Search Results (229)

Gel precursors were formed by reacting bismuth nitrate pentahydrate, acetic acid, sodium metavanadate, and NaOH. pH was adjusted using NaOH solution followed by calcination to obtain bismuth vanadate (BiVO₄) photocatalysts. During synthesis, pH directly influenced the formation and structure of the gel network. Therefore, the effects of pH on the microstructure and photocatalytic activity of BiVO₄ were investigated. At pH 3, the sample consisted of microspheres formed by tightly packed small particles. At pH 5, the microspheres transformed into aggregated flakes. Photocatalytic performance was evaluated through methylene blue (MB) degradation, revealing the sample prepared at pH 7 (7-BVO) demonstrated the highest efficiency. The electronic band structure, bandgap, and band edge positions of 7-BVO were probed by density functional theory (DFT) and UV-vis absorption spectra. Furthermore, photoluminescence spectroscopy, electrochemical measurements, active species trapping experiments and liquid chromatography mass spectrometry technique collectively revealed the possible mechanistic pathways for MB photodegradation by 7-BVO. Full article

Divinylisoprene rubber, a copolymer of butadiene and isoprene, is used as raw material for rubber technical products, combining isoprene rubber’s elasticity and butadiene rubber’s wear resistance. These properties depend quantitatively on the copolymer composition, which depends on the kinetics of its synthesis. This work aims to theoretically describe how the monomer mixture composition in the butadiene–isoprene copolymerization affects the activity of the TiCl₄-Al(i-C₄H₉)₃ catalytic system (expressed by active sites concentration) via kinetic modeling. This enables development of a reliable kinetic model for divinylisoprene rubber synthesis, predicting reaction rate, molecular weight, and composition, applicable to reactor design and process intensification. Active sites concentrations were calculated from experimental copolymerization rates and known chain propagation constants for various monomer compositions. Kinetic equations for active sites formation were based on mass-action law and Langmuir monomolecular adsorption theory. An analytical equation relating active sites concentration to monomer composition was derived, analyzed, and optimized with experimental data. The results show that monomer composition’s influence on active sites concentration is well described by a two-step kinetic model (physical adsorption followed by Ti–C bond formation), accounting for competitive adsorption: isoprene adsorbs more readily, while butadiene forms more stable active sites. Full article

Leveraging Fourier optics theory and Abbe’s imaging principle, this study establishes that optical imaging fundamentally involves selective spatial spectrum recombination at the Fourier plane. Three classical experiments quantitatively validate universal spectrum manipulation mechanisms: (1) The Abbe-Porter experiment confirmed spectral filtering, directly demonstrating image synthesis from transmitted spectral components. (2) Zernike phase-contrast microscopy quantified spectral phase modulation, overcoming the weak-phase-object detection limit by significantly enhancing contrast. (3) Optical joint transform correlation (JTC) demonstrated efficient spectral amplitude modulation for high-speed, high-accuracy image recognition. Collectively, these results form a comprehensive framework for active light field manipulation at the spectral plane, extending modulation capabilities to phase and amplitude dimensions. This work provides a foundational theoretical and technical framework for designing advanced optical systems, extending modulation capabilities to phase and amplitude dimensions. Full article

The development of novel platinum-based anticancer agents remains a critical objective in medicinal inorganic chemistry, particularly in light of resistance and toxicity limitations associated with cisplatin. In this study, the synthesis, structural characterization, quantum chemical analysis, and cytotoxic evaluation of four new acetylplatinum(II) complexes (cis-[Pt(COMe)₂(PASO₂)₂], cis-[Pt(COMe)₂(DAPTA)₂], trans-[Pt(COMe)Cl(DAPTA)₂], and trans-[Pt(COMe)Cl(PASO₂)]: 1–4, respectively) bearing cage phosphine ligands PASO₂ (2-thia-1,3,5-triaza-phosphaadamantane 2,2-dioxide) and DAPTA (3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane) are presented. The coordination geometries and NMR spectral features of the cis/trans isomers were elucidated through multinuclear NMR and DFT calculations at the B3LYP/6-311++G(d,p)/LanL2DZ level, with strong agreement between experimental and theoretical data. Quantum Theory of Atoms in Molecules (QTAIM) analysis was applied to investigate bonding interactions and assess the covalent character of Pt–ligand bonds. Cytotoxicity was evaluated against five human cancer cell lines. The PASO₂-containing complex in cis-configuration, 1, demonstrated superior activity against thyroid (8505C) and head and neck (A253) cancer cells, with potency surpassing that of cisplatin. The DAPTA complex 2 showed enhanced activity toward ovarian (A2780) cancer cells. These findings highlight the influence of ligand structure and isomerism on biological activity, supporting the rational design of phosphine-based Pt(II) anticancer drugs. Full article

Type 2 diabetes mellitus (T2DM) demands safer and more effective therapies to control postprandial hyperglycemia. Here, we report the synthesis and in vitro evaluation of ten salicylic acid-derived Schiff base derivatives (4a–4j) as α-glucosidase inhibitors. Compounds 4e, 4g, 4i, and 4j exhibited potent enzyme inhibition, with IC₅₀ values ranging from 14.86 to 18.05 µM—substantially better than acarbose (IC₅₀ = 45.78 µM). Molecular docking and 500 ns molecular dynamics simulations revealed stable enzyme–ligand complexes driven by π–π stacking, halogen bonding, and hydrophobic interactions. Density Functional Theory (DFT) calculations and molecular electrostatic potential (MEP) maps highlighted key electronic factors, while ADMET analysis confirmed favorable drug-like properties and reduced nephrotoxicity. Structure–activity relationship (SAR) analysis emphasized the importance of halogenation and aromaticity in enhancing bioactivity. Full article

This paper presents some of the most significant findings in the design of a hydraulic servomechanism for flight controls, which were primarily achieved by the first author during his activity in an aviation institute. These results are grouped into four main topics. The first one outlines a classical theory, from the 1950s–1970s, of the analysis of nonlinear automatic systems and namely the issue of absolute stability. The uninformed public may be misled by the adjective “absolute”. This is not a “maximalist” solution of stability but rather highlights in the system of equations a nonlinear function that describes, for the case of hydraulic servomechanisms, the flow-control dependence in the distributor spool. This function is odd, and it is therefore located in quadrants 1 and 3. The decision regarding stability is made within the so-called Lurie problem and is materialized by a matrix inequality, called the Lefschetz condition, which must be satisfied by the parameters of the electrohydraulic servomechanism and also by the components of the control feedback vector. Another approach starts from a classical theorem of V. M. Popov, extended in a stochastic framework by T. Morozan and I. Ursu, which ends with the description of the local and global spool valve flow-control characteristics that ensure stability in the large with respect to bounded perturbations for the mechano-hydraulic servomechanism. We add that a conjecture regarding the more pronounced flexibility of mathematical models in relation to mathematical instruments (theories) was used. Furthermore, the second topic concerns, the importance of the impedance characteristic of the mechano-hydraulic servomechanism in preventing flutter of the flight controls is emphasized. Impedance, also called dynamic stiffness, is defined as the ratio, in a dynamic regime, between the output exerted force (at the actuator rod of the servomechanism) and the displacement induced by this force under the assumption of a blocked input. It is demonstrated in the paper that there are two forms of the impedance function: one that favors the appearance of flutter and another that allows for flutter damping. It is interesting to note that these theoretical considerations were established in the institute’s reports some time before their introduction in the Aviation Regulation AvP.970. However, it was precisely the absence of the impedance criterion in the regulation at the appropriate time that ultimately led, by chance or not, to a disaster: the crash of a prototype due to tailplane flutter. A third topic shows how an important problem in the theory of automatic systems of the 1970s–1980s, namely the robust synthesis of the servomechanism, is formulated, applied and solved in the case of an electrohydraulic servomechanism. In general, the solution of a robust servomechanism problem consists of two distinct components: a servo-compensator, in fact an internal model of the exogenous dynamics, and a stabilizing compensator. These components are adapted in the case of an electrohydraulic servomechanism. In addition to the classical case mentioned above, a synthesis problem of an anti-windup (anti-saturation) compensator is formulated and solved. The fourth topic, and the last one presented in detail, is the synthesis of a fuzzy supervised neurocontrol (FSNC) for the position tracking of an electrohydraulic servomechanism, with experimental validation, in the laboratory, of this control law. The neurocontrol module is designed using a single-layered perceptron architecture. Neurocontrol is in principle optimal, but it is not free from saturation. To this end, in order to counteract saturation, a Mamdani-type fuzzy logic was developed, which takes control when neurocontrol has saturated. It returns to neurocontrol when it returns to normal, respectively, when saturation is eliminated. What distinguishes this FSNC law is its simplicity and efficiency and especially the fact that against quite a few opponents in the field, it still works very well on quite complicated physical systems. Finally, a brief section reviews some recent works by the authors, in which current approaches to hydraulic servomechanisms are presented: the backstepping control synthesis technique, input delay treated with Lyapunov–Krasovskii functionals, and critical stability treated with Lyapunov–Malkin theory. Full article

Plasmodium falciparum is the causative agent of malaria, a parasitic disease that affects millions of people in terms of prevalence and is associated with hundreds of thousands of deaths. Current antimalarial medications, in addition to exhibiting moderate to serious adverse reactions, are not efficacious enough due to factors such as drug resistance. In silico approaches can speed up the discovery and design of new molecules with wide-spectrum antimalarial activity. Here, we report a unified computational methodology combining a perturbation theory machine learning model based on multilayer perceptron networks (PTML-MLP) and the fragment-based topological design (FBTD) approach for the prediction and design of novel molecules virtually exhibiting versatile antiplasmodial activity against diverse P. falciparum strains. Our PTML-MLP achieved an accuracy higher than 85%. We applied the FBTD approach to physicochemically and structurally interpret the PTML-MLP, subsequently extracting several suitable molecular fragments and designing new drug-like molecules. These designed molecules were predicted as multi-strain antiplasmodial inhibitors, thus representing promising chemical entities for future synthesis and biological experimentation. The present work confirms the potential of combining PTML modeling and FBTD for early antimalarial drug discovery while opening new horizons for extended computational applications for antimicrobial research and beyond. Full article

This study presents the synthesis, physicochemical characterization, and biological evaluation of a novel ternary nickel(II) complex with isoleucine and 1,10-phenanthroline ligands, [Ni(Phen)(Ile)₂]∙6H₂O, designed as a potential antitumor agent. Single-crystal X-ray diffraction revealed a monoclinic structure (C2-space group) with an octahedral Ni(II) coordination involving Phen and Ile ligands. A Hirshfeld surface analysis highlighted intermolecular interactions stabilizing the crystal lattice, with hydrogen bonds (H···H and O···H/H···O) dominating (99.1% of contacts). Density functional theory (DFT) calculations, including solvation effects (in water and methanol), demonstrated strong agreement with the experimental geometric parameters and revealed higher affinity to the water solvent. The electronic properties of the complex, such as HOMO−LUMO gaps (3.20–4.26 eV) and electrophilicity (4.54–5.88 eV), indicated a charge-transfer potential suitable for biological applications through interactions with biomolecules. Raman and infrared spectroscopic studies showed vibrational modes associated with Ni–N/O bonds and ligand-specific deformations, with solvation-induced shifts observed. A study using ultraviolet–visible–near-infrared absorption spectroscopy demonstrated that the complex remains stable in solution. In vitro cytotoxicity assays against MCF-7 (breast adenocarcinoma) and HCT-116 (colorectal carcinoma) cells showed dose-dependent activity, achieving 47.6% and 65.3% viability reduction at 100 μM (48 h), respectively, with lower toxicity to non-tumor lung fibroblasts (GM07492A, 39.8%). Supporting the experimental data, we performed computational modeling to examine the pharmacokinetic profile, with particular focus on the absorption, distribution, metabolism, and excretion properties and drug-likeness potential. Full article

Coumarin and cytisine and their derivatives have significant biological activity. In addition, the electronic properties of coumarin derivatives are very sensitive to the molecular environment, which allows for their use as sensors for bioluminescent imaging. Due to the fact that cytisine exhibits high activity in binding to nicotinic acetylcholine receptors, a compound combining parts of cytisine and coumarin may have a broader spectrum of biological activity and also act as a photoactive element for promising use in optoelectronic devices. This article reports the synthesis of a crystalline cytisine–coumarin complex (IUPAC: N-(2-oxo-2H-chromene-3-carbonyl)cytisine), along with the results of both theoretical and experimental investigations of its structural and electronic properties. The structure of this new compound was established on the basis of X-ray diffraction and Fourier transform infrared spectroscopy data and was confirmed through density functional theory calculations using periodic crystal and single-molecule approaches. Interpretations of the IR absorption peaks and the atomic patterns of the vibrational modes are given. The electronic band structure and the contributions of individual atoms to the electronic density of states are analyzed. The structural and optical properties considered may be useful for quality control of the compound and for studying similar matrices. Full article

This conceptual paper introduces the Green Lean Operational Excellence (GLOE) framework to address the limitations of conventional lean systems in responding to sustainability and resilience challenges. Rooted in sustainability science and operations management, the model reconceptualizes operational excellence by integrating green imperatives—such as environmental accountability, adaptability, and systemic feedback—into lean methodologies. Rather than focusing solely on cost-efficiency, lean practices have also been recognized for enhancing quality, process stability, and organizational flexibility (e.g., Womack & Jones, 1996), which makes them valuable foundations for sustainability integration. The framework was developed through an interdisciplinary synthesis of the literature on lean operations, green supply chains, and adaptive organizational systems. It proposes a structured flow from strategic preconditions to hybrid mechanisms and sustainability-linked outcomes, supported by continuous refinement loops. Key propositions are offered for empirical testing. GLOE redefines excellence beyond traditional cost-driven paradigms, extending lean theory toward strategic sustainability, and bridging gaps between operational practice and sustainability science. It also provides a roadmap for future research, emphasizing empirical validation, indicator development, and digital integration. The model offers practical guidance for managers to move beyond siloed CSR programs and embed sustainability into the core of operational strategy. Ultimately, GLOE positions operations as active contributors to organizational resilience and long-term value in an era of climate disruption and socio-ecological complexity. 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

Background: Beach volleyball (BVb) is a highly demanding Olympic sport characterized by intense physical activity and unique environmental challenges, including varying weather conditions and sandy, unstable court surfaces. Despite its popularity, there is a notable lack of scientific research addressing the metabolic and immune responses of elite female athletes in this sport. This study aims to address this gap by investigating two world-class Olympic medalists, female BVb players, who represent a country with a rich history in the sport. Methods: Two athletes underwent a simulated competition day consisting of two matches. A standardized protocol was utilized to collect blood and urine samples at seven time points, allowing for analysis throughout the competition and recovery phases. The analysis included various electrolytes, as well as hematological, metabolic, and inflammatory markers. Additionally, we assessed selected hormones, such as insulin, serotonin, ACTH, and cortisol, along with amino acids related to energy metabolism and neurotransmitter synthesis. Results: Both athletes presented a trend toward electrolyte disturbances, especially hypokalemia, with a mean decrease of 15% and individual values reaching as low as 3.3 mmol/L post-match. This indicates that BVb may pose a risk for such disturbances. Additionally, the matches led to 20% to 60% increases in muscle injury markers, with incomplete recovery even after a day of rest, signaling persistent physiological stress post-competition. This increase was matched by stimulating stress hormones (ACTH and cortisol rose up to 4-fold and 3-fold, respectively), and markers of exercise intensity, such as lactate and ammonium. Moreover, the simulated BVb competition day impacted the amino acid response, with the Fischer ratio (BCAA/AAA) and blood tryptophan decreasing to a minimum of 60% of the initial levels and blood serotonin increasing by up to 180%, which are signs of an increased risk of central fatigue onset, according to the Fischer and Newsholme theory. Conclusions: The responses examined in this exploratory study contribute to a deeper understanding of the metabolic and immune demands placed on elite female BVb players, suggesting practical applications. By addressing the similar physiological responses observed among the athletes and emphasizing their unique individual responses—despite following the same protocol under identical conditions and sharing similar life habits for an extended period—this study highlights the critical necessity for the n-of-1 monitoring of athletes. Full article

Utilizing isomeric monomers to construct covalent organic frameworks (COFs) could easily and precisely regulate their structure in order to raise the photocatalytic performance towards two-step single-electron oxygen reduction reaction (ORR) to hydrogen peroxide (H₂O₂). Herein, isomeric anthraquinone (AQ)-based COFs (designated as 1,4-DQTP and 2,6-DQTP) were successfully fabricated through a simple yet effective one-step solvothermal synthesis approach, only utilizing isomeric monomers with alterations in the catalysts. Specifically, the black 1,4-DQTP displayed a high photocatalytic H₂O₂ production rate of 865.4 µmol g⁻¹ h⁻¹, with 2.44-fold enhancement compared to 2,6-DQTP (354.7 µmol g⁻¹ h⁻¹). Through a series of experiments such as electron paramagnetic resonance (EPR) spectroscopy and the free radical quenching experiments, as well as density functional theory (DFT) calculations, the photocatalytic mechanism revealed that compared with 2,6-DQTP, 1,4-DQTP possessed a stronger and broader visible light absorption capacity, and thus generated more photogenerated e⁻-h⁺ pairs. Ultimately, more photogenerated electrons were enriched on the AQ motif via a more apparent electron push–pull effect, which provided a stable transfer channel for e⁻ and thus facilitated the generation of superoxide anion radical intermediates (•O₂⁻). On the other hand, the negative charge region of AQ’s carbonyl group evidently overlapped with that of TP, indicating that 1,4-DQTP had a higher chemical affinity for the uptake of protons, and thus afforded a more favorable hydrogen donation for H⁺. As a consequence, the rational design of COFs utilizing isomeric monomers could synergistically raise the proton-coupled electron transfer (PCET) kinetics for two-step single-electron ORR to H₂O₂ under visible light illumination. This work provides some insights for the design and fabrication of COFs through rational isomer engineering to modulate their photocatalytic activities. Full article

Background/Objective: Avapritinib is an orally bioavailable tyrosine kinase inhibitor and was approved by the FDA in 2020 for gastrointestinal stromal tumor treatments. Although avapritinib is known to be chiral, its stereochemistry was initially established randomly. This study aims to develop a definitive method for determining avapritinib’s absolute configuration and propose a universal methodology for stereochemical characterization of flexible chiral drugs. Methods: The absolute configuration of avapritinib was determined through an integrated approach combining chiral resolution, chiroptical spectroscopy and synthetic validation. Enantiomeric separation was achieved via chiral liquid chromatography, followed by comprehensive chiroptical characterization including electronic circular dichroism (ECD), specific optical rotation and optical rotatory dispersion. Conformational analysis and density functional theory (DFT) calculations correlated experimental spectra with theoretical predictions, facilitating definitive configurational assignment. The stereochemical determination were further verified through ECD derivatization and chemical synthesis. Finally, the enantiomers’ kinase inhibition profiles against c-KIT D816V were quantitatively assessed. Results: Two enantiomers of avapritinib were resolved via chiral HPLC and a Chiralpak IG column. Through combined experimental ECD spectra and time-dependent DFT calculations employing the core extraction method, the levo-isomer was unambiguously determined as S configuration. This stereochemical assignment was confirmed by p-cyanobenzaldehyde derivatization and de novo synthesis. Biological evaluation revealed (S)-(−)-avapritinib exhibited superior c-KIT D816V inhibitory activity compared to its (R)-(+)-counterpart, a finding corroborated by molecular docking studies elucidating their differential target interactions. Conclusions: This study advances avapritinib stereochemical understanding and establishes a definitive protocol for its absolute configuration assignment, serving as a paradigm for flexible chiral drug characterization. Full article

The electrocatalytic CO₂ reduction reaction (CO₂RR) into value-added multi-carbon C₂₊ products holds significant promise for sustainable chemical synthesis and carbon-neutral energy cycles. Among the various strategies developed to enhance CO₂RR, the use of ionic liquids (ILs) has emerged as a powerful approach for modulating the local microenvironment and electronic structure of Cu-based metal catalysts. In this study, to unravel the molecular-level mechanisms underlying these enhancements, density functional theory calculations (DFTs) were employed to systematically explore how ILs with different terminal groups modulate the electronic reconstruction of the Cu surface, further affecting the *CO–*CO coupling and product selectivity. Electronic structure analyses reveal that ILs bearing polar moieties (–SH, –COOH) can synergistically enhance the interfacial electron accumulation and induce an upshift of the Cu d-band center, thereby strengthening *CO adsorption. In contrast, nonpolar IL (CH₃) exhibits negligible effects, underscoring the pivotal role of ILs’ polarity in catalyst surface-state engineering. The free energy diagrams and transition state analyses reveal that ILs with polar groups significantly lower both the reaction-free energy and activation barrier associated with the *CO–*CO coupling step. This energetic favorability selectively inhibits the C₁ product pathways and hydrogen evolution reaction (HER), further improving the selectivity of C₂ products. These theoretical insights not only unveil the mechanistic origins of IL-induced performance enhancement but also offer predictive guidance for the rational design of advanced IL–catalyst systems for efficient CO₂ electroreduction. Full article