Supramolecular hydrophobic eutectogels (HEG) are an emerging class of soft materials. They combine the high solvation ability and sustainability profile of hydrophobic eutectic solvents (HES) with the mechanical stability and easy separation and handling of supramolecular gels. However, the relationship between the molecular organization of the HES liquid phase confined within the supramolecular gel, the bulk properties of the gel matrix, and the functional performance of the final material remains largely unexplored. Here, HEG were prepared by self‐assembly of the low‐molecular‐weight gelator 1,3:2,4‐dibenzylidene‐D‐sorbitol (DBS) at two concentrations (2 and 5 wt%) in four nonionic HES (trioctylphosphineoxide:DL‐menthol, trioctylphosphineoxide:dodecanoic acid, DL‐menthol:oleic acid, and octanoic acid:dodecanoic acid). The HEG were investigated by a combination of rheology, high‐resolution magic‐angle spinning (HRMAS) NMR spectroscopy, and diffusion measurements, providing a comprehensive description of the materials covering mechanical properties, molecular organization, and translational mobility under confinement. Their potential as economically and environmentally sustainable sorbents in water remediation was demonstrated in the removal of bisphenol A (BPA) from aqueous solutions. The extraction efficiency and cross‐contamination arising from HEG component leaching were shown to depend on the interplay between HES‐specific intermolecular interactions and DBS‐induced confinement. Indeed, the supramolecular organization induced by the gelator introduces an additional level of control over molecular mobility, thus affecting both BPA uptake and leaching. Among the investigated systems, trioctylphosphineoxide‐based HEG provided the most favorable balance between BPA removal and leaching of the HEG components, while maintaining their structural and molecular properties after extraction. BPA extraction efficiencies above 98.5% were achieved for the systems containing 5 wt% DBS after 16 h, while quantitative NMR analysis showed low leaching of HEG components (<0.3 wt%). These findings support HEG as versatile materials where molecular organization and mobility, mechanical properties, and pollutant affinity can be tailored to design functional soft materials for separation processes and beyond.
A novel, highly sensitive surfactant‐supported method was developed for vilazodone (VLD) determination using a boron‐doped diamond (BDD) electrode. This study represents the first VLD detection on a BDD electrode and the first application of surfactant‐supported voltammetry for this antidepressant. The electrochemical behavior of VLD was evaluated at different pH values using differential pulse voltammetry (DPV). The peak potential shifted negatively up to pH 7.0 and stabilized thereafter, indicating a proton‐involved oxidation mechanism with a pKa near 7.0. The effects of CTAB, SDS, and Tween 20 were investigated, with Tween 20 providing the greatest peak‐current enhancement due to its nonionic character, interfacial organization, and microcolloidal environment, improving mass transport and suppressing adsorption‐controlled pathways. Under optimized conditions, excellent linearity (R2 >0.988) was obtained over 5.0 × 10−10–1.0 × 10−6 M. Recoveries of 98%–102% were achieved in pharmaceutical formulations and spiked human serum samples, demonstrating applicability to complex matrices. Density functional theory calculations showed highest occupied molecular orbital localization mainly over the nitrogen‐containing conjugated region and partly on the piperazine moiety, supporting piperazine nitrogen involvement in anodic oxidation. The proposed DPV‐BDD platform provides a rapid, sensitive, and reliable approach for VLD analysis with nonionic surfactant‐assisted signal enhancement.
This study aimed to characterize the volatile and fatty acid constituents of S. peruviana and investigate their potential anti‐inflammatory mechanisms. Volatile compounds were identified by headspace solid‐phase microextraction coupled with gas chromatography–mass spectrometry (HS‐SPME‐GC–MS), whereas fatty acids were analyzed by GC–MS following derivatization. The identified phytochemicals were subjected to target prediction, followed by protein–protein interaction (PPI), Gene Ontology (GO), Kyoto Encyclopedia of Genes and Genomes (KEGG) pathway enrichment analyses, and molecular docking. HS‐SPME‐GC–MS analysis identified 11 volatile compounds, predominantly hexahydrofarnesyl acetone (48.4%) and dihydroactinidiolide (23.5%), followed by dehydro‐β‐ionone (5.6%), 2‐methylbutanal (5.5%), and 3‐methylbutanal (5.1%). Fatty acid profiling revealed palmitic acid as the predominant fatty acid (47.7%), followed by α‐linolenic acid (29.9%), linoleic acid (11.6%), and stearic acid (10.8%). Network pharmacology identified 253 overlapping targets between phytochemical‐associated proteins and inflammation‐related genes, with TNF, IL1B, PTGS2, EGFR, STAT3, and PPARG emerging as the principal hub proteins. KEGG enrichment analysis revealed significant enrichment in inflammation‐associated pathways, including NF‐κB, IL‐17, NOD‐like receptor, and advanced glycation end‐products (AGE)‐receptor for advanced glycation end‐products (RAGE) signaling pathways. Molecular docking predicted interactions between the major phytochemicals and the selected targets, with palmitic acid showing the lowest predicted binding energy for COX‐2 (−7.0 kcal/mol), while hexahydrofarnesyl acetone and stearic acid showed the lowest predicted binding energies for PPARγ (−8.3 kcal/mol).
This study investigates the adsorption mechanisms of the organic azo dye azorubine (E122) on the surface of alumina (γ‐Al2O3), using molecular dynamics simulations, density functional theory (DFT), noncovalent interaction, and reduced density gradient analyses. The chemical reactivity of E122 was evaluated using DFT with the B3PW91 hybrid exchange–correlation functional and the LANL2DZ relativistic pseudopotential basis set. Speciation analysis showed that pH strongly influences the distribution of E122's ionic forms according to their pKa values, with forms 1, 2, and 3 predominating across the studied pH range, and the dye exhibiting strong affinity for the adsorbent surface in aqueous medium. DFT analysis identified key active sites and electronic properties governing dye–surface interactions and adsorbent affinity. Form 2 showed the highest adsorption energy (−917.107 kcal/mol), followed by forms 1 and 3 (−861.553 and −806.286 kcal/mol, respectively). These adsorption properties were further confirmed through density field and energy distribution analyses, while radial distribution function profiles, with all interatomic distances within 3.5 Å, confirmed a chemisorption‐driven mechanism. Overall, γ‐Al2O3 is an effective, low‐cost, recyclable, and eco‐friendly adsorbent for dye removal.
A green and efficient method was developed for propranolol delivery utilizing manganese‐based bioactive metal–organic frameworks (MOFs) as biocompatible drug carriers. Mn‐based bioactive MOFs with a high aspect ratio were synthesized and characterized for size (average, 17 µm), morphology, stability, elemental composition, crystallinity, functionality, charge character, and biocompatibility (a protein adsorption capacity of 0.03 µg µg−1 (5 h) and a hemolysis ratio of < 0.5%). Afterward, the MOFs were utilized for drug loading via an encapsulation method, and the drug release studies were also performed. The drug loading was confirmed using the zeta potential, CHN analysis, and thermogravimetric analysis (TGA) measurements. An encapsulation efficiency of 96% (0.5 W/W (drug/MOFs)) and a maximal capacity (Qmax) of 0.526 mg mg−1 were obtained. The drug release showed that 93.72% of the loaded drug was released after 10 h for a composite of 0.25 W/W (drug/MOFs), while for 0.5 W/W (drug/MOFs), the drug release reached a plateau after 3 h. The kinetic studies showed longer release times and higher release rates for higher drug loading efficiency. Overall, herein, a bioactive platform for efficient delivery of propranolol was developed to improve the therapeutic efficacy by enhancing the drug loading and achieving controlled drug release.
