Electronic Resonance Research Articles

Rapid Analysis of DEER Signals Including Short Distances.

Double electron electron resonance (DEER) spectroscopy is an important technique to measure distance distributions P(r) for studying protein structures and protein-protein interactions. DEER data analysis can at times become challenging due to the lack of a detailed analytical signal expression or numerical methods with rapid computation time. We have derived an analytical expression κFULL, which includes both the pseudo-secular dipolar coupling (PSDC) and the finite pulse effects, especially important for shorter distances. Analyses of experiments by κFULL yield accurate and consistent P(r) values for three DEER nitroxide-rulers with distances (rAVG) in the range of 15 to 32 Å, while the current standard analysis produces erroneous results for rAVG < 20 Å. Computation times for deriving P(r) vary between 1 min and 4 min, which is usually much shorter than previous methods that include pseudo-secular and other effects. The expression can be applied to all types of DEER spin probes with little or no modifications.

Quantification of Rapid Cooling of Glycerol/Water Solutions Based on Photoluminescence from Thioflavin T.

Rapid cooling to a solid state allows intermediates in chemical and biomolecular processes that occur in solution near room temperature to be trapped for subsequent measurements by magnetic resonance spectroscopies, electron microscopy, or other techniques. In time-resolved solid state nuclear magnetic resonance and rapid freeze-quench electron paramagnetic resonance studies, solutions are typically frozen by spraying into a cold bath or onto a cold metal surface. Although simulations suggest freezing on millisecond or submillisecond time scales, direct experimental measurements of cooling rates have been elusive. Here, we describe a method for quantification of rapid cooling rates based on measurements of temperature-dependent photoluminescence from thioflavin T (ThT). In our experiments, a jet of ThT solution in glycerol/water, with 10.8 m/s jet velocity and 30 μm diameter, freezes on a cold, rotating copper surface. Images of ThT photoluminescence on the copper surface indicate that the cooling rate of the solution increases linearly with the surface velocity over the 0.45-6.2 m/s range. At surface velocities greater than 3.8 m/s, the time to cool from 300 to 260 K or from 300 to 230 K is less than 100 μs or less than 700 μs. The experimental results do not agree quantitatively with calculations in which a layer of glycerol/water cools by thermal conduction when suddenly brought in contact with a cold copper surface. Discrepancies between experimental results and simplistic calculations illustrate the importance of direct measurements of cooling rates.

Electroless Synthesis of Cobalt Nanowires in Magnetic Field and their Characterization by Resonant Magnetometry Methods

In this paper, a simple and effective low-temperature electroless chemical method that provides the synthesis of cobalt micro- and nanowires due to the processes of self-organization of magnetic cobalt nanoparticles under the influence of a magnetic field, using the technology of chemical synthesis of magnetic nanoparticles and nanowires is proposed. Cobalt nanoparticles have magnetic dipole moments. An external magnetic field forces them to be oriented parallel to it. Dipole-dipole interactions between magnetic nanoparticles lead to attraction between cobalt nanoparticles leading to their self-organization into nanowires, reducing their total energy. The resulting smaller nanoparticles fill the gaps between the ordered nanoparticles, leading to the formation of smooth cobalt nanowires. The magnetic and structural properties of the synthesized and commercial nanowires polarized by a magnetic field in the epoxy matrix were studied using the resonant radio-frequency magnetometry and electron microscopy methods. These methods are of interest for optimizing the coercive force of cobalt nanowires with a view to their possible use in creating permanent magnets that do not use rare earth elements, as well as in information processing devices and sensors.

Low‐Frequency Whistler Waves Excited by Electron Butterfly Distributions in Turbulent Reconnection Outflow

AbstractWhistler waves, leading to electron scattering and energy transport, are frequently observed in magnetic reconnection. High‐energy electrons produced by magnetic reconnection are expected to excite low‐frequency whistler waves. However, the study on low‐frequency whistler waves in magnetic reconnection is still quite scarce. Utilizing high‐resolution data from the Magnetospheric Multiscale (MMS) mission, we provide observations of low‐frequency whistler waves in a turbulent reconnection outflow. The quasi‐antiparallel propagating whistler waves have power peaked at ∼0.1 and wave number of ∼0.43 in the plasma rest frame. It can be excited through the cyclotron resonance by the electron butterfly distributions, which can be interpreted by a model comprising the addition of electron beams hosting perpendicular anisotropy to electron isotropy distributions. The energy of resonant electrons is calculated as 1.06∼4.16 keV, the parts corresponding to lower frequency (&lt;∼0.1) falling into suprathermal energy range. Our study can promote the understanding of generation of whistler waves in magnetic reconnection.

Real-Time TDDFT Using Noncollinear Functionals.

Recently, we proposed a method to generalize collinear functionals to noncollinear functionals, called multicollinear approach, which has been applied in density functional theory (DFT) and linear-response time-dependent DFT (TDDFT) for the ground state and excited states calculations, respectively. In this work, we demonstrate the application of this method in real-time TDDFT by simulating electronic absorption spectra, Rabi resonance, and precession of a two-magnetic center system. Thanks to the nonvanishing local exchange-correlation torque provided by multicollinear functionals, research into the torques in the evolution of magnetization vector is carried out, which is useful for the exploration on spin dynamics.

New eco-friendly succinimide linseed oil resin: synthesis, characterization, DFT and docking studies for surface coating

Purpose The purpose of this study is to develop a new protective coating formulation for industrial use, using new eco-friendly succinimide linseed oil resin. Design/methodology/approach Epoxidized linseed oil and N-(4-hydroxy phenyl) succinimide are reacted to create succinimide-modified epoxy (SIE) compounds. The synthesized compound was confirmed by different analyses, gas chromatography, Fourier transform infrared, proton nuclear magnetic resonance and scanning electron microscopy. The prepared compound has been blended with a primer paint formulation, then their physical and mechanical properties have been studied. Density function theory is used to calculate Frontier molecular orbital including highest occupied molecular orbital and least unoccupied molecular orbital to indicate the charge transfer from molecule to biological media and molecular electrostatic potential map was used to indicate the chemically reactive zone suitable for drug action. Findings The results of the paint formulation confirmed their best performance and provided good mechanical properties and high chemical and corrosion resistance. Research limitations/implications Resin compounds are the most used antimicrobial additives. Other functionalities of these compounds, such as corrosion inhibitors, might be studied to see if they are suited for these applications. Practical implications Because of the efficiency of the SIE when incorporated with primer, paint against microbial has also been examined in silico using the docking study which contributed to the analysis of their protein binding. This type of epoxy compound is environmentally friendly and can be used as a biocide with different paint formulations. As a result, paint compositions including this compound as additives can be used as dual-purpose paint and for a variety of industrial applications. Originality/value This research demonstrates how a low-cost paint composition based on synthesized SIE compounds may be used as a dual-function paint for industrial use.

Model-predictive kinetic control with data-driven models on EAST

Abstract In this work, model-predictive control (MPC) was combined for the first time with singular perturbation theory, and an original plasma kinetic control method based on extremely simple data-driven models and a two-time-scale MPC algorithm has been developed. A comprehensive review is presented in this paper. Slow and fast semi-empirical models are identified from data, by considering the fast kinetic plasma dynamics as a singular perturbation of a quasi-static equilibrium, which itself is governed, on the slow time scale, by the flux diffusion equation. This control technique takes advantage of the large ratio between the time scales involved in magnetic and kinetic plasma transport. It is applied here to the simultaneous control of the safety factor profile, q(x), and of several kinetic variables, such as the poloidal beta parameter, βp, and the internal inductance parameter, li, on the EAST tokamak. In the experiments, the available control actuators were lower hybrid current drive (LHCD) and co-current neutral beam injection (NBI) from different sources. Ion cyclotron resonant heating (ICRH) and electron cyclotron resonant heating (ECRH) are used as additional actuators in control simulations. In the controller design, an observer provides, in real time, an estimate of the system states and of the mismatch between measured and predicted outputs, which ensures robustness to model errors and offset-free control. A number of control applications are described in the paper, either in nonlinear simulations with EAST-like parameters or in real experiments on EAST. Various controller configurations were tested, with up to three controlled variables chosen among q0 = q(x=0), q1 = q(x=0.5), βp and li. Both the extensive nonlinear simulations and the experiments described in this paper have demonstrated the relevance of combining model-predictive control, data-driven models and singular perturbation methods for plasma kinetic control.

Spin polarization effect on linear polarization of photon emission following resonant electron capture of lithiumlike ions

Spin polarization effect on linear polarization of photon emission following resonant electron capture of lithiumlike ions

Crop resilience enhancement through chitosan-based hydrogels as a sustainable solution for water-limited environments

Frequent droughts significantly affect agricultural productivity and highlight the need for effective solutions to improve water availability for crops. This study investigates the potential of chitosan-based hydrogels, biodegradable biopolymers known for their water-retaining properties, to improve soil moisture and promote plant growth during drought periods. Chitosan hydrogels were synthesized using Pluronic F127 and compared with chitosan and chitosan in combination with sodium alginate (CS/Alg-Na). Comprehensive chemical characterizations were performed by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR) and field emission scanning electron microscopy (FESEM). The CS/Pl-F127 hydrogels showed high porosity and a water absorption capacity of 81.5 %, while the CS/Alg-Na exhibited a denser network with a capacity of 93.35 % and improved mechanical strength. Plants in the CS/Pl-F127 hydrogel had a shoot elongation rate of 5.9 mm/day on Day 9, which continued until Day 40. In contrast, shoot elongation in the CS/Alg-Na hydrogel peaked at 7.1 mm/day on Day 20 and maintained growth under drought conditions until Day 33. These results show that all chitosan-based hydrogels improve water use efficiency. CS/Alg-Na provides the best support for plant growth under drought conditions, followed by CS/Pl-F127 and pure chitosan.

Experimental study on mechanical and durability properties of concrete incorporating various polyvinyl alcohol fiber lengths and dosages

To inquire about the properties of concrete reinforced with polyvinyl alcohol (PVA) fiber (various fiber lengths and dosages), different experimental tests including mechanical property, cracking resistance, and chloride resistance were investigated. The overall performance of PVA fiber-reinforced concrete (FRC) was innovatively analyzed integrating mechanical indicators and crack resistance parameters. Furthermore, nuclear magnetic resonance (NMR) and scanning electron microscope (SEM) were selected to analyze the causes and mechanisms underlying the alterations in the performance of PVA-FRC. The experimental results demonstrate that the flexural strength, the crack resistance characteristic and chloride ion penetration resistance of PVA-FRC are significantly improved compared to ordinary concrete. Increasing fiber length plays a key role in flexural strength, compared with fiber dosage. Considering both mechanical properties and durability, PVA-FRC containing 0.25% volume fraction of 12 mm PVA fibers (F12-0.25) demonstrated optimal performance.

MEMS Precision Sensors Based on Process Innovation Technology

This article introduces a novel process for achieving micro-scale thermal isolation through solid porous 3D microstructures. It proposes a method to improve existing thermal MEMS devices by utilizing thin-film membrane structures, develops a model for estimating the thermal conductivity of porous microstructures, and constructs porous 3D microstructures made of three different powder materials, studying their applicability for thermal isolation. Breakthroughs have been achieved in process preparation technology, enabling the production of precision MEMS sensors. These sensors are expected to find wide applications in smart cars, intelligent healthcare, electronic resonance sensors, and other fields.

Eustigmatophyte model of red-shifted chlorophyll a absorption in light-harvesting complexes

Photosynthetic organisms harvest light for energy. Some eukaryotic algae have specialized in harvesting far-red light by tuning chlorophyll a absorption through a mechanism still to be elucidated. Here, we combined optically detected magnetic resonance and pulsed electron paramagnetic resonance measurements on red-adapted light-harvesting complexes, rVCP, isolated from the freshwater eustigmatophyte alga Trachydiscus minutus to identify the location of the pigments responsible for this remarkable adaptation. The pigments have been found to belong to an excitonic cluster of chlorophylls a at the core of the complex, close to the central carotenoids in L1/L2 sites. A pair of structural features of the Chl a403/a603 binding site, namely the histidine-to-asparagine substitution in the magnesium-ligation residue and the small size of the amino acid at the i-4 position, resulting in a [A/G]xxxN motif, are proposed to be the origin of this trait. Phylogenetic analysis of various eukaryotic red antennae identified several potential LHCs that could share this tuning mechanism. This knowledge of the red light acclimation mechanism in algae is a step towards rational design of algal strains in order to enhance light capture and efficiency in large-scale biotechnology applications.

Structure-Function Correlation in Cobalt-Induced Brain Toxicity.

Cobalt toxicity is difficult to detect and therefore often underdiagnosed. The aim of this study was to explore the pathophysiology of cobalt-induced oxidative stress in the brain and its impact on structure and function. Thirty-five wild-type C57B16 mice received intraperitoneal cobalt chloride injections: a single high dose with evaluations at 24, 48, and 72 h (n = 5, each) or daily low doses for 28 (n = 5) or 56 days (n = 15). A part of the 56-day group also received minocycline (n = 5), while 10 mice served as controls. Behavioral changes were evaluated, and cobalt levels in tissues were measured with particle-induced X-ray emission. Brain sections underwent magnetic resonance imaging (MRI), electron microscopy, and histological, immunohistochemical, and molecular analyses. High-dose cobalt caused transient illness, whereas chronic daily low-dose administration led to long-term elevations in cobalt levels accompanied by brain inflammation. Significant neurodegeneration was evidenced by demyelination, increased blood-brain barrier permeability, and mitochondrial dysfunction. Treated mice exhibited extended latency periods in the Morris water maze test and heightened anxiety in the open field test. Minocycline partially mitigated brain injury. The observed signs of neurodegeneration were dose- and time-dependent. The neurotoxicity after acute exposure was reversible, but the neurological and functional changes following chronic cobalt administration were not.

Exploring electronic resonances in pyridine: Insights from orbital stabilization techniques.

Electron attachment to pyridine results in electronic resonances, metastable states that can decay through electronic or nuclear degrees of freedom. This study uses orbital stabilization techniques combined with bound electronic structure methods, based on equation of motion coupled cluster or multi-reference methods, to calculate positions and widths of electronic resonances in pyridine that exist below 10eV. We report four 2B1 and four 2A2 resonances, including one 2B1 not previously reported experimentally and two 2A2 resonances not reported at all in the literature. The two lower energy resonances are one-particle shape resonances, while the remaining are mixed or primarily core-excited resonances. Multi-reference perturbation theory provides the best description of these resonances, especially when their character is mixed. We describe the character of these resonances qualitatively and calculate Dyson orbitals, which provide information about their decay channels.

Triad photosensitizers based on iodo-aza-Bodipy and naphthalenediimides (NDI) with broadband absorption: Study of resonance energy transfer and electron transfer

Two organic photosensitizers based on resonance energy transfer (A-1 and A-2) are prepared. Naphthalenediimides was used as intramolecular energy donor and iodo-aza-Bodipy was used as intramolecular energy acceptor/spin converter. A-1 (ε = 42,800 at 618 nm and ε = 59,600 at 674 nm) and A-2 (ε = 33,300 at 514 nm and ε = 68,300 at 674 nm) give the two strong absorption band and both of them show broadband absorption in visible region. The photophysical properties of the compounds were studied with steady state and time-resolved spectroscopy in detail. With steady state and time-resolved spectroscopy, we found that photoexcitation into the energy donor was followed by singlet energy transfer, then via the intersystem crossing (ISC) of the energy acceptor. By nanosecond time-resolved transient absorption spectroscopy and DFT calculation, triplet excited state is localized on the iodo-aza-Bodipy moiety. Quantum yield of singlet oxygen of A-1 and A-2 is 39.7 % and 40.9 %, respectively. Based on fluorescence lifetime quenching, the efficiency of intramolecular energy transfer is estimated to be 15.9 % and 27.7 % for A-1 and A-2. And PET is responsible for the relatively low efficiency, which is identified by the calculation of kcs/kFRET and the Gibbs free energy change (△G0cs). A-1 and A-2 were used for singlet oxygen (1O2) mediated photooxidation of 1,5-dihydroxylnaphthalene and the photosensitizing ability are more efficient than the triplet photosensitizers with the mono-chromophore photosensitizer.

Attosecond formation of charge-transfer-to-solvent states of aqueous ions probed using the core-hole-clock technique

Charge transfer between molecules lies at the heart of many chemical processes. Here, we focus on the ultrafast electron dynamics associated with the formation of charge-transfer-to-solvent (CTTS) states following X-ray absorption in aqueous solutions of Na+, Mg2+, and Al3+ ions. To explore the formation of such states in the aqueous phase, liquid-jet photoemission spectroscopy is employed. Using the core-hole-clock method, based on Auger–Meitner (AM) decay upon 1s excitation or ionization of the respective ions, upper limits are estimated for the metal-atom electron delocalization times to the neighboring water molecules. These delocalization processes represent the first steps in the formation of hydrated electrons, which are determined to take place on a timescale ranging from several hundred attoseconds (as) below the 1s ionization threshold to only 20 as far above the 1s ionization threshold. The decrease in the delocalization times as a function of the photon energy is continuous. This indicates that the excited electrons remain in the vicinity of the studied ions even above the ionization threshold, i.e., metal-ion electronic resonances associated with the CTTS state manifolds are formed. The three studied isoelectronic ions exhibit quantitative differences in their electron energetics and delocalization times, which are linked to the character of the respective excited states.

Electric Field-Induced Enhanced Raman Spectroscopy Sensor and Photocatalysis with Thermoelectric-Plasmonic Metal Nanocomposites.

Electric field-induced surface-enhanced Raman scattering (E-SERS) substrates have been proven to further enhance the attained Raman intensity. Herein, integrated with plasmonic Ag nanoparticles (Ag NPs), the thermoelectric Bi2Te3 plate as an E-SERS substrate decreased the limit of detection by 2 orders of magnitude and increased the SERS signal by >20 times compared to those without electrical field induction. The thermoelectric potential produced by the Bi2Te3 plate could modulate the electron density and subsequently change the Fermi level of Ag. This increases the resonant electron transition probability using a broad range of molecules. The plasmon-activated catalytic reactions of the interconversion between p-nitrothiophenol and p,p'-dimercaptoazobenzene could be controlled through the E-SERS template. On the basis of the finite element method, explicit theoretical analysis indicated that the Ag NP-Bi2Te3-molecule charge transfer could improve our understanding of the SERS and photocatalytic mechanism.

A bis-Phenolate Carbene-Supported bis-μ-Oxo Iron(IV/IV) Complex with a [FeIV(μ-O)2FeIV] Diamond Core Derived from Dioxygen Activation.

The diiron(II) complex, [(OCO)Fe(MeCN)]2 (1, MeCN = acetonitrile), supported by the bis-phenolate carbene pincer ligand, 1,3-bis(3,5-di-tert-butyl-2-hydroxyphenyl)benzimidazolin-2-ylidene (OCO), was synthesized and characterized by single-crystal X-ray diffraction, 1H nuclear magnetic resonance, infrared (IR) vibrational, ultraviolet/visible/near-infrared (UV/vis/NIR) electronic absorption, 57Fe Mössbauer, X-band electron paramagnetic resonance (EPR) and SQUID magnetization measurements. Complex 1 activates dioxygen to yield the diferric, μ-oxo-bridged complex [(OCO)Fe(py)(μ-O)Fe(O(C═O)O)(py)] (2) that was isolated and fully characterized. In 2, one of the iron-carbene bonds was oxidized to give a urea motif, resulting in an O(CNHC═O)O binding site, while the other Fe(OCO) unit remained unchanged. When the reaction is performed at -80 °C, an intensively colored, purple intermediate is observed (INT, λmax = 570 nm; ε = 5600 mol L-1 cm-1). INT acts as a sluggish oxidant, reacting only with easily oxidizable substrates, such as PPh3 or 2-phenylpropionic aldehyde (2-PPA). The identity of INT can be best described as a dinuclear complex containing a closed diamond core motif [(OCO)FeIV(μ-O)2FeIV(OCO)]. This proposal is based on extensive spectroscopic [UV/vis/NIR electronic absorption, 57Fe Mössbauer, X-band EPR, resonance Raman (rRaman), X-ray absorption, and nuclear resonance vibrational (NRVS)] and computational studies. The conversion of the diiron(II) complex 1 to the oxo diiron(IV) intermediate INT is reminiscent of the O2 activation process in soluble methane monooxygenases (sMMO). Most importantly, the low reactivity of INT supports the consensus that the [FeIV(μ-O)2FeIV] diamond core in sMMO is kinetically inert and needs to open up to terminal FeIV═O cores to react with the strong C-H bonds of methane.

Reinterpreting radio frequency heating and current drive theory in a tokamak

Quasilinear treatments are widely used for tokamaks to evaluate radio frequency (rf) heating and current drive. Even though the core of a tokamak plasma is weakly collisional, the solution of the linearized kinetic equation is evaluated using unperturbed collisionless trajectories while often treating successive poloidal circuits of the passing (and trapped) particles as uncorrelated or nearly so. In addition, the most important effect of tokamak geometry, the mirror force, is usually mistreated or ignored when obtaining the solution. These concerning aspects of rf treatments are clarified by considering lower hybrid heating and current drive to illustrate that the electrons in resonance with the applied rf are enclosed by narrow collisional boundary layers, and that tokamak geometry makes it necessary to retain poloidal variation when solving a weakly collisional linearized kinetic equation. Other aspects such as collisional boundary layers at the trapped–passing boundary, cyclotron resonances, and the limitations of quasilinear theory are also considered. The new insights lead to a fundamentally different formulation and interpretation of the solution of the linearized Fokker–Planck equation used for rf quasilinear theory in a tokamak, while retaining many of the features that have contributed to its successful application to rf heating and current drive.

Gal-3 blocks the binding between PD-1 and pembrolizumab

IntroductionImmune checkpoint inhibitors (ICI) have revolutionized the treatment of metastatic malignant melanoma (MM) and improved long-term survival. Despite the impressive results, some patients still have progressive disease, and the search...