Search Results (269)

The condensation reaction of pyromellitic dianhydride and (aminomethyl)phosphonic acid in imidazole yielded N,N′-bis(phosphonomethyl)pyromellitimide ([(H₂O₃P)CH₂-(C₁₀H₂N₂O₄)-CH₂(PO₃H₂)]∙2H₂O). Recrystallization of this compound from deionized water, by placing the solution in a desiccator to allow slow diffusion of HCl, afforded suitable single crystals for X-ray crystallographic studies. The compound crystallizes in the monoclinic space group P2₁/n. The flexible methylene phosphonic acid groups appended to both nitrogen termini adopt a trans configuration. The phosphonate and carbonyl groups (acceptors: P=O and C=O), together with water molecules [donor: O(6)—H∙∙∙O], participate in an extensive network of hydrogen-bonding interactions. Two of the phosphonate groups are protonated as P—OH (donors) and interact with oxygen atoms of neighboring phosphonate groups and water molecules. Hirshfeld surface analysis and associated two-dimensional fingerprint plots indicate that O∙∙∙H/H∙∙∙O (56.1%) contacts are the primary contributors to the crystal packing, followed by H∙∙∙H (16.3%) and C∙∙∙O/O∙∙∙C (13.4%) interactions. No significant π–π interactions were observed. The direct optical bandgap value, estimated from the Tauc plot, is 3.24 eV, indicating semiconducting behavior. The compound also exhibits thermal stability up to ~270 °C. These properties suggest that this compound may be a promising candidate for future investigation in organic electronic and optoelectronic materials. Full article

Three new isomeric pyridone fluorenone hydrazone-based boron complexes, 3-BrN to 5-BrN, with bromination at the 3-, 4-, or 5-position of the pyridone ring and their corresponding σ-platinum complexes trans-Pt(PEt₃)₂(n-N)X (n = 3, 4, or 5; X = Cl, Br, I) resulting from oxidative addition of the aryl-Br bond of n-BrN to Pt(PEt₃)₂ and, for X = Cl, I, subsequent substitution of the halogenide ligand, were synthesized and characterized by NMR, UV–Vis absorption, and photoluminescence spectroscopy. The molecular structures of dyes 3-BrN to 5-BrN and of seven complexes, including the cis-isomer of the bromo complex resulting from 3-BrN, were established by single X-ray diffraction. The nearly orthogonal orientation of the Pt coordination plane with respect to the plane of the dye ligand limits intermolecular π-stacking interactions in the crystalline state while giving rise to extensive C-H···halogen and C-H···π interactions, resulting in intricate packing patterns. Electronic absorption spectra of dyes 3-BrN to 5-BrN show a prominent HOMO-LUMO absorption band at ca. 520 nm, which is red-shifted and intensifies on platination. All compounds are dual fluorescence and phosphorescence emitters in the range of 520 to 670 nm, or at ca. 1000 nm, both at room temperature and at 77 K. The population of an excited triplet state and their photostability even towards continuous light irradiation renders these compounds efficient sensitizers for singlet oxygen generation and catalysts for the photo-oxidation of triphenylphosphine. Full article

To promote green chemistry and improve the utilization of plant resources, flavonoids from Dalbergia pinnata (Lour.) Prain were extracted in this study by combining NADES (natural deep eutectic solvents) with UAE (ultrasound-assisted extraction). Among the 13 synthesized NADES, choline chloride (ChCl)–urea (NADES-13) exhibited the highest extraction rate, outperforming traditional organic solvents. The optimal conditions determined by response surface methodology (RSM) were as follows: ChCl–urea molar ratio of 1:3, moisture content of 60%, liquid-to-material ratio of 28.5 mL/g, ultrasonic extraction time of 49 min, and temperature of 62 °C. Under these conditions, the extraction rate reached 117.95 ± 5.97 mg/g, a 73.5% improvement compared with 80% EtOH extraction. The comparison of the two algorithms showed that RSM (R = 0.9981, RMSE = 0.6570) had better fitting accuracy and prediction stability under small sample conditions than MLP (R = 0.9427, RMSE = 5.261) and RF (R = 0.9431, RMSE = 5.2442). DFT (density functional theory) analysis demonstrated that hydrogen bonds, Van der Waals forces, and cation–π interactions mediate the interaction between NADES-13 and flavonoids. Ultrasonic cavitation-induced cell wall damage and the hydrogen-bond network of NADES-13 were confirmed separately by SEM (scanning electron microscopy) and FTIR (Fourier transform infrared spectroscopy). In vitro experiments showed that the extract possessed concentration-dependent antioxidant activity and strong antibacterial activity, with an inhibition rate of 96.87 ± 5.09% against Escherichia coli at a concentration of 0.04 mg/mL. In this study, a “Smart Optimization–Molecular Mechanism–Activity Verification” green extraction system was developed, which offers an efficient and environmentally friendly strategy for extracting plant bioactive components and contributes to the progress of green chemistry. Full article

This study demonstrates the high efficiency and selectivity of p-toluenesulfonic acid-based deep eutectic solvents (DESs) for simultaneous extractive denitrogenation (EDN) and desulfurization (EDS) of model fuel. Three DESs—TBPB:PTSA, TBAB:PTSA, and ChCl:PTSA (1:1 molar ratio)—were synthesized and evaluated for their effectiveness against representative heteroaromatic pollutants: thiophene, dibenzothiophene, pyridine, and carbazole. The phosphonium-based TBPB:PTSA exhibited the highest extraction performance, achieving over 96% removal of nitrogen species and up to 85% removal of sulfur species at 40 °C. Increasing the temperature enhanced desulfurization by reducing viscosity, thereby improving mass transfer kinetics. Additionally, a 3:1 ratio of DES to fuel provided an optimal balance between solvent economy and operational efficiency. Denitrogenation was driven by strong acid–base protonation facilitated by PTSA, while desulfurization was governed by π–π and dispersion interactions, modulated by the hydrophobicity of the cations. The DES achieved nearly quantitative nitrogen removal and satisfactory sulfur extraction after three reuse cycles, while multistage operation enabled complete purification within four extraction steps. ¹H NMR analysis confirmed that no DES components were found in the raffinate phase, verifying the immiscibility and stability of the solvent. These results indicate that TBPB:PTSA is a robust, regenerable, and environmentally benign solvent, effectively enabling simultaneous EDN–EDS of hydrocarbon fuels and positioning it as a promising green alternative to traditional hydrogen-based refining methods. Full article

1-Phenyl-4-p-tolyl-[1,2,3]triazole was obtained via a CuAAC reaction involving phenyl azide and 1-ethynyl-4-methylbenzene. The NMR spectra of the compound are discussed, and its crystal structure was studied by X-ray analysis. According to the latter analysis and a Hirshfeld surface analysis, the predominant intermolecular C-H⋅⋅⋅N and C-H⋅⋅⋅π interactions in this molecule are responsible for crystal packing. Full article

Background/Objectives: 2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD) is a highly toxic environmental contaminant whose adverse biological effects are primarily mediated through activation of the aryl hydrocarbon receptor (AhR). Upon ligand binding, AhR undergoes conformational changes that initiate nuclear translocation and transcriptional activation of xenobiotic-responsive genes, contributing to toxicity, carcinogenesis, and dysregulated immune and metabolic responses. Understanding the molecular basis of AhR activation by TCDD is therefore critical for the rational development of targeted therapeutic strategies. Methods: In this study, molecular docking simulations were employed to characterize the interaction of TCDD and selected AhR antagonists (CH223191, BAY 2416964, GNF-351) with the ligand-binding domain of AhR, with particular emphasis on the canonical PAS-B domain. Results: Docking analyses identified the PAS-B cavity (pocket C1) as the most biologically relevant binding site for high-affinity ligands, consistent with experimental evidence. Comparative docking of known AhR antagonists revealed stable binding poses characterized by hydrophobic packing, π–π interactions, and hydrogen-bonding networks that competitively block agonist access and prevent receptor activation. These findings support a competitive antagonism mechanism as a viable approach to counteract TCDD-induced AhR signaling. Conclusions: Collectively, this in silico study provides mechanistic insight into TCDD toxicity at the molecular level and highlights AhR antagonism as a promising strategy for the development of targeted therapies against dioxin-related pathologies. Full article

We present a modular building block strategy for synthesizing phosphonated polyaromatic systems as an alternative to the conventional late-stage phosphonation of prefabricated aromatic scaffolds, which often requires harsh conditions and has limited tolerance for functional groups. A monophosphonated biphenyl building block was obtained via nickel-catalyzed phosphonation of dibromobiphenyl at 170 °C for three hours. This synthesis is more economical and milder than typical high-temperature palladium systems. In parallel, a borated pyrene derivative was prepared by Suzuki–Miyaura borylation. The final palladium-catalyzed Suzuki cross-coupling reaction produced the target compound, octaethyl(pyrene-tetrakis(biphenyl))tetrakis(phosphonate), Et₈-PyTPPE. Single-crystal X-ray diffraction reveals a centrosymmetric molecule that crystallizes in the triclinic space group P–1, with the inversion center located at the central C–C bond of the pyrene core. The pyrene unit is essentially planar, while the biphenylphosphonate arms are highly twisted relative to the core and to each other. The crystal packing is dominated by weak intermolecular interactions, and no significant π–π stacking is observed. Hirshfeld surface analysis shows that H···H (60.5%) and C···H (22.5%) contacts predominate, while O···H interactions (14.4%) with phosphoryl oxygen atoms represent the most relevant directed contacts. From photophysical investigations, Et₈-PyTPPE exhibits blue fluorescence (λ_em. = 452 nm) in solution and aggregation-induced red-shifted emission with nanosecond lifetimes in the solid state, confirming purely fluorescent behavior. Full article

Rice is a globally indispensable staple food and a major dietary source of phenolic compounds, whose nutritional and functional properties are influenced by their interactions within the rice matrix. This review provides a comprehensive synthesis of current knowledge on rice phenolics distribution and their macromolecule interactions, integrating evidence from binary, and ternary systems, to whole-matrix perspectives and examines their structural, functional, and nutritional consequences. Across rice genotypes, 76 polyphenols have been identified and quantified, encompassing phenolic acids, flavonoids, proanthocyanidins, and anthocyanins. Their abundance, chemical structure, and localization significantly dictated by grain anatomy, pigmentation, and processing. Mechanistically, phenolic binding is dominated by non-covalent interactions, including hydrogen bonding, hydrophobic interactions, electrostatic forces, CH–π interactions, and π–π stacking, facilitating multiscale structural reorganizations through amylose inclusion complexation, protein conformational rearrangements, lipid-assisted V-type crystallization, and dietary fiber binding. In ternary systems, competitive and synergistic interactions further modulate binding strength and structural organization. Functionally, these matrix-mediated interactions regulate stability and bioaccessibility of phenolic, macronutrient digestibility, glycemic response, and key technofunctional properties. By integrating compositional, mechanistic, and functional evidence, this review establishes a robust framework for understanding rice matrix–phenolic interactions and supports the rational design of phenolic-enriched, low-glycemic rice products with targeted nutritional benefits. Full article

This study proposes a circular economy strategy to recover phenolic compounds by valorizing shrimp shell waste into a chitosan biosorbent (CH-B). Its adsorption efficiency was evaluated compared to commercial activated carbon (AC) and synthetic XAD-4 resin. Kinetic analysis revealed that while both pseudo-first-order (PFO) and pseudo-second-order (PSO) models exhibited high correlations (R²$\ge$ 0.96), both CH-B and XAD-4 resin were best described by the PFO model. This aligns with diffusion-controlled processes consistent with the porous and physical nature of these adsorbents. In contrast, AC followed the PSO model. Isotherm modeling indicated that CH-B and AC fit the Temkin model, reflecting heterogeneous surfaces, whereas XAD-4 followed the Langmuir model (monolayer adsorption). Notably, CH-B exhibited a maximum adsorption capacity (q_m) of 229.2 mg/g, significantly outperforming XAD-4 (104.8 mg/g) and AC (90.2 mg/g). Thermodynamic and kinetic modeling confirmed that the adsorption mechanism was governed by a combination of electrostatic interactions, π–π stacking, and hydrogen bonding between the hydroxyl/amine groups of chitosan and phenolic compounds. Optimization using Box–Behnken design for CH-B showed optimal acidic pH and moderate temperature but non-significant effect of CH-B dose in the experimental domain. Optimisation results showed unexpected high removal efficiency at low CH-B dosages. A tentative explanation may be adsorbent aggre-gation, which needs to be confirmed by further experimental evidence. Full article

Two crystals of N,N′-bis(phosphonomethyl)-1,4,5,8-naphthalenediimide were grown in the presence of neutral (water) and charged (imidazolium cation) species, yielding [(H₂O₃P)CH₂-(C₁₄H₄N₂O₄)-CH₂(PO₃H₂)]∙H₂O (1) and [C₃H₅N₂][(H_1.5O₃P)CH₂-(C₁₄H₄N₂O₄)-CH₂(PO₃H_1.5)] (2), respectively. The ligand N,N′-bis(phosphonomethyl)-1,4,5,8-naphthalenediimide was synthesized via the condensation of naphthalene-1,4,5,8-tetracarboxylic dianhydride with (aminomethyl)phosphonic acid in N,N′-dimethylformamide or imidazole. The flexible N-methyl phosphonic acid groups adopt a cis configuration in compound 1 and a trans configuration in compound 2. In compound 1, the phosphonate groups engage in extensive hydrogen bonding, as well as with water molecules and π–π stacking, resulting in a three-dimensional closely packed structure. Compound 2 forms a densely packed three-dimensional network stabilized by charge-assisted hydrogen bonding (anion-cation), anion–π interactions, and π–π stacking interactions. Hirshfeld surface analysis was conducted and the associated two-dimensional fingerprint plots were generated to further elucidate the nature and contributions of these noncovalent interactions. Direct bandgap measurements estimated from Tauc plots yielded values of 2.92 eV and 2.85 eV for compounds 1 and 2, respectively, highlighting their potential as promising n-type organic semiconductors. Thermal analysis reveals that compound 2 exhibits greater thermal stability than compound 1. Full article

Perimidine derivatives are versatile heterocycles with growing significance in medicinal chemistry and materials sciences. However, their structural variety remains limited. This study focused on the synthesis and crystal structure characterization of a new perimidine-based molecule. A bicyclic perimidine lactone, (1S,4R)-4,7,7-trimethyl-1-(1H-perimidin-2-yl)-2-oxabicyclo[2.2.1]heptan-3-one (1), was synthesized through an intramolecular dehydration of a monoamide intermediate formed from 1,8-diaminonaphthalene and (1S)-(–)-camphanic chloride under basic conditions. The product was purified and crystallized from acetone, giving single crystals suitable for X-ray diffraction. Structural analysis revealed two stereogenic centers and crystallization in the chiral tetragonal P4₃2₁2 space group, with stabilization through N—H···O and C—H···N hydrogen bonds as well as C—H···π interactions. Full article

Organophosphate pesticides are among the most persistent and toxic contaminants in aquatic environments, requiring effective strategies for detection and remediation. In this work, density functional theory (DFT) calculations were employed to investigate the adsorption of nine representative organophosphates (glyphosate, malathion, diazinon, azinphos-methyl, fenitrothion, parathion-methyl, disulfoton, tokuthion, and ethoprophos) on mercaptobenzothiazole disulfide (MBTS) and MBTS-functionalized graphene (G–MBTS). All simulations were performed in aqueous solution using the SMD solvation model with dispersion corrections and counterpoise correction for basis set superposition error. MBTS alone displayed a range of affinities, suggesting potential selectivity across the organophosphates, with adsorption energies ranging from 0.27 to 1.05 eV, malathion being the strongest binder and glyphosate the weakest. Anchoring of MBTS to graphene was found to be highly favorable (1.26 eV), but the key advantage is producing stable adsorption platforms that promote planar orientations and $\pi$–$\pi$/dispersive interactions. But the key advantage is not stronger binding but the tuning of interfacial electronic properties: all G–MBTS–OP complexes show uniform, narrow HOMO-LUMO gaps (∼0.79 eV) and systematically larger charge redistribution. These features are expected to enhance electrochemical readout even when adsorption strength was comparable or slightly lower (0.47–0.88 eV) relative to MBTS alone. A Quantum Theory of Atoms in Molecules (QTAIM) analysis of the G–MBTS–malathion complex revealed a dual stabilization mechanism: multiple weak C–H⋯$\pi$ interactions with graphene combined with stronger S⋯O and hydrogen-bonding interactions with MBTS. These results advance the molecular-level understanding of pesticide–surface interactions and highlight MBTS-functionalized graphene as a promising platform for the selective detection of organophosphates in water. Full article

Polymorphism critically influences the solid-state properties of organic molecules, affecting stability, solubility, and functionality. We investigated the polymorphic behavior of enantiomerically pure (+)-(6aS,11aS)-medicarpin through combined experimental and computational analyses. Single-crystal X-ray diffraction revealed two distinct chiral polymorphs: the previously reported monoclinic P2₁ form and a newly identified orthorhombic P2₁2₁2₁ form with a fully chiral packing arrangement. The discovery of this previously unreported polymorph underscores the subtle yet decisive effects of solvent and conformational flexibility in directing crystallization. Detailed structural analysis reveals that, whereas the P2₁ form is only stabilized by a single dominant electrostatic interaction, the P2₁2₁2₁ form features a more complex network comprising C-H···π contacts, bifurcated C-H···O hydrogen bonds, and aromatic edge-to-face interactions. Further investigation of a functionalized p-nitrobenzoate derivative corroborates the critical influence of molecular substituents and crystallization conditions on packing motifs. Lattice energy DFT calculations confirm that each polymorph is stabilized by distinct electrostatic and dispersive interaction patterns, illustrating the complex energetic landscape of polymorph selection. Altogether, this work provides a framework for understanding and anticipating which polymorph is likely to form under specific solvent and crystallization conditions, offering insights for future strategies in materials design and guiding the pursuit of patentable crystalline forms in pharmaceutical applications. Full article

Surfactants are used in various washing applications with potential negative environmental and health impacts. The ion-pair 1,3-dioctadecyl-1H-1,2,3-triazol-3-ium-tetraphenylborate (DODTA–TPB) was used to fabricate the potentiometric sensor for the quantification of anionic surfactants. The computational analysis of the DODTA⁺–TPB⁻ adduct reveals a dynamic, thermodynamically favorable interaction driven primarily by hydrophobic C–H∙∙∙π contacts and the flexibility of the C-18 chains, rather than electrostatic or π–π stacking forces. These findings, supported by the MM-PBSA, RDF, and structural analyses, align with broader trends in molecular recognition and provide a foundation for designing advanced ion-pair-based sensors. The sensor showed advanced analytical properties to anionic surfactants with low interfering effects of selected anions. The response of the SDS was investigated in the range from 8.1 × 10⁻⁸ M to 1.0 × 10⁻² M, with a slope of −59.2 mV and a limit of detection (LOD) of 3.1 × 10⁻⁷ M; and DBS was in the range of 8.1 × 10⁻⁸ M to 2.5 × 10⁻³ M with a slope of −57.5 mV and an LOD of 5.9 × 10⁻⁷ M. The sensor was tested on potential interfering ions. Potentiometric titrations of technical-grade anionic surfactants had high recovery rates from 100.2 to 100.4%. The recovery test for spiked samples of surface waters was from 94.2 to 96.5%. The sensor was tested on commercial samples containing anionic surfactants, and the results were compared and showed a good agreement with the two-phase titration method. Full article

A novel series of multifunctional tacrine–quinoline hybrids were designed, synthesized, and evaluated as potential anti-Alzheimer’s agents. These compounds incorporate tacrine for cholinesterase’s inhibition and 8-hydroxyquinoline for metal chelation. Piperazine was selected as a linker to provide conformational flexibility and to create favorable cation–π interactions with residues in the mid-gorge region of AChE, enhancing dual-site binding with AChE to inhibit Aβ aggregation. In vitro studies demonstrated submicromolar inhibitory activity toward both AChE and BuChE, particularly for compounds 16e (IC₅₀ = 0.10 μM for AChE, 0.043 μM for BuChE) and 16h (IC₅₀ = 0.21 μM for AChE, 0.10 μM for BuChE). These compounds also exhibited potent inhibition of self-induced Aβ_1–42 aggregation (16e: 80.5% ± 4.4%, 16h: 93.2% ± 3.9% at 20 μM). Kinetic analyses revealed mixed-type inhibition, suggesting dual binding to both CAS and PAS of AChE. UV–vis spectrometry confirmed the chelation of Cu²⁺ and Zn²⁺ ions by the 8-hydroxyquinoline moiety. These findings highlight the tacrine–quinoline scaffold as a promising platform for the discovery of a multitarget-directed anti-AD drug. Full article