Chemical Methodologies

Abstract Early stroke detection is limited by a lack of sensors that can capture early inflammatory biomarkers. interleukin-6 (IL-6), tumor necrosis factor-α (TNF-α), and C-reactive protein (CRP) rise rapidly during neuroinflammation, serving as key early indicators. This study used all-atom molecular dynamics (MD) simulations (100 ns, triple replicates) to analyze interactions between these cytokines and silica-functionalized graphene oxide (GO–SiNP), directly comparing it to pristine graphene oxide (GO) and contextualizing findings against literature reports for SiNP, AuNP, and PEGylated carriers. Within our simulations, GO–SiNP provided superior stabilization versus GO alone, showing lower Root-mean-square deviation (RMSD) values (0.18–0.26 nm) and 20–35% reduced residue flexibility. The hybrid surface formed more persistent hydrogen bonds (6.5–11.0 on average) with the cytokines, supported by sharp radial distribution function (RDFs) peaks at 0.25–0.32 nm, indicating strong, short-range polar coordination with silica oxygen atoms. MM-PBSA calculations confirmed significantly stronger binding to GO–SiNP (−158 to −172 kJ.mol⁻¹) than to GO (−128 to −140 kJ.mol⁻¹). Crucially, silica functionalization did not hinder graphene's aromatic activity, maintaining 9–11 π–π contacts per cytokine versus 5–7 on GO. The binding affinity order was consistently TNF-α >IL-6 >CRP. These results demonstrate that GO–SiNP enables a dual-mode stabilization mechanism—combining polar anchoring with π-π interactions—unachievable by its individual components. Compared to conventional nanocarriers optimized for a single interaction type, this hybrid design represents a distinct, integrative strategy for robust biomarker capture. This work provides a molecular framework for designing advanced biosensors for early stroke detection.

Abstract The Fe(III)/Fe(II) redox pair in ferrocene derivatives has long been recognized as a model system for understanding redox processes and as a promising platform for electrochemical energy storage applications. This review critically synthesizes experimental and computational studies that investigate substituent effects on the redox behavior of ferrocene derivatives, with particular emphasis on redox potential modulation, cyclic voltammetry (CV) characteristics, and structure–property relationships. The reviewed literature demonstrates that electron-donating and electron-withdrawing substituents induce systematic shifts in Fe(III)/Fe(II) redox potentials by altering the electronic structure of the ferrocene core. Strong linear correlations between redox potentials (E₁/₂) and Hammett substituent constants are consistently reported, highlighting the predictive value of substituent-based electronic descriptors. These experimental trends are further supported by Density Functional Theory (DFT) calculations, which reveal how substituent-induced changes in frontier molecular orbital energies govern redox thermodynamics and electron-transfer behavior. To extend the relevance of substituent-controlled redox tuning beyond ferrocene systems, related redox-active organic frameworks such as substituted s-tetrazines are also discussed. Literature reports show that substituent effects enable controlled adjustment of discharge voltages, heterogeneous electron-transfer rates (k₀), and Li-ion diffusivity (Dₗᵢ) in Li-ion cell electrodes. By linking molecular-level electronic modulation with electrochemical performance, this review provides a coherent framework for the rational design of efficient and tunable redox-active molecular materials, contributing to the advancement of next-generation energy storage technologies, with improved performance, resource efficiency, and long-term sustainability.

Abstract This study introduces a novel biomedical composite material made of poly (methyl methacrylate) (PMMA) reinforced with a ceramic blend of magnesium oxide (MgO), aluminum oxide (Al₂O₃), and silicon dioxide (SiO₂)—collectively called MAS. The MAS powder was prepared using a solid-state reaction method, with boric acid added to lower the required processing temperature and improve phase formation. After testing different heating conditions, calcination at 1,200 °C was found produced the best crystalline structure, primarily consisting of α- and μ-cordierite phases, as confirmed by XRD and FESEM. Once optimized, the MAS powder was mixed into PMMA at different weight percentages to create PMMA/MAS composites. These materials underwent thorough testing to evaluate their structural, mechanical, thermal, and biological properties. SEM–EDX analysis confirmed a uniform distribution of MAS within the PMMA matrix. The mechanical tests further revealed significant enhancements in strength and durability with increasing ceramic content. Thermal studies revealed better heat conductivity and reduced heat retention, suggesting these composites could be useful in medical applications requiring temperature regulation. In biological tests, the composites demonstrated strong antibacterial effects against Streptococcus mutans, eliminating over 99.998% of bacteria. Additionally, cell viability tests showed that the material could effectively inhibit the growth of cancer cells, further supporting its potential for both antibacterial and anticancer applications. Overall, the PMMA/MAS composites combine excellent wear resistance, thermal management, and antimicrobial properties, making them highly promising for medical implants where strength, heat regulation, and infection control are crucial.

Abstract This work presents a thermodynamic investigation of the silicon–carbon–oxygen (Si–C–O) system aimed at optimizing the carbothermic reduction of silica for industrial production of silicon. Ellingham and thermodynamic predominance phase (TPP) diagrams were constructed across a wide temperature range (1,227–2,227 °C; 1,500–2,500 K) to evaluate the stability and equilibrium of key phases. The results reveal a sequential reduction pathway originating with silicon carbide (SiC) formation at moderate temperatures, followed by gaseous silicon monoxide (SiO) and carbon monoxide (CO) as dominant intermediates, culminating in the stabilization of metallic silicon at elevated temperatures under strongly reducing conditions. The Ellingham analysis confirms the broad thermodynamic favorability of SiC formation, while free silicon becomes stable only above approximately 1,800–2,200 °C (2,073–2,473 K), depending on system openness. TPP diagrams highlight the crucial role of gas-phase transport phenomena and charge composition in phase equilibria, with gas retention strategies proving essential to maximize silicon yield. Comparative evaluations with existing literature underscore the importance of optimizing carbon-to-SiC ratios and controlling gas-phase composition to improve energy efficiency and process efficiency. This study offers vital thermodynamic insights for advancing silicon manufacturing technologies through precise control of temperature, gas species, and feedstock composition.

Abstract In this study, an eco-friendly CuO/NiO/BN nanocomposite was developed through a simple phytosynthesis method using the aqueous extract of Stachys schtschegleevii (SSC). The plant extract serves as both a natural reducing agent and a stabilizing medium, facilitating the gentle and controlled formation of CuO and NiO nanoparticles on the bentonite (BN) surface. This green approach not only eliminates harsh chemicals, but also provides a reliable method for producing a stable, well-dispersed nanocomposite. The structure and composition of the nanocomposite were thoroughly verified using various analyses, including XRD (X-ray diffraction), FT-IR (Fourier transform infrared spectroscopy), FE-SEM (Field emission scanning electron microscopy), TEM (Transmission electron microscopy), TGA (Thermogravimetric analysis), DSC (Differential scanning calorimetry), ICP (inductively coupled plasma spectroscopy), and EDS (energy dispersive spectroscopy). The nanocomposite exhibited remarkable efficiency as a heterogeneous catalyst for the N-formylation of different amines. A wide range of substrates yielded corresponding N-formylated products in excellent yields (82-96%) within short reaction times (12-45 min) under mild and friendly conditions. The synergistic effect of CuO and NiO substantially facilitated the reaction, leading to enhanced activity relative to single-component systems. Importantly, the catalyst could be easily recovered through simple filtration and reused over several cycles with only minimal reduction in performance, as confirmed by post-reaction analyses, including XRD, FT-IR, and FE-SEM. Overall, this study highlights a sustainable and plant-assisted strategy for designing robust metal-oxide nanocatalysts, demonstrating their strong potential in promoting green and efficient organic transformations.

Abstract This study investigates the phase transformation dynamics during the synthesis of non-stoichiometric strontium ferromolybdate (Sr₂Fe₁.₂Mo₀.₈O₆₋δ, SFMO) via solid-state reaction from SrCO₃, Fe₂O₃, and MoO₃. Intermediate phases SrFeO₃ and SrMoO₄ form sequentially between 500–850 K and hinder complete SFMO crystallization due to kinetic limitations at high temperatures (≥1270 K). To overcome this, combined synthesis modes involving controlled heating rates and intermediate grinding were developed, enabling the production of single-phase SFMO with 89% Fe/Mo superstructural ordering. Magnetic characterization revealed that reduced cation ordering increases antiferromagnetic clustering, suppressing long-range ferrimagnetic order and lowering magnetization in field-cooling measurements. Zero-field-cooling data confirmed superparamagnetic behavior, indicating magnetic inhomogeneity with coexisting superparamagnetic nanoparticles and ferrimagnetic grains. The results demonstrate that precise control of synthesis conditions is essential to minimize kinetic barriers, suppress defect formation, and achieve reproducible magnetic properties in SFMO, a promising candidate for spintronic applications.

Abstract Magnesium Schiff base complex immobilized on magnetite nanoparticles was prepared and used as a magnetically heterogeneous and reusable catalyst for the synthesis of 5-methyl-N,7-diphenyl-4,7-dihydro-[1,2,4]triazolo[1,5-a] pyrimidine-6-carboxamide compounds by the one-pot multi-component condensation reaction of some aromatic aldehydes containing various electron withdrawing and donating substitutions such as fluorine, chlorine, bromine, methoxy, benzyloxy, nitro, hydroxyl and cyano croups on their ring with acetoacetanilide and 3-amino-1,2,4-triazole (12 examples) at 70 °C under solvent-less condition. All products were prepared in high yields (85-95 %) and in short reaction times (25 minutes) with an interesting suggested mechanism. Simple work up, mild reaction condition, high yield of products, short reaction times, compliance with green chemistry protocols and the recyclability of the catalyst were some important benefits of the presented research. Fe₃O₄@SiO₂ C₃H₆ magnesium Schiff base complex as a catalyst due to magnetic property was easily separated from the reaction mixture and reused successfully for four times without noticeable reduction in reaction efficiency.

Abstract Psoriasis is a chronic inflammatory disease of the skin that needs to be managed in the long term, and the aryl hydrocarbon receptor (AhR) has turned out to be an effective therapeutic target because of its ability to control keratinocyte differentiation and immune signaling. Based on the approved pharmacophore template named Tapinarof, a pharmacophore model was used to screen the ZINC Natural Products Library to identify alternative scaffolds. Three of them, ZINC69482103 (-11.132 kcal/mol), ZINC4098639 (-11.008 kcal/mol), and ZINC13485093 (-10.909 kcal/mol)), more strongly predicted binding to the AhR PAS-B domain than Tapinarof (-10.209 kcal/mol). These molecules also replicate the important aromatic stacking and hydrogen-bond interactions that are significant in the modulation of AhR. The molecular mechanics/generalized Boron surface area (MM-GBSA) analysis also confirmed their high binding potential with ZINC69482103, presenting a favorable ΔGbind value. Simulations of 100 ns using molecular dynamics (MD) ensured the stability of the interaction between the ligands and proteins, remaining at constant values of Root Mean Square Deviation (RMSD), and the contact profile was maintained during the simulation. Drug-likeness and bioavailability assessments with ADMETlab showed that all three compounds were within reasonable physicochemical ranges, with ZINC13485093 exhibiting the most moderate ADMET parameters. In general, the results identified three natural product scaffolds as potential candidates for the development of next-generation AhR modulators for the treatment of psoriasis, particularly ZINC69482103 and ZINC13485093. Their therapeutic potential should be validated through further experiments.