g-, hyperfine-, quadrupole tensors) of two types of doublet-state nitroxide spin probes in glass-forming ortho-terphenyl solution: a five-membered ring system of pyrroline type (model for the commonly used methane thiosulfonate spin label) and a six-membered ring system of piperidine type (model for the commonly used TOAC spin label). The analysis of the g- and hyperfine tensors in terms of their isotropic and anisotropic parts reveals at least two mechanisms of motion that are responsible for the temperature dependence of the interaction parameters. The first mechanism is attributed to the overall small-angle motion of the nitroxide molecule in the glassy matrix; it leads to an averaging of the anisotropies of the EPR parameters. The second mechanism originates in an intramolecular out-of-plane motion of oxygen in the nitroxide group. This type of motion is evidenced by comparing the experimental findings for the spin-interaction parameters with the results of density functional theory calculations. The harmonic oxygen out-of-plane vibrations result in a variation of both the isotropic and anisotropic parts of the g- and hyperfine tensors. In contrast, the quadrupole tensor is not influenced by this vibration mechanism in the temperature range under study (90–240 K). Consequences of the applicability of such typical nitroxide radicals for probing details of their protein environment and for studying librational dynamics in frozen solutions are discussed.     

Phase transition in Cu2+-doped RbH2 PO4 as observed by EPR

The electron paramagnetic resonance (EPR) spectra of Cu²⁺-doped RbH₂ PO₄ at elevated temperatures indicate a phase transition at 358 K. The EPR-silent state at this temperature is attributed to a so-called polymeric phase transition. After the transition when the temperature is lowered to 293 K, the EPR signal does not appear; therefore, the transition is irreversible. This result seems to be in agreement with the other observations. The EPR spectra for the sample indicate the presence of two sites for Cu²⁺, and the values of EPR parameters are in accord with the literature on Cu²⁺-doped single crystals. Any other phase transitions could not to be observed at low temperatures down to 113 K.     

Incommensurate Phases of the MgSiF6·6H2O Crystals: EPR and Group-Theoretical Studies

The group-theoretical study of the structural phase transition to incommensurate state of MgSiF₆·6H₂O crystals, revealed by the electron paramagnetic resonance (EPR) method, as well as analysis of the EPR results, are presented. The consideration of temperature dependences of Mn²⁺ admixture ion EPR spectrum symmetry and parameters leads to the conclusion that at T _i1 = 370 ± 0.3 K they undergo second-order structural phase transition to incommensurately modulated state, the order parameter of this transition may be the angle of [Mg(H₂O)₆]²⁺ octahedra rotation around crystal C ₃ axis. At temperature decreasing below T _i1 the gradual transformation of plane-wave modulation of lattice displacements into soliton mode occurs, which is interrupted by the first-order phase transition at T _i2 = 343 ± 0.3 K accompanied by abrupt decrease in modulation amplitude. At T _c = 298.5 ± 0.3 K the first-order improper ferroelastic phase transition into monoclinic phase occurs. The group-theoretical analysis of the phase transition at T _i1 in the investigated crystals, carried out for the first time, has shown that the existence of the incommensurately modulated phase is conditioned by the fundamental reasons (presence of Lifshitz invariant). The conclusions of this analysis on the nature of order parameter, the structural motifs of incommensurate phase and the possible character of temperature evolution of the structure are in agreement with the EPR investigation data.     

Synthesis and electron paramagnetic resonance study of a nitroxide free radical covalently bonded on aminopropyl-silica gel

A solid spin-labeled material was obtained starting from 2-chloro-3,5-dinitro-N-(4-(2,2,6,6-tetramethyl-piperidine-1-oxyl)-benzamide) and aminopropyl-silica gel. Stability tests showed that even after several months the spin-labeled material had the same properties as immediately after synthesis. EPR properties of the TEMPO-derivatized silica were studied as a function of solvent polarity and temperature. Rotational correlation times were calculated from EPR spectra and correlated with solvent characteristics and temperature. Polar solvents induce a fast motion of the spin-label, clearly seen in the EPR spectra by the apparition of the well-known TEMPO radical triplet. The solid spin-labeled (dry) sample showed a high interspin interaction, which can be disrupted not only by different (liquid) solvents, but also by absorption of different solids, like cyclodextrins, dendrimers or polyethyleneglycols. Also, changes induced by the temperature were studied in the case of toluene wet sample. From 150 to 370 K, the spectrum is changing from a slow motion spectrum type to a fast motion regime. The preparative procedures to obtain the spin-labeled silica as well as some of its parameters are described.     

Fe2+ spin transition in [Fe(trz)(Htrz)2](BF4) as evidenced by a variable temperature EPR study

The EPR of Fe³⁺ ions has been used for the first time to evidence a low-spin (S=0) to high-spin (S=2) transition of Fe²⁺ ions in an octahedral ferrous complex [Fe(trz)(Htrz)₂](BF₄). The temperature dependence of the intensity of the Fe³⁺ EPR line atg=4.3 reveals a spin transition which occurs for the Fe²⁺ ions, with hysteresis. The transition temperatures areT _c↑=374 K in the warming mode andT _c↓=345 K in the cooling mode. The analysis of the EPR spectral data indicates the presence of a structural phase transition accompanying the spin transition.     

EPR evidence of the low temperature phase transition in C60

A standard EPR technique has been applied to perform temperature studies of polycrystalline samples of C₆₀ fullerene. A comparison of the three main parameters of EPR spectra obtained for a C₆₀ sample before and after (solvent free) purification has been made in temperatures from 4 to 300 K. When compared to the spectrum of the as-obtained (crude) sample the spectrum of the purified sample revealed considerable changes i.e. an increase in the EPR signal intensity and evidence of a phase transition at about 90 K. This transition is proved to be related to the two processes: freezing of the orientational motion of C₆₀ molecules and redistribution of the positive and negative charge observed as paramagnetic centres localized on C₆₀ molecules.     

EPR study of the ferroelectric phase transition in chromium-doped DMAAS

X-band electron paramagnetic resonance (EPR) investigations of single crystals of Cr³⁺-doped dimethylammonium aluminium sulphate hexahydrate are presented from 100 K to room temperature. The crystal undergoes a phase transition at 152 K from the ferroelastic to the ferroelectric phase. The spin-Hamiltonian parameters have been determined for both phases. The spin-Hamiltonian parameters in the ferroelectric phase are:g=1.980±0.003,b ₂ ⁰ =(1140±15)·10^?4 cm^?1,b ₂ ² =(214±10)·10^?4 cm^?1. Remarkable EPR line width changes confirm the order-disorder character of the ferroelectric phase transition on a microscopic level and demonstrate that the dimethylammonium reorientation freezing-out is the prime reason for this transition.     

Phase transition study in α-Fe2WO6 compound by EPR

The temperature dependence of the EPR spectrum for the α-phase of iron tungstate has been investigated in the temperature range of 40–260 K. At temperatures betweenT ₁ ≈ 250 K andT ₂ ≈ 205 K where the antiferromagnetic phase transition occurs, a relatively narrow EPR line arising from the dominant iron(III) species has emerged, gaining intensity with the temperature increase. Its linewidth temperature evolution could be described by Huber equation, with T_N = 200 K, which is consistent with the peak seen in magnetic susceptibility measurements, while the correspondingg-factor shifts to higher fields reflecting the build-up of internal field emerging from increasing shortrange order in the spin system. At temperatures lower than T₂, a very broad and distorted EPR line with temperature dependentg-factor and linewidth has been observed reflecting the corresponding rise of the magnetic susceptibility below the antiferromagnetic phase transition, presumably arising from magnetic clusters embedded in the antiferromagnetic background.     

EPR spectroscopy and imaging of TEMPO-labeled magnetite nanoparticles

The article presents results of a study of TEMPO-labeled polymer coated superparamagnetic iron(II,III) oxide nanoparticles using both Electron Paramagnetic Resonance (EPR) spectroscopy and Electron Paramagnetic Resonance imaging technique (EPRI). The X-band (9.4 GHz) EPR spectroscopy was used to investigate the behavior of TEMPO-labeled polymer coated magnetite nanoparticles in different conditions (temperature and orientation in magnetic field). The broad line, which comes from the core of Fe₃O₄ nanoparticles, shows anisotropy. This signal broadens with decreasing temperature, its intensity increases with increasing temperature and the g factor decreases with increasing temperature. The shape of the signal from nitroxide radical strongly depends on temperature. When temperature is higher than 200 K, a narrow triplet appears, but when it is lower than 200 K the signal consists of broad asymmetric lines. Analysis of the signal allowed characterization of the motion of the spin label attached to nanoparticles. Values of anisotropy parameter ɛ and rotational correlation time τ_c were calculated for TEMPO in the fast rotation regime.The ability of TEMPO-labeled PEG coated magnetite nanoparticles to diffuse within the hydrogel medium was also investigated. The EPR imaging of nanoparticles diffusion in hydrogel was made at room temperature using an EPR L-band (1 GHz) spectrometer. EPRI has been proved effective for evaluation of changes in the spatial distribution of nanoparticles in the sample.     

A microwave absorption study in the thermochromic SrMnO3

We report electron paramagnetic resonance (EPR) and magnetically modulated microwave absorption spectroscopy (MAMMAS) studies at X-band (8.8–9.6 GHz) on powdered SrMnO₃ in the 90–400 K temperature range. EPR spectrum shows one broad single-line at room temperature, which is observed only above 280.5 K, being compatible with an antiferromagnetic order. The onset of the para–antiferromagnetic transition has been determined from the temperature dependence of three main parameters extracted from the EPR spectra: resonant field (H_res), peak-to-peak linewidth (ΔH_pp) and integrated intensity (I_EPR). The MAMMAS response shows a change in the region 276–283 K, compatible with the para–antiferromagnetic transition, without presenting any significant change in the region of thermochromism.     

The large polaron in a magnetic field: Possible existence of a phase transition

It is shown that the ground state energy of a polaron in a magnetic field (calculated in the Feynman approximation) exhibits a discontinuity in the first derivative with respect to α (the electron-phonon coupling constant) if ω_c/ω_o (cyclotron frequency to LO-phonon frequency) is larger than 2.24. This discontinuity has the characteristics of a first order phase transition if α is interpreted as an inverse temperature. For ω_c/ω_o = 2.24 the transition is second order. We found that below the transition point the phonon cloud cannot follow the electron in its motion in the magnetic field.     

Angle-selective measurements of spin soliton in ladder polydiacetylene by pulsed 94 GHz EPR

Angle-selection experiments of a spin soliton in randomly oriented ladder polydiacetylene were carried out by pulsed electron paramagnetic resonance (EPR) at W-band. EPR measurement using 94 GHz microwaves increased the difference in the resonance field due tog anisotropy of the spin soliton to allow the orientation dependence of transient nutation, electron nuclear double resonance (ENDOR) and spin relaxations to be investigated. The shape of theg anisotropy-resolved nutation spectrum was discussed on the basis of the EPR transition moments and the differences between spin relaxation times. Reliable assignments of hyperfine couplings to the β protons (H_β) of the alkyl side chains were achieved with the support of W-band ENDOR measurements. No significant orientational dependence in theT ₁ andT ₂ processes was found in terms of isotropy of the H_β-hyperfine interaction.     

Physical and Instrumental Considerations in the Use of Lithium Phthalocyanine for Measurements of the Concentration of the Oxygen

The use of crystals of lithium phthalocyanine (LiPc) to measure the concentration of oxygen in vivo and in vitro by electron paramagnetic resonance leads to experimental constraints due to the very narrow EPR lines that may occur (as narrow as 11-13 mG in the absence of O₂), distortions induced by the automatic frequency control system, anisotropy in the spectra (orientation-dependent linewidth is 11-17 mG in the absence of O₂), microwave power saturation, and the effect of physiological motion. These constraints can be overcome if recognized. This article highlights the experimental and theoretical basis of these properties of the EPR signal of LiPc and suggests some technical solutions. It is most important to recognize that paramagnetic species such as LiPc present problems that are not commonly encountered in EPR spectroscopy.