Electronic Resonance Research Articles

Resonances in electron scattering from H2 around the H(2l) + H−(1s2) dissociation limit

We have performed high-level R-matrix scattering calculations to identify and characterise the resonances potentially involved in dissociative electron attachment (DEA) of H2 at around 14.5 eV. DEA experiments (Krishnakumar et al 2018 Nat. Phys. 4 149) indicate an asymmetric production of H− around this scattering energy that can only be explained if more than one resonance is involved in the process. The theoretical description of the anion distribution requires accurate data (energy and lifetime) for the resonances involved, currently missing from the literature. We attempt to provide these data for all the resonances identified in the appropriate energy range for bond lengths 1.1 a 0 to 4.0 a 0. Our resonance results are insufficient to confirm the validity of a simple model of anion yield asymmetry used to reproduce the experimental results.

Solar Gas-Phase CO2 Hydrogenation by Multifunctional UiO-66 Photocatalysts.

Solar-assisted CO2 conversion into fuels and chemical products involves a range of technologies aimed at driving industrial decarbonization methods. In this work, we report on the development of a series of multifunctional metal-organic frameworks (MOFs) based on nitro- or amino-functionalized UiO-66(M) (M: Zr or Zr/Ti) supported RuOx NPs as photocatalysts, having different energy band level diagrams, for CO2 hydrogenation under simulated concentrated sunlight irradiation. RuOx(1 wt %; 2.2 ± 0.9 nm)@UiO-66(Zr/Ti)-NO2 was found to be a reusable photocatalyst, to be selective for CO2 methanation (5.03 mmol g-1 after 22 h;, apparent quantum yield at 350, 400, and 600 nm of 1.67, 0.25, and 0.01%, respectively), and to show about 3-6 times activity compared with previous investigations. The photocatalysts were characterized by advanced spectroscopic techniques like femto- and nanosecond transient absorption, spin electron resonance, and photoluminescence spectroscopies together with (photo)electrochemical measurements. The photocatalytic CO2 methanation mechanism was assessed by operando FTIR spectroscopy. The results indicate that the most active photocatalyst operates under a dual photochemical and photothermal mechanism. This investigation shows the potential of multifunctional MOFs as photocatalysts for solar-driven CO2 recycling.

Hybrid Moiré Excitons and Trions in Twisted MoTe2-MoSe2 Heterobilayers.

We report experimental and theoretical studies of MoTe2-MoSe2 heterobilayers with rigid moiré superlattices controlled by the twist angle. Using an effective continuum model that combines resonant interlayer electron tunneling with stacking-dependent moiré potentials, we identify the nature of moiré excitons and the dependence of their energies, oscillator strengths, and Landé g-factors on the twist angle. Within the same framework, we interpret distinct signatures of bound complexes among electrons and moiré excitons in nearly collinear heterostacks. Our work provides a fundamental understanding of hybrid moiré excitons and trions in MoTe2-MoSe2 heterobilayers and establishes the material system as a prime candidate for optical studies of correlated phenomena in moiré lattices.

Ligand efficacy modulates conformational dynamics of the µ-opioid receptor

The µ-opioid receptor (µOR) is an important target for pain management1 and molecular understanding of drug action on µOR will facilitate the development of better therapeutics. Here we show, using double electron–electron resonance and single-molecule fluorescence resonance energy transfer, how ligand-specific conformational changes of µOR translate into a broad range of intrinsic efficacies at the transducer level. We identify several conformations of the cytoplasmic face of the receptor that interconvert on different timescales, including a pre-activated conformation that is capable of G-protein binding, and a fully activated conformation that markedly reduces GDP affinity within the ternary complex. Interaction of β-arrestin-1 with the μOR core binding site appears less specific and occurs with much lower affinity than binding of Gi.

Four Parallel Pathways in T4 Ligase-Catalyzed Repair of Nicked DNA with Diverse Bending Angles.

The structural diversity of biological macromolecules in different environments contributes complexity to enzymological processes vital for cellular functions. Fluorescence resonance energy transfer and electron microscopy are used to investigate the enzymatic reaction of T4 DNA ligase catalyzing the ligation of nicked DNA. The data show that both the ligase-AMP complex and the ligase-AMP-DNA complex can have four conformations. This finding suggests the parallel occurrence of four ligation reaction pathways, each characterized by specific conformations of the ligase-AMP complex that persist in the ligase-AMP-DNA complex. Notably, these complexes have DNA bending angles of ≈0°, 20°, 60°, or 100°. The mechanism of parallel reactions challenges the conventional notion of simple sequential reaction steps occurring among multiple conformations. The results provide insights into the dynamic conformational changes and the versatile attributes of T4 DNA ligase and suggest that the parallel multiple reaction pathways may correspond to diverse T4 DNA ligase functions. This mechanism may potentially have evolved as an adaptive strategy across evolutionary history to navigate complex environments.

Mechanical Properties and Sulfate Freeze–Thaw Resistance of Calcium Carbonate Whisker-Reinforced Iron Ore Tailings Concrete

Iron ore tailings from iron ore mines pose environmental challenges. However, their reuse could provide significant environmental benefits. This study focused on producing clean concrete using iron ore tailings as crushed stone aggregate (IOTA) and calcium carbonate whiskers (CWs) as reinforcement. Five mixture groups were prepared: normal concrete (NAC) with natural crushed stone aggregate (NA), iron ore tailings concrete (TAC) with IOTA, and CW (10%, 20%, and 30%)-reinforced TAC (TAC-CW). Mechanical properties like the compressive strength (fcu) and splitting tensile strength (fst), as well as sulfate freeze–thaw (F-T) cycle resistance, were thoroughly investigated. Additionally, pore structure and microstructure were characterized using nuclear magnetic resonance (NMR) and scanning electron microscopy (SEM) techniques. The results showed that IOTA’s complete replacement of NA decreased concrete mechanical properties and frost resistance, but incorporating CWs effectively compensated for these losses. Specifically, the fcu and fst of TAC-CW20 with 20% CWs increased by 23.26% and 49.6% compared to TAC and were higher than those of NAC. With increasing F-T cycles, concrete internal pore structure significantly deteriorated, and corrosive products increased significantly, which was further confirmed by SEM. TAC-CW20 significantly optimized pore structure. Overall, the successful application of iron ore tailings as eco-friendly materials enhanced concrete performance and reduced the environmental impact of construction activities.

Studying Structure and Functions of Nucleosomes with Atomic Force Microscopy.

Chromatin is an epigenetic platform for implementation of DNA-dependent processes. Nucleosome, as a basic level of chromatin compaction, largely determines its properties and structure. In the study of nucleosomes structure and functions physicochemical tools are actively used, such as magnetic and optical "tweezers", "DNA curtains", nuclear magnetic resonance, X-ray crystallography, and cryogenic electron microscopy, as well as optical methods based on Förster resonance energy transfer. Despite the fact that these approaches make it possible to determine a wide range of structural and functional characteristics of chromatin and nucleosomes with high spatial and time resolution, atomic force microscopy (AFM) complements the capabilities of these methods. The results of structural studies of nucleosome focusing on the AFM method development are presented in this review. The possibilities of AFM are considered in the context of application of other physicochemical approaches.

DFT and EPR study of spin-assisted processes in poly(3-alkylthiophene) oligomers and their composites

Correlations of spin, electronic and magnetic resonance parameters of charge carriers stabilized in poly(3-alkylthiophene) oligomers with their band structure, polymerization degree, side substitutes, and conformation established by using the density functional theory and electron paramagnetic resonance methods. The comparison of calculated and experimental data identified spin distribution on oligomer chains with different conformations. The type and size of alkyl substituent of polymer matrix governs the band gap, mobility, and spin-orbit coupling of polaron charge carriers. The introduce of small aromatic additives between oligomer chains initiates their self-assembly crystallization and formation of organic:organic spinterfase which accelerate spin-assisted electronic and magnetic processes in the composite. The research revealed that embedding aromatic hydrocarbons into oligomer bulk allows continuous and discrete handling of electronic spin-assisted processes carrying out in respective organic/organic composites. The key role of spinterfacial effects in the development of a new generation of molecular devices with actively tuned spin-assisted functionality is described.

Colorimetric detection of Fe2+ and Cr2O72− in environmental water samples based on dual-emitting RhB-embedded Zr-MOFs

Three dye-loaded tunable dual-emission colorimetric fluorescent probes RhB@UiO-66-Ph (R@U-P) were prepared by in-situ encapsulation method under solvothermal conditions. The resonance energy transfer between UiO-66-Ph and RhB made the dual emission of R@U-P easily tunable with the embedded dye content changing. The R@U-P composites achieved emission from purple light to red light, and served as probes to realize comparative detection of Fe3+, Fe2+ and Cr2O72− in water through colorimetric or quenching detection mode. Mechanism study indicates that the resonance energy transfer or electron transfer interactions between R@U-P composites and inorganic ions resulted in the relative changes of the two emission peaks and realized the selective detection of analytes. The preparation and application of R@U-P probes provide a promising strategy for the in-situ encapsulation dye to obtain two dual-emission composites for the comparative detection of Fe3+, Fe2+ and Cr2O72− in water samples.

Resonant electron capture by polycyclic aromatic hydrocarbon molecules: Effects of aza-substitution.

Resonant electron capture by aza and diaza derivatives of phenanthrene (7,8-benzoquinoline and 1,10-phenanthroline) and anthracene (acridine and phenazine) at incident free electron energies (Ee) in the range of 0-15eV was studied. All compounds except 7,8-benzoquinoline form long-lived molecular ions (M-) at thermal electron energies (Ee ∼ 0eV). Acridine and phenazine also form such ions at epithermal electron energies up to Ee = 1.5-2.5eV. The lifetimes (τa) of M- with respect to electron autodetachment are proportional to the extent of aza-substitution and increase on going from molecules with bent geometry of the fused rings (azaphenanthrenes) to linear isomers (azaanthracenes). These regularities are due to an increase in the adiabatic electron affinities (EAa) of the molecules. The EAa values of the molecules under study were comprehensively assessed based on a comparative analysis of the measured τa values using the Rice-Ramsperger-Kassel-Marcus theory, the electronic structure analysis using the molecular orbital approach, as well as the density functional calculations of the total energy differences between the molecules and anions. The only fragmentation channel of M- ions from the compounds studied is abstraction of hydrogen atoms. When studying [M-H]- ions, electron autodetachment processes were observed, the τa values were measured, and the appearance energies were determined. A comparative analysis of the gas-phase acidity of the molecules and the EAa values of the [M-H]· radicals revealed their proportionality to the EAa values of the parent molecules.

Reciprocity relations in a biologically inspired nanomagnonic system with dipolar coupling

Magnetosome chains in magnetotactic bacteria present ideal nanomagnonic model systems for studying collective resonance modes of dipolar-coupled single domain particles in relation to their spatial arrangement. Using microresonator-based ferromagnetic resonance (FMR) spectroscopy, electron microscopy, and micromagnetic modeling, we here provide insights into the complex magnonic activity within a single magnetosome chain. While the angular dependence of its FMR spectrum is dominated by twofold symmetry features due to the uniaxial anisotropy of linear chain segments, we also observed an unexpected behavior such as interrupted lines and flat bands due to the intricate geometrical details of this particular chain, such as a cross-like structural anomaly where a pair of particles is oriented perpendicular to the main axis of the chain and thus breaks the prevailing axial dipolar coupling symmetry. Such a cross junction formed by four particles exhibits interesting magnonic network properties. Notably, we observe reciprocity in the sense that the spectral response of one particle to an excitation of another one is identical to the response of the latter given an excitation of the former. Furthermore, we have identified that magnonic coupling between A and B can be facilitated via a dark state, as in magnonic stimulated Raman adiabatic passage, and that this dark-state coupling can be made non-reciprocal between A and B by breaking the symmetry of the spatial arrangement of the four particles.

Deduction of lignite liquefaction mechanism based on carbon structure analysis and free radical determination

The liquefaction performance of lignite is closely related to its structural evolution. The carbon structure and the free radical concentrations of Naomaohu (NMH) coal and liquefaction products were characterized by modified nuclear magnetic resonance (NMR) spectroscopy and electron paramagnetic resonance (EPR), respectively. The results showed that the oil yield increased gradually with the increase in temperature, and it reached a maximum of 64.91% at 430 °C. The carbon spectrum of the liquefied oil showed that the increase in temperature had little effect on the aromatic carbon connected with the aliphatic carbon, but had a greater effect on the aromatic proton carbon of the liquefied oil. The stability of aromatic carbon in asphaltene was greater than that of aliphatic carbon, and the temperature rise had a significant impact on the different types of aliphatic carbon of the asphaltene. The aromatic side chain of asphaltene gradually broke, and the bridgehead carbon content of the aromatic carbon increased due to the intensification of the condensation reaction at high temperature. On the other hand, the concentration of free radicals in liquefied oil increased with temperature, while the concentration of free radicals in asphaltene first increased and then decreased with temperature, indicating a positive correlation between its change trend and respective yield. With the increase in temperature, the aromatic ring substances with strong bond energy were gradually opened, the side chains were broken, thus forming more low molecular compounds. In summary, based on the above changes in the carbon structure and free radicals, the lignite pyrolysis and liquefaction mechanism have been deduced at the molecular level.

Chloride ion permeability of concrete containing recycled composite powder from building demolition waste

Buildings in the marine environment are vulnerable to chloride ion erosion, which threatens the service life of concrete structures. To facilitate the application of concrete containing construction demolition waste in the marine environment, recycled composite powder concrete (RCPC) was prepared using recycled composite powder as cement substitute. The chloride ion permeability of RCPC was evaluated by chloride ion diffusion test and rapid chloride ion migration test (RCM). The chloride ion permeability of RCPC continued to enhance with growing content of recycled composite powder. During the immersion age, the surface chloride ion content of the samples containing recycled composite powder increased by an average of 18.3–65.3% over the control group, with a corresponding average increase in chloride ion diffusion coefficients ranging from 17.0% to 31.5%. The chloride ion migration coefficients in the RCM test raised by 9.5–24.7%. A series of microscopic tests such as nuclear magnetic resonance (NMR), X-ray diffraction (XRD) and scanning electron microscope-energy dispersive spectrometer (SEM-EDS) suggested that the total porosity increased by 11.9–29.5% with the addition of recycled composite powder. The chloride ion diffusion coefficients exhibited a linear increase with growing total porosity and porosity of capillary pores, whereas an exponential increase with the porosity of transitional pores. The poor reactivity of the recycled composite powder resulted in a looser microstructure and weakened chloride binding capacity, and these factors boosted chloride ion transport. A chloride ion diffusion model of RCPC considering the time dependence of chloride ion transport was developed, and the reliability of the model was verified by experimental data.

Microstructure and chloride transport of aeolian sand concrete under long-term natural immersion

Abstract River sand was consumed in large quantities, and alternatives to river sand were urgently needed. There are a large number of natural resources of aeolian sand in western China. Aeolian sand was prepared into aeolian sand concrete (ASC). It can greatly reduce the consumption of river sand and inhibit the process of desertification to protect the environment. ASC is a new type of concrete material prepared by using aeolian sand as fine aggregate. To clarify the chloride ion transport behaviour in the ASC under long-term natural immersion, the aeolian sand was 100% substituted for the river sand to prepare the full ASC with three water–binder ratios. The ASC was naturally immersed in 3 and 6% NaCl solutions for a long time, and nuclear magnetic resonance and microscopic scanning electron microscopy techniques were used. The change rule of chloride ion content at different depths of the ASC was studied, and its microstructure characteristics under different erosion times were analysed. The results showed that the free chloride ion concentration at different depths of the ASC increased with increasing water–binder ratio, immersion time, and chloride concentration. After soaking in the salt solution, the hydration products in the ASC reacted with chloride ions to form Friedel salt, which filled the internal pores and microcracks of the ASC, improved its interface transition zone structure, and increased the compactness of the test piece. The porosity of the three groups of ASC with different water–binder ratios decreased by 0.95, 1.03, and 1.15% after soaking in 6% salt solution for 12 m. To study the diffusion law of chloride ions in ASC, combined with influencing factors such as temperature, humidity, D value, deterioration effect and chloride ion combination, Fick’s second law was modified, and a chloride ion diffusion model of ASC with high accuracy was established, with a fitting correlation number above 0.93, which provided a reference for the research and application of ASC in saline areas.

Proximal ligand tunes active site structure and reactivity in bacterial L. monocytogenes coproheme ferrochelatase

Ferrochelatases catalyze the insertion of ferrous iron into the porphyrin during the heme b biosynthesis pathway, which is fundamental for both prokaryotes and eukaryotes. Interestingly, in the active site of ferrochelatases, the proximal ligand coordinating the porphyrin iron of the product is not conserved, and its catalytic role is still unclear. Here we compare the L. monocytogenes bacterial coproporphyrin ferrochelatase native enzyme together with selected variants, where the proximal Tyr residue was replaced by a His (i.e. the most common ligand in heme proteins), a Met or a Phe (as in human and actinobacterial ferrochelatases, respectively), in their Fe(III), Fe(II) and Fe(II)–CO adduct forms. The study of the active site structure and the activity of the proteins in solution has been performed by UV–vis electronic absorption and resonance Raman spectroscopies, biochemical characterization, and classical MD simulations.All the mutations alter the H-bond interactions between the iron porphyrin propionate groups and the protein, and induce effects on the activity, depending on the polarity of the proximal ligand. The overall results confirm that the weak or non-existing coordination of the porphyrin iron by the proximal residue is essential for the binding of the substrate and the release of the final product.

Classical, semiclassical, and quantum-optical models for an x-ray planar cavity with electronic resonance

Classical, semiclassical, and quantum-optical models for an x-ray planar cavity with electronic resonance

Electronic resonances in expanding non-neutral ultracold plasma

Calculations of the spectrum of eigen oscillations of an inhomogeneous ultracold plasma are presented both in the absence and in the presence of charge imbalance. The collective modes of these plasma oscillations are recorded in experiments as absorption resonances of a radio frequency electric field. It is shown that in the presence of friction of the electronic component, a discrete spectrum of plasma eigen oscillations is formed. The dependence of the frequency of these resonances on the plasma expansion time in the presence of a charge imbalance is obtained. There is good agreement with the experiments of different authors.

Cleaving DNA with DNA: Cooperative Tuning of Structure and Reactivity Driven by Copper Ions.

A copper-dependent self-cleaving DNA (DNAzyme or deoyxyribozyme) previously isolated by in vitro selection has been analyzed by a combination of Molecular Dynamics (MD) simulations and advanced Electron Paramagnetic Resonance (Electron Spin Resonance) EPR/ESR spectroscopy, providing insights on the structural and mechanistic features of the cleavage reaction. The modeled 46-nucleotide deoxyribozyme in MD simulations forms duplex and triplex sub-structures that flank a highly conserved catalytic core. The DNA self-cleaving construct can also form a bimolecular complex that has a distinct substrate and enzyme domains. The highly dynamic structure combined with an oxidative site-specific cleavage of the substrate are two key-aspects to elucidate. By combining EPR/ESR spectroscopy with selectively isotopically labeled nucleotides it has been possible to overcome the major drawback related to the "metal-soup" scenario, also known as "super-stoichiometric" ratios of cofactors versus substrate, conventionally required for the DNA cleavage reaction within those nucleic acids-based enzymes. The focus on the endogenous paramagnetic center (Cu2+ ) here described paves the way for analysis on mixtures where several different cofactors are involved. Furthermore, the insertion of cleavage reaction within more complex architectures is now a realistic perspective towards the applicability of EPR/ESR spectroscopic studies.

Bi-allelic NIT1 variants cause a brain small vessel disease characterized by movement disorders, massively dilated perivascular spaces, and intracerebral hemorrhage

PurposeTo describe a recessively inherited cerebral small vessel disease, caused by loss-of-function variants in Nitrilase1 (NIT1). MethodsWe performed exome sequencing, brain magnetic resonance imaging, neuropathology, electron microscopy, western blotting, and transcriptomic and metabolic analyses in 7 NIT1-small vessel disease patients from 5 unrelated pedigrees. ResultsThe first identified patients were 3 siblings, compound heterozygous for the NIT1 c.727C>T; (p.Arg243Trp) variant and the NIT1 c.198_199del; p.(Ala68∗) variant. The 4 additional patients were single cases from 4 unrelated pedigrees and were all homozygous for the NIT1 c.727C>T; p.(Arg243Trp) variant. Patients presented in mid-adulthood with movement disorders. All patients had striking abnormalities on brain magnetic resonance imaging, with numerous and massively dilated basal ganglia perivascular spaces. Three patients had non-lobar intracerebral hemorrhage between age 45 and 60, which was fatal in 2 cases. Western blotting on patient fibroblasts showed absence of NIT1 protein, and metabolic analysis in urine confirmed loss of NIT1 enzymatic function. Brain autopsy revealed large electron-dense deposits in the vessel walls of small and medium sized cerebral arteries. ConclusionNIT1-small vessel disease is a novel, autosomal recessively inherited cerebral small vessel disease characterized by a triad of movement disorders, massively dilated basal ganglia perivascular spaces, and intracerebral hemorrhage.

Resonant Tunneling-Enhanced Photoresponsivity in a Twisted Graphene van der Waals Heterostructure.

Leveraging its ultrahigh carrier mobility, zero-bandgap linear dispersion, and extremely short response time, graphene exhibits remarkable potential in ultrafast broad-band photodetection. Nonetheless, the inherently low responsivity of graphene photodetectors, due to the low photogenerated carrier density, significantly impedes the development of practical devices. In this study, we present an improved photoresponse within a graphene-hexagonal boron nitride-graphene vertical tunnel junction device, where the crystallographic orientation of the two graphene electrodes is aligned. Through meticulous device structure design and the adjustment of bias and gate voltages, we observe a 2 orders of magnitude increase in tunneling photocurrent, which is attributed to the momentum-conserving resonant electron tunneling. The enhanced external photoresponsivity is evident across a wide temperature and spectral range and achieves 0.7 A/W for visible light excitation. This characteristic, coupled with the device's negative differential conductance, suggests a novel avenue for highly efficient photodetection and high-frequency, logic-based optoelectronics using van der Waals heterostructures.