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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 Murun massif (Aldan shield, Russia) is particularly intriguing due to its group of alkali Ca-(K)-(Na) silicates, which includes many new and rare species. Additionally, it is also of interest for its beryllium mineralization. One of the unique beryllium Ca-(K)-(Na) silicates, odintsovite K2Na4Ca3Ti2Be4Si12O38, was investigated in this study. The aim of this study is to provide new insights into the crystal chemistry and spectroscopic properties of odintsovite. DFT modelling was used to interpret the experimental IR and Raman spectra. Determining the crystal-chemical formula of odintsovite is challenging due to the presence of atoms in different structural positions with varying valence states. The distribution of cations was determined by combining electron probe microanalysis with the results of crystal structure refinement. Luminescence of Eu3+ was observed in odintsovite upon excitation at around 532 nm. Analysis of the luminescence band splitting is related to the 4f–4f transitions in Eu3+ ions. Additionally, upon excitation at around 370 nm, luminescence with a peak at around 410 nm, associated with 5d–4f transitions in Ce3+ ions, was observed. [ABSTRACT FROM AUTHOR]

The authors study the formation of crystals of Fe-Ga oxides and Fe–Ga–Cu borates in a multicomponent flux system based on Bi2Mo3O12–Na2B4O7. The Curie–Weiss temperature (θCW = 289 K) and the temperature of the ferrimagnet–paramagnet phase transition (TC = 288 K) are determined from the electron spin resonance (ESR) spectrum and the magnetization of an Fe1.1Ga0.9O3 single crystal, depending on temperature. Lines of spin-wave resonance are observed in the spectrum of magnetic resonance in the ordered phase. [ABSTRACT FROM AUTHOR]

Li3V2(PO4)3-based composites as a lithium-ion battery cathode material were synthesized by the hydrothermal method with subsequent annealing in an Ar atmosphere. The as-prepared samples were characterized by X-ray diffraction analysis and electron spin resonance (ESR) methods. Based on ESR, data the quantitative estimation of V4+ content was performed. The tetravalent vanadium ions arised instead of trivalent vanadium ions due to lithium nonstoichiometry in Li3V2(PO4)3 structure. This method of identifying nonstoichiometry via ESR detection of V4+ ions is very simple and demonstrative and can be used to characterize not only as-prepared samples but also samples after multiple electrochemical cycling. This technique of the lithium nonstoichiometry detection in Li3V2(PO4)3 can be used if the valence state of vanadium ions is stable and investigated samples are not degraded during a long time. To clarify the question, the additional ESR measurements were performed for Li3V2(PO4)3 samples which were air-stored over a long period (up to 2 years). The obtained data proved the sample degradation in the form of increasing in V4+ content. It was found that in the presence of LiPO3 salt in the composite the number of magnetic centers increased significantly, so it contributed to sample degradation, while the pure Li3V2(PO4)3 sample Li3V2(PO4)3/C were most stable. [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).

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 studied the electron spin resonance (ESR) spectra of nitrogen atoms stabilized in nitrogen-neon nanoclusters immersed in superfluid 4 He. The nanoclusters were formed during the condensation of the products of the discharge in N 2 –Ne–He gas mixtures into bulk superfluid 4 He at temperature 1.5 K. We studied nanoclusters formed by injection of gas mixtures with different ratios of heavy impurities in the helium N 2 /(Ne + N 2 ) ranging from 2% to 90%. Analysis of the ESR spectra of nitrogen atoms stabilized in nitrogen-neon nanoclusters provides important information about the environment of the stabilized atoms and a shell structure of the nanoclusters was revealed. For all samples studied, preferential stabilization of N atoms on the surfaces of the nanoclusters was observed. Annealing of the collection of the nanoclusters in the temperature range 1.1–10 K resulted in substantial changes in the structure of the nanoclusters. [ABSTRACT FROM AUTHOR]

We report on electron spin resonance studies of H atoms stabilized in solid H 2 films at temperature 0.7 K and in a magnetic field of 4.6 T. The H atoms were produced by bombarding H 2 films with 100 eV electrons from a radiofrequency discharge run in the sample cell. We observed a one order of magnitude faster H atom accumulation in the films made of para-H 2 gas with a small ortho-H 2 concentration (0.2% ortho-H 2 ) as compared with those made from normal H 2 gas content (75% ortho-H 2 ). We also studied the influence of ortho-H 2 molecules on spatial diffusion of H atoms in solid H 2 films. The spatial diffusion of H atoms in both normal and para-H 2 films is faster than the diffusion obtained from the measurement of H atom recombination. The rate of spatial diffusion of H atoms in para-H 2 films was slower in comparison with that in the normal H 2 films. We discuss possible explanations of these observations. [ABSTRACT FROM AUTHOR]

Glass-nanocomposites (GNCs) samples of composition [(100−x) Li2B4O7–xPbTiO3] with x = 5, 10, 15 and 20 mol% were prepared by melt quenching method. The two phases of the GNCs samples, a glassy phase and PbTiO3 nanoparticles/clusters phase, can be seen in the energy dispersive X-ray spectra and scanning electron microscopic micrographs. Fourier transformation infrared spectra of the GNCs samples exhibited bands due to triangular with NBO's and tetrahedral borate groups. Additionally, the Ti4+ ions exist in both TiO4 and TiO6 structural units while the Ti3+ ions exist in TiO6 structural units. The electron spin resonance (ESR) spectra of the GNCs samples exhibit two ESR signals, broad and narrow, corresponding to the Ti3+ (3d1) ions in both tetragonal deformed octahedral and in the other structural configuration, respectively. The optical transmission spectra of the GNCs samples exhibited three transmission bands, 3Γ5 → 2Γ3, 2B2g → 2B1g and 2B2g → 2A1g transitions, in the visible region. The variation in optical band gap (Eopt) with increasing PbTiO3 content were due to the conversion between BO3 with NBOs and BO4 units as well as the reduction of Ti4+ to Ti3+ ions in the GNCs matrix. These results demonstrate that the present GNCs may be used for practical applications such as optical devices. [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]

The electron spin resonance‐based photosafety test (ESR‐PT) was modified using a new parameter, photoreactivity index (PRI), to detect singlet oxygen and free radical photoproducts simultaneously. With this modification, the modified ESR‐PT is expected to reduce the number of false negative results due to chemicals producing free radical photoproducts other than singlet oxygen. The assay performance of the modified ESR‐PT was evaluated using 56 chemicals, including hydrophobic chemicals. When using the PRI cutoff value of 2.0 in the modified ESR‐PT, the accuracy relative to photosafety reference data was 91.1%, and the applicability (100%) was better than the other non‐animal photosafety test. Among the chemicals producing positive results, bithionol, fenticlor, and doxycycline HCl were considered positive based on the detection of free radical photoproducts, suggesting that these three chemicals may have phototoxic or photoallergic potential via radical reactions. Additionally, this finding demonstrated the fundamental advantage of the modified ESR‐PT using ESR spectroscopy, which can detect radicals selectively and quantitatively. Accordingly, the new parameter PRI is effective for photosafety evaluations based on not only singlet oxygen but also free radical photoproducts generated from chemicals. Therefore, the modified ESR‐PT has a great potential for a photosafety test method applicable to various chemicals. We established a modified electron spin resonance‐based photosafety test (ESR‐PT), which uses the photoreactivity index (PRI) for simultaneous detection of singlet oxygen and free radical photoproducts generated from chemicals. The assay performance of the modified ESR‐PT was evaluated by testing 56 chemicals, and the accuracy with comparison to the known photosafety reference data was confirmed to be 91.1% using the PRI cutoff value of 2.0. [ABSTRACT FROM AUTHOR]

The output of photovoltaic (PV) devices is mostly independent of the wavelength of the incident light, whereas an anomalous wavelength‐dependent photovoltaic effect (WDPE) has recently been observed in antimony chalcohalide‐chalcogenide (SbSI:Sb2S3) PVs. Remarkably, the open‐circuit voltage (VOC) exhibits a reversible change between low VOC for short wavelengths and high VOC for long wavelengths. Herein, this work presents i) insights into the underlying mechanisms of this phenomenon by electron spin resonance (ESR) measurements and ii) the switchable character of WDPE depending on the hole transport material (HTM). Operando ESR measurements with light irradiation revealed that the hole density in the HTM is significantly suppressed when the ultraviolet component is included in the irradiation light. This indicated interfacial charge recombination rather than hole transfer to the HTM under short‐wavelength light irradiation, providing a basis for understanding the mechanism of WDPE. Furthermore, the use of poly(triarylamine) as the HTM unexpectedly exhibit the opposite wavelength‐VOC dependence, where a low VOC is observed with long‐wavelength light. In addition, the introduction of a polar gas accelerated the response speed of these effects. These findings shed light on the expansion of unique wavelength‐responsive single junction devices. [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]

Dehydrogenation of formic acid (FA) via photocatalytic technology is an attractive strategy to meet the enhanced demand of hydrogen. Regarding the existing complex modification strategies and unclear mechanism of visible-light response CdS-based photocatalytic materials for dehydrogenation of FA, a simple surface nickel-modified CdS nanocrystals has been constructed for boosting the hydrogen production from FA. In situ infrared spectroscopy and electron spin resonance technology were utilized to study the entire photocatalytic decomposition process of FA, which have limited study in previous work. The surface nickel-modification promoted the adsorption of formic acid on the material surface and the generation of key intermediate hydroxyl radicals, leading to faster hydrogen production and enhanced stability. Consequently, the photocatalytic activity was 12.8 times higher than that of unmodified CdS materials after 48 h irradiation. This work provides a new approach for constructing simple and efficient visible-light response CdS-based photocatalysts for hydrogen production from FA under mild condition. Surface nickel modification promotes the adsorption of formic acid on the surface of photocatalysts and the generation of key reaction intermediates hydroxyl radicals, in addition to enhancement of photo-response and separation of photogenerated carrier, thereby improving dehydrogenation from formic acid. [Display omitted] • A simple Ni-modification of CdS enhances photocatalytic dehydrogenation of FA. • Ni modification promotes adsorption of FA and favors the dehydrogenation pathway. • Ni modification facilitates the generation of key species hydroxyl radicals. • Ni modification accelerates the consumption of formate. [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]

An amphotropic liquid crystal polyacetylene derivative with pyrimidine–type two-ringed mesogenic core, exhibiting both thermotropic and lyotropic liquid crystallinity, was synthesized in this study. The polyacetylene derivative showed a lyotropic liquid crystal in d-limonene. The cis configuration of the main chain was confirmed via1H NMR. Heat treatment induced cis–trans isomerization of the as-prepared polymer. Gas-phase iodine doping of the polymer initiated a chemical interaction between the polyene and iodine, acting as an electron acceptor, generating charge carriers (radical cations, solitons) detected with the electron spin resonance spectroscopy. Moreover, gas phase doping of the polymer induced cis–trans isomerization. [ABSTRACT FROM AUTHOR]

A σ-bonded dimer of 4,8,10-trioxotriangulene (TOT) was newly synthesized and its electronic spin structure was characterized. The neutral diradical had a singlet ground state due to the strong antiferromagnetic interaction through the σ-bond. The strong intramolecular interaction within the σ-dimer caused a near-infrared photoabsorption of around 700-1,000 nm, which is close to that of the π-stacked dimer of TOT monoradical. [ABSTRACT FROM AUTHOR]

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.

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.

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.

[Display omitted] • Crystals of good homogeneity of FeIn 2x Cr 2-2x S 4 (0.6 ≤ x ≤ 1) were obtained using the CVT method. • Temperature-dependent FMR spectra for all samples was obtained in the temperature range 80 < T < 700 K. • The H R and Δ H P P parameters clearly show the changes produced by distortions and the anisotropies generated. • Long-range spin-glass-like behavior for the x=0.6 and 0.7 and a reentrant spin-glass type for x=0.9 and 1.0 was observed. • From 1/A N vs T curve we found three temperature regions bounded by temperatures named T 1 and T 2 related to In diffusion. Electron spin resonance (ESR) was employed to investigate the effects of composition and temperature on the FeIn 2x Cr 2-2x S 4 semiconductor system. The samples were synthesized using Chemical Vapor Transport (CVT), and their structural characteristics were analyzed through X-ray diffraction and Scanning Electron Microscopy (SEM). For magnetic characterization, magnetization curves M(H) and temperature-dependent magnetization curves M(T) were obtained under both zero-field and field cooling conditions. A paramagnetic behavior was observed for all samples above 180 K, transitioning to a potential long-range spin-glass-like behavior below this temperature. By comparing the results with those presented in the literature, we suggest a reentrant spin glass behavior for the samples with higher Cr concentration. The Electron spin resonance (ESR) spectra revealed asymmetric signals indicative of strong magnetic anisotropies. The inverse of the normalized area in the ESR spectra revealed three distinct regions above the Néel temperature; this observation is consistent with the sensitivity of the lattice parameters of indite. The study elucidates the intricate magnetic behaviors influenced by composition and temperature in the FeIn 2x Cr 2-2x S 4 semiconductor system, contributing to a deeper understanding of the material's properties. This comprehensive investigation, utilizing a range of analytical techniques, advances our knowledge of the system's magnetic characteristics and provides valuable insights for future research in related semiconductor materials. [ABSTRACT FROM AUTHOR]

Establishing chronologies of archaeological sites by using a single dating method may not always reliably constrain the age of a deposit or a fossil, as potential biases may naturally arise, particularly in complex sedimentary settings such as caves. In this study, we performed a multi-technique dating approach that targets different materials in two caves from the Cueva Mayor-Cueva del Silo karst system, Sierra de Atapuerca, Spain. Two new fossil teeth from lithostratigraphic unit LU4 (GE-I pit) at Galería de las Estatuas have been dated by combined U-series/ESR and Amino Acid Racemisation (AAR) methods. The former provides ages of 117 ± 13 and 87 ± 9 ka that agree with previous dating studies of this Neandertal site, confirming the assignment of level LU4 to Marine Isotope Stage (MIS) 5. In contrast, AAR analyses produce very scattered ages, pointing to significant post-burial chemical modifications in dentine. A first set of ages is presented for the Cata Litario pit at Sala de los Cíclopes, a palaeontological site formed exclusively of cave bear fossils belonging to the Middle Pleistocene species Ursus deningeri. We provide U-series/ESR and AAR ages for two bear teeth from lithostratigraphic unit LU5, and extended-range luminescence ages for the sediment deposits that host, and immediately underlie and overlie, the bear accumulation. Depositional ages of the sediment were obtained using single-grain thermally-transferred optically stimulated luminescence (TT-OSL) dating of individual quartz grains and post-infrared-infrared stimulated luminescence (pIR-IR) dating of K-feldspars. Several speleothems, both in situ and reworked fragments embedded in the different lithostratigraphic units, have additionally been dated by U-series to constrain the timing of the sequence formation. The results indicate that the sediment originally entered the cave between MIS-12 and MIS-10 (444 ± 28 ka to 367 ± 32 ka). Nevertheless, the AAR and U-series/ESR fossil ages, as well as some of the speleothem fragment ages from LUs 5 and 6 are significantly younger. Leaving aside methodologically questionable results for one of the bear tooth samples, the most reliable AAR and U-Series/ESR ages range from 287 ± 23 ka to 256 ± 24, while the speleothem fragments indicate several formation episodes between 444 ± 19 and 284 ± 8 ka. The apparent difference between the U-Series/ESR ages on the fossils and the luminescence ages on the host sediment are not likely to be wholly explained by uncertainties on uranium uptake modelling or gamma dose rate evaluation, and thus is most likely related to taphonomic processes or a complex site formation history. The presence of fossils and eroded speleothem clasts of younger age within these levels is consistent with either an event of prior erosion, transport and resedimentation of LUs 4, 5 and 6, and/or a complex post-depositional mixing history for the stratigraphic sequence at Cata Litario. This study highlights the importance of using different dating methods to reconstruct reliable chronological frameworks, and to understand the geological factors that can affect the dated materials. This includes the accumulation and taphonomic histories of fossils, post-depositional mixing or reworking processes affecting sediments during the residence time within the karst system. [ABSTRACT FROM AUTHOR]

The subnanometer distance between tip and sample in a scanning tunneling microscope (STM) enables the application of very large electric fields with a strength as high as ∼1 GV/m. This has allowed for efficient electrical driving of Rabi oscillations of a single spin on a surface at a moderate radiofrequency (RF) voltage on the order of tens of millivolts. Here, we demonstrate the creation of dressed states of a single electron spin localized in the STM tunnel junction by using resonant RF driving voltages. The read-out of these dressed states was achieved all electrically by a weakly coupled probe spin. Our work highlights the strength of the atomic-scale geometry inherent to the STM that facilitates the creation and control of dressed states, which are promising for the design of atomic scale quantum devices using individual spins on surfaces.

[Display omitted] • Pd nanoparticles promoted the generation and stabilization of atomic H*. • An atomic H* mediated electrochemical reduction method was applied for removal contaminants from wastewater. • Atomic H* was proved by electrochemical characterizations, HRMS and DFT. • Quantification of transient atomic H* was achieved by double integration of the ESR signal. Electro-generated atomic hydrogen (H*) plays a crucial role in the electrochemical reduction process, serving as the key species that mediates the electrocatalytic hydrogenation reduction of stubborn contaminants in wastewater treatment. However, precisely identifying and quantifying transient atomic H* presents a significant challenge due to its limited lifespan and its existence solely within the boundary layer at the electrode/solution interface. Herein, we developed the electrodeposition of palladium nanoparticles onto carbon cloth and assessed its effectiveness as a cathode for generating and stabilizing atomic H*. The environmental application of atomic H* was validated through the dechlorination of 2, 4-dichlorophenol wastewater and the reduction of antimonite wastewater. Additionally, the identification of atomic H* was verified by electrochemical measurements, high-resolution mass spectra, and density functional theory. Moreover, introducing an excess of a spin trapping agent (5,5-dimethyl-1-pyrroline-N-oxide) and fast in-situ spin trapping facilitated creating favorable conditions for efficient trapping of atomic H* and subsequent electron spin resonance (ESR) spectroscopy quantification analysis. Subsequently, the quantification of atomic H* was achieved by double integration of the ESR signal of spin adduct and comparison with the external standard agent (4-hydroxy-2,2,6,6-tetramethyl-1-piperidine 1-oxyl). This study introduces a novel method for in-situ spin trapping and quantification of atomic H*, facilitating the advancement of electrochemical reduction technology and its application in wastewater treatment. [ABSTRACT FROM AUTHOR]

Spectral diffusion of electron spin polarization plays a key part in dynamic nuclear polarization (DNP). It determines the distribution of polarization across the electron spin resonance (ESR) line and consequently the polarization that is available for transfer to the nuclear spins. Various authors have studied it experimentally by means of electron–electron double resonance (ELDOR) and proposed and used macroscopic models to interpret these experiments. However, microscopic models predicting the rate of spectral diffusion are scarce. The present article is an attempt to fill this gap. It derives a spectral diffusion equation from first principles and uses Monte Carlo simulations to determine the parameters in this equation. The derivation given here builds on an observation made in a previous article on nuclear dipolar relaxation: spectral diffusion is also spatial diffusion and the random distribution of spins in space limits the former. This can be modelled assuming that rapid flip-flop transitions between a spin and its nearest neighbour do not contribute to diffusion of polarization across the ESR spectrum. The present article presents predictions of the spectral diffusion constant and shows that this limitation may lower the spectral diffusion constant by several orders of magnitude. As a check the constant is determined from first principles for a sample containing 40 mM TEMPOL. Including the limitation then results in a value that is close to that obtained from an analysis of previously reported ELDOR experiments. [Display omitted] • Electron spectral diffusion in spin system is also spatial diffusion. • Random spatial distribution of spins decreases spectral diffusion rate. • Decrease modelled by excluding flip-flop transitions with nearest neighbours. • Spins not on speaking terms treated introducing low effective concentration. [ABSTRACT FROM AUTHOR]

This paper reports the structural, optical and thermoluminescence properties of Gd3+ ions incorporated alumino-borosilicate glasses, prepared through the melt-quench technique. The amorphous nature of the glasses is confirmed through XRD study. Network vibrations of borate and silicate groups, vibrations of hydrogen bonding and hydroxyl groups are realized via FTIR study. The Gd3+ transition peaks are absent in the near ultraviolet, visible and NIR regions, and the indirect bandgap values were determined through UV–Visible–NIR study. Photoluminescence measurements showed a concentration quenching in the glasses beyond 1.5 mol % of Gd3+ ions. Based on the thermoluminescence (TL) data, the 2 mol % of Gd 2 O 3 doped glass (BSGD5) was chosen as optimum sample because of the presence of maximum TL intensity. The BSGD5 glass displayed TL response linearity in 0.25–1 kGy dose region giving a high signal sensitivity of 220,068 counts. g−1 kGy−1 in this region. With nearer tissue equivalence and a minimum detectable dose of 0.02 Gy, the suitability of BSGD5 glass for gamma dosimetry application was deducted. Electron spin resonance (ESR) study validated the presence of intrinsic defects in Gd3+ glasses which are responsible for changes in the intensity and shape of TL glow curves. Hence, from the obtained results Gd3+ doped alumino borosilicate glasses can be considered as potential candidates for gamma dosimetry application. • Photoluminescence emission spectra showed a concentration quenching beyond 1.5 mol % of Gd 2 O 3 content. • Thermoluminescence (TL) glow curves exhibited concentration quenching for Gd 2 O 3 > 2 mol % (BSGD5). • BSGD5 glass was selected as optimum glass for TL dosimetry application. • BSGD5 glass displayed TL response linearity in 0.25–1 kGy dose region. • Electron spin resonance (ESR) study validated the presence of intrinsic defects due to Gd3+ doping and gamma irradiation. [ABSTRACT FROM AUTHOR]

The environmental behaviour of neonicotinoid insecticides (NNIs) is of momentous concern due to their frequent detection in aquatic environment and their biotoxicity for non-target organisms. Phototransformation is one of the most significant transformation processes, which is directly related to NNIs exposure and environmental risks. In this study, the photodegradation of dinotefuran (DIN, 1-Methyl-2-nitro-3-(tetrahydro-3-furanylmethyl)-guanidine), one of the most promising NNIs, was conducted under irritated light in the presence of Cl−, DOM along with the effect of pH and initial concentration. The findings demonstrated that in ultra-pure (UP) water, the photolysis rate constants (k) of DIN rose with increasing initial concentration. Whereas, in tap water, at varied pH levels, and in the presence of Cl-, the outcomes were reversed. At the same time, lower concentration of DOM promoted DIN photolysis processes due to the production of reactive oxygen species, while higher concentrations of DOM inhibited the photolysis by the predominance of light shielding effects. The singlet oxygen (1O 2) was produced in the photolysis processes of DIN with Cl− and DOM, which was confirmed by electron spin resonance (EPR) analysis. Four main photolysis products and three intermediates were identified by UPLC-Q-Exactive Orbitrap MS analysis. The possible photodegradation pathways of DIN were proposed including the oxidation by 1O 2 , reduction and hydrolysis after the removal of nitro group from parent compounds. This study expanding our understanding of transformation behavior and fate of NNIs in the aquatic environment, which is essential for estimating their environmental risks. [Display omitted] • The aqueous photodegrability of DIN was investigated under simulated sunlight. • 1O 2 formation was confirmed by electron paramagnetic resonance during photolysis. • Photodegradation pathways were proposed based on structures of four photoproducts. • Cl−, pH, DOM influenced the photolysis rate constants of DIN in different ways. [ABSTRACT FROM AUTHOR]

• Rare-earth (RE = Y, La, Gd, Ho) substituted magnetite based ferrofluids have been prepared. • Crystallite sizes of the magnetic nanoparticles (MNPs) are of the order of 8 nm to 14 nm. • Magnetic measurement reveals superparamagnetic behaviour of the MNPs. • Spin resonance parameters and spin–spin relaxation time are calculated. • Rheological study of the ferrofluids under a shear flow and varying magnetic field has been carried out. In the present study, magnetite based ferrofluids having the composition Fe 3-x RE x O 4 (x = 0.0, 0.06) (RE = Y, La, Gd, Ho) have been prepared using chemical co-precipitation method to study the role of different rare-earth (RE) substitution on the various structural, microstructural, magnetic and rheological properties. X-ray diffraction (XRD) study confirm the spinel structure of the ferrite, which is further supported by fourier transform infrared spectroscopy (FTIR) study. The crystallite sizes of the samples are calculated from the XRD data using Scherrer formula, and found to be in the range 8 nm to 14 nm which is in agreement with the particle size obtained from transmission electron microscope (TEM) study. Dynamic light scattering (DLS) study shows the hydrodynamic particle size in the range 42 nm to 68 nm which is comparatively higher than those obtained from XRD, indicating the presence of aggregates in the ferrofluid samples. Vibrating sample magnetometer (VSM) measurement shows superparamagnetic behaviour for the investigated samples which is desirable for biomedical applications. Various parameters like resonant field (H rf), g-value, peak-to peak linewidth (ΔH pp) and spin–spin relaxation time (T 2) are calculated from the electron spin resonance spectroscopy (ESR) studies. It is observed that ΔH pp decreased with RE substitution indicating improvement in magnetic homogeneity, while the spin–spin relaxation time (T 2) is found to be of the order of picoseconds which points towards their suitability for magnetic resonance applications. Rheological measurements have been performed under a shear rate flow at varying magnetic field to investigate the flow properties of the ferrofluid samples. Shear thinning behaviour with large yield stress is observed in the non-Newtonian fluids. [ABSTRACT FROM AUTHOR]

Nanocrystalline Ni 0.5 Co 0.5 RE 0.03 Fe 1.97 O 4 (RE = Ce, Nd, Gd) were synthesized by glycol-thermal method. Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD) results confirm the formation of single-phase spinel ferrite. The crystallite sizes ranged from 6.29 nm to 9.41 nm which was comparable to results obtained using Williamson-Hall (W–H) method. Lattice parameters were found to vary from 8.356 Å to 8.370 Å depending on an ionic radii of a substituted rare-earth elements. Large specific surface areas ranging between 120 m2/g and 160 m2/g were associated with smaller crystallite sizes. Scanning electron microscope (SEM) revealed homogeneous and clustered nanoparticles. The energy dispersive X-ray (EDS) spectra revealed the existence of nickel (Ni), cobalt (Co), iron (Fe), and oxygen (O) in an undoped sample. The additional characteristic peaks of cerium (Ce), neodymium (Nd) and gadolinium (Gd) were observed for doped samples. The electron spin resonance (ESR) results demonstrated g -values ranging between 3.10 and 3.79 which indicated strong exchange interaction between nanoparticles, type of morphology, and crystalline nature of particles. These high g -values make Ni 0.5 Co 0.5 RE 0.03 Fe 1.97 O 4 (RE = Ce, Nd, Gd) materials suitable for applications in high-frequency devices. The Mössbauer spectroscopy results revealed the formation of broadened Zeeman lines and quadrupole-split lines as well as the presence of the Fe3+ ions at B sites in the samples. [Display omitted] • Ni 0.5 Co 0.5 RE 0.03 Fe 0.197 O 4 (RE = Ce, Nd, Gd) nanoferrites were synthesized by glycol-thermal process. • XRD and FTIR confirmed the single-phase formation and cubic spinel structure. • Large ESR parameters make these materials suitable for applications in high-frequency devices. • Mössbauer results revealed presence of paramagnetic state. [ABSTRACT FROM AUTHOR]

Oleogels are made by structuring oils with an oleogelator, e.g., ethyl cellulose (EC), and can be used as fat replacers in foods. Also, oleogels made from oils rich in bioactives, e.g., tucumã oil (TCO), could possess additional nutritional benefits. However, sensitive compounds are often degraded during the harsh conditions of most oleogelation procedures. Here we present an adapted low-temperature indirect method (IM) to structure TCO with EC, which is based on emulsification with aqueous ethanol as continuous phase, and the physicochemical properties are compared to oleogels with the same composition but produced by a direct method (DM) at high temperature. For IM, TCO was emulsified with EC ethanolic dispersions, followed by solvent removal and shearing. DM resulted in weak gels (G' < 10000 Pa), with low oil binding capacity (OBC) (12.63–66.26%), low carotenoid retention (CR) (20.7–31.6%) and complete depletion of α-tocopherol. Conversely, IM provided strong oleogels (G' > 10000 Pa), with high OBC (87.82–100.04%), CR (>95%) and α-tocopherol content (293–322 mg/kg). TCO oleogels with different physical properties and retention of sensitive compounds were obtained by DM and IM, showing the potential of IM oleogelation to preserve bioactives in the oleogels and producing healthier fat alternatives for the food industry. • First report of tucumã oil oleogels produced by direct and indirect methods. • Effective use of ethyl cellulose as oleogelator in emulsion-templated oleogelation. • Strong oleogels with high retention of bioactives were obtained by indirect gelation. • Weak oleogels prepared directly showed great loss of carotenoids and α-tocopherol. [ABSTRACT FROM AUTHOR]

• Ultrasonic irradiation of carbonated water generated long-lived nanobubbles (NBs). • NB suspension and its atomized mist showed strong, durable bactericidal activity. • The bactericidal activity was attributed to NBs filled with high-pressure CO 2 gas. • A mechanism was proposed for reactive oxygen species generation from the NBs. Our previous study showed that nanobubbles (NBs) encapsulating CO 2 gas have bactericidal activity due to reactive oxygen species (ROS) (Yamaguchi et al., 2020). Here, we report that bulk NBs encapsulating CO 2 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 CO 2 molecules strongly interact with water at the NB interface to weaken the interface, and high-pressure CO 2 gas erupts from this weakened interface to generate ROS with bactericidal activity. [ABSTRACT FROM AUTHOR]

[Display omitted] • The oxidative stability of fish oil-loaded capsules was studied by ESR-spin trapping. • The oxygen permeability of MCT oil-loaded capsules was investigated by ESR-oximetry. • Electrosprayed capsules oxidized faster than spray-dried capsules. • Spray-dried capsules had low oxygen permeability through the encapsulating wall. • The oxidative stability of the capsules correlated well with their oxygen permeability. The oxidative stability and the oxygen permeability of oil-loaded capsules were investigated by Electron Spin Resonance (ESR). The capsules were produced by spray-drying or electrospraying in the monoaxial or coaxial configuration using glucose syrup as the encapsulating agent. ESR-spin trapping results showed that electrosprayed capsules oxidized faster and during the early stages of incubation, irrespective of the emitter configuration (monoaxial or coaxial), when compared to those produced by spray-drying. Furthermore, ESR oximetry showed that oxygen inside the spray-dried capsules reached equilibrium with the surrounding atmosphere significantly slower than the monoaxially electrosprayed capsules (i.e., ∼2h and ∼10 min, respectively). These findings have been attributed to the larger particle size of the spray-dried capsules influencing the oxygen diffusion area (i.e., lower surface-to-volume ratio) and diffusion path (i.e., thicker encapsulating wall for a fixed oil load). Together, the lower oxygen uptake reported for the spray-dried capsules correlated well with their higher oxidative stability. [ABSTRACT FROM AUTHOR]

Radicals produced in alanine by irradiation of 2–7 keV X-rays were investigated by ESR applications; i.e., CW-ESR, pulse-ESR and ESR imaging. The relative radical yield decreased with the decreasing photon energy and the increasing dose. The 2D imaging showed that the radical concentration at the surface was extremely low even though the absorption of X-rays exponentially decreased with the penetration depth. The depth of the radical concentration peak was almost the same as the penetration depth for the X-ray irradiation with an energy lower than 5-keV. The product formed by radical recombination was observed by an LC/MS (liquid chromatograph-mass spectrum) analysis. For the soft X-ray irradiation, many radicals will be lost by the efficient radical-radical recombination due to the higher density of the radicals, similar to the high-LET irradiation by heavy ions. The spin-spin relaxation rate (1/T 2), which correlates with the radical concentration, increased by the decreasing photon energy. The values of 1/T 2 for the soft X-rays were compatible to that for the heavy ions with the high-LET. Based on these observations, it is concluded that the effects of irradiation by soft X-rays are similar to high-LET irradiation. • The relative radical yield from soft X-rays decreased with decreasing photon energy. • The radical concentration at the surface was much lower than the energy dispersion. • The spin-spin relaxation rate increased with decreasing photon energy. • The product formed from the radical recombination was observed by LC/MS analysis. • The effects of irradiation by soft X-rays are similar to high-LET irradiation. [ABSTRACT FROM AUTHOR]

Artificial organelles (AnOs) are in the spotlight as systems to supplement biochemical pathways in cells. While polymersome-based artificial organelles containing enzymes to reduce reactive oxygen species (ROS) are known, applications requiring control of their enzymatic activity and cell-targeting to promote intracellular ROS detoxification are underexplored. Here, we introduce advanced AnOs where the chemical composition of the membrane supports the insertion of pore-forming melittin, enabling molecular exchange between the AnO cavity and the environment, while the encapsulated lactoperoxidase (LPO) maintains its catalytic function. We show that H 2 O 2 outside AnOs penetrates through the melittin pores and is rapidly degraded by the encapsulated enzyme. As surface attachment of cell-penetrating peptides facilitates AnOs uptake by cells, electron spin resonance revealed a remarkable enhancement in intracellular ROS detoxification by these cell-targeted AnOs compared to nontargeted AnOs, thereby opening new avenues for a significant reduction of oxidative stress in cells.

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 E a 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 E a 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., Competing Interests: The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Li Yongfu reports financial support was provided by Guizhou Provincial Basic Research Program (Natural Science). Li Yongfu reports a relationship with Guizhou Provincial Basic Research Program (Natural Science) that includes: funding grants. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2024 The Authors.)