A low-noise X-band microwave source with digital automatic frequency control for electron paramagnetic resonance spectroscopy

We report a new design of microwave source for X-band electron paramagnetic resonance spectrometer.The microwave source is equipped with a digital automatic frequency control circuit.The parameters of the digital automatic frequency control circuit can be flexibly configured for different experimental conditions,such as the input powers or the quality factors of the resonator.The configurability makes the microwave source universally compatible and greatly extends its application.To demonstrate the ability of adapting to various experimental conditions,the microwave source is tested by varying the input powers and the quality factors of the resonator.A satisfactory phase noise as low as-135 d Bc/Hz at 100-k Hz offset from the center frequency is achieved,due to the use of a phase-locked dielectric resonator oscillator and a direct digital synthesizer.Continuous-wave electron paramagnetic resonance experiments are conducted to examine the performance of the microwave source.The outstanding performance shows a prospect of wide applications of the microwave source in numerous fields of science.

Electron paramagnetic resonance study of amphiphiles partitioning behavior in desiccation-tolerant moss during dehydration

Desiccation tolerance is a crucial characteristic for desert moss surviving in arid regions. Desiccation procedure always induces amphiphiles transferring from the polar cytoplasm into lipid bodies. The behavior of amphiphiles transferring can contribute to the enhancement of desiccation tolerance and the reduction of plasma membrane integrity simultaneously. The effects of amphiphiles partitioning into the lipid phase during water loss has been studied for pollen and seeds using electron paramagnetic resonance （EPR） spectroscopy. However, desiccation-tolerant high plants occur among mosses, several angiosperms and higher plants seeds or pollens. They have different strategies for survival in dehydration and rehydration. A desiccation-tolerant moss Tortula desertorurn was used to investigate the behaviors of amphiphilic molecules during drying by spin label technology. There are small amount of amphiphilic probes partitioning into membrane during moss leaves dehydration, comparing with that in higher plants. Cytoplasm viscosity changed from 1.14 into glass state only dehydration less than 60 min. Moss leaves lost plasma membrane integrity slightly,from 0.115 to 0.237, occurred simultaneously with amphiphiles partition. The results showed the more advantages of mosses than higher plants in adapting fast dehydration. We propose that EPR spin label is feasible for studying the amphiphiles partitioning mechanisms in membrane protection and damage for desiccation-tolerant mosses.

Electron paramagnetic resonance characterization of aluminum ion implantation-induced defects in 4H-SiC

Deep-level defects in silicon carbide(SiC)are critical to the control of the performance of SiC electron devices.In this paper,deep-level defects in aluminumion-implanted 4H-SiC after high-temperature annealingwere studied using electron paramagnetic resonance(EPR)spectroscopy at temperatures of 77 K and 123 K under different illumination conditions.Results showed that the main defect in aluminum ion-implanted 4H-SiC was the positively charged carbon vacancy(VC+),and the higher the doping concentration was,the higher was the concentration of VC+.Itwas found that the type of material defectwas independent of the doping concentration,although more VC+defects were detected during photoexcitation and at lower temperatures.These results should be helpful in the fundamental research of p-type 4H-SiC fabrication in accordance with functional device development.

Electron paramagnetic resonance studies of the chelate-based ionic liquid in different solvents

The electron paramagnetic resonance spectra of the chelate-based ionic liquid[C_(10)mim][Cu(F_6-acac)_3]in different solvents have been obtained at 120 K.It was found that the values of the^(63)Cu hyperfine coupling constants(A_(IL))of[C_(10)mim][Cu(F_6-acac)_3]in molecular solvents were from 116 to 180 Gauss.Moreover,the A_(IL)values in general ionic liquids are more complicated,and two sets of peaks can often be observed in their electron paramagnetic resonance spectra.Based on the Kamlet-Taft parameters,relative permittivity,the experimental results were discussed in terms of solvation effect and coordination of the solvents.

Electron Paramagnetic Resonance and Optical Absorption Studies on Copper Ions in Mixed Alkali Cadmium Phosphate Glasses

Electron paramagnetic resonance （EPR） and optical absorption studies were carried out at room temperature on copper doped mixed alkali cadmium phosphate （LiNaCdP） glasses to understand the nature and symmetry of dopant. Three samples with varying concentrations of alkali ions have been prepared. The spin Harniltonian parameters obtained from room temperature EPR spectra are： gli=2.437, 9⊥=2.096, A‖=117×10-4 cm-1, A⊥=26×10-4 cm-1 for LiNaCdP1, g‖=2.441, g⊥=2.088, A‖=121×10-4 cm-1, A⊥=25×10-4 cm-1 for LiNaCdP2and g‖=2.433,g⊥=2.096, A‖=125×10 4cm-1, A⊥=32×10-4cm-1 for LiNaCdP3. TheseEPR results indicate that the dopant Cu2＋ ion enters the glass matrix into a tetragonally elongated octahedral site. The bonding parameters evaluated by correlating optical and EPR data suggest that bonding between the central metal ion and ligands is partially covalent. The mixed alkali effect in cadmium phosphate glasses was reported.

Effect of local structure on electron paramagnetic resonance spectra for trigonal [Cr(H_2O)_6]^(3+) coordination complex in the sulfate alums series:a ligand field theory study

A simple theoretical method is introduced for studying the interrelation between electronic and molecular structures.By diagonalizing the 120 × 120 complete energy matrices,the relationships between zero-field splitting （ZFS） parameter D and local distortion parameter △θ for Cr^3＋ ions doped,separately,in α- and β- alums are investigated.Our results indicate that there exists an approximately linear relationship between D and △θ in a temperature range 4.2-297 K and the signs of D and △θ are opposite to each other.Moreover,in order to understand the contribution of spin-orbit coupling coefficient ζ to ZFS parameter D,the relation between D and ζ is also discussed.

Developing in situ electron paramagnetic resonance characterization for understanding electron transfer of rechargeable batteries

Electrochemical energy storage devices are pivotal in achieving“carbon neutrality”by enabling the storage of energy generated from renewable sources.To facilitate the development of these devices,it is important to gain insight into the underlying the single-/multi-electron transfer process.This can be achieved through in-time detection under operational conditions,but there are limited tools available for monitoring electron transfer under operando conditions.Electron paramagnetic resonance(EPR)is a powerful technique that can meet these expectations,as it is highly sensitive to unpaired electrons and can detect changes of paramagnetic centres.Despite the long history of in situ electrochemical EPR research,its potential has been surprisingly underutilized due to the need for strict operando cell design under special testing conditions.This review comprehensively summarizes recent efforts to understand energy storage mechanisms using in situ/operando EPR,with the aim of drawing researchers’attention to this powerful technique.After introducing the fundamental principles of EPR,we describe the critical advances made in detecting batteries using operando EPR,along with the remaining challenges and opportunities for future development of this technology in batteries.We emphasize the need for strict operando cell design and the importance of designing experiments that closely mimic real-world conditions.We believe that this review will provide innovative solutions to solve tough problems that researchers may encounter during their battery research,and ultimately contribute to the development of more efficient and sustainable energy storage devices.

Correlations between trace elements in pyrite and gold mineralization of gold deposits on the North China platform

By studying both the microscopic physical and chemical typomorphic characteristics of typical mineral pyrite samples associated with representative gold deposits on the north-central margin of the North China Platform,this paper seeks to identify macroscopic metallogenic mechanisms of gold deposits and to reveal the formation mechanism of lattice gold in pyrite.Typomorphic characteristics of pyrite reveal that pyrite grain size has a negative correlation with gold content.Cubic pyrite,as the dominant crystal form,contains more gold than pentagonal dodecahedral pyrite.Both pyrite crystal forms and chemical compositions indicate that the replacement style of gold deposit formed in a low saturability,low sulfur fugacity,and at temperatures either much higher or much lower than its best forming temperature;comparatively,that of the quartz vein style of gold deposit occurred under conditions with the best temperature,rich in sulfur,and with high sulfur fugacity.The Au/Ag ratios of the pyrites show that both the replacement and quartz vein styles of deposits are mesothermal and hypothermal,while the Co/Ni ratios of the pyrites indicate that the quartz vein style is of magmatic-hydrothermal origin.The X-ray diffraction intensity of pyrite rich in gold is lower than that of pyrite poor in gold at the quartz vein style.In general,with an increase in gold content in pyrite,the total sum intensityΣI decreases.The pyroelectricity coefficient has a negative correlation trend with the values of(Co+Ni+Se+Te)-As and(Co+Ni+Se+Te)/As.The pyrite pyroelectricity of the replacement style is N-type,indicating that it formed under low sulfur fugacity,while that of the quartz vein style is a mixture of P-N types,indicating that it formed under high sulfur fugacity.On the pyroelectricity-temperature diagram,pyrite of the replacement style is mainly distributed between 200 and 270°C,while that of the quartz vein style varies between 90–118 and274–386°C,demonstrating a multistage forming process.In contrast to previous researchers'conclusions,the authors confirm the existence of lattice gold in pyrites through the use of an electron paramagnetic resonance(EPR)test.Au in the form of Au~+,entering pyrite as an isomorph and producing electron–hole centers,makes the centers produce spin resonance absorption and results in EPR absorption peak II.The intensity of auriferous pyrite absorption peak II has certain direct positive correlations with pyrite gold content.The#I and#III absorption peaks of pyrites possibly result from the existence of Ni^(2+)and/or Cu^(2+).γ1,γ2,andγ3 are the strongest and most typical absorption peaks of the infrared spectra of the pyrites.Generally,with the increase in gold content in the pyrite samples,γ1,γ2,andγ3 tend to shift to higher wavenumbers,and the gold content in the pyrite samples has a positive correlation with their relative absorbance.

Thermoluminescent response of gamma irradiated Na^(+)–Cu^(+) ionexchanged silicate glass in large dose range

The introduction of metals into vitreous matrices is the origin of various interesting phenomena;in particular,the presence of copper ions in glass has been the subject of considerable research because of its numerous applications.The ion-exchange process is primarily used to introduce copper ions into glass matrices.The thermoluminescence(TL)of silicate glass was studied to evaluate its potential as gamma-sensitive material for dosimetric applications;the effect of copper doping on the thermoluminescent sensitivity was investigated using the Cu-Na ion-exchange technique for different concentrations and doping conditions,over a wide dose range of 10 mGy to 100 kGy.The results showed that Cu doping significantly improved the sensitivity of the glasses to gamma radiation.After the ion-exchange,two peaks appeared in the glow curves at approximately 175 and 230°C,respectively,which possibly originated from the Cu^(+) centers,along with a weak TL peak at around 320℃.We also attempted to explain the origin of the observed thermoluminescence by exploiting the Electron paramagnetic resonance(EPR)spectra.The results clearly show quenching of the TL emission with increasing copper concentrations.The present work indicates that the thermoluminescence response of these glasses to gamma rays can be reasonably measured in the range of 0.001-100 kGy.This study also facilitates the understanding of the basic TL mechanism in this glass system.

Investigation on Spin Hamiltonian Parameters for Tetragonal Ytterbium Center in Lutetium Orthovanadate

Rare earth doped orthovanadate crystal LuVO4∶Yb3+ shows high power laser applications because of the low quantum defect and the high thermal conductivity. Since electronic paramagnetic resonance (EPR) is a powerful tool to analyze the electronic properties and the local structures of paramagnetic impurity centers in crystals, the EPR spectra of the Yb3+ centers in LuVO4 crystal were measured recently. However, the above experimental results have not been theoretically interpreted. In this work, The EPR g factors and the hyperfine structure constants of 171Yb3+ and 173Yb3+ isotopes in LuVO4 crystal were theoretically studied from the perturbation formulae of the spin Hamiltonian parameters for 4f13 ion in tetragonal symmetry. The needed crystal parameters were obtained from the superposition model and the local structure of the studied system. The calculated results were in reasonable agreement with the observed values.

Effects of La, Ce, Y and Tb ions on Free Radical Mediated Peroxidation of Human Erythrocyte Membrane

The effects of the lanthanides in various concentration on the peroxidation of 'ghost' of human erythrocyte with free radicals were studied by methods of fluorometry, spectrophotometry and electron paramagnetic resonance. It is shown that La 3+ and Ce 3+ in the range of 2×10 -4 ～2×10 -7 mol·L -1 inhibit the t BHP mediated peroxidation significantly. Tb 3+ and Y 3+ inhibit the t BHP mediated peroxidation in low concentration (<2×10 -5 mol·L -1 ), but promotes the peroxidation when the concentration is higher than 2×10 -5 mol·L -1 .

Structural,electrical and magnetic studies on Y-Fe-O system

The compounds of iron substituted yttrium oxide systems have been prepared for the importance in the field of magneto electric materials.The polycrystalline samples of Y2–xFexO3–y(x=0.1,0.2) were prepared by solid-state reaction method.The single-phase formation of these compounds was confirmed by X-ray diffraction studies.It was found that the samples crystallized in tetragonal phase and the lattice parameters were calculated as a=1.0559(7) nm,c=1.0832(9) nm for Y1.9Fe0.1O3–y and a=1.0545(6) nm,c=1.0841(8)...

Chemical and physical characteristics of quartz from gold deposits in the North China platform: relationship to gold mineralization

This paper seeks to identify macroscopic metallogenic mechanisms of various mineral deposits by studying microscopic typomorphic characteristics of typical minerals associated with the deposits and to reveal the mechanism of lattice gold in detail by studying both physical and chemical characteristics of quartz from representative gold deposits in the North China Platform.As part of their extensive research,the authors examine the relationship between trace elements with wall rock,the ore-forming media,and gold immigration of various types of gold deposits,including their salinity,type,temperature.These are key factors to revealing the mineralization mechanism,and indicators for mineral prospecting,exploration,mining,and metallurgical technology.In order to address the questions posed,the following methods were used:field investigations of geology and sampling of the representative gold deposits,physical study and chemical analysis of quartz including,but not limited to,fluid inclusions as well as their compositions and trace elements in quartz,the unit cell parameters,electron paramagnetic resonance spectrum(EPR),and infrared spectroscopic analysis(ISA).As a result of this study,the authors observe the following key findings:unit cell parameters of quartz vary with their contents of foreign elements including gold,paragenetic stage,wall rock type,and other factors;the higher the forming temperature and the lower the gold content in quartz,the smaller the unit cell parameters,and vice versa.Additionally,the EPR absorption lines resulted from the O–Al defect center.The density of these types of hole centers increases and the EPR signal strengthens when the temperature decreases.Based on the findings,the authors conclude that lattice gold exists in quartz.Gold,in the form of Au^(+)and/or Au^(3+),entering quartz and producing an electron–hole center,namely,the O-Au hole center,makes the center produce spin resonance absorption and results in the EPR absorption peak#I.Both unit cell parameters and EPR of quartz can potentially be used in mineral prospecting,relative ore-forming temperature determination,and grade control during mining.

Electron paramagnetic resonance in monitoring of nitric oxide production after kidney transplantation in rats

Background Much research has been focused on ischemia/reperfusion injury (IRI) to the transplanted organs. As a free radical, nitric oxide (NO) plays an important role in IRI. In this study, the production of NO and its functions during IRI were monitored in rat models after allotransplantation of kidney grafts.Methods Of 75 male LEW rats, 30 served as donors, and the remaining 45 rats were divided into three groups (15 rats in each group): controls (group 1), kidney allotransplantation followed by bilateral nephrectomy during reperfusion (group 2), 2 hours before operation, donors and recipients were treated with NG-nitro L-arginine methyl ester (L-NAME), a NO synthase inhibitor, at a dose of 30 mg/kg (group 3). Bilateral nephrectomies were performed while kidney grafts were reperfused. The kidney grafts were hypothemically stored for 24 hours. The production of NO before and after reperfusion was measured by electron paramagnetic resonance (EPR). The creatinine level, the glomerular filtration rate (GFR) and the protein carbonyl content in tissue samples were recorded on the first and the fifth day after operation. The data were evaluated by one-way analysis of variance. Differences were considered to be statistically significant when a P value was less than 0.05.Results After reperfusion for 15 minutes, the production of NO increased remarkably and kept increasing till 120 minutes, after which the level returned to normal. In group 3, which was pretreated with L-NAME, creatinine levels were higher than those in group 2 at the 24th hour (4.10±0.50 mg/dl vs. 3.77±0.42 mg/dl, P<0.05) and the 120th hour (3.19±0.79 mg/dl vs. 2.22±0.53 mg/dl, P<0.05). GFR levels in group 3 were lower than those in group 2 at the 24th hour (0.50±0.12 ml/min vs. 0.71±0.19 ml/min, P<0.05) and the 120th hour (0.59±0.38 ml/min vs. 1.27±0.23 ml/min, P<0.01). The content of protein carbonyl in tissue samples of group 3 was lower than that in group 2 at the 24th hour (29.01±7.02 nmol/mg protein vs. 49.39±13.13 nmol/mg protein, P<0.05), but was higher than that at the 120th hour (75.71±16.74 nmol/mg protein vs. 57.93±15.32 nmol/mg protein, P<0.05).Conclusions After transplantation of hypothemically stored kidney grafts, the increased NO production in the early stage has protective effects on the transplanted kidney. Application of L-NAME to inhibit NO production is harmful to the recovery of the renal functions of kidney grafts.

Magnetic Properties of Perovskite Manganite La_ (0.3)Ca_ (0.7)Mn_ (0.96)W_ (0.04)O_3 in Charge Ordering Phase

The sample La_ 0.3Ca_ 0.7Mn_ 0.96W_ 0.04O_3 was prepared by the solid-state method. Magnetic properties of La_ 0.3Ca_ 0.7Mn_ 0.96W_ 0.04O_3 was studied through the measurement of M-T curve, M-H curves and ESR curves of the sample. The results show that: charge ordering (CO) phase forms at 265 K; the system exhibits paramagnetism when T>265 K; it exhibits long-range anti-ferromagnetism (there is a little FM component in AFM background) and the coexistence of a little FM phase and AFM/CO phase forms when T<225 K; the system transforms from paramagnetism to antiferromagnetism in charge-ordering state with temperature decreasing from 265 to 225 K. The width of ESR spectrum line of the sample La_ 0.3Ca_ 0.7Mn_ 0.96W_ 0.04O_3 was measured, and the value of the line width of paramagnetic resonance ΔH_ PP increases with temperature decreasing, which indicates that ferromagnetic connection of the sample strengthens with temperature decreasing.

EPR study of charge separation associated states and reversibility of surface bound superoxide radicals in SrTiO_(3) photocatalyst

Understanding the processes of charge generation, transfer and capture is important for the design and synthesis of efficient photocatalysts. In this work, light-induced charge separation and effect of O_(2) on electron transfer processes in SrTiO_(3) were investigated by electron paramagnetic resonance(EPR). It was found that photoinduced electron transfer from O_(2)- to Ti^(4+) produced Ti^(3+) and O- redox radical pairs under vacuum condition. Under oxygen atmosphere, however, surface bound superoxide radicals O_(2)-were formed by electron reduction of adsorbed oxygen at initial photoirradiation stage, and quenched by the reverse electron transfer to Ti^(4+) upon further photoirradiation. Formation of long-lived charge separation associated [Ti^(3+)---O-] species and the reversibility of surface bound superoxide radicals mediating the processes of photogenerated electrons may be accountable for the high activity of SrTiO_(3) in photocatalytic water splitting reaction.

A design of resonant cavity with an improved coupling-adjusting mechanism for the W-band EPR spectrometer

We report a new design of resonant cavity for a W-band electron paramagnetic resonance(EPR)spectrometer.An improved coupling-adjusting mechanism,which is robust,compact,and suits with both solenoid-type and split-pair magnets,is utilized on the cavity,and thus enables both continuous-wave(CW)and pulsed EPR experiments.It is achieved by a tiny metal cylinder in the iris.The coupling coefficient can be varied from 0.2 to 17.9.Furthermore,two pistons at each end of the cavity allow for adjustment of the resonant frequency.A horizontal TE_(011) geometry also makes the cavity compatible with the two frequently used types of magnets.The coupling-varying ability has been demonstrated by reflection coefficient(S_(11))measurement.CW and pulsed EPR experiments have been conducted.The performance data indicates a prospect of wide applications of the cavity in fields of physics,chemistry and biology.

A Peptide-mediated Fenton Reaction in Wood-degrading Fungi

Gt factor is a low-molecular-weight peptide isolated from the extracellular culture of wood-degrading fungus Gloeophyllum trabeum. It is capable of enhancing degradation of cellulose. Its action mechanism was investigated and it was found that Gt factor could reduce Fe3+ to Fe2+. Electron paramagnetic resonance (EPR) spectroscopy revealed in the presence of O2, Gt factor could drive the formation of H2O2 via a superoxide anion O2.- intermediate and mediate the generation of hydroxyl radical HO˙ in a Fenton-type reaction. All these provided evidence for the formation of HO˙ in some wood-degrading fungi.

Superoxide and hydrogen peroxide productions by NO-inhibited complex Ⅲ

Complex Ⅲ plays a central role in the mitochondrial respiratory chain transferring electrons from ubiquinol to cytochrome c and pumping protons to the intermembrane space,contributing to the protonmotive force.Furthermore,complex Ⅲ can act as a source of O_(2^(·-))in the presence of ubiquinol and antimycin,an expermiental condition in which the oxidation of the cytochrome b hemes is blocked.The O_(2^(·-))dismutation catalyzed by superoxide dismutase produces H2O2,a known second messenger in redox signalling.Results from our laboratory have shown that NO,released from GSNO or from SPER-NO or generated by mtNOS,inhibits electron transfer at ubiquinone-cytochrome b area producing antimycin-like effects.Thus,both antimycin-and NO-inhibited complex Ⅲ showed a high content of cytochromes b in the reduced state(79 and 71%,respectively)and an enhancement in the ubisemiquinone EPR signal at g=1.99(42 and 35%,respectively).As consequence,O_(2^(·-))and H2O2 productions were increased,being the O_(2^(·-))/H_(2)O_(2) ratio equal to 1.98 in accordance with the stoichiometry of the O_(2^(·-))disproportionation.The interruption of the oxidation of cytochromes b by NO leads to an enhancement of the steady-state concentration of UQH·,allowing cytochrome bc1 complex to act as a source of reactive oxygen species in physiological conditions.

Sodium and potassium in the bones of penguin and skua revealed by EPR and SR-XRF technique

Penguin and skua in the maritime Antarctic have high salt loadings in the body due to almost exclusive diet consumption of marine invertebrates.However,the storage and turnover of sodium and potassium in these animals are poorly investigated.Here we determined the concentration and microscopic distribution of the two elements in the bones of penguin and skua.The average concentrations of sodium and potassium in penguin bone were comparable with that in skua bone（0.18% and 0.82% for penguin bone;0.19% and 0.76% for skua bone in dry weight）.The ratios of sodium to calcium and potassium to calcium（0.0330 and 0.0075 for penguin,0.0335 and 0.0082 for skua in average by weight） were somewhat higher than the reported ratios for terrestrial animals,indicating these marine animals＇ bone enrichment of salt.The ratios of sodium to potassium in average by weight were 6.75 and 4.65 for penguin and skua,respectively.This value is much lower compared with the bulk sea water ratio of about 27.0,implying that potassium is favorable to reside in the bone rather than sodium.Both sodium and potassium were found to significant correlation with the content of organic materials in bone based upon the intensity of native signal determined by electron paramagnetic resonance（EPR）.It was estimated that almost all of potassium is kept within the organic phases,while about 30% of sodium is stored in organic phases and the other 70% within mineral phase.The microscopic distributions of potassium in the cross-section and/or surface were revealed by synchrotron radiation Xray fluorescence（SR-XRF） technique.The ratio of potassium to calcium based upon the SR-XRF intensity counter varied considerably from the surface to the interior,and on the surface the highest concentration of potassium was observed in the middle section with decreasing amounts toward the edge.This indirectly documented that exchange of potassium between fluid and bone organic phase maybe occur.