Search Results (491)

The unique properties of graphene have allowed for the development of graphene-based field-effect transistors (GFETs) for applications in biosensors and chemical devices. However, the modeling and optimization of GFET performance exhibit great challenges. Herein, we propose a quantum transport simulation model for graphene-based field-effect transistors (GFETs) implemented in the open-source Octave programming language. The proposed simulation model (named SimQ) combines the Landauer–Büttiker formalism with self-consistent Schrödinger–Poisson solutions, enabling reliable simulations of transport phenomena. Our approach agrees well with established models, achieving Landauer–Büttiker transmission and tunneling transmission of 0.28 and 0.92, respectively, which are validated against experimental data. The model can predict key GFET characteristics, including carrier mobilities (500–4000 cm²/V·s), quantum capacitance effects, and high-frequency operation (80–100 GHz). SimQ offers detailed insights into charge distribution and wave function evolution, achieving an enhanced computational efficiency through optimized algorithms. Our work contributes to the modeling of graphene-based field-effect transistors, providing a flexible and accessible simulation platform for designing and optimizing GFETs with potential applications in the next generation of electronic devices. Full article

The pharmaceutical industry faces significant challenges when promising drug candidates fail during development due to suboptimal ADME (absorption, distribution, metabolism, excretion) properties or toxicity concerns. Natural compounds are subject to the same pharmacokinetic considerations. In silico approaches offer a compelling advantage—they eliminate the need for physical samples and laboratory facilities, while providing rapid and cost-effective alternatives to expensive and time-consuming experimental testing. Computational methods can often effectively address common challenges associated with natural compounds, such as chemical instability and poor solubility. Through a review of the relevant scientific literature, we present a comprehensive analysis of in silico methods and tools used for ADME prediction, specifically examining their application to natural compounds. Whereas we focus on identifying the predominant computational approaches applicable to natural compounds, these tools were developed for conventional drug discovery and are of general use. We examine an array of computational approaches for evaluating natural compounds, including fundamental methods like quantum mechanics calculations, molecular docking, and pharmacophore modeling, as well as more complex techniques such as QSAR analysis, molecular dynamics simulations, and PBPK modeling. Full article

Fibrate pharmaceuticals (fibrates), as a widespread class of emerging contaminants, pose potential risks to both ecological systems and human health. The photocatalytic system based on nitrogen (N) and fluorine (F) co-doped TiO₂ nanotube arrays (NF-TNAs) provides a renewable solution for fibrate pharmaceutical removal from water, powered by inexhaustible sunlight. In this study, the degradation of two typical fibrates, i.e., bezafibrate (BZF) and ciprofibrate (CPF), under simulated sunlight irradiation through NF-TNAs were investigated. The photocatalytic degradation of BZF/CPF was achieved through combined radical and non-radical oxidation processes, while the generation and reaction mechanisms of associated reactive oxygen species (ROS) were examined. Electron paramagnetic resonance detection and quenching tests confirmed the existence of h⁺, •OH, O₂^•−, and ¹O₂, with O₂^•− playing the predominant role. The transformation products (TPs) of BZF/CPF were identified through high-resolution mass spectrometry analysis combined with quantum chemical calculations to elucidate the degradation pathways. The influence of co-existing ions and typical natural organic matters (NOM) on BZF/CPF degradation were also tested. Eventually, the ecological risk of BZF/CPF transformation products was assessed through quantitative structure–activity relationship (QSAR) modeling, and the results showed that the proposed photocatalytic system can largely alleviate fibrate toxicity. Full article

The solvatochromic properties of 48 solvents of three benzo-[f]-quinolinium methylids (BfQs) were analyzed within the theories of the variational model and Abe’s model of the liquid. The electro-optical properties of BfQs in the first excited state were determined based on the charge transfer process that occurs from the ylid carbon to the nitrogen atom. The dipole moments and the polarizabilities in the first excited state were calculated according to the two models. The quantum chemical calculations helped in understanding the relationship between the molecular structure and absorption properties of the ground state. It is concluded that several key parameters modulate the strength of the charge transfer and they work in synergy, and the most important are as follows: (i) isomerism around the single polar bond, and (ii) the properties of the solvent. The link between geometrical conformation and the zwitterionic character make the studied BfQs very sensitive chromophores for sensors and optical switching devices. Full article

During atmospheric reentry, a significant number of chemical reactions are produced inside the high-temperature shock wave formed upstream of the spacecraft. Chemical reactions can significantly alter the flowfield structure surrounding the vehicle and affect surface properties, including heat transfer, pressure, and skin friction coefficients. In this scenario, the primary goal of this investigation is to evaluate the Quantum-Kinetic chemistry model for computing rarefied reactive gas flow over simple and complex geometries. The results are compared with well-established reaction models available for the transitional flow regime. The study focuses on two configurations, a sphere and the Orion capsule, analyzed at different altitudes to assess the impact of chemical nonequilibrium across varying flow rarefaction levels. Including chemical reactions led to lower post-shock temperatures, broader shock structures, and significant species dissociation in both geometries. These effects strongly influenced the surface heat flux, pressure, and temperature distributions. Comparison with results from the literature confirmed the validity of the implemented QK model and highlighted the importance of including chemical kinetics when simulating hypersonic flows in the upper atmosphere. Full article

It is well known that aqueous solutions can emit electromagnetic waves in the radio frequency range. However, the physical nature of this process is not yet fully understood. In this work, the possible role of gas nanobubbles formed in the bulk liquid is considered. We develop a theoretical model based on the concept of gas bubbles stabilized by ions, or “bubstons”. The role of bicarbonate and hydronium ions in the formation and stabilization of bubstons is explained through the use of quantum chemical simulations. A new model of oscillating bubstons, which takes into account the double electric layer formed around their gas core, is proposed. Theoretical estimates of the frequencies and intensities of oscillations of such compound species are obtained. It was determined that oscillations of negatively charged bubstons can occur in the GHz frequency range, and should be accompanied by the emission of electromagnetic waves. To validate the theoretical assumptions, we used dynamic light scattering (DLS) and showed that, after subjecting aqueous solutions to vigorous shaking with a force of 4 or 8 N (kg·m/s²) and a frequency of 4–5 Hz, the volume number density of bubstons increased by about two orders of magnitude. Radiometric measurements in the frequency range of 50 MHz to 3.5 GHz revealed an increase in the intensity of radiation emitted by water samples upon the vibrational treatment. It is argued that, according to our new theoretical model, this radiation can be caused by oscillating bubstons. Full article

A modified activated carbon (AC) was developed by modifying with poly(diallyldimethylammonium) chloride (PDADMAC) to enhance its adsorption performance for water treatment applications. Different PDADMAC concentrations were explored and evaluated using methyl red as a model contaminant, with 8 w/v% PDADMAC yielding the best adsorption performance. The kinetics data were well described by the pseudo-first-order equation and homogeneous surface diffusion model. The Freundlich isotherm fit the equilibrium data well, indicating multilayer adsorption and diverse interaction types. The removal efficiency remained similar across a pH range of 5–9 and in the presence of background inorganic (NaCl)/organic compounds (sodium acetate) at different concentrations. Rapid small-scale column tests were performed to simulate continuous flow conditions, and the PDADMAC-modified AC effectively delayed the breakthrough of the contaminant compared to raw AC. Regeneration experiments showed that 0.1 M NaOH with 70% methanol effectively restored the adsorption capacity, retaining 80% of the initial efficiency after five cycles. Quantum chemical analysis revealed that non-covalent interactions, including electrostatic and Van der Waals forces, governed the adsorption mechanism. Overall, the results of this study prove that PDADMAC-AC shows great potential for enhanced organic contaminant removal in water treatment systems. Full article

Vibrational analysis of peptides in solution and the theoretical determination of the effects of the microenvironment on infrared and Raman spectra are of key importance in many fields of chemical interest. In this work, we present a computational study combining static quantum mechanical calculations with ab initio molecular dynamics simulations to investigate the vibrational behavior of three peptide models in both the gas phase and in explicit water, under non-periodic boundary conditions. The vibrational spectra of the main amide bands, namely amide I-III and A, were analyzed using a time–frequency approach based on the wavelet transform, which allows the resolution of transient frequency shifts and mode couplings along the trajectories. This combined approach enabled us to perform a time-resolved vibrational analysis revealing how vibrational frequencies, especially of the C=O and N–H stretching modes, evolve over time due to dynamical microsolvation. These fluctuations modulate vibrational couplings and lead to spectral broadening and frequency shifts that correlate with the local structuring of the solvent. In conclusion, our results highlight how the proposed protocol allows for the direct connection between vibrational modes and local structural changes, providing a link from the spectroscopic observable to the structure, the peptide backbone, and its microenvironment. Full article

In this study, we investigate the fractional Tzitzéica equation, a nonlinear evolution equation known for modeling complex phenomena in various scientific domains such as solid-state physics, crystal dislocation, electromagnetic waves, chemical kinetics, quantum field theory, and nonlinear optics. Using the (G′/G, 1/G)-expansion approach, we derive different categories of exact solutions, like hyperbolic, trigonometric, and rational functions. The beta fractional derivative is used here to generalize the classical idea of the derivative, which preserves important principles. The derived solutions with broader nonlinear wave structures are periodic waves, breathers, peakons, W-shaped solitons, and singular solitons, which enhance our understanding of nonlinear wave dynamics. In relation to these results, the findings are described by showing the solitons’ physical behaviors, their stabilities, and dispersions under fractional parameters in the form of contour plots and 2D and 3D graphs. Comparisons with earlier studies underscore the originality and consistency of the (G′/G, 1/G)-expansion approach in addressing fractional-order evolution equations. It contributes new solutions to analytical problems of fractional nonlinear integrable systems and helps understand the systems’ dynamic behavior in a wider scope of applications. Full article

A series of new isatin hydrazones bearing phosphorus-containing moiety was synthesized through a simple, high-yield and easy work-up reaction of phosphine oxide (Phosenazide) or phosphinate (2-chloroethyl (4-(dimethylamino)phenyl)(2-hydrazinyl-2-oxoethyl)phosphinate, CAPAH) hydrazides with aryl-substituted isatins. The ³¹P NMR technique showed that, in most cases, out of 12 examples in solution, the ratio of the two spatial isomers varied from 1:1 to 1:3. Quantum chemical calculations confirmed the predominance of Z,syn form both in the gas phase and in solution. According to X-ray analysis data in crystals, they exist only in Z,syn form too. Most of the phosphine oxide derivatives and 5-methoxy- and 5-bromoaryl phosphinate analogs exhibit anti-aggregant activity at the level of acetylsalicylic acid but inhibit platelet activation processes more effectively. The 5-chloro type phosphinate derivative exhibits anti-aggregant properties more effectively than acetylsalicylic acid under the conditions of the tissue factor (TF)-activated thromboelastography (TEG) model, the ex vivo thrombosis model. Thus, all the obtained results can become the basis for future pharmaceutical developments to create effective anti-aggregation drugs with broad antithrombotic potential. Full article

Millimeter-wave-supported detonation (MSD) is a unique detonation phenomenon driven by a supersonically propagating ionization front, sustained by intense millimeter-wave beams. Microwave Rocket, which utilizes MSD to generate thrust from atmospheric air in a pulse detonation engine (PDE) cycle, is a promising low-cost alternative to conventional chemical propulsion systems for space transportation. However, insufficient air intake during repetitive PDE cycles has limited achievable thrust performance. To address this issue, a model equipped with a six-stage reed valve system (36 valves in total) was developed to ensure sufficient air intake, which measured 500 mm in length, 28 mm in radius, and 539 g in weight. Launch demonstration experiments were conducted using a 170 GHz, 550 kW gyrotron developed at the National Institutes for Quantum Science and Technology (QST). Continuous thrust was successfully generated by irradiating up to 50 pulses per experiment at each frequency between 75 and 150 Hz, in 25 Hz increments, corresponding duty cycles ranging from 0.09 to 0.18. A maximum thrust of 9.56 N and a momentum coupling coefficient $C_m$ of 116 N/MW were obtained. These values represent a fourfold increase compared to previous launch experiments without reed valves, thereby demonstrating the effectiveness of the reed valve configuration in enhancing thrust performance. Full article

Carbon nanotubes (CNTs) functionalized with metal oxides exhibit synergistic properties that enhance their performance across various applications, particularly in electrochemistry. Recent advancements have highlighted the potential of CNT–metal oxide heterostructures, with a specific focus on their electrochemical properties, which are pivotal for applications in sensors, supercapacitors, batteries, and catalytic systems. Among these, nickel oxide (NiO)-modified CNTs have garnered significant attention due to their cost-effectiveness, facile synthesis, and promising gas-sensing capabilities. This study employs quantum-chemical calculations within the framework of density functional theory (DFT) to elucidate the interaction mechanisms between CNTs and NiO. The results demonstrate that the adsorption process leads to the formation of stable CNT-NiO complexes, with detailed analysis of adsorption energies, equilibrium distances, and electronic structure modifications. The single-electron spectra and density of states (DOS) of the optimized complexes reveal significant alterations in the electronic properties, particularly the modulation of the energy gap induced by surface and edge functionalization. Furthermore, the interaction of CNT-NiO composites with acetone (C₃H₆O) and carbon dioxide (CO₂) is modeled, revealing a physisorption-dominated mechanism. The adsorption of these gases induces notable changes in the electronic properties and charge distribution within the system, underscoring the potential of CNT-NiO composites for gas-sensing applications. This investigation provides a foundational understanding of the role of metal oxide modifications in tailoring the sensory activity of CNTs toward trace amounts of diverse substances, including metal atoms, inorganic molecules, and organic compounds. The findings suggest that CNT-NiO systems can serve as highly sensitive and selective sensing elements, with potential applications in medical diagnostics and environmental monitoring, thereby advancing the development of next-generation sensor technologies. Full article

In this study, the chemopreventive effects of rosmarinic acid (RA), a major phenolic acid of the plant Rosmarinus officinalis L., against the carcinogenic naturally occurring mycotoxin aflatoxin B1 (AFB1) were investigated using both in silico and in vitro approaches. The in silico investigation of the chemical reactions between rosmarinic acid and the carcinogenic metabolite of AFB1, aflatoxin B1 exo-8,9-epoxide (AFBO), was conducted by activation free energies calculations with DFT functionals M11-L and MN12-L, in conjunction with the 6-311++G(d,p) flexible basis set and implicit solvation model density (SMD), according to a newly developed quantum mechanics-based protocol for the evaluation of carcinogen scavenging activity (QM-CSA). Following the computational analyses, the chemoprotective effects of RA were further studied in vitro in human hepatocellular carcinoma HepG2 cells by analyzing its influence on AFB1-induced genotoxicity using a comet assay, γH2AX, and p-H3, while its impact on cell proliferation and cell cycle modulation was assessed using flow cytometry. Our computational results revealed that the activation free energy required for the reaction of RA with AFBO (14.86 kcal/mol) is significantly lower than the activation free energy for the competing reaction of AFBO with guanine (16.88 kcal/mol), which indicates that RA acts as an efficient natural scavenger of AFBO, potentially preventing AFB1-specific DNA adduct formation. The chemoprotective activity of RA was confirmed through in vitro experiments, which demonstrated a statistically significant (p < 0.05) reduction in AFB1-induced single- and double-strand breaks in HepG2 cells exposed to a mixture of AFB1 and RA at non-cytotoxic concentrations. In addition, RA reversed the AFB1-induced reduction in cell proliferation. Full article

Lithium-ion batteries (LIBs) have come to hold ever greater significance across diverse fields. However, thermal runaway and associated fire incidents have undeniably constrained the application and development of LIBs. Consequently, gaining a profound understanding of the reaction mechanisms of LIB electrolytes during thermal runaway is of critical importance for ensuring the fire protection of LIBs. In this study, quantum chemical calculations were employed to construct oxidation reaction models of electrolytes, and a comprehensive summary of the sources of fire gas generation during the thermal runaway of LIBs is presented. During the sequence of oxidation reactions, the -COH functional group emerged as the most critical intermediate product. Under conditions of low oxygen availability, it was prone to decompose into CO, whereas in the presence of sufficient oxygen, it could undergo further oxidation to form -COOH and subsequently decompose into CO₂. Moreover, the reaction chains associated with electrolyte oxidation were found to be highly intricate, characterized by multiple branches and a wide variety of intermediate products. Furthermore, an in-depth analysis was carried out on the generation mechanisms of several typical fire gases. The analysis revealed that CH₃OH and C₂H₅OH could be considered as the characteristic products of the oxidation reactions of DMC and DEC, respectively. It is anticipated that this research will provide a robust theoretical foundation for elucidating the complex reactions involved in LIB fires and offer reaction models for fire simulation purposes, thereby contributing to the enhancement of the safety and reliability of LIBs in various applications. Full article

The phenomena of regio- and stereoselectivity and the molecular mechanism of the [2 + 2] cycloaddition reaction between (E)-2-arylnitroethenes and the ynamine molecular system were analyzed using wb97xd/6-311 + G(d) (PCM) quantumchemical calculations. It was found that, independently of the stepwise nature of the cycloaddition, the full retention of the stereoconfiguration of the nitroalkene can be interpreted and explained. Next, the analysis of the electronic properties of the localized reaction intermediate suggests its possible zwitterionic nature. Additionally, the solvent and the substituent effect on the reaction course were also evaluated. In consequence, the proposed mechanism can be treated as general for some groups of [2 + 2] cycloaddition processes. Lastly, for the model process, the full Bonding Evolution Theory (BET) analysis along the reaction coordinate was performed. It was found that the [2 + 2] cycloaddition reaction between (E)-2-phenylonitroethene and ynamine begins with the formation of two pseudoradical centers at the C2 and C3 atoms. First, a C2-C3 single bond is formed in phase V by combining two pseudoradical centers, while the formation of a second C4-C1 single bond begins at the last, eleventh phase of the reaction path. A BET analysis of intermediate (I) allows it to be classified as a compound with a pseudoradical structure. Next to zwitterions and biradicals, it is evidently new type of intermediate on the path of the [2 + 2] cycloaddition reaction. Full article