Electron Density Research Articles

Free Electron Density Gradients Enhanced Biosensor for Ultrasensitive and Accurate Affinity Assessment of the Immunotherapy Drugs.

Accurate affinity assessments play an important role in drug discovery, screening, and efficacy evaluation. Label-free affinity biosensors are recognized as a dependable and standard technology for addressing this challenge. This study constructs a free electron density gradient-enhanced meta-surface plasmon resonance (FED-MSPR) biosensor through a finite-difference time-domain simulation model, the biosensor demonstrates superior detection performance in accurately determining affinity and kinetic rate constants. By controlling the dielectric properties of the metal on the surface of the nanocup arrays, the plasmon resonance effects are easily tuned without changing the nanostructure design. Compared with the single-layer gold chip, the triple-layer FED-MSPR chip demonstrated a four-fold improvement in resolution at the optimal resonance peak. Additionally, the sensitivity and figure of merit (FOM) of the multi-layer chip increased by 3.5 and 7.99 times, respectively. Following modification with high- and low-staggered carboxylation, the noise-signal ratio and baseline stability of the real-time kinetic curves based on these chips are significantly enhanced. The developed carboxylation FED-MSPR platform is successfully used to perform affinity assays for Adalimumab and TNF-α protein, resulting in favorable dynamic curves. These findings validate the proposed FED-MSPR biosensor platform as cost-effective, rapid, sensitive, and label-free, facilitating real-time quality control in drug development.

Strong Lewis-acid coordinated PEO electrolyte achieves 4.8 V-class all-solid-state batteries over 580 Wh kg−1

Polyethylene oxide (PEO) based electrolytes critically govern the security and energy density of solid-state batteries, but typically suffer from poor oxidation resistance at high voltages, which limits the energy density of batteries. Here, we report a Lewis-acid coordinated strategy to significantly improve the cyclic stability of 4.8 V-class PEO-based battery. The introduced Mg2+ and Al3+ with strong electron-withdrawing capability weaken the electron density of ether oxygen (EO) chains via chelation in the coordination structure, resulting in a locally limited interaction between the EO chains and the surface of cathodes at high state of charge. The batteries using Lewis-acid coordinated electrolytes and Ni-rich cathodes achieve high voltage stability of 4.8 V over 300 cycles. Further, the realization of industrial-scale electrolyte membranes, and Ah-level pouch cells over 586 Wh kg‒1 with good cyclic stability, suggests the potential of our strategy in practical applications of all-solid-state batteries.

Zero-dimensional simulations of DC ns-pulsed plasma jet in N2 at near atmospheric pressure: validation of the vibrational kinetics

Abstract A Direct Current (DC) nanosecond (ns)-pulsed plasma jet fed with N2 at near atmospheric pressure (20 000 Pa) is studied using a transient zero-dimensional (0-D) model coupled with a two-term Boltzmann equation solver. Good agreement is observed between the simulated and measured plasma properties: including the electron density and the ratios of the N2(v = 1, 2, 3, 4) densities to the gas density. A variety of theoretical approaches are considered to determine the Vibrational-Vibrational (V-V) and Vibrational-Translational (V-T) rate coefficients. For the V-V kinetics, the simple form of an Harmonic Oscillator (sfHO), the Schwartz–Slawsky–Herzfeld (SSH) and the Forced Harmonic Oscillator (FHO) approaches are used. The SSH approach used in this study is an improved version based on the pure SSH approach. For the V-T kinetics, the sfHO, a fit function of the Semi-Classical (ffSC) calculations and a fit function of the Quasi-Classical Trajectory (ffQCT) calculations are used. The influence of these different approaches on the calculated temporal evolution profiles of the vibrational distribution functions (VDFs) within one pulse modulation cycle is revealed. It is observed that the use of these different approaches does not strongly affect the densities of the low vibrational levels (v < 5), whereas larger influences on the higher level densities are found. In addition, it is found that the simulated evolution of the VDFs are sensitive to the probabilities of the neutral wall reaction N2(v) + wall → N2(v − 1) in the range of 1 × 10−2 to 1 × 10−4. A further analysis of the wall quenching probabilities of N2(0 < v < 58) is of importance for a more accurate prediction of the VDFs.

Theoretical and Experimental Study of the Stability of Thiamethoxam Under Different Environmental Conditions

The neonicotinoid insecticide thiamethoxam (TMX) is widely applied in agriculture, owing to its high spectrum of target pests. Its frequent use contributed to its accumulation in the environment, mainly in water; therefore, its natural degradation mechanisms are relevant to understand the physicochemical factors that can accelerate its decomposition. So, this study evaluated the stability of TMX against variations in pH, temperature, and exposure time to solar radiation, with the purpose of assessing the natural mechanisms of its degradation in water. Further, simulations of the reaction mechanisms at the molecular level were performed. It was observed that the degradation of TMX in the environment is favored by its exposure to solar radiation for several days and in more acidic pH conditions. However, TMX degradation did not result in reduced ecotoxicity. Basic pH values also help in the degradation of TMX, but by a lower percentage than that in an acid medium. Although exposure of TMX to solar radiation promotes heating of the compound, the isolated effect of thermal energy (temperature) is not sufficient for its degradation. The computer simulations showed the regions with higher electron densities and that the TMX structure is stable, preventing the bonds from breaking with increasing temperature, up to 60 °C. The HO− and H3O+ ions do not interact significantly with the molecule to the point of modifying its structure. With solar radiation, an electron can change to the excited state, contributing to TMX degradation due to a triplet configuration that allows it to react with the ions in the solution. In this way, the present work contributed to jointly present a theoretical and experimental study of the forms of natural degradation of the TMX contaminant.

Effects of discharge parameters on plasma acceleration and transmission characteristics of a coaxial gun operated in gas-prefilled mode

The effects of discharge parameters on the discharge process and plasma transport characteristics of a coaxial gun in the gas-prefilled mode are studied. The plasma optical intensity and ejection velocity are measured by photodiodes, the optical emission spectrum is taken by a spectroscopic system, and the plasma evolution in the transport process is captured by a high-speed camera. The plasma acceleration characteristics under different discharge parameters show that the velocity and electron density of the ejection plasma are mainly determined by the pre-filled pressure and discharge current, which is consistent with the snowplow model. The kinetic energy of ejection plasma can be significantly increased by reducing the outer loop inductance, which is conducive to increasing the energy utilization efficiency. The time-varying images of plasma radiation and the plasma density at different transport locations illuminate the transmission characteristics of coaxial gun discharge plasma. The results show that the snowplow effect continues to play a role in the plasma transport process, and the plasma accumulation is induced by the combination of shock wave compression. The current-driven magneto hydrodynamics instability occurs during the transport process, and the luminous signal of the plasma current sheet oscillates periodically. In addition, the plasma impact effect is obvious and the gas retarding effect is enhanced with the increase in the gas pressure. These results give us a more comprehensive view of the coaxial gun discharge process and plasma transport and provide a certain reference for optimizing the parameters selection and physical design of coaxial gun discharge plasma characteristics.

Machine learning analysis of high-repetition-rate two-dimensional Thomson scattering spectra from laser-produced plasmas

Abstract With the emergence of high-repetition-rate two-dimensional Thomson scattering (TS) measurements, improving spec- tral data analysis is a key area of interest. We present a new way to derive the electron temperature and density of laser-driven blast waves in plasmas from their TS spectra with machine learning (ML). This analysis occurs in both the non-collective (α < 1) and collective (α > 1) scattering regimes with the goal of autonomously and more accurately determining Te and ne both where spectral data has been collected and to give the ability to predict these attributes in regions where data has not been collected. We introduce three ML models, one trained only on experimental data, one only on synthetic data, and one using transfer learning, and compare their speed and accuracy with the conventional TS inversion algorithms in the open source PlasmaPy python package.

Quantum chemical calculations and molecular docking studies of 5-amino-3-(2,5-dimethoxyphenyl)-1-isonicotinoyl-2,3-dihydro-1H-pyrazole-4-carbonitrile

Abstract The five-membered heterocycle pyrazole has two nitrogen atoms next to each other. Natural items and pharmaceuticals using pyrazole as the nucleus have demonstrated a wide range of biological activity. Medications with pyrazole cores may have better pharmacokinetics and pharmacological effects than medicines with similar heterocyclic rings. This is because the pyrazole core has unique physicochemical properties. In this study, 5-amino-3-(2,5-dimethoxyphenyl)-1-isonicotinoyl-2,3-dihydro-1H-pyrazole-4-carbonitrile is synthesized and characterized by means of spectrum and quantum chemical techniques. Using UV–vis absorption technique, Fourier transform infrared (FT-IR), and Fourier transform Raman (FT-Raman) techniques, the spectroscopic properties were examined. There were two regions visible in the experimental Raman as well as infrared spectra: 4,000–400 cm−1 along with 4,000–100 cm−1. The ideal molecular shape, vibrational frequencies, infrared intensity levels, and scattering from Raman were all assessed using density functional theory. The 13C (carbon) and 1H (proton) chemical shifts of the molecule were determined using nuclear magnetic resonance (NMR). The TD-DFT scheme was utilized to figure out speculative ultraviolet values and compare them to oscillator strength, electron excitation energies, and spectrum data from experiments. It is evident from the predicted HOMO-LUMO band separation energies that the transmission of charge takes place within a molecule’s structure. The chemical reactivity of the molecule has been calculated along with other global descriptive properties. Scientists investigated how charges move and the density of electrons inside a molecule using NBO analysis of the chemical they were studying. After examining the molecular electrostatic potential (MEP), a 3D picture was created that shows the compound’s nucleophilic and electrophilic areas. In addition to meeting all pertinent pharmacokinetic requirements, 5-amino-3-(2,5-dimethoxyphenyl)-1-isonicotinoyl-2,3-dihydro-1H-pyrazole-4-carbonitrile is also readily absorbed by the gastrointestinal system. Additionally, the chemical that was synthesized had a positive interaction with the target proteins of treatments for viruses, asthma, and heart failure, as shown by molecular docking.

Reply to Graille, "InsPection of electron density maps supports wrongly modeled hexakisphosphate (InsP6) bound to African swine fever mRNA-decapping enzyme g5Rp".

Reply to Graille, "InsPection of electron density maps supports wrongly modeled hexakisphosphate (InsP6) bound to African swine fever mRNA-decapping enzyme g5Rp".

Removal of Residual Additive Enabling Perfect Crystallization of Photovoltaic Perovskites

Achieving high‐efficiency perovskite solar cells (PSCs) hinges on the precise control of the perovskite film crystallization process, often improved by the inclusion of additives. While dimethyl sulfoxide (DMSO) is traditionally used to manage this process, its removal from the films is problematic. In this work, methyl phenyl sulfoxide (MPSO) was employed instead of DMSO to slow the crystallization rate, as MPSO is more easily removed from the perovskite structure. The electron delocalization associated with the benzene ring in MPSO decreases the electron density around the oxygen atom in the sulfoxide group, thus reducing its interaction with PbI2. This strategy not only sustains the formation of a crystallization‐slowing intermediate phase but also simplifies the elimination of the additive. Consequently, the optimized PSCs achieved a leading power conversion efficiency (PCE) of 25.95% along with exceptional stability. This strategy provides a novel method for fine‐tuning perovskite crystallization to enhance the overall performance of photovoltaic devices.

Facile synthesis of azines by carboxylic acid esters as catalyst and facilitation of intersystem crossing (ISC) in azines by azine chromophore

Development of new organic synthetic methods fascinating the researchers which facilitating the increasing demands of the modern society, environmental friendly with high efficiency and low cost. The introduction of chromophores in an organic molecules facilitating intersystem crossing (ISC) to harvest both singlet and triplet excitons is also currently demanding field. We report a facile synthesis of symmetrical azines from carbonyl compounds and hydrazine hydrate with carboxylic acid esters as catalyst in methanol. This reaction presents a condensation of primary amino groups in hydrazine hydrate and carbonyl compounds took place simultaneously in a very short refluxing time. The prepared azines 1–10 were structurally analysed by various analytical techniques such as LC-MS1, H NMR13, C NMR, UV-Vis, FTIR and single crystal X-ray diffraction. Photoluminescence properties of prepared azines were recorded in CCl4 at 1 × 10−3 M and excitation range from 329 to 362 nm. The photoluminescence analysis results revealed that compounds 1–10 (except 8) were showed delayed fluorescence and 8 was showed fluorescence property. The photophysical properties of compounds 1–10 such as electron density and band gap energies was calculated by density function theory. This results revealed that the intra-molecular charge transfer occurs within the azines. The azine function in the azines enabling intersystem crossing hence, it is showing phosphorescence.

MAX phase borides, the potential alternative of well-known MAX phase carbides: A case study of V2AB [A = Ge, P, Tl, Zn] via DFT method

This study predicted four new MAX phase borides via the DFT method, with a comprehensive and thorough approach. The stability of the predicted phases has been thoroughly studied using formation energy, phonon dispersion curve (PDC), and elastic constants (Cij). The metallic nature of the studied phases is confirmed through the computation of the electronic band structure and density of states (DOS). Their bonding nature is disclosed using the partial density of states, Mulliken population analysis, and charge density mapping. The mechanical behavior is investigated in depth by calculating elastic constants, elastic moduli, Poisson's & Pugh ratio, machinability index, and Vickers hardness. Different anisotropic indices are also computed to demonstrate the elastic anisotropy. The Debye temperature (ΘD), Grüneisen parameter (γ), phonon thermal conductivity (kph), minimum thermal conductivity (kmin), thermal expansion coefficient (TEC), and melting temperature (Tm) are all calculated, and the suitability of the studied phases as thermal barrier coating (TBC) materials has been discussed. Finally, the optical constants are calculated and analyzed, further certifying the metallic nature of the herein-studied phases. The reflectivity spectra of all the herein selected compounds reveal their potential as coating materials to lessen solar heating. Among the studied phases, V2PB exhibits the best thermo-mechanical properties for potential applications in diverse fields, such as structural components and TBC materials. The potential applications of our findings are vast, and the obtained results reveal that the predicted phases are indeed potential alternatives to their counterpart carbides.

Experimental and computational studies of steric factors in the isomerization of internal alkynes within the coordination environment of half-sandwich metal complexes.

The isomerization of internal alkynes Ar1C≡CAr2 within the coordination environment of low-valent half-sandwich [Ru(dppe)Cp]+ complexes via a 1,2-migration process affords vinylidene species [Ru{=C=C(Ar1)Ar2}(dppe)Cp]+. The rearrangement reactions of symmetrically and asymmetrically substituted substrates featuring different electron-donating and -withdrawing groups and of varying steric bulk were modelled using density functional theory (DFT), and the conclusions supported by experimental observations. Examination of the reaction pathway and associated activation barriers reveal a high solvent dependency for the generation of the key intermediate species [Ru(dppe)Cp]+ from [RuCl(dppe)Cp] by Na+ induced halide abstraction , with the lattice enthalpy of the NaCl by-product playing a critical role in the overall thermochemical balance of the reaction. The activation barriers associated with the reaction of [Ru(dppe)Cp]+ with Ar1C≡CAr2, and the relative energies of the alkyne complexes [Ru(h2-Ar1C≡CAr2)(dppe)Cp]+, are sensitive to the electron density of the alkyne and conformational changes associated with the 'bend-back' of the substrate. The latter differs by up to 66.1 kJ/mol, which in turn impacts the barrier height of the subsequent 1,2-migration step . The relative importance of these factors is evinced by the successful rearrangement of the very sterically congested 1(9-anthryl)-2(9-phenanthryl) acetylene into the fully characterized diaryl vinylidene complex, which was isolated in 89% yield.

Tyramine as a Prolific Coformer in Crystal Engineering: Insights from Classical Crystal Structure Analysis and Electron Density Studies

Tyramine as a Prolific Coformer in Crystal Engineering: Insights from Classical Crystal Structure Analysis and Electron Density Studies

N‐Arylphenothiazines and N,N‐Diarylphenazines as Tailored Organophotoredox Catalysts for the Reductive Activation of Alkenes

AbstractA small library of N‐arylphenothiazines, N‐arylbenzo[b]phenothiazines and N,N‐diarylphenazines has been synthesized as strongly reducing organophotocatalysts without the need for sacrificial reagents or electrochemistry. Their opto‐electronic properties and their suitability as organophotoredox catalysts for the efficient activation of olefins was investigated using the addition of methanol to α‐methylstyrene as a model reaction. The findings were supported by DFT calculations. Three photocatalysts were identified that allowed quantitative yields with 10 mol % catalyst loading and 20 h irradiation by a 365 nm LED. The catalyst loading was gradually reduced to 0.5 mol % and the irradiation time was reduced to only 20 min. These experiments revealed that N,N‐diisobutyl‐4′‐(10H‐phenothiazin‐10‐yl)‐[1,1′‐biphenyl]‐4‐amine is the most efficient photocatalyst among the N‐arylphenothiazines. This chromophore combines high electron density introduced by the diisobutylamino phenyl group with high absorptivity at 365 nm caused by the phenylene bridge to the phenothiazine core. In an attempt to shift the excitation wavelength into the visible light range for selectivity and sustainability purposes (potential use of sunlight as a light source), N‐arylbenzo[b]phenothiazines N,N‐diarylphenazines were designed that exhibit a red‐shifted and broad absorbance shoulder into the visible range, but only N,N‐diarylphenazines allow photocatalysis and the one‐electron activation of alkenes by visible light (450 nm LED).

Structural, Electronic, and Mechanical Properties of α(U) and α(U-Zr) Alloy Fuels

Uranium-zirconium (U-Zr) alloy fuels have been taken into consideration for fast reactors because of their superior reactor safety, high uranium (U) density, and excellent thermal conductivity. In this paper, the structural and mechanical properties of metallic U and U-Zr alloy fuels are calculated at the atomic level by density functional theory–based calculations with Hubbard U (density functional theory + U) corrections. Several structure-property relations, such as lattice volume, bulk modulus, Young’s modulus, shear modulus, electronic density of states, etc. are calculated for U metal and U-Zr alloy fuels. In addition, the Zr content in metallic U fuel is adjusted from roughly 5 at. % to 15 at. % in order to determine how the Zr content affects the characteristics of U-Zr fuel material. A linear relationship between the volume and Zr concentrations is observed. The concentration of Zr in the fuel affects the mechanical characteristics of U-Zr alloy fuel. It is also observed that the electronic structure of the α-U phase is not changed significantly in the presence of Zr. Our computations provide insight into how U-Zr alloy fuels behave in reactor conditions.

Optical properties of CVD-grown multilayer graphene on nickel using spectroscopic ellipsometry

Incorporating graphene into relevant technologies requires its integration with commercially suitable substrates. Understanding the interactions between graphene and these substrates is crucial, as graphene serves as an ideal model system for investigating electronic phenomena. In this work, we report the optical properties of multilayer graphene on nickel substrates using spectroscopic ellipsometry. We provide information on the spectral dependence of optical properties of multilayer graphene, such as the complex dielectric constant, refractive index, and optical conductivity in the energy range of 1.6–5.0 eV. The optical conductivity profile obtained from SE analysis showed a symmetrical peak at 4.38 eV, suggesting an interband transition from the π to π∗ orbital at the M point. The graphene/Ni interaction generated changes in the number of available states below the Fermi level, leading to significant changes in electron density. Our result provides the information essential for understanding relevant research and developing graphene-based optoelectronic applications.

DFT investigation of thermodynamic, electronic, optical, and mechanical properties of XLiH3 (X= Mg, Ca, Sr, and Ba) hydrides for hydrogen storage and energy harvesting

The present study investigates the hydrogen storage capacity and physical properties of the perovskite hydrides XLiH3 (X = Mg, Ca, Sr, and Ba). The studied compounds MgLiH3, CaLiH3, SrLiH3, and BaLiH3 have lattice constants 3.76, 4.29, 4.64, and 5.04 Å, respectively. These compounds are also observed to be stable in cubic phase under atmospheric pressure and temperature conditions. They have hydrogen storage capacities 8.76 wt%, 5.99 wt%, 3.07 wt%, and 2.03 %, respectively. The SrLiH3 compound has the greatest Debye temperature (θD) of 344.41 K. The analysis of the electronic band structure and density of states reveals that perovskite hydrides have semiconducting characteristics with indirect band gap values of 2.66, 2.34, 1.94, and 1.37 eV, respectively. The materials are semiconductors and have suitable band gaps to be utilized in optical devices. Therefore, the optoelectronic properties of dielectric constants, absorption, and energy loss have been determined to predict the potential of materials for optoelectronic applications. Furthermore, the elastic constants, moduli, and anisotropy are also calculated for the observed materials. The Possion and Pugh ratios indicate these compounds exhibit ductile behaviour and significant anisotropy. Therefore, large values of hydrogen capacities, stabilities, and extraordinary physical behaviour make them important for hydrogen storage systems.

A N-heterocyclics induced π-π interaction strategy to synthesis hyper-crosslinked polymers with enhanced porosity for xenon adsorption

Hyper-crosslinked polymers (HCPs) with large specific surface areas play an important role in gas adsorption and separation. However, the method to enhance the specific surface area of HCPs and gas adsorption performance without changing the polyaromatic hydrocarbons (PAHs) monomer structure and reaction condition is still missing. Here, we present a general and facile N-heterocyclics induced π-π interaction strategy to increase the specific surface area of HCPs by simply adding N-heterocyclics during the Friedel-Crafts alkylation reaction. The specific surface areas of HCP (tetraphenylmethane based HCPs, TPMBPy-TCM) increased up to 7.78 times compared to the one without adding N-heterocyclics. The crosslinking and stacking of PAHs was influenced by the π-π stacking between the N-heterocyclic complexes and PAHs. More importantly, N-heterocyclics coordinated with Lewis acids have lower electron density and do not react with PAHs in the Friedel-Crafts alkylation reaction, which can be removed easily from HCPs. The HCPs obtained shown good xenon adsorption performance with Xe uptake of 3.63 mmol/g, which is the highest value for organic adsorbents reported in literature. This work provides new insight into the preparation of high-performance HCPs.

Mechanistic studies on phosphine-catalyzed [4 + 3] annulation of β′-acetoxy allenoate with 1C,3N-dinucleophile

The mechanism and role of catalyst on the PPh3-catalyzed [4 + 3] annulation reaction have been systematically investigated using density functional theory (DFT) method. Based on the calculations, the possible mechanism contains six steps: nucleophilic addition of PPh3 to allenoate to give Z-configured intermediate, cleavage of CO bond for forming phosphonium diene, nucleophilic addition of phosphonium diene with anionic 1C,3N-dinucleophile, intramolecular [1,5]-proton shift, ring-closure, and dissociation of catalyst. Non-covalent interaction (NCI) analysis shows that the O⋯P interaction would be the key for leading to the Z-configured pathway more favorable and electron localization function (ELF) analysis indicates that the implication of PPh3 can significantly lower the energy barrier involved in CO cleavage process, which mainly because the addition of PPh3 reduces the electron density of CO bond and thus facilities the cleavage of CO bond. This theoretical study would provide some clues for understanding the role of catalyst in a catalytic reaction.

Sustainable di-functional stimuli-responsive imprinted nanozymes for reversible colorimetric sensing of tetracycline

Regenerable nanozymes with high catalytic specificity and sustainability may serve as substitutes for naturally occurring enzymes, but their application is hindered by inadequate and nonselective catalytic activity. In this study, we constructed a photo-responsive molecularly imprinted layer on the Fe3O4 nanozyme surface (P-MIPs) using an ATRP method and obtained high-specificity reversible colorimetric sensing of tetracycline (TC). Due to the photo-responsive properties of P-MIPs, the imprinted nanozyme undergoes reversible release and uptake of TC under alternating irradiation at 365/440 nm based on the photo-regulated conformational transformation of the 4-[(4-methacryloyloxy)phenylazo] benzenesulfonic acid (MAPASA) at the polymer receptor sites, which may be confirmed by calculating the electron densities of the trans-/cis-MAPASA forms. Simultaneously, these processes can be visualized through the change in the color of the substrates. Highly specific P-MIPs-based nanozyme also exhibit adequate stability and sustainable catalytic activity after multiple cycles. This method can be used to achieve nanozymes with high selectivity for the enrichment, separation, and detection of hazardous substances and contribute to material sustainability.