Spin dynamics in continuous wave and pulsed ENDOR spectroscopy of coals

ENDOR experiments on coals recorded using continuous wave (CW) and pulsed techniques appear to give qualitatively different spectra. A matrix proton signal dominates the ENDOR spectrum of coals recorded in the CW ENDOR experiment while both a matrix and local proton ENDOR signals with huperfine couplings of up to 20 MHz are observed in spectra recorded using pulsed excitation techniques. Analysis of these spectra lead to different implications for the structure of the molecules that host the unpaired electron. Using a combination of pulsed EPR (Electron Spin Echo, FID detected hole burning) and pulsed Electron Nuclear Multiple Resonance (Sub-level relaxation, hyperfine selective ENDOR, EPR sub-spectra) experiments, we investigate the electron and nuclear spin dynamics in order to reconcile the different signal amplitudes observed in the CW and pulsed ENDOR spectra. In the CW ENDOR experiment, the results of the FID detected hole burning experiments prove that the low ENDOR signal intensity can not be attributed to spectral diffusion mechanisms competing with ENDOR mechanisms. Instead, we find that an unfavorable ratio of the electron and nuclear spin relaxation rates results in small local ENDOR signals. The matrix line dominates the spectrum because of the large number of matrix protons. In the pulsed ENDOR experiment, the hyperfine contrast selectivity mechanism suppresses the intensity of the matrix ENDOR signal and enhances the amplitudes of the local ENDOR signals. In addition, the ENDOR signal is not a function of the ratio of the electron and nuclear relaxation rates.     

Spin-label W-band EPR with Seven-Loop–Six-Gap Resonator: Application to Lens Membranes Derived from Eyes of a Single Donor

Spin-label W-band (94 GHz) electron paramagnetic resonance (EPR) with a five-loop–four-gap resonator (LGR) was successfully applied to study membrane properties (Mainali et al. J Magn Reson 226:35–44, 2013). In that study, samples were equilibrated with the selected gas mixture outside the resonator in a sample volume ~100 times larger than the sensitive volume of the LGR and transferred to the resonator in a quartz capillary. A seven-loop–six-gap W-band resonator has been developed. This resonator permits measurements on aqueous samples of 150 nL volume positioned in a polytetrafluoroethylene (PTFE) gas permeable sample tube. Samples can be promptly deoxygenated or equilibrated with an air/nitrogen mixture inside the resonator, which is significant in saturation-recovery measurements and in spin-label oximetry. This approach was tested for lens lipid membranes derived from lipids extracted from two porcine lenses (single donor). Profiles of membrane fluidity and the oxygen transport parameter were obtained from saturation-recovery EPR using phospholipid analog spin-labels. Cholesterol analog spin-labels allowed discrimination of the cholesterol bilayer domain and acquisition of oxygen transport parameter profiles across this domain. Results were compared with those obtained previously for membranes derived from a pool of 100 lenses. Results demonstrate that EPR at W-band can be successfully used to study aqueous biological samples of small volume under controlled oxygen concentration.     

EPR spectroscopy of poorly characterized systems: A historical and current view

Modeling of the CW-EPR spectra due to transition metal ions in non-crystalline systems grew in sophistication from the early 1960’s until fairly recently. A number of important effects have been introduced into the simulation of CW spectra over the past decade or so. These include allowance for local strain effects, the so-called “g-strain” and correlated “g-A strain”, the latter especially important in multifrequency spectroscopy. Limits have been reached in what is reasonable by way of guesses regarding the underlying lineshape function and further information can only be sought via ENDOR or ESEEM experiments in favourable cases. A clear understanding of the simplest way to describe field swept EPR via a master equation derived in the frequency domain will be reviewed in which asymmetric field swept lines sometimes occur naturally as a consequence of the theory. The paper will provide a review of the history of computer simulations and various statistical approaches to correlation effects covering examples as diverse as proteins and glasses. It is hoped that sufficient progress will have been achieved with a new Bruker ESP 380 pulsed spectrometer that some new results can also be reported.     

Effect of nonuniform mechanical stresses on the domain structure of iron borate

A magnetooptic method is used to study the effect of nonuniform radial mechanical stresses on the domain structure, magnetic susceptibility, and magnetic hysteresis loops of a FeBO₃ single crystal. When a magnetic field is applied in the basal plane of FeBO₃ along the stress vector, a system of tapered domains appears in the crystal during magnetization. These domains exist in a certain temperature-dependent field range H₀ ≤ H ≤ H _c . The appearance of a system of tapered domains is found to substantially affect the technical magnetization of a stressed crystal. The results obtained are discussed within the thermodynamic theory of a domain structure. A theoretical model used is shown to adequately describe the experimental temperature and field dependences of the ratio \({D \mathord{\left/ {\vphantom {D {\sqrt L }}} \right. \kern-\nulldelimiterspace} {\sqrt L }}\) (where D and L are the average width and length of a tapered domain, respectively). The calculated value of D is approximately 1.3 times smaller than the experimentally observed domain width.     

Miscibility phase diagrams of giant vesicles containing sphingomyelin

Saturated sphingomyelin (SM) lipids are implicated in lipid rafts in cell plasma membranes. Here we use fluorescence microscopy to observe coexisting liquid domains in vesicles containing SM, an unsaturated phosphatidylcholine lipid (either DOPC or POPC), and cholesterol. We note similar phase behavior in a model membrane mixture without SM (DOPC/DPPC/Chol), but find no micron-scale liquid domains in membranes of POPC/PSM/Chol. We delineate the onset of solid phases below the miscibility transition temperature, and detail indirect evidence for a three-phase coexistence of one solid and two liquid phases.     

Membrane fluidity profiles as deduced by saturation-recovery EPR measurements of spin-lattice relaxation times of spin labels

There are no easily obtainable EPR spectral parameters for lipid spin labels that describe profiles of membrane fluidity. The order parameter, which is most often used as a measure of membrane fluidity, describes the amplitude of wobbling motion of alkyl chains relative to the membrane normal and does not contain explicitly time or velocity. Thus, this parameter can be considered as nondynamic. The spin-lattice relaxation rate () obtained from saturation-recovery EPR measurements of lipid spin labels in deoxygenated samples depends primarily on the rotational correlation time of the nitroxide moiety within the lipid bilayer. Thus, can be used as a convenient quantitative measure of membrane fluidity that reflects local membrane dynamics. profiles obtained for 1-palmitoyl-2-(n-doxylstearoyl)phosphatidylcholine (n-PC) spin labels in dimyristoylphosphatidylcholine (DMPC) membranes with and without 50 mol% cholesterol are presented in parallel with profiles of the rotational diffusion coefficient, R_⊥, obtained from simulation of EPR spectra using Freed’s model. These profiles are compared with profiles of the order parameter obtained directly from EPR spectra and with profiles of the order parameter obtained from simulation of EPR spectra. It is shown that and R_⊥ profiles reveal changes in membrane fluidity that depend on the motional properties of the lipid alkyl chain. We find that cholesterol has a rigidifying effect only to the depth occupied by the rigid steroid ring structure and a fluidizing effect at deeper locations. These effects cannot be differentiated by profiles of the order parameter. All profiles in this study were obtained at X-band (9.5 GHz).     

Ultra-stable temperature control in EPR experiments: thermodynamics of gel-to-liquid phase transition in spin-labeled phospholipid bilayers and bilayer perturbations by spin labels

An ultra-stable variable temperature accessory for EPR experiments with biological samples has been designed and tested. The accessory is comprised from a digitally controlled circulator bath that pumps fluid through high-efficiency aluminum radiators attached to an EPR resonator of a commercial X-band EPR spectrometer. Temperature stability of this new accessory after a 15 min re-equilibration is at least +/-0.007 K. For a standard 1-cm-long capillary sample arranged inside an EPR tube filled with silicon oil, the temperature variations do not exceed +/-0.033 K over the sample temperature range from 283 to 333 K. This new accessory has been tested by carrying out a comparative spin-labeling EPR and differential scanning calorimetry (DSC) study of the gel-to-liquid phase transition in multilamellar vesicles (MLV) composed of a synthetic phospholipid 1,2-dimyristoyl-sn-glycero-3-phosphatidylcholine (DMPC). We demonstrate that the gel-to-liquid phase transition temperatures of MLV DMPC measured by EPR and DSC agree within +/-0.02 K experimental error even though the sample for EPR study was labeled with 1 mol% of 5PC (1-palmitoyl-2-stearoyl-(5-doxyl)-sn-glycero-3 phosphocholine). Cooperative unit number measured by EPR, N=676+/-36, was almost 50% higher than that obtained from DSC (N=458+/-18). These high values of N indicate that (i) the lipid domains should include at least several spin-labeled lipid molecules and (ii) the spin-probe 5PC molecules are not excluded into domains that are different from the bulk lipid phase as was speculated earlier. Overall, our data provide DSC and EPR evidence that in studies of the gel-to-liquid phase transition, the effect of bilayer perturbation by spin-labeled lipids is negligible and therefore thermodynamic parameters of the phase transition can be accurately measured by spin-labeling EPR. This might serve as an indication when spin-labeled molecules with structures similar to those of lipids are introduced at low concentrations, they are easily accommodated by fluid phospholipid bilayers without significant losses of the lipid cooperativity.     

Observation of broad EPR spectra of transient free radicals by FT-EPR

Application of electron spin echo Fourier transform EPR (ESE-FT-EPR) to photo-induced chemical reactions is presented. Main purpose of this study is to observe broad EPR spectra of free radicals having very shortT ₂ ^* by means of the ESE-FT-EPR technique. Details of the experimental procedures are described. In ESE experiments design of the resonator is important to obtain sufficient spectral bandwidth because of use of multiple pulses which decrease the bandwidth. We designed and constructed Loop-Gap-Resonantors (LGR) for light irradiation experiments and their specifications were examined. The phase cycling method is essential to obtain pure ESE signals and proper time resolution by eliminating unwanted FID signals which result from imperfect pulse angles. We applied this technique to observe the photo-induced electron transfer reaction between tetraphenylporphinato zinc(II) (ZnTPP) and duroquinone (DQ) in an ethanol solution, and successfully observed the time resolved EPR spectra of the both Zn(TPP) cation and DQ anion radicals by ESE-FT-EPR of the Hahn echo. The half-height full-width of envelope of EPR spectrum of Zn(TPP)⁺, which is never observed in ordinary FT-EPR, is about 16 MHz. Specificity of spectra and the time resolution are compared among the ESE-FT-, FT- and cw-Time-Resolved-EPR (cw-TREPR) techniques.     

EPR and longitudinal response signals in spin systems consisting of localized (<Emphasis Type="Italic">s</Emphasis>=1/2) and delocalized spins

The spin system of many new promising materials, such as high-temperature superconductors, fullerenes, fullerides, or manganites with colossal magnetoresistance, consists of localized spins (s-spins of impurity paramagnetic centers) and delocalized spins (e-spins of charge carriers). The two sorts of spins are coupled by exchange interaction, which leads to coupled precession of the corresponding magnetizations. When the materials mentioned above are investigated by EPR methods, the measured longitudinal (T₁) and transverse (T₂) relaxation times provide the most valuable information. However, the presence of inhomogeneous broadening of the EPR of s-spins often makes it difficult to measure T₂, while small values of T₁ do not allow one to measure it by conventional methods. Atsarkin and colleagues [4, 7, 8] proposed a new version of the method for measuring T₁ by longitudinal response signals induced in a longitudinal spin coil (oriented along the constant magnetic field) under low-frequency modulation of the microwave power, which saturates the EPR, even though very weakly. Earlier, the results obtained in experiments on measuring the longitudinal response for samples containing interacting s-and e-spins were interpreted using formulas for an individual sort of spins. In this paper, the magnetization of s-and e-spins that precess under the condition of relaxational coupling is considered, which is characteristic, for example, of fullerides. The complete EPR susceptibility is represented in a form that makes it possible to determine the origin (from s-or e-spins) of two Lorentzians, each of which is characterized by one of the normal decay rates of two coupled oscillators (i.e., of precessing transverse magnetization components). The common EPR line analytically decomposed into those Lorentzians, and special factors take into account the influence of the other sort of spins on the amplitude of the signal generated by the sort under consideration. Similarly to the EPR absorption signals, the expressions for the longitudinal response are decomposed into parts originating from s-and e-spins, and each part is proportional to the form factor of one of the modes (s-or e-like). The qualitative comparison shows good agreement with experimental data in terms of EPR and longitudinal response in a fulleride.     

A Variable Temperature X- and W-Band EPR Study of Fe-Doped SiCN Ceramics Annealed at 1000, 1100, and 1285 °C: Dangling Bonds,Ferromagnetism and Superparamagnetism

Polymer-derived SiCN ceramics, annealed (also referred to as pyrolyzed) at 1000, 1100, and 1285 °C, and doped with Fe(III) acetylacetonate, are investigated by electron paramagnetic resonance (EPR) from 4 to 120 K at X-band (9.425 GHz). In addition, the SiCN ceramic, annealed at 1100 °C, was studied by EPR at 300 K at W-band (93.96 GHz). There was observed a significant increase in EPR linewidth due to dangling bonds (g = 2.001) below 20 K at X-band. The low-field X-band FMR line (g ≈ 12) indicated the presence of ferromagnetic Fe₅Si₃ crystallites. There were found two EPR lines due to carbon-related dangling bonds: (1) those present as defects on the surface of the free-carbon phase (as sp² carbon-related dangling bonds with g = 2.0011) and (2) those present within the bulk of carbon phase (as sp³ carbon-related dangling bonds with g = 2.0033). On the other hand, the intense low-field EPR signal observed at X-band was not observed at W-band. As well, there was observed splitting of the single broad EPR signal observed at g = 2.05 at X-band into two signals at W-band at g = 1.99 and g = 2.06, due to two different Fe-containing superparamagnetic nanocrystallites. Two new EPR signals, not observed at X-band, were observed at W-band, namely at g = 2.28 and g = 3.00, which are also due to g_∥ of these superparamagnetic nanocrystallites.     

Electron spin polarization of doublet state species due to interaction with excited triplet states in single crystals

Doublet states species trapped in crystalline solids show transient spin polarized EPR spectra if the crystal is illuminated by visible or UV light. The spin polarization is accounted for by the interaction of the doublet species with photoexcited triplet states. The mechanism of the process producing the spin polarization is examined and some experimental examples are discussed. The analysis of the time evolution of the transient variation of the EPR signal allows the measurements of the spin lattice relaxation time and in some cases of the diffusion rate of mobile triplet excitations in the crystal lattice.     

Selective reflection of laser radiation from submicron layers of Rb and Cs atomic vapors: Applications in atomic spectroscopy

We studied selective reflection (SR) of laser radiation from a window of a nanocell with thickness L ~ λ_1,2/2 filled with Rb and Cs atoms, where λ₁ = 780 nm and λ₂ = 852 nm are the wavelengths resonant with the D₂ laser lines for Rb and Cs, respectively. It is demonstrated that the negative derivative of the SR signal profile for L > λ/2 changes to the positive one for L < λ/2. It is shown that the real-time formation of the SR signal profile derivative (SRD) with the spectral width 30–40 MHz and located at the atomic transition is, in particular, a convenient frequency marker of D₂ transitions in Rb and Cs. The amplitudes of SRD signals are proportional to the atomic transition probabilities. A comparison with the known saturated absorption (SA) method demonstrated a number of advantages, such as the absence of cross-over resonances in the SRD spectrum, the simplicity of realization, a low required power, etc. An SRD frequency marker also operates in the presence of the Ne buffer gas at a pressure of 6 Torr, which allowed us to determine the Ne–Rb collisional broadening, whereas the SA method is already inapplicable at buffer gas pressures above 0.1 Torr. The realization simplicity makes the SRD method a convenient tool for atomic spectroscopy. Our theoretical model well describes the SRD signal.     

EPR and photoluminescence spectra of smooth CD<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> films from T-10 tokamak: The effect of iron impurity

The electron and spin structure of thick smooth hydrocarbon CD _x films (“flakes”) with a high relative deuterium concentration of x ~ 0.5, redeposited from deuterium plasma discharge onto the walls of the vacuum chamber of the T-10 tokamak and containing ~1 at % of 3d-metal impurities due to erosion of the chamber walls, are studied using electron paramagnetic resonance (EPR) and photoluminescence (PL). The resulting spectra are compared for the first time to the EPR and photoluminescence spectra of polymer (soft) a-C:H(D) films (H(D)/C ~ 0.5), which are considered model analogues of smooth CD _x films. A certain similarity of the CD _x films with a-C:H films was found in the electronic structure of the valence band. At the same time, the differences in the EPR and photoluminescence spectra were observed due to the presence of 3d-metal impurities in the CD _x samples, contributing to the conversion of sp ³ → sp ² in the formation of films in the tokamak and upon heating and thermal desorption. An impurity of, presumably, 3d metals was detected for the first time by EPR in the a-C:H films in an amount of approximately 0.2 ppm, related to the evaporation of graphite.     

The phenomenon of tristable stochastic resonance driven by $$\alpha $$-noise

In this paper, the tristable stochastic resonance (SR) phenomenon induced by \(\alpha \)-stable noise is analysed. The mechanism for realizing resonance is explored based on research concerning the potential function and resonant output of a system. The rules for resonance system parameters q, p, skewness parameter r and intensity amplification factor Q of \(\alpha \)-stable noise to act on the resonant output are explored under different values of stability index \(\alpha \) and asymmetric skewness \(\beta \) of \(\alpha \)-stable noise. The results will contribute to a reasonable selection of parameter-induced tristable SR system parameters under \(\alpha \)-stable noise, and lay the foundation for a practical engineering application of weak signal detection based on the SR.     

Frequency reference for atomic transitions of Rb D<Subscript>2</Subscript>-line based on the effect of selective reflection

On an example of the D₂-line of the Rb atoms the work of the frequency reference of atomic transitions is demonstrated, based on the application of the spectrum of a selective reflectance (SR) from the boundary of atom vapors with the use of nano-cell (NC) with the thickness L ~ λ/2, where λ is the laser wavelength equal to 780 nm. When changing the thickness of the nano-cell near the thickness L ~ λ/2, we observe the inversion of sign of the SR slope profile which is positive when L < λ/2 and negative when L > λ/2. In the case when the incidence angle of the laser beam on the surface of the nano-cell is close to the normal, in real-time it is possible to form the derivative of the SR which represents a resonance peak with ~35 MHz spectral linewidth and located at the atomic transition. The phenomenon of oscillation of the sign of slope while changing the nano-cell thickness from L ~ λ/2 up to L ~ 3/2λ is demonstrated. The practical application of the SR is noted.     

Pulsed 95 GHz high-field EPR heterodyne spectrometer with high spectral and time resolution

Various time resolved EPR methods are applied to different test samples to demonstrate the abilities of pulsed high-field EPR spectroscopy. Two-pulse-echo field swept EPR spectroscopy on a nitroxide radical shows the increased spectral resolution by separating different spin systems by their relaxation properties. Additionally N¹⁴ electron-spin-echo-envelope-modulation (ESEEM) is observed for these systems at fields as high as 3.5 T. Thus, the N¹⁴ hyperfine interaction couplings can be probed by ESEEM and pulsed ENDOR (electron-nuclear-double-resonance) experiments. The sensitivity of pulsed ENDOR experiments is compared with cw-ENDOR. The different linewidths and amplitudes of the two methods are discussed. Transient nutation experiments on light induced triplet states demonstrate the high sensitivity and time resolution of high-field pulsed EPR. The sensitivity and time resolution of our 95 GHz spectrometer are determined and compared with pulsed X-band EPR spectrometer performances.     

Alteration of the Axial Met Ligand to Electron Acceptor A0 in Photosystem I: An Investigation of Electron Transfer at Different Temperatures by Multifrequency Time-Resolved and CW EPR

The ambient temperature and low-temperature electron transfer properties of Photosystem I (PS I) from the M688N_PsaA and M668N_PsaB mutant strains of the cyanobacterium Synechocystis sp. PCC 6803 are studied using transient electron paramagnetic resonance (EPR) and continuous-wave (CW) EPR. The two mutations are expected to alter the midpoint potentials of, and the reorganization energies around, the primary electron chlorophyll acceptors A_0A and A_0B, which should lead to a change in the yield and/or rate of electron transfer to the phylloquinone acceptors A_1A and A_1B, respectively. At ambient temperature it is known that both quinone acceptors are active in electron transfer. At low temperature there are at least two fractions that undergo either reversible or irreversible electron transfer. The EPR data of the two PS I variants are used to investigate the relationship between these low-temperature fractions and the ambient temperature electron transfer pathway. The results show that mutation in the PsaA-branch increases the rate of $ {\text{A}}_{{1{\text{A}}}}^{. - } $ to F_X electron transfer at ambient temperature, while the corresponding mutation in the PsaB-branch has no effect on the electron transfer rate observable by transient EPR. An analysis of the complete time/field datasets from both variants suggests that the yield of electron transfer in the branch carrying the mutation is reduced. The mutations have no effect on the low-temperature CW EPR spectra of the iron–sulfur clusters if the samples are frozen under illumination but they both cause a decrease in the yield of reduced F_A and F_B if the samples are frozen in the dark and then illuminated. The PsaA-branch mutation greatly reduces the intensity and changes the polarization pattern of the radical pair $ {\text{P}}_{700}^{ + } {\text{A}}_{1}^{. - } $ . Possible causes of the changes in the polarization pattern are discussed and it is suggested that the mutations introduce structural heterogeneity in the vicinity of the A₀ binding site. No clear correlation between the yield of electron transfer in a particular branch and the yield of stable charge separation is found.     

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.     

Electron Paramagnetic Resonance Investigations of ZnSe:Mn Nanocrystals

Colloidal nanocrystals of ZnSe doped with Mn²⁺ were synthesized in non-polar medium using hot-injection technique. Obtained samples were characterized by means of photoluminescence and absorption spectroscopies. To confirm the incorporation of Mn²⁺ impurity and to reveal its state and localization, electron paramagnetic resonance (EPR) spectroscopy was employed. As a result, EPR spectra were analyzed and hyperfine splitting constant and g-factor for Mn²⁺ dopant were determined.     

Studies of Nanosized Iron-Doped TiO<Subscript>2</Subscript> Photocatalysts by Spectroscopic Methods

Iron-doped TiO₂ nanoparticles with iron content in the range of 0.005 < Fe/Ti < 0.3 were prepared using the flame spray pyrolysis method and investigated with CW X-band electron paramagnetic resonance (EPR), X-ray diffraction, and Fourier transform infrared spectroscopy. This allowed for the clarification of the internal organization of Fe–TiO₂ nanoparticles. Different types of Fe(III) centers were distinguished in the samples: isolated high-spin paramagnetic Fe(III) ions (S = 5/2) in rhombic ligand fields state at 0.005 < Fe/Ti < 0.05, and Fe(III) ferromagnetic clusters at Fe/Ti < 0.1. All Fe-doped samples had rather high activity for the photocatalytic mineralization of oxalic acid under visible light illumination (λ > 400 nm) at 25 °C. Correlations were made between EPR and photocatalytic activity results. The specific surface area [S] data allowed us to deduce that the isolated Fe(III) centers were responsible for the photomineralisation of oxalic acid, while the Fe(III) ferromagnetic aggregates decreased the total efficiency of the system.