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Oxalyldihydrazide (ODH) and coffee extracted fuel (CEF) were used to synthesize Ceria (CeO 2) nanoparticles by solution combustion synthesis route. The cubic fluorite structure, crystalline nature, crystallite size and particle size of ceria nanoparticles were confirmed using the powder X-ray diffraction (PXRD) and High-Resolution Transmission Electron Microscope patterns respectively. Field Emission Scanning Electron Microscope (FESEM) images were used to understand the Surface morphology of the synthesized samples. Based on XRD results the volume of coffee husk extract for the optimum phase formation is found to be 40 mL. The fluorite structure of the samples and the presence of oxygen vacancies in the samples were confirmed from the Raman spectral analysis. ESR (Electron Spin Resonance) studies confirmed formation of relatively more intrinsic defects in CEF-ceria nanoparticles compared to ODH-ceria nanoparticles. The semiconducting nature of the synthesized samples was confirmed by analysing UV–visible absorbance spectra. The functional group confirmation was obtained by analysing Fourier Transform Infrared (FTIR) spectra of both the samples. AC conductivity and dielectric relaxation studies of the samples in pellet form were carried out over a wide frequency (20Hz–10 MHz) and temperature (200–640 °C) range using a precision impedance analyser. A higher value of dielectric constant was observed for CEF-ceria nanoparticles. [ABSTRACT FROM AUTHOR]

The exhaustion of conventional light oils necessitates the shift towards unconventional sources such as biomass, heavy oil, oil shale, and coal. Non-catalytic thermal cracking by a free radical mechanism is at the heart of the upgrading, prior to refining into valuable products. However, thermal pyrolysis is hindered by the formation of asphaltenes, precursors to coke, limiting cracking, causing equipment fouling, and reducing product stability. Free radicals are inherently present in heavy fractions and are generated during thermal processes. This makes these reactive intermediates central to understanding these mechanisms and limiting coking. Electron spin resonance (ESR) spectroscopy facilitates such mechanistic studies. Over the past decade, there has been no review of using in-situ ESR for studying thermal processes. This work begins with a brief description of free radicals' chain reactions during thermal reactions and the wealth of information ESR provides. We then critically review the literature that uses ESR for mechanistic studies in thermal pyrolysis of biomass, heavy oil, shales, and coal. We conclude that limited literature exist, and more investigations are necessary. The key findings from existing literature are summarized to know the current state of knowledge. We also explicitly highlight the research gaps. [ABSTRACT FROM AUTHOR]

ABSTRACT Characterising the spatial and temporal distribution of the S‐N‐trending rift in southern Tibet is crucial for elucidating the dynamics of E‐W extension within the Tibetan Plateau since the Miocene. The Kung Co–Tangra Yumco rift, located in the central part of the rift system, was initiated at the peak of rifting development. While the initiation of rifting has been ascertained through low‐temperature thermochronology, direct timing constraints remain absent for the Gangga Graben in the southernmost region. Utilising the quartz electron spin resonance (ESR) dating technique, we ascertained the onset age of the eastern boundary fault of the Gangga Graben to be 12.00 ± 1.80 Ma, with an accelerated activity phase at 9.17 ± 1.19 Ma, and an activity age for the western boundary fault at 2.22 ± 0.24 Ma. U‐series dating conducted on the western boundary disclosed a time span of 20–13 ka for hot spring fissure activity. Seismic evidence, inclusive of those from the Gongdapu Horst, indicates persistent activity of the Gangga Graben since the Pleistocene. Comparative analysis of age data from the Kung Co–Tangra Yumco rift suggests that it commenced almost synchronously along its strike at ~14.5–12 Ma. Considering the rifts trending from west to east in southern Tibet and the genetic mechanism of leucogranite, we propose an E‐W extension mechanism in southern Tibet. At ~26–14 Ma, the lithosphere experienced weakened delamination and asthenosphere upwelling, leading to a series of magmatic activities and onset of E‐W extension in southern Tibet. At ~17–7 Ma, as the basal shearing of the underthrusting Indian Plate increased, it marked the peak phase of rifting in southern Tibet. [ABSTRACT FROM AUTHOR]

Abstract The emergence of the Middle Palaeolithic, and its variability over time and space are key questions in the field of prehistoric archaeology. Many sites have been documented in the south-eastern margins of the Massif central and the middle Rhône valley, a migration path that connects Northern Europe with the Mediterranean. Well-dated, long stratigraphic sequences are essential to understand Neanderthals dynamics and demise, and potential interactions with Homo sapiens in the area, such as the one displayed at the Maras rock shelter (“Abri du Maras”). The site is characterised by exceptional preservation of archaeological remains, including bones dated using radiocarbon (14C) and teeth using electron spin resonance combined with uranium series (ESR/U-series). Optically stimulated luminescence was used to date the sedimentary deposits. By combining the new ages with previous ones using Bayesian modelling, we are able to clarify the occupation time over a period spanning 200,000 years. Between ca. 250 and 40 ka, the site has been used as a long-term residence by Neanderthals, specifically during three interglacial periods: first during marine isotopic stage (MIS) 7, between 247 ± 34 and 223 ± 33 ka, and then recurrently during MIS 5 (between 127 ± 17 and 90 ± 9 ka) and MIS 3 (up to 39,280 cal BP).

The emergence of the Middle Palaeolithic, and its variability over time and space are key questions in the field of prehistoric archaeology. Many sites have been documented in the south-eastern margins of the Massif central and the middle Rhône valley, a migration path that connects Northern Europe with the Mediterranean. Well-dated, long stratigraphic sequences are essential to understand Neanderthals dynamics and demise, and potential interactions with Homo sapiens in the area, such as the one displayed at the Maras rock shelter ("Abri du Maras"). The site is characterised by exceptional preservation of archaeological remains, including bones dated using radiocarbon (14C) and teeth using electron spin resonance combined with uranium series (ESR/U-series). Optically stimulated luminescence was used to date the sedimentary deposits. By combining the new ages with previous ones using Bayesian modelling, we are able to clarify the occupation time over a period spanning 200,000 years. Between ca. 250 and 40 ka, the site has been used as a long-term residence by Neanderthals, specifically during three interglacial periods: first during marine isotopic stage (MIS) 7, between 247 ± 34 and 223 ± 33 ka, and then recurrently during MIS 5 (between 127 ± 17 and 90 ± 9 ka) and MIS 3 (up to 39,280 cal BP). [ABSTRACT FROM AUTHOR]

The effect of storage time and solvent on 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical stability was studied using electron spin resonance. Tetrahydrofuran affected the g-factor due to a rearrangement within the DPPH structure that changed the radical centre. There was also a change in the spins concentration when modifying the solvent and storage times. The more than 96 % decrease in spins after 12 weeks, consistent with a change in the pH and color, was attributed to the electron- and hydrogen-donor capabilities of the solvents, leading to a shift among the different DPPH ionic states. Tetralin instantly interacted with the DPPH capping many radicals.

Abstract The Periadriatic Fault system (PAF) ranks among the largest post-collisional structures of the European Alps. Recent geodetic data suggest that a fraction of the Adria–Europe convergence is still being accommodated in the Eastern Alps. However, the historical seismicity records along the easternmost segment of the PAF are ambiguous, and instrumental records indicate that seismotectonic deformation is mostly concentrated in the adjacent Southern Alps and Dinarides. Both electron spin resonance (ESR) and optically stimulated luminescence (OSL) dating methods can be used to date coseismic slip (with a combined range covering a few decades to a couple of million years) in slowly deforming fault zones, such as the PAF. Since the saturation doses of the quartz ESR signals are larger than quartz and feldspar OSL, ESR enables establishing a maximum age of the last resetting event of the system, while OSL allows constraining their minimum age when the signal is in saturation. We collected fault gouge samples from three localities along the easternmost segment of the PAF. For ESR, we measured the signals from the Al center in quartz comparing the results from the single aliquot additive dose (SAAD) and single aliquot regenerative (SAR) dose protocols. For OSL, we recorded the infrared stimulated luminescence signal at 50°C (IR50) and post-infrared infrared-stimulated luminescence signal at 225 °C (pIRIR225). Our dating results indicate that the studied segment of the PAF system accommodated seismotectonic deformation during the Quaternary, with a maximum age for the last resetting event of the system ranging from 1075 ± 48 to 552 ± 26 ka (ESR SAR) and minimum ages in the range from 196 ± 12 to 281 ± 16 ka (saturation of pIRIR225). The obtained ages suggest that the studied segment of the PAF could be considered at least as a potentially active fault. Graphical abstract

We investigated the temperature dependence of agglomeration systems consisting of interacting single-domain magnetic nanoparticles (MNPs). In our study, we utilized electron spin resonance (ESR) experiments to measure how temperature-induced change in agglomerate state affects the peak-to-peak width of ESR spectra (Hpp) and validated these observations through simulations. Micromagnetic simulations were conducted by combining the classical magnetic dipolar Metropolis Monte Carlo method with the semi-classical macro-spin Landau-Lifshitz-Gilbert finite element method, and the results were compared with experimental findings. Our research elucidates the behavior of thermally-induced disruption of MNP agglomerates. We discovered that the temperature at which MNPs are completely dispersed might correspond to one at which the temperature dependence of Hpp disappears.

The Periadriatic Fault system (PAF) ranks among the largest post-collisional structures of the European Alps. Recent geodetic data suggest that a fraction of the Adria–Europe convergence is still being accommodated in the Eastern Alps. However, the historical seismicity records along the easternmost segment of the PAF are ambiguous, and instrumental records indicate that seismotectonic deformation is mostly concentrated in the adjacent Southern Alps and Dinarides. Both electron spin resonance (ESR) and optically stimulated luminescence (OSL) dating methods can be used to date coseismic slip (with a combined range covering a few decades to a couple of million years) in slowly deforming fault zones, such as the PAF. Since the saturation doses of the quartz ESR signals are larger than quartz and feldspar OSL, ESR enables establishing a maximum age of the last resetting event of the system, while OSL allows constraining their minimum age when the signal is in saturation. We collected fault gouge samples from three localities along the easternmost segment of the PAF. For ESR, we measured the signals from the Al center in quartz comparing the results from the single aliquot additive dose (SAAD) and single aliquot regenerative (SAR) dose protocols. For OSL, we recorded the infrared stimulated luminescence signal at 50°C (IR50) and post-infrared infrared-stimulated luminescence signal at 225 °C (pIRIR225). Our dating results indicate that the studied segment of the PAF system accommodated seismotectonic deformation during the Quaternary, with a maximum age for the last resetting event of the system ranging from 1075 ± 48 to 552 ± 26 ka (ESR SAR) and minimum ages in the range from 196 ± 12 to 281 ± 16 ka (saturation of pIRIR225). The obtained ages suggest that the studied segment of the PAF could be considered at least as a potentially active fault. [ABSTRACT FROM AUTHOR]

The crystal structures of three mixed‐valence copper cyanide alkanolamine polymers are presented, together with thermogravimetric analysis (TGA) and electron spin resonance (ESR) data. In all three structures, a CuII moiety on a crystallographic center of symmetry is coordinated by two alkanolamines and links two CuICN chains via cyanide bridging groups to form diperiodic sheets. The sheets are linked together by cuprophilic CuI–CuI interactions to form a three‐dimensional network. In poly[bis(μ‐3‐aminopropanolato)tetra‐μ‐cyanido‐dicopper(I)dicopper(II)], [Cu4(CN)4(C3H8NO)2]n, 1, propanolamine bases have lost their hydroxyl H atoms and coordinate as chelates to two CuII atoms to form a dimeric CuII moiety bridged by the O atoms of the bases with CuII atoms in square‐planar coordination. The ESR spectrum is very broad, indicating exchange between the two CuII centers. In poly[bis(2‐aminopropanol)tetra‐μ‐cyanido‐dicopper(I)copper(II)], [Cu3(CN)4(C3H9NO)2]n, 2, and poly[bis(2‐aminoethanol)tetra‐μ‐cyanido‐dicopper(I)copper(II)], [Cu3(CN)4(CH7NO)2]n, 3, a single CuII atom links the CuICN chains together via CN bridges. The chelating alkanolamines are not ionized, and the OH groups form rather long bonds in the axial positions of the octahedrally coordinated CuII atoms. The coordination geometries of CuII in 2 and 3 are almost identical, except that the Cu—O distances are longer in 2 than in 3, which may explain their somewhat different ESR spectra. Thermal decomposition in 2 and 3, but not in 1, begins with the loss of HCN(g), and this can be correlated with the presence of OH protons on the ligands in 2 and 3, which are not present in 1. [ABSTRACT FROM AUTHOR]

We investigated the temperature dependence of agglomeration systems consisting of interacting single-domain magnetic nanoparticles (MNPs). In our study, we utilized electron spin resonance (ESR) experiments to measure how temperature-induced change in agglomerate state affects the peak-to-peak width of ESR spectra (H pp) and validated these observations through simulations. Micromagnetic simulations were conducted by combining the classical magnetic dipolar Metropolis Monte Carlo method with the semi-classical macro-spin Landau-Lifshitz-Gilbert finite element method, and the results were compared with experimental findings. Our research elucidates the behavior of thermally-induced disruption of MNP agglomerates. We discovered that the temperature at which MNPs are completely dispersed might correspond to one at which the temperature dependence of H pp disappears. [ABSTRACT FROM AUTHOR]

Li3V2(PO4)3 cathodes for Li-ion batteries (LIBs) were synthesized using a hydrothermal method with the subsequent annealing in an argon atmosphere to achieve optimal properties. The X-ray diffraction analysis confirmed the material's single-phase nature, while the scanning electron microscopy revealed a granular structure, indicating a uniform particle size distribution, beneficial for electrochemical performance. Magnetometry and electron spin resonance studies were conducted to investigate the magnetic properties, confirming the presence of the relatively low concentration and highly uniform distribution of tetravalent vanadium ions (V4+), which indicated low lithium deficiency values in the original structure and a high degree of magnetic homogeneity in the sample, an essential factor for consistent electrochemical behavior. For this pure phase Li3V2(PO4)3 sample, devoid of any impurities such as carbon or salts, extensive electrochemical property testing was performed. These tests resulted in the experimental discovery of a remarkably high lithium diffusion coefficient D = 1.07 × 10−10 cm2/s, indicating excellent ionic conductivity, and demonstrated impressive stability of the material with sustained performance over 1000 charge–discharge cycles. Additionally, relithiated Li3V2(PO4)3 (after multiple electrochemical cycling) samples were investigated using scanning electron microscopy, magnetometry and electron spin resonance methods to determine the extent of degradation. The combination of high lithium diffusion coefficients, a low degradation rate and remarkable cycling stability positions this Li3V2(PO4)3 material as a promising candidate for advanced energy storage applications. [ABSTRACT FROM AUTHOR]

Magnetic nanoparticles are of great interest to scientists as potential drug carriers. Therefore, it is essential to analyze the processes these nanoparticles undergo at the cellular level. The present paper demonstrates the effect of a constant and rotating magnetic field on penetration of TEMPOL-functionalized magnetite nanoparticles into yeast cells. The interactions between nanoparticles and yeast cells without and with a magnetic field were studied using electron spin resonance spectroscopy (ESR). The results showed that the ESR method can monitor the effect of a magnetic field on the magnetite nanoparticle penetration rate into the cells. [ABSTRACT FROM AUTHOR]

Abstract Background Eucommia ulmoides (E. ulmoides) leaves are identified as a new resource of medicine and food homology. In this study, the structural characterization, physicochemical properties, and antioxidant activity of E. ulmoides polysaccharides (EUP) were studied. Results Three components with different molecular weights of 1.51 × 105 Da (EUP1), 3.05 × 104 Da (EUP2) and 1.17 × 105 Da (EUP3) were purified from E. ulmoides leaves. They were composed of l -rhamnose (Rha), d -arabinose (Ara), d -mannose (Man), d-glucose (Glu) and d -galactose (Gal), while EUP2 also contained small amounts of d -xylose (Xyl). Three components all had typical polysaccharides absorption peaks, which may be polysaccharides with β configuration of pyranose structure, and amorphous structure of acid polysaccharides with good thermal stability below 270 ℃. However, the molecular weight, monosaccharide composition and apparent morphology of the three components were different, resulting in a stronger scavenging ability of EUP2 and EUP3 against DPPH and OH free radicals. Conclusion The results will provide a theoretical reference for developing EUP-related foods and drugs. Graphical Abstract

Various studies have demonstrated that employing ESR spin trapping to detect free radicals yields valuable insights into the vulnerability of bulk oils to oxidation. Consequently, this method can be employed to assess and compare the oxidative stability of different samples. This study was conducted to investigate the production and transformation of free radicals and trans isomers in linseed oil when subjected to different temperatures and durations of heating. These analyses revealed that the peak levels of free radicals PBN adducts were evident in linseed oil heated to 120 °C, while these levels decreased within 90 min and were absent at a higher temperature of 180 °C. Free radical PBN adducts were readily degraded at 180 °C. Levels of heat-induced trans isomers rose in linseed oil samples with rising temperatures but began to degrade at temperatures exceeding 240 °C partially. The content examination of these trans isomers revealed that the double bonds located at positions 9 and 15 exhibited a higher susceptibility to isomerization compared to the double bond at position 12. Furthermore, the values of k and Ea indicated that the synthesis of tri-trans-α-linolenic acid (TALAs) was more challenging compared to double-TALAs, and double-TALAs were more challenging than single-TALAs. This was because the tri-TALAs has a higher Ea value than the mono-TALAs and double-TALAs. The study has demonstrated that subjecting linseed oil to high-temperature heating leads to the production of free radicals and trans isomers. And PBN radical adduct is unstable at 180 °C and the double bonds at positions 9 and 15 could be isomerized more easily than that at position 12. These results indicated that controlling the formation of free radicals and single-TALAs isomers may be the key way to reduce the trans isomers of linolenic acid during cooking oil heating. In the follow-up study, we found that VE, VK3, ethyl caffeic acid and resveratrol had significant inhibitory effects on the formation of TALAs of linolenic acid, and the highest inhibitory rate of resveratrol with 5% addition could be reached to 30.86%. The above substances can be applied to the thermal processing of linseed oil to prevent the formation of TALAs.

Our previous study showed that nanobubbles (NBs) encapsulating CO2 gas have bactericidal activity due to reactive oxygen species (ROS) (Yamaguchi et al., 2020). Here, we report that bulk NBs encapsulating CO2 can be efficiently generated by ultrasonically irradiating carbonated water using a piezoelectric transducer with a frequency of 1.7 MHz. The generated NBs were less than 100 nm in size and had a lifetime of 500 h. Furthermore, generation of ROS in the NB suspension was investigated using electron spin resonance spectroscopy and fluorescence spectrometry. The main ROS was found to be the hydroxyl radical, which is consistent with our previous observations. The bactericidal activity lasted for at least one week. Furthermore, a mist generated by atomizing the NB suspension with ultrasonic waves was confirmed to have the same bactericidal activity as the suspension itself. We believe that the strong, persistent bactericidal activity and radical generation phenomenon are unique to NBs produced by ultrasonic irradiation of carbonated water. We propose that entrapped CO2 molecules strongly interact with water at the NB interface to weaken the interface, and high-pressure CO2 gas erupts from this weakened interface to generate ROS with bactericidal activity.

Food irradiation aims to eliminate biohazards such as pathogens, microbes, fungi, etc., as the identification of irradiated food and dose assessment ensures its safe use. Hazelnut is the most universal widespread nut and can be found as a whole fruit or as an ingredient in many food types. Electron paramagnetic resonance (EPR) was used to identify irradiated hazelnut and assess radiation doses delivered to it using fractions of its kernel and/or shells. In this paper, parameters affecting the proper detection and evaluation of irradiated hazelnut kernels and shells are studied and analyzed, including the response to Cs-137 gamma rays, the effect of the change in microwave power and modulation amplitude values during EPR spectra acquisition, and the time dependence of the induced radicals. The stability study of the radiation-induced radicals suggests that it is better to perform EPR measurements for irradiated hazelnut during the first month following irradiation. [ABSTRACT FROM AUTHOR]

Among the 5d transition metal iridates, Sr2IrO4, which has a layered chalcogenide structure, has received much attention due to its strong spin–orbit coupling (SOC), which produces Mott insulating states and anomalous physical behaviors. In this paper, the microscopic magnetism of Sr2IrO4 is studied with electron spin resonance (ESR) measurements. The Lande factor g of the ferromagnetic resonance signal of Sr2IrO4 shows anomalous behavior compared to typical ferromagnets. It gradually decreases, and the corresponding resonance field Hr increases, with decreasing temperature. The various physical parameters. including the saturated magnetic field Hs derived from M-H, Hr, ΔHpp, the g factor and the intensity I extracted from ESR spectra, are analyzed in detail. Eventually, it is revealed that the anomalous behavior of the g-factor is induced by in-plane Dzyaloshinsky–Moriya interaction (DMI) rather than the SOC effect. [ABSTRACT FROM AUTHOR]

Background: Eucommia ulmoides (E. ulmoides) leaves are identified as a new resource of medicine and food homology. In this study, the structural characterization, physicochemical properties, and antioxidant activity of E. ulmoides polysaccharides (EUP) were studied. Results: Three components with different molecular weights of 1.51 × 105 Da (EUP1), 3.05 × 104 Da (EUP2) and 1.17 × 105 Da (EUP3) were purified from E. ulmoides leaves. They were composed of l-rhamnose (Rha), d-arabinose (Ara), d-mannose (Man), d-glucose (Glu) and d-galactose (Gal), while EUP2 also contained small amounts of d-xylose (Xyl). Three components all had typical polysaccharides absorption peaks, which may be polysaccharides with β configuration of pyranose structure, and amorphous structure of acid polysaccharides with good thermal stability below 270 ℃. However, the molecular weight, monosaccharide composition and apparent morphology of the three components were different, resulting in a stronger scavenging ability of EUP2 and EUP3 against DPPH and OH free radicals. Conclusion: The results will provide a theoretical reference for developing EUP-related foods and drugs. [ABSTRACT FROM AUTHOR]

Block copolymers are a class of materials that are particularly interesting with respect to their capability to self-assemble in ordered structures. In this context, the coupling between environment and dynamics is particularly relevant given that movements at the molecular level influence various properties of macromolecules. Mixing the polymer with a second macromolecule appears to be an easy method for studying these relationships. In this work, we studied blends of poly(methyl methacrylate) (PMMA) and a block copolymer composed of PMMA as the first block and poly(3-methyl-4-[6-(methylacryloyloxy)-hexyloxy]-4′-pentyloxy azobenzene) as the second block. The relaxational properties of these blends were investigated via electron spin resonance (ESR) spectroscopy, which is sensitive to nanometric length scales. The results of the investigations on the blends were related to the dynamic behavior of the copolymers. At the nanoscale, the study revealed the presence of heterogeneities, with slow and fast dynamics available for molecular reorientation, which are further modulated by the ability of the block copolymers to form supramolecular structures. For blends, the heterogeneities at the nanoscale were still detected. However, it was observed that the presence of the PMMA as a major component of the blends modified their dynamic behavior. [ABSTRACT FROM AUTHOR]

In order to create new biodegradable nanocomposites for biomedicine, packaging, and environmentally effective adsorbents, ultra-thin composite fibers consisting of poly(3-hydroxybutyrate) (PHB) and graphene oxide (GO) were obtained by electrospinning. Comprehensive studies of ultrathin fibers combining thermal characteristics, dynamic electron paramagnetic resonance (ESR) probe measurements, and scanning electron microscopy (SEM) were carried out. It is shown that at the addition of 0.05, 0.1, 0.3, and 1% OG, the morphology and geometry of the fibers and their thermal and dynamic characteristics depend on the composite content. The features of the crystalline and amorphous structure of the PHB fibers were investigated by the ESR and DSC methods. For all compositions of PHB/GO, a nonlinear dependence of the correlation time of molecular mobility TEMPO probe (τ) and enthalpy of biopolyether melting (ΔH) is observed. The influence of external factors on the structural-dynamic properties of the composite fiber, such as hydrothermal exposure of samples in aqueous medium at 70 °C and ozonolysis, leads to extreme dependencies of τ and ΔH, which reflect two processes affecting the structure in opposite ways. The plasticizing effect of water leads to thermal destruction of the orientation of the pass-through chains in the amorphous regions of PHB and a subsequent decrease in the crystalline phase, and the aggregation of GO nanoplates into associates, reducing the number of GO-macromolecule contacts, thus increasing segmental mobility, as confirmed by decreasing τ values. The obtained PHB/GO fibrillar composites should find application in the future for the creation of new therapeutic and packaging systems with improved biocompatibility and high-barrier properties. [ABSTRACT FROM AUTHOR]

Several types of biological samples, including hair strands, are found at crime scenes. Apart from the identification of the value and the contributor of the probative evidence, it is important to prove that the time of shedding of hair belonging to a suspect or victim matches the crime window. To this end, to estimate the ex vivo aging of hair, we evaluated time-dependent changes in melanin-derived free radicals in blond, brown, and black hairs by using electron paramagnetic resonance spectroscopy (EPR). Hair strands aged under controlled conditions (humidity 40%, temperature 20-22°C, indirect light, with 12/12 hour of light/darkness cycles) showed a time-dependent decay of melanin-derived radicals. The half-life of eumelanin-derived radicals in hair under our experimental settings was estimated at 22 ± 2 days whereas that of pheomelanin was about 2 days suggesting better stabilization of unpaired electrons by eumelanin. Taken together, this study provides a reference for future forensic studies on determination of degradation of shed hair in a crime scene by following eumelanin radicals by utilizing the non-invasive, non-destructive, and highly specific EPR technique.

Coherent control of individual atomic and molecular spins on surfaces has recently been demonstrated by using electron spin resonance (ESR) in a scanning tunneling microscope (STM). Here, a combined experimental and modeling study of the ESR of a single hydrogenated Ti atom that is exchange‐coupled to a Fe adatom positioned 0.6–0.8 nm away by means of atom manipulation is presented. Continuous wave and pulsed ESR of the Ti spin show a Rabi rate with two contributions, one from the tip and the other from the Fe, whose spin interactions with Ti are modulated by the radio‐frequency electric field. The Fe contribution is comparable to the tip, as revealed by its dominance when the tip is retracted, and tunable using a vector magnetic field. The new ESR scheme allows on‐surface individual spins to be addressed and coherently controlled without the need for magnetic interaction with a tip. This study establishes a feasible implementation of spin‐based multi‐qubit systems on surfaces. [ABSTRACT FROM AUTHOR]

xMgO–(30–x)BaO–69.5B2O3 glass systems were synthesized with the doping of transition metal ions (Mn2+) by applying the melt quench method. These glass systems are then observed using analysis by XRD, UV-VIS absorption and electron paramagnetic resonance. Mn2+ absorption spectrum has its own broadband at about 21000 cm–1 (476 nm), which is ascribed to be of 6A1g(S) → 4T1g (G) transition. The typical six-line hyperfine structure with a core at g ≈ 2.0 was observed in the Mn2+ EPR spectra. The close octahedral site symmetry for the Mn2+ contamination ions was established by spectroscopic examinations of the obtained data. Structural transformations were discovered using Fourier transform infrared and Raman spectra. Assessments were done on several physical parameters, together with density, refractive index, optical basicity, molar volume, energy gap, Urbach energy and interaction parameter. [ABSTRACT FROM AUTHOR]

We have trapped BaF molecules in neon ice and used laser-induced fluorescence spectroscopy to map out their optical transitions. Our measurements show that the neon lattice does not significantly perturb certain optical transitions in trapped BaF molecules. We used one such transition to optically pump and detect spin resonances in the molecules. This demonstration of optical control of trapped heavy polar molecules offers opportunities to advance physical chemistry and ultra-high-energy physics. [ABSTRACT FROM AUTHOR]

In critically ill patients requiring intensive care, increased oxidative stress plays an important role in pathogenesis. Sedatives are widely used for sedation in many of these patients. Some sedatives are known antioxidants. However, no studies have evaluated the direct scavenging activity of various sedative agents on different free radicals. This study aimed to determine whether common sedatives (propofol, thiopental, and dexmedetomidine (DEX)) have direct free radical scavenging activity against various free radicals using in vitro electron spin resonance. Superoxide, hydroxyl radical, singlet oxygen, and nitric oxide (NO) direct scavenging activities were measured. All sedatives scavenged different types of free radicals. DEX, a new sedative, also scavenged hydroxyl radicals. Thiopental scavenged all types of free radicals, including NO, whereas propofol did not scavenge superoxide radicals. In this retrospective analysis, we observed changes in oxidative antioxidant markers following the administration of thiopental in patients with severe head trauma. We identified the direct radical-scavenging activity of various sedatives used in clinical settings. Furthermore, we reported a representative case of traumatic brain injury wherein thiopental administration dramatically affected oxidative-stress-related biomarkers. This study suggests that, in the future, sedatives containing thiopental may be redeveloped as an antioxidant therapy through further clinical research. [ABSTRACT FROM AUTHOR]

β-glucan has been shown to be effective for several diseases such as immune regulation and blood pressure suppression. Seaweed contains a β-1,3/1,6-glucan called laminaran. The present commercial source of β-glucan is black yeast; however, a fermentation process using organic carbon substrates makes production unsustainable, whereas macroalgae provide a sustainable alternative with the use of CO2 and seawater as growth substrates. However, bioactivity studies on laminaran are limited. We aimed to evaluate whether laminaran can scavenge reactive oxygen species (ROS) and attenuate cytotoxicity caused by clinical drugs such as indomethacin (Ind) and dabigatran (Dab). Electron spin resonance assay revealed that laminaran scavenged singlet oxygen (1O2) and superoxide anions (O2•−) directly but did not scavenge hydroxyl radicals (•OH). Mitochondrial ROS detection dye showed that laminaran scavenged mitochondrial O2•− produced upon administration of Ind or Dab. Moreover, significant reductions in •OH and peroxynitrate (ONOO−) levels were observed. Since •OH and ONOO− are generated from O2•− in the cells, laminaran could indirectly suppress the generation of •OH and ONOO− via the removal of O2•−. Both Ind and Dab induce cell injury via ROS production. Laminaran attenuated the cytotoxicity derived from these drugs and may represent a functional food with anti-aging and disease prevention properties. [ABSTRACT FROM AUTHOR]

In this paper, a microstrip resonator based on double split rings is used to build an electron spin resonance (ESR) measurement system. The resonator is optimized by the finite element electromagnetic simulation and the 3 dB bandwidth is 58.7 MHz. Due to the open structure of the resonator, large-size samples with high dielectric loss can be measured nondestructively. The ESR signal of 2,2-diphenyl-1-picrylhydrazyl (DPPH) powder with different quality is measured at room temperature, and the result indicated that the spin detection limit of this system can reach 9.66 ×1012 spins/Gs Hz1/2. It is demonstrated that the system can be used to characterize films deposited on different substrates such as silicon, glasses or ceramics regardless of its high frequency losses through the measurement of DPPH sample spin-coated on silicon and zerodur. Our system provides a convenient approach to research the defect of thin films and to characterize their performances within microwave frequency.

Crystal-chemical features of a sulfide-bearing variety of the cancrinite-group mineral balliranoite from the Tuluyskoe lapis lazuli deposit, Baikal Lake area, Siberia, Russia, have been investigated using a multimethodic approach based on infrared (IR), Raman, and electron spin resonance (ESR), as well as ultraviolet, visible and near infrared (UV–Vis–near IR) absorption spectroscopy methods, luminescence spectroscopy, electron microprobe analysis, selective sorption of CO2 and H2O from annealing products, and single-crystal X-ray structure analysis. Holotype balliranoite and its sulfate analogue, davyne, were studied for comparison. The crystal-chemical formula of the studied sample from Tultuyskoe is Na5.4K0.1Ca2.4(Si6Al6O24)Cl2[(CO3)0.7(SO4)0.18S*0.95Cl0.1(H2O)0.16], where the content of the wide zeolite channel is given in square brackets; S* is total sulfide sulfur occurring as disordered S2●−, cis- and trans-S4, S52−, minor S3●−, and HS− groups. The presence of S52− and HS− groups, the absence of CO2 molecules, and the association with pyrrhotite and Fe-free pargasite indicate that the studied sample crystallized under highly reducing, low-temperature conditions, unlike holotype balliranoite whose formation was related to the Somma-Vesuvius volcanic complex, Italy. Irradiation of balliranoite from Tultuyskoe with X-rays results in the transformations of polysulfide groups other than S3●− into S3●− in accordance with the scheme: S52− → S2●− + S3●−; 3S2●− → 2S3●− + e−; S4 + S2●− + e− → 2S3●−; S4 + S2●− + e− → 2S3●−; S4 + S52− + e− → 3S3●− (e− = electron). [ABSTRACT FROM AUTHOR]

Sediments and fossil content of Gediz Delta (Eastern Aegean Sea-İzmir) were examined from the samples collected from three drilling cores from the west (seaward) to east (landward) of the delta. Each drilling core contains Quarternary marine deposits with a marine fauna of foraminifers, bivalves, gastropods, echinoids, and ostracods at the bottom and Quaternary continental delta deposits at the top. According to our Electron Spin Resonance (ESR) age model marine sediments of the Aegean Sea started to cover the western Gediz Delta area before 19.9 ka (thousand years). Following the Last Glacial Maximum (LGM), after the transgression due to deglaciation occurred 15.3 ka ago, the coastline progressed 15-20 km eastward and covered the entire delta area. At the end of the LGM, as a result of the overflow of Manisa Gediz Lake depending on the deglaciation in Western Anatolia, and its flow from the Emiralem Strait to the İzmir Bay, the continental deposits reaching the West Gediz Delta region are younger than 11.4 ka. [ABSTRACT FROM AUTHOR]

Impact by hailstone, volcanic rock, bird strike, or also dropping tools can cause damage to aircraft materials. For maximum safety, the goal is to increase Charpy impact strength (auc) of a carbon-fiber-reinforced thermoplastic polyphenylene sulfide polymer (CFRTP-PPS) composite for potential application to commercial aircraft parts. The layup was three cross-weave CF plies alternating between four PPS plies, [PPS-CF-PPS-CF-PPS-CF-PPS], designated [PPS]4[CF]3. To strengthen, a new process for CFRP-PPS was employed applying homogeneous low voltage electron beam irradiation (HLEBI) to both sides of PPS plies prior to lamination assembly with untreated CF, followed by hot press under 4.0 MPa at 573 K for 8 min. Experimental results showed a 5 kGy HLEBI dose was at or near optimum, increasing auc at each accumulative probability, Pf. Optical microscopy of 5 kGy sample showed a reduction in main crack width with significantly reduced CF separation and pull-out; while, scanning electron microscopy (SEM) and electron dispersive X-ray (EDS) mapping showed PPS adhering to CF. Electron spin resonance (ESR) of a 5 kGy sample indicated lengthening of PPS chains as evidenced by a reduction in dangling bond peak. It Is assumed that 5 kGy HLEBI creates strong bonds at the interface while strengthening the PPS bulk. A model is proposed to illustrate the possible strengthening mechanism. [ABSTRACT FROM AUTHOR]

This work presents the results of studying paramagnetic activity of humic and hymatomelanic acids, lipids and initial brown coal of the Otoryinsk field in the Nether-Polar Urals. Two methods were used for quantitative research: the method of ABS spins and the double resonator method relative to TEMPO. The two methods were compared. Concentrations of paramagnetic cents per gram and molecular weights of assumed paramagnetic molecules were calculated. Based on the results obtained, it was concluded that humic acids have higher paramagnetic activity than hymatomelanic acids. The differences in paramagnetic activity of the studied samples were identified. [ABSTRACT FROM AUTHOR]

Abstract Coherent control of individual atomic and molecular spins on surfaces has recently been demonstrated by using electron spin resonance (ESR) in a scanning tunneling microscope (STM). Here, a combined experimental and modeling study of the ESR of a single hydrogenated Ti atom that is exchange‐coupled to a Fe adatom positioned 0.6–0.8 nm away by means of atom manipulation is presented. Continuous wave and pulsed ESR of the Ti spin show a Rabi rate with two contributions, one from the tip and the other from the Fe, whose spin interactions with Ti are modulated by the radio‐frequency electric field. The Fe contribution is comparable to the tip, as revealed by its dominance when the tip is retracted, and tunable using a vector magnetic field. The new ESR scheme allows on‐surface individual spins to be addressed and coherently controlled without the need for magnetic interaction with a tip. This study establishes a feasible implementation of spin‐based multi‐qubit systems on surfaces.

Magnetic nanoparticles are of great interest to scientists as potential drug carriers. Therefore, it is essential to analyze the processes these nanoparticles undergo at the cellular level. The present paper demonstrates the effect of a constant and rotating magnetic field on penetration of TEMPOL-functionalized magnetite nanoparticles into yeast cells. The interactions between nanoparticles and yeast cells without and with a magnetic field were studied using electron spin resonance spectroscopy (ESR). The results showed that the ESR method can monitor the effect of a magnetic field on the magnetite nanoparticle penetration rate into the cells.

Ultrasonic cavitation in organic solvents remains poorly understood in contrast with aqueous systems, largely because of complexities related to solvent decomposition. In this study, we sonicated different types of organic solvents (i.e. linear alkanes, aliphatic alcohols, aromatic alcohols, and acetate esters) under argon saturation. The average temperature of the cavitation bubbles was estimated using the methyl radical recombination method. We also discuss the effects of the physical properties of the solvents, such as vapor pressure and viscosity, on the cavitation temperature. The average cavitation bubble temperature and sonoluminescence intensity were higher in organic solvents with lower vapor pressure; for aromatic alcohols, these values were particularly high. It was found that the specific high sonoluminescence intensities and average cavitation temperatures exhibited in aromatic alcohols are caused by the highly resonance-stable generated radicals. The results obtained in this study are very useful for acceleration of sonochemical reaction in organic solvents, which are indispensable for organic synthesis and material synthesis.

Background: Early Life Stress (ELS) may exert long-lasting biological effects, e.g., on PBMC energy metabolism and mitochondrial respiration. Data on its effect on brain tissue mitochondrial respiration is scarce, and it is unclear whether blood cell mitochondrial activity mirrors that of brain tissue. This study investigated blood immune cell and brain tissue mitochondrial respiratory activity in a porcine ELS model.Methods: This prospective randomized, controlled, animal investigation comprised 12 German Large White swine of either sex, which were weaned at PND (postnatal day) 28–35 (control) or PND21 (ELS). At 20–24 weeks, animals were anesthetized, mechanically ventilated and surgically instrumented. We determined serum hormone, cytokine, and “brain injury marker” levels, superoxide anion (O2•¯) formation and mitochondrial respiration in isolated immune cells and immediate post mortem frontal cortex brain tissue.Results: ELS animals presented with higher glucose levels, lower mean arterial pressure. Most determined serum factors did not differ. In male controls, TNFα and IL-10 levels were both higher than in female controls as well as, no matter the gender in ELS animals. MAP-2, GFAP, and NSE were also higher in male controls than in the other three groups. Neither PBMC routine respiration and brain tissue oxidative phosphorylation nor maximal electron transfer capacity in the uncoupled state (ETC) showed any difference between ELS and controls. There was no significant relation between brain tissue and PBMC, ETC, or brain tissue, ETC, and PBMC bioenergetic health index. Whole blood O2•¯ concentrations and PBMC O2•¯ production were comparable between groups. However, granulocyte O2•¯ production after stimulation with E. coli was lower in the ELS group, and this effect was sex-specific: increased O2•¯ production increased upon stimulation in all control animals, which was abolished in the female ELS swine.Conclusion: This study provides evidence that ELS i) may, gender-specifically, affect the immune response to general anesthesia as well as O2•¯ radical production at sexual maturity, ii) has limited effects on brain and peripheral blood immune cell mitochondrial respiratory activity, and iii) mitochondrial respiratory activity of peripheral blood immune cells and brain tissue do not correlate.

Cyclic 3d-4f molecular magnets have received considerable attention owing to their potential applications in high-density data storage and quantum information processing. As a rare example of ferromagnetic polynuclear Cr rings, {Cr8Y8} represents a valuable test bed to directly study the magnetic interaction between Cr3+ ions in large hexadecametallic {Cr8Ln8} (Ln = 4f metal) molecules. We have proposed a "single-J" model to approximate the low-temperature spin dynamics of {Cr8Y8} in our earlier study, while a zero-field splitting (ZFS) of the quantum levels was also suggested by the heat capacity data. In order to have a deeper understanding of the magnetism of {Cr8Y8}, it is necessary to verify the ZFS by means of high-resolution spectral methods and identify its origin. In this work, we present a high-frequency electron spin resonance (HF-ESR) study on the ZFS of {Cr8Y8}. The X-band ESR spectra consists of multi-peak structure, indicative of magnetic anisotropy that breaks the degeneracy between spin states in the absence of a magnetic field. HF-ESR spectra are collected to extract the ZFS parameters. We observed a sharp resonance peak due to the transitions between the S = 11 quantum levels and a broadband corresponding to a distribution of resonance peaks due to the ZFS of the S = 12 quantum levels. By analyzing HF-ESR spectra, we confirm the expected S = 12 ground state and determine its ZFS parameter D as −0.069 K, and, furthermore, we reproduce the spectra recorded at 154 GHz. The macrospin model proves to still be valid. The ZFS is attributed to the axial magnetic anisotropy, as found in some other Cr-based molecular wheels. The detailed HF-ESR investigation presented in this paper will benefit the studies on other {Cr8Ln8} wheels with magnetic Ln3+ ions and highlights the importance of the HF-ESR method as a high-resolution probe in determining the ZFS parameters with very small magnitude. [ABSTRACT FROM AUTHOR]

Among the 5d transition metal iridates, Sr2IrO4, which has a layered chalcogenide structure, has received much attention due to its strong spin–orbit coupling (SOC), which produces Mott insulating states and anomalous physical behaviors. In this paper, the microscopic magnetism of Sr2IrO4 is studied with electron spin resonance (ESR) measurements. The Lande factor g of the ferromagnetic resonance signal of Sr2IrO4 shows anomalous behavior compared to typical ferromagnets. It gradually decreases, and the corresponding resonance field Hr increases, with decreasing temperature. The various physical parameters. including the saturated magnetic field Hs derived from M-H, Hr, ΔHpp, the g factor and the intensity I extracted from ESR spectra, are analyzed in detail. Eventually, it is revealed that the anomalous behavior of the g-factor is induced by in-plane Dzyaloshinsky–Moriya interaction (DMI) rather than the SOC effect.

Food irradiation aims to eliminate biohazards such as pathogens, microbes, fungi, etc., as the identification of irradiated food and dose assessment ensures its safe use. Hazelnut is the most universal widespread nut and can be found as a whole fruit or as an ingredient in many food types. Electron paramagnetic resonance (EPR) was used to identify irradiated hazelnut and assess radiation doses delivered to it using fractions of its kernel and/or shells. In this paper, parameters affecting the proper detection and evaluation of irradiated hazelnut kernels and shells are studied and analyzed, including the response to Cs-137 gamma rays, the effect of the change in microwave power and modulation amplitude values during EPR spectra acquisition, and the time dependence of the induced radicals. The stability study of the radiation-induced radicals suggests that it is better to perform EPR measurements for irradiated hazelnut during the first month following irradiation.

Residual doses may cause overestimation of electron spin resonance (ESR) ages for fluvial sediments. However, ESR residual doses in outburst megaflood sediments have rarely been evaluated. The Jinsha River, situated in the southeastern Tibetan Plateau, is characterized by active faults, narrowed canyons, and dammed lakes. Consequently, the river is a rare opportunity for a reconstruction study of outburst flood events from a paleo-dammed lake. After the destruction of the Baige dammed lake in the upper Jinsha River in 2018, outburst megafloods formed a thick diluvium that was deposited in broad valley land along the lower Jinsha River. Based on detailed field investigation and laboratory studies, preliminary hydraulics estimates and residual quartz ESR signals indicate the following. 1) Among the multiple quartz ESR centers, the Al, E1ʹ, Ti-H, and Ti-Li centers could be measured. The Ti-H center had the lowest residual dose and would provide relatively accurate ages for outburst megaflood sediment. 2) The Ti-Li and Al centers commonly used for ESR dating provide overestimates of 283 ± 42 ka ∼ 462 ± 63 ka and 1,010 ± 88 ka ∼ 1,400 ± 219 ka, respectively, for present outburst megaflood sediment. 3) The diverse ages given by the same ESR signal may be caused by various precursors of megaflood sediments, which are mainly sourced from landslide dams and from various terraces and slope sediments along the river. Results demonstrated that the apparent ESR ages observed for the outburst megaflood sediment in the southeastern Tibetan Plateau may be counterfeit, providing an age much older than its real age. This could be interpreted to mean that the narrowed lower channel makes the upper reaches of the broad valley appear lake-like, with diluvium deposits having large non-negligible residual ESR signals without enough exposure to adequate sunlight, despite having good stratification and sorting characteristics similar to those of fluvio-lacustrine sediments. Thus, abrupt reversal in quartz ESR ages in multiple centers observed in the geochronological framework of the fluvial sedimentary profile may indicate a diluvial or flood layer in the absence of other inducements.

Dynamic nuclear polarization (DNP) has enabled enormous gains in magnetic resonance signals and led to vastly accelerated NMR/MRI imaging and spectroscopy. Unlike conventional cw-techniques, DNP methods that exploit the full electron spectrum are appealing since they allow direct participation of all electrons in the hyperpolarization process. Such methods typically entail sweeps of microwave radiation over the broad electron linewidth to excite DNP but are often inefficient because the sweeps, constrained by adiabaticity requirements, are slow. In this paper, we develop a technique to overcome the DNP bottlenecks set by the slow sweeps, using a swept microwave frequency comb that increases the effective number of polarization transfer events while respecting adiabaticity constraints. This allows a multiplicative gain in DNP enhancement, scaling with the number of comb frequencies and limited only by the hyperfine-mediated electron linewidth. We demonstrate the technique for the optical hyperpolarization of 13C nuclei in powdered microdiamonds at low fields, increasing the DNP enhancement from 30 to 100 measured with respect to the thermal signal at 7T. For low concentrations of broad linewidth electron radicals [e.g., TEMPO ((2,2,6,6-tetramethylpiperidin-1-yl)oxyl)], these multiplicative gains could exceed an order of magnitude.

The electron spin resonance (ESR)-based photosafety test (ESR-PT) is a non-animal prediction test for photosafety evaluations that can be used even for hydrophobic chemicals; the method is based on the detection of singlet oxygen generation using ESR spectroscopy and showing high accuracy for compounds with known photosafety information. During the process of extending the application data for ESR-PT, we found three false-negative chemicals: bithionol, fenticlor and cilnidipine. These chemicals did not show the characteristic triplet signal of 4-hydroxy-2,2,6,6-tetramethyl-piperidine-1-oxyl (4-hydroxy-TEMPO), which is used as a classifier for positive or negative chemicals; instead, bithionol and fenticlor induced an apparent single peak signal with a g-value of 2.0048, while cilnidipine produced a small, fragmented signal. Bithionol and fenticlor reportedly induce free radicals, and positive phototoxic or photoallergic evidence have been reported. Although the small, fragmented signal observed for cilnidipine was confirmed to be identical to that of a phenylnitroxy radical by the computer simulation, the significance of this chemical for photosafety considerations may be low because cilnidipine has quite a low incidence of phototoxic or photoallergic reactions in humans. Accordingly, the current ESR-PT protocol should be improved to detect free radical photoproducts generated from chemicals such as bithionol and fenticlor, thereby helping to reduce false negatives in ESR-PT. [ABSTRACT FROM AUTHOR]

Photocatalytic water oxidation over titanium dioxide (TiO2) was overviewed by surveying briefly the history of water photo-oxidation, followed by profiling the research for the molecular mechanism of oxygen evolution reaction (OER) at the TiO2 surface. As the experimental approach to investigate the reaction mechanism, ESR, NMR, and STM were described as well as FTIR spectroscopy. Detection of reactive oxygen species, which are the intermediate species in the OER, was also involved in discussing the mechanism. As the theoretical approach to the reaction mechanism, some research with density functional theory (DFT) for anatase (101) surface was illustrated. Since the OER activity of rutile TiO2 is higher than that of anatase, and the rutile (011) surface has been assigned to the oxidation facet, we performed a DFT calculation for a (011) surface model molecule. The results were successfully discussed with the reported mechanism. The first oxidation step occurs at the bridging OH site, which faces a Ti5C site. The water molecule which coordinates both sites is oxidized, and the resultant radical coordinates the Ti5C site to form a trapped hole Ti-O•. In the second step, a coordinated water molecule is oxidized at the Ti-O• site to form a Ti-OOH structure. [ABSTRACT FROM AUTHOR]

Nitrogen-doped carbon nanomaterial (NDCNM) was synthesized by grinding a mixture of graphene oxide and melamine in a planetary mill with both balls and milling chamber of zirconium dioxide. In the electron spin resonance spectrum of NDCNM, a broad signal with g = 2.08 was observed in addition to a narrow signal at g = 2.0034. In the study using a vibrating-sample magnetometer, the synthesized material is presumably a ferromagnet with a coercive force of 100 Oe. The specific magnetization at 10,000 Oe is approximately 0.020 and 0.055 emu/g at room temperature and liquid nitrogen temperature, respectively. [ABSTRACT FROM AUTHOR]