In the present work, a straightforward, highly competent and green route for synthesis of 3-methyl-4-(hetero aromatic/arylmethylene)isoxazole-5(4H)-ones by multicomponent reaction of aromatic or heteroaromatic aldehydes, ethyl acetoacetate and hydroxylamine was established by using unique combination of β-cyclodextrin (β-CD) and DES (deep eutectic solvent) of urea-choline chloride as green and environmentally sustainable solvent and catalyst. All derivatives of 3-methyl-4-(hetero aromatic/arylmethylene)isoxazole-5(4H)-ones were successfully synthesized within 17–20 min in DES using 20 mol% β-cyclodextrin with good to excellent yields (80–97 %) at 27 °C. Moreover, operational simplicity, green reaction medium, short reaction time, atom and step economy, low operational temperature, use of cost effective and easily available reagents and environmentally sustainable are some appealing features of this reported synthetic protocol to access small drug-like entities with structural diversity and molecular complexity for their utilization in medicinal chemistry. More importantly, this combination of environmental benign catalyst and solvent system (β-CD-urea-ChCl) was easily restored and reused up to five times without noticeable drop in product quality and yields.
本研究以独特的β-环糊精（β-CD）和深共晶溶剂DES（深共晶溶剂）作为绿色环保的溶剂和催化剂，以芳香或杂芳香醛、乙酰乙酸乙酯和羟胺为原料，建立了一条简单、高效、绿色的合成3-甲基-4-（杂芳/芳基亚甲基）异恶唑-5(4H)-的多组分反应路线。所有3-甲基-4-（杂芳香/芳基亚甲基）异唑-5(4H)-衍生物在27℃下，用20 mol%的β-环糊精在17-20 min内合成成功，产率达到80 - 97%。此外，操作简单，绿色反应介质，反应时间短，原子和步骤经济，操作温度低，使用成本效益高且易于获得的试剂以及环境可持续性是该合成方案的一些吸引人的特点，可以获得具有结构多样性和分子复杂性的小型药物实体，用于药物化学。更重要的是，这种环境友好的催化剂和溶剂体系（β- cd -尿素- chcl）的组合很容易恢复和重复使用多达五次，而产品质量和收率没有明显下降。
{"title":"Synthesis of 3-methyl-4-(hetero aromatic/arylmethylene)isoxazole-5(4H)-ones using deep eutectic solvent (DES) of urea-choline chloride and β-cyclodextrin as green and sustainable combination of solvent and catalyst","authors":"Sakshi Pathak , Komal Rathi , Ved Prakash Verma , Rahul Shrivastava","doi":"10.1016/j.molliq.2025.129147","DOIUrl":"10.1016/j.molliq.2025.129147","url":null,"abstract":"<div><div>In the present work, a straightforward, highly competent and green route for synthesis of 3-methyl-4-(hetero aromatic/arylmethylene)isoxazole-5(4H)-ones by multicomponent reaction of aromatic or heteroaromatic aldehydes, ethyl acetoacetate and hydroxylamine was established by using unique combination of β-cyclodextrin (β-CD) and DES (deep eutectic solvent) of urea-choline chloride as green and environmentally sustainable solvent and catalyst. All derivatives of 3-methyl-4-(hetero aromatic/arylmethylene)isoxazole-5(4H)-ones were successfully synthesized within 17–20 min in DES using 20 mol% β-cyclodextrin with good to excellent yields (80–97 %) at 27 °C. Moreover, operational simplicity, green reaction medium, short reaction time, atom and step economy, low operational temperature, use of cost effective and easily available reagents and environmentally sustainable are some appealing features of this reported synthetic protocol to access small drug-like entities with structural diversity and molecular complexity for their utilization in medicinal chemistry. More importantly, this combination of environmental benign catalyst and solvent system (β-CD-urea-ChCl) was easily restored and reused up to five times without noticeable drop in product quality and yields.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"444 ","pages":"Article 129147"},"PeriodicalIF":5.2,"publicationDate":"2025-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145839338","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-18DOI: 10.1016/j.molliq.2025.129166
Yuhua Song , Ru Yan , Rui Dong, Ping Wen, Mingjin Fan
The rational design of lubricants that exploit robust interfacial adsorption and friction-induced tribofilm formation is crucial for achieving tailored performance. Conventional ester lubricants often suffer from weak adsorption and the formation of inferior metal soap films. Herein, we report a molecular engineering strategy to synthesize a series of nitrilotriacetate esters with customizable structures by regulating alkyl chain length, branching, and ester group count. The optimized tridecyl 2,2′,2″-nitrilotriacetate (TDNA) exhibits superlative lubrication performance. Its trigonal pyramidal geometry, featuring three ester groups coordinated with a central nitrogen atom, facilitates a stable five-membered chelate structure that acts as a powerful “atomic anchor” to the metal surface, ensuring strong interfacial adhesion. The three linear alkyl chains further self-assemble via intensive van der Waals interactions, forming a dense and highly ordered molecular film. Under rubbing incitation, this robust adsorbed layer acts as a sacrificial precursor, undergoing in-situ degradation and metal-catalyzed reorganization into a protective graphene-like carbon tribofilm, rather than conventional metal soaps. This synergistic mechanism of atomic anchoring and controllable graphitization establishes a self-renewing lubrication system, resulting in significantly reduced friction and wear. This work provides profound insights into the molecular-level design of high-performance, sustainable lubricants.
{"title":"Atomic anchoring and friction-induced graphitization in nitrilotriacetate esters for customizable lubrication","authors":"Yuhua Song , Ru Yan , Rui Dong, Ping Wen, Mingjin Fan","doi":"10.1016/j.molliq.2025.129166","DOIUrl":"10.1016/j.molliq.2025.129166","url":null,"abstract":"<div><div>The rational design of lubricants that exploit robust interfacial adsorption and friction-induced tribofilm formation is crucial for achieving tailored performance. Conventional ester lubricants often suffer from weak adsorption and the formation of inferior metal soap films. Herein, we report a molecular engineering strategy to synthesize a series of nitrilotriacetate esters with customizable structures by regulating alkyl chain length, branching, and ester group count. The optimized tridecyl 2,2′,2″-nitrilotriacetate (TDNA) exhibits superlative lubrication performance. Its trigonal pyramidal geometry, featuring three ester groups coordinated with a central nitrogen atom, facilitates a stable five-membered chelate structure that acts as a powerful “atomic anchor” to the metal surface, ensuring strong interfacial adhesion. The three linear alkyl chains further self-assemble <em>via</em> intensive van der Waals interactions, forming a dense and highly ordered molecular film. Under rubbing incitation, this robust adsorbed layer acts as a sacrificial precursor, undergoing <em>in-situ</em> degradation and metal-catalyzed reorganization into a protective graphene-like carbon tribofilm, rather than conventional metal soaps. This synergistic mechanism of atomic anchoring and controllable graphitization establishes a self-renewing lubrication system, resulting in significantly reduced friction and wear. This work provides profound insights into the molecular-level design of high-performance, sustainable lubricants.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"443 ","pages":"Article 129166"},"PeriodicalIF":5.2,"publicationDate":"2025-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145799261","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-18DOI: 10.1016/j.molliq.2025.129128
Mohamed A. Migahed , Rasha S. Kamal , Reham I. El-shazly , Nashwa M. Saleh , Nour E.A. Abd El-Sattar , Amr Elgendy , Ahmed H. Elged
This work is aimed to investigate two newly synthesized organic compounds derived from oxalamide and abbreviated as 3 N and 6 N, respectively, as dual-function compounds for corrosion mitigation and killer of SRB in oilfield applications. The compounds were synthesized and assessed via 1H NMR & 13C NMR spectroscopy. Their efficacy in corrosion inhibition was assessed on carbon steel (CS) in oil well formation water (FW) under sweet conditions (0.5 bar of CO₂, 50 °C) using (EIS and PDP) techniques. The inhibition efficiency (IE%) was strongly influenced by two key factors, namely the concentration of the inhibitor and the nature of its molecular structure. At an optimum concentration of 300 ppm, the efficiency values increased significantly, reaching 87.46 % for compound 3 N and as high as 93.56 % for compound 6 N. The adsorption process adhered to the Langmuir isotherm model, indicating that the interaction encompassed both physical and chemical adsorption mechanisms. Atomic Force Microscopy (AFM) revealed a notable diminution of surface degradation in the presence of the inhibitors. In addition, the antimicrobial activity of the compounds was assessed against sulfate-reducing bacteria (SRB) using the serial dilution method. The results demonstrated notable antibacterial properties alongside effective corrosion inhibition, suggesting the synthesized compounds act as very good multifunctional additives. Density Functional Theory (DFT) calculations were performed to correlate molecular structure with inhibition performance, offering theoretical insights into the observed trends. Ultimately, a plausible mechanism describing the corrosion inhibition process was proposed and critically analysed to provide deeper insight into the protective action of the inhibitors.
本文旨在研究草草酰胺衍生的两种新合成的有机化合物，分别缩写为3n和6n，作为油田应用中缓蚀剂和SRB杀手的双重功能化合物。合成了化合物，并通过1H NMR和13C NMR谱进行了鉴定。采用EIS和PDP技术，在低温度条件下（0.5 bar CO₂，50°C）对油井地层水中的碳钢（CS）进行了缓蚀效果评估。抑制效率（IE%）受两个关键因素的强烈影响，即抑制剂的浓度和其分子结构的性质。在最佳浓度为300 ppm时，化合物3 N的吸附效率显著提高，达到87.46%，化合物6 N的吸附效率高达93.56%。吸附过程符合Langmuir等温线模型，表明相互作用包括物理和化学吸附机制。原子力显微镜（AFM）显示，在抑制剂的存在下，表面降解明显减少。此外，采用连续稀释法评估了化合物对硫酸盐还原菌（SRB）的抑菌活性。结果表明，合成的化合物具有显著的抗菌性能和有效的缓蚀作用，是一种很好的多功能添加剂。密度泛函理论（DFT）计算将分子结构与抑制性能联系起来，为观察到的趋势提供理论见解。最后，提出了一种描述腐蚀抑制过程的合理机制，并对其进行了批判性分析，以更深入地了解抑制剂的保护作用。
{"title":"Synthesis, characterization, and determination of the performance of novel bifunctional compounds as corrosion inhibitors and biocides under CO2 and SRB environment","authors":"Mohamed A. Migahed , Rasha S. Kamal , Reham I. El-shazly , Nashwa M. Saleh , Nour E.A. Abd El-Sattar , Amr Elgendy , Ahmed H. Elged","doi":"10.1016/j.molliq.2025.129128","DOIUrl":"10.1016/j.molliq.2025.129128","url":null,"abstract":"<div><div>This work is aimed to investigate two newly synthesized organic compounds derived from oxalamide and abbreviated as 3 N and 6 N, respectively, as dual-function compounds for corrosion mitigation and killer of SRB in oilfield applications. The compounds were <u><u>synthesized</u></u> and assessed via <sup>1</sup>H NMR & <sup>13</sup>C NMR spectroscopy. Their efficacy in corrosion inhibition was assessed on carbon steel (CS) in oil well formation water (FW) under sweet conditions (0.5 bar of CO₂, 50 °C) using (EIS and PDP) techniques. The inhibition efficiency (IE%) was strongly influenced by two key factors, namely the concentration of the inhibitor and the nature of its molecular structure. At an optimum concentration of 300 ppm, the efficiency values increased significantly, reaching 87.<u><u>46 %</u></u> for compound 3 N and as high as 93.<u><u>56 %</u></u> for compound 6 N. The adsorption process adhered to the Langmuir isotherm model, indicating that the interaction encompassed both physical and chemical adsorption mechanisms. Atomic Force Microscopy (AFM) revealed a notable diminution of surface degradation in the presence of the inhibitors. In addition, the antimicrobial activity of the compounds was assessed against sulfate-reducing bacteria (SRB) using the serial dilution method. The results demonstrated notable antibacterial properties alongside effective corrosion inhibition, suggesting the <u><u>synthesized</u></u> compounds act as very good multifunctional additives. Density Functional Theory (DFT) calculations were performed to correlate molecular structure with inhibition performance, offering theoretical insights into the observed trends. Ultimately, a plausible mechanism describing the corrosion inhibition process was proposed and critically <u><u>analysed</u></u> to provide deeper insight into the protective action of the inhibitors.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"443 ","pages":"Article 129128"},"PeriodicalIF":5.2,"publicationDate":"2025-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145838454","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-18DOI: 10.1016/j.molliq.2025.129145
Jessica A.O. Rodrigues , Antonio D.S.G. Lima , João G. de Oliveira Neto , Natan A.B. de Sousa , Thallysson J.D. de Sousa , Adenilson O. dos Santos , Clenilton C. dos Santos , Aramys S. Reis , Mateus M. Pereira , Eliana B. Souto , Alan S. de Menezes , Mateus R. Lage , Francisco F. de Sousa
The present study describes the synthesis, characterization, and the antibacterial properties of a triclinic crystal, [Cu(phen)(L-asn)H2OCl]H2O, formed by Cu(II) with L-asparagine (L-asn) and 1,10-phenanthroline (phen). Geometric, thermodynamic, electronic, and spectroscopic properties were studied herein. Complementarily, density functional theory (DFT) calculations were carried out both in vacuum and under solvated conditions using the Solvation Model based on Density (SMD), an implicit solvent model with water and ethanol. The theoretical study disclosed the spatial distributions and energies of frontier molecular orbitals, from which chemical reactivity indices were derived. Electronic properties, including spin distribution, partial atomic charges, and electrostatic potential maps, were also calculated for each medium. Calculated metal-ligand bond lengths were compared to those obtained from Powder X-Ray Diffraction (PXRD) measurements, confirming the accuracy of the PBE1PBE functional for studying coordination complexes. For the first time, a vibrational study for [Cu(phen)(L-asn)H2OCl]H2O crystal with space group is described. Experimental Raman and Infrared (IR) bands showed correlation with theoretical intramolecular vibration bands calculated for the complex. In addition, an in vitro assessment was conducted to evaluate the antibacterial effects of the crystal against eight bacterial strains (including both Gram-positive and Gram-negative species), with the best results obtained against Staphylococcus aureus, Streptococcus mutans, Escherichia coli-ESBL, and Pseudomonas aeruginosa. A molecular docking study was also conducted to evaluate the interaction mechanism between the complex and double-stranded deoxyribonucleic acid (DNA), resulting in a binding energy of −7.3 kcal/mol.
{"title":"Synthesis, physicochemical properties, DFT calculations, molecular docking, and antibacterial profile of copper crystals complexed with 1,10-phenanthroline and L-asparagine","authors":"Jessica A.O. Rodrigues , Antonio D.S.G. Lima , João G. de Oliveira Neto , Natan A.B. de Sousa , Thallysson J.D. de Sousa , Adenilson O. dos Santos , Clenilton C. dos Santos , Aramys S. Reis , Mateus M. Pereira , Eliana B. Souto , Alan S. de Menezes , Mateus R. Lage , Francisco F. de Sousa","doi":"10.1016/j.molliq.2025.129145","DOIUrl":"10.1016/j.molliq.2025.129145","url":null,"abstract":"<div><div>The present study describes the synthesis, characterization, and the antibacterial properties of a triclinic crystal, [Cu(phen)(L-asn)H<sub>2</sub>OCl]H<sub>2</sub>O, formed by Cu(II) with L-asparagine (L-asn) and 1,10-phenanthroline (phen). Geometric, thermodynamic, electronic, and spectroscopic properties were studied herein. Complementarily, density functional theory (DFT) calculations were carried out both in vacuum and under solvated conditions using the Solvation Model based on Density (SMD), an implicit solvent model with water and ethanol. The theoretical study disclosed the spatial distributions and energies of frontier molecular orbitals, from which chemical reactivity indices were derived. Electronic properties, including spin distribution, partial atomic charges, and electrostatic potential maps, were also calculated for each medium. Calculated metal-ligand bond lengths were compared to those obtained from Powder X-Ray Diffraction (PXRD) measurements, confirming the accuracy of the PBE1PBE functional for studying coordination complexes. For the first time, a vibrational study for [Cu(phen)(L-asn)H<sub>2</sub>OCl]H<sub>2</sub>O crystal with <span><math><mi>P</mi><mover><mn>1</mn><mo>¯</mo></mover><mspace></mspace><mfenced><msubsup><mi>C</mi><mi>i</mi><mn>1</mn></msubsup></mfenced></math></span> space group is described. Experimental Raman and Infrared (IR) bands showed correlation with theoretical intramolecular vibration bands calculated for the complex. In addition, an <em>in vitro</em> assessment was conducted to evaluate the antibacterial effects of the crystal against eight bacterial strains (including both Gram-positive and Gram-negative species), with the best results obtained against <em>Staphylococcus aureus</em>, <em>Streptococcus mutans</em>, <em>Escherichia coli-ESBL</em>, and <em>Pseudomonas aeruginosa</em>. A molecular docking study was also conducted to evaluate the interaction mechanism between the complex and double-stranded deoxyribonucleic acid (DNA), resulting in a binding energy of −7.3 kcal/mol.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"444 ","pages":"Article 129145"},"PeriodicalIF":5.2,"publicationDate":"2025-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145814179","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Nanoparticles are widely used to modify the properties of substrates, imparting either affinity or repellency toward adsorbates. This study investigates zinc stearate (ZnSt)-modified polyurethane (PU) substrates using molecular dynamics simulations. First, the effect of varying ZnSt concentrations (4 wt%, 9 wt%, 13 wt%, 16 wt%, and 26 wt%) on surface structure was examined. The optimal concentration (∼13 wt%) was identified based on the interactions between ZnSt chains and PU chains, as evaluated through mean square displacement (MSD) profiles and adsorption energy. This concentration was further confirmed to influence surface wettability by analyzing the relative concentration distribution and the contact angle of a water droplet. Subsequently, the effects of temperature, salinity, and pH were assessed to determine their impact on water-surface wettability. Increasing NaCl concentration to simulate salinity, adjusting pH between 1 and 13 to represent acidic and basic conditions, and varying temperature from 298 K to 373 K caused only minor changes (∼3 % deviation) in the water contact angle. Under the optimal ZnSt-modified PU conditions, the water contact angle (WCA) was significantly enhanced to 169° ± 2. Notably, this superhydrophobic state was maintained, as changes in temperature, salinity, and pH did not substantially affect wettability. Overall, this study provides molecular-level insights into the design of stable superhydrophobic materials. It demonstrates how an optimal nanoparticle concentration can generate surfaces that preserve their high efficiency under elevated temperatures, saline environments, and variable pH conditions that closely reflect real-world applications.
{"title":"Molecular investigation of optimal zinc stearate nanoparticles to modified polyurethane foam and effect of temperature, salinity and pH on stability surface","authors":"Fatemeh Sadati , Reza Mossayebi Behbahani , Yousef Tamsilian","doi":"10.1016/j.molliq.2025.129162","DOIUrl":"10.1016/j.molliq.2025.129162","url":null,"abstract":"<div><div>Nanoparticles are widely used to modify the properties of substrates, imparting either affinity or repellency toward adsorbates. This study investigates zinc stearate (ZnSt)-modified polyurethane (PU) substrates using molecular dynamics simulations. First, the effect of varying ZnSt concentrations (4 wt%, 9 wt%, 13 wt%, 16 wt%, and 26 wt%) on surface structure was examined. The optimal concentration (∼13 wt%) was identified based on the interactions between ZnSt chains and PU chains, as evaluated through mean square displacement (MSD) profiles and adsorption energy. This concentration was further confirmed to influence surface wettability by analyzing the relative concentration distribution and the contact angle of a water droplet. Subsequently, the effects of temperature, salinity, and pH were assessed to determine their impact on water-surface wettability. Increasing NaCl concentration to simulate salinity, adjusting pH between 1 and 13 to represent acidic and basic conditions, and varying temperature from 298 K to 373 K caused only minor changes (∼3 % deviation) in the water contact angle. Under the optimal ZnSt-modified PU conditions, the water contact angle (WCA) was significantly enhanced to 169° ± 2. Notably, this superhydrophobic state was maintained, as changes in temperature, salinity, and pH did not substantially affect wettability. Overall, this study provides molecular-level insights into the design of stable superhydrophobic materials. It demonstrates how an optimal nanoparticle concentration can generate surfaces that preserve their high efficiency under elevated temperatures, saline environments, and variable pH conditions that closely reflect real-world applications.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"445 ","pages":"Article 129162"},"PeriodicalIF":5.2,"publicationDate":"2025-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145923366","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-18DOI: 10.1016/j.molliq.2025.129157
Prapti Bansal, Mohit Garg, Somak Chatterjee
Groundwater, a primary source of drinking water, is becoming increasingly contaminated with toxic heavy metals, particularly lead. The unregulated discharge of industrial effluents into water bodies further exacerbates the problem. Accordingly, an effective system is required to treat these pollutants. Although there are existing solutions with certain challenges, this study aims to develop efficient composite polymeric beads composed of cellulose acetate and magnesium oxide nanoparticles for effective removal of lead from contaminated water. Prepared beads were spherical, synthesized by the phase inversion of polymer solution with the help of a needle-syringe assembly. As-prepared beads were characterized based on its morphological and chemical characteristics, revealing porous texture with considerable crystallinity. Presence of PbO bond in FTIR spectra post lead adsorption highlighted synergy between lead ions and MgOH groups. Uptake mechanism involved the substitution of hydrogen ions by lead ions, resulting in the formation of stable MgOPb complexes. This was facilitated by lead's lower electronegativity in contaminated water. Lead uptake by composite beads was governed by monolayer adsorption as evident from isotherm studies. A maximum uptake capacity of 500 mg/g was observed at 298 K, which increased to 600 mg/g at 318 K. Optimum dosage of 1 g/l was identified as ideal for achieving equilibrium conditions. Thermodynamic parameters confirmed that the adsorption process was spontaneous and endothermic in nature. Regeneration studies showed effective reusability up to two cycles, after which the removal capacity reached saturation. Isoelectric point was obtained at a pH value of 9.7. Presence of MgO helped in stabilising lead ions and prevented precipitate formation in alkaline medium, providing a minor reduction in lead removal, as compared to conventional adsorbents. Furthermore, Density functional theory (DFT) based simulation was performed suggesting collective indication of consistent trends, with both approaches converging towards the same adsorption behaviour and PbO interaction patterns.
{"title":"Magnesium oxide nanoparticles-cellulose acetate based composite beads for lead uptake from contaminated stream: Experimental and DFT based study","authors":"Prapti Bansal, Mohit Garg, Somak Chatterjee","doi":"10.1016/j.molliq.2025.129157","DOIUrl":"10.1016/j.molliq.2025.129157","url":null,"abstract":"<div><div>Groundwater, a primary source of drinking water, is becoming increasingly contaminated with toxic heavy metals, particularly lead. The unregulated discharge of industrial effluents into water bodies further exacerbates the problem. Accordingly, an effective system is required to treat these pollutants. Although there are existing solutions with certain challenges, this study aims to develop efficient composite polymeric beads composed of cellulose acetate and magnesium oxide nanoparticles for effective removal of lead from contaminated water. Prepared beads were spherical, synthesized by the phase inversion of polymer solution with the help of a needle-syringe assembly. As-prepared beads were characterized based on its morphological and chemical characteristics, revealing porous texture with considerable crystallinity. Presence of Pb<img>O bond in FTIR spectra post lead adsorption highlighted synergy between lead ions and Mg<img>OH groups. Uptake mechanism involved the substitution of hydrogen ions by lead ions, resulting in the formation of stable Mg<img>O<img>Pb complexes. This was facilitated by lead's lower electronegativity in contaminated water. Lead uptake by composite beads was governed by monolayer adsorption as evident from isotherm studies. A maximum uptake capacity of 500 mg/g was observed at 298 K, which increased to 600 mg/g at 318 K. Optimum dosage of 1 g/l was identified as ideal for achieving equilibrium conditions. Thermodynamic parameters confirmed that the adsorption process was spontaneous and endothermic in nature. Regeneration studies showed effective reusability up to two cycles, after which the removal capacity reached saturation. Isoelectric point was obtained at a pH value of 9.7. Presence of MgO helped in stabilising lead ions and prevented precipitate formation in alkaline medium, providing a minor reduction in lead removal, as compared to conventional adsorbents. Furthermore, Density functional theory (DFT) based simulation was performed suggesting collective indication of consistent trends, with both approaches converging towards the same adsorption behaviour and Pb<img>O interaction patterns.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"443 ","pages":"Article 129157"},"PeriodicalIF":5.2,"publicationDate":"2025-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145799219","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-18DOI: 10.1016/j.molliq.2025.129154
Marta Wojcieszak-Michalak , Paweł Misiak , Jacek Różański , Julia Kowalska , Katarzyna Materna
The amphiphilic molecular structure of carriers is crucial for the effectiveness and precision of targeted delivery of bioactive substances in topical treatments. Due to this, the behavior of compounds with cholesterol end-capped poly(N-isopropylacrylamide) was studied. Surface activity, wettability, and topography analysis were evaluated. The conducted research demonstrated that cholesterol-based polymers behave as surface-active agents. This is evidenced by Critical Micelle Concentration (CMC) values ranging from 0.0010 to 0.0022 mmol/L and a surface coverage of more than 26 % following the evaluation of the topography of model mica surface. Subsequently, the prepared emulgels containing the aforementioned compounds were analyzed for their physicochemical properties, including rheological and other relevant criteria such as spreadability, microorganism presence, organoleptic evaluations and texture analysis. The results showed a spreadability of approximately 5.0 cm, with pH values between 4.00 and 6.00, a range compatible with adult skin. In turn, the microbiological tests confirmed the absence of microbes in the formulation. The utilization of cholesterol-based emulsifiers transforms emulgels into a potent protective barrier for the skin, offering innovative solutions in the medical and cosmetic sectors.
{"title":"Emulgels for dermal delivery based on amphiphilic polymers bearing cholesteryl moiety: tuning surface properties via polymer chain length","authors":"Marta Wojcieszak-Michalak , Paweł Misiak , Jacek Różański , Julia Kowalska , Katarzyna Materna","doi":"10.1016/j.molliq.2025.129154","DOIUrl":"10.1016/j.molliq.2025.129154","url":null,"abstract":"<div><div>The amphiphilic molecular structure of carriers is crucial for the effectiveness and precision of targeted delivery of bioactive substances in topical treatments. Due to this, the behavior of compounds with cholesterol end-capped poly(<em>N</em>-isopropylacrylamide) was studied. Surface activity, wettability, and topography analysis were evaluated. The conducted research demonstrated that cholesterol-based polymers behave as surface-active agents. This is evidenced by Critical Micelle Concentration (CMC) values ranging from 0.0010 to 0.0022 mmol/L and a surface coverage of more than 26 % following the evaluation of the topography of model mica surface. Subsequently, the prepared emulgels containing the aforementioned compounds were analyzed for their physicochemical properties, including rheological and other relevant criteria such as spreadability, microorganism presence, organoleptic evaluations and texture analysis. The results showed a spreadability of approximately 5.0 cm, with pH values between 4.00 and 6.00, a range compatible with adult skin. In turn, the microbiological tests confirmed the absence of microbes in the formulation. The utilization of cholesterol-based emulsifiers transforms emulgels into a potent protective barrier for the skin, offering innovative solutions in the medical and cosmetic sectors.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"443 ","pages":"Article 129154"},"PeriodicalIF":5.2,"publicationDate":"2025-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145838542","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-18DOI: 10.1016/j.molliq.2025.129161
Vitaly V. Chaban
The proton transfer between cations and anions is an exotic phenomenon in ionic liquids (ILs). We previously reported such proton transfers in tetraalkylphosphonium and trialkylsulfonium ILs, containing reactive aprotic anions. The interionic proton transfer changes the physicochemical properties of ILs. It can be seen as a factor of IL's inherent kinetic instability and signifies the first step of degradation of the substance. Spontaneous transitions between the ionic state of IL and its molecular state must be appropriately understood. Herein, we characterize the possible neutralization of a few carbanionic ILs by simulating thermochemistry and kinetics related to the proton transfer from the tetraalkylphosphonium cation to malononitrile, methylmalononitrile, ethylmalononitrile, and phenylmalononitrile anions. We reveal the effects of various substituents, concluding that phenyl is the most efficient protector against IL degradation. Further, we conclude that phosphonium carbanions are systematically more resilient to neutralization than previously reported aprotic heterocyclic anions.
{"title":"Quantification of inherent stability of phosphonium-based carbanion ionic liquids: first-principles simulations of proton transfers","authors":"Vitaly V. Chaban","doi":"10.1016/j.molliq.2025.129161","DOIUrl":"10.1016/j.molliq.2025.129161","url":null,"abstract":"<div><div>The proton transfer between cations and anions is an exotic phenomenon in ionic liquids (ILs). We previously reported such proton transfers in tetraalkylphosphonium and trialkylsulfonium ILs, containing reactive aprotic anions. The interionic proton transfer changes the physicochemical properties of ILs. It can be seen as a factor of IL's inherent kinetic instability and signifies the first step of degradation of the substance. Spontaneous transitions between the ionic state of IL and its molecular state must be appropriately understood. Herein, we characterize the possible neutralization of a few carbanionic ILs by simulating thermochemistry and kinetics related to the proton transfer from the tetraalkylphosphonium cation to malononitrile, methylmalononitrile, ethylmalononitrile, and phenylmalononitrile anions. We reveal the effects of various substituents, concluding that phenyl is the most efficient protector against IL degradation. Further, we conclude that phosphonium carbanions are systematically more resilient to neutralization than previously reported aprotic heterocyclic anions.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"443 ","pages":"Article 129161"},"PeriodicalIF":5.2,"publicationDate":"2025-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145799268","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-17DOI: 10.1016/j.molliq.2025.129148
Ubaid Ur Rehman , Kashaf Ul Sahar , Chun-Ming Wang
Nanofluids, which are colloidal suspensions of nanoparticles in base fluids, have been extensively explored for advanced heat transfer and thermal management. Despite their promising thermal conductivities in laboratory studies, their large-scale adoption remains limited, giving rise to the nanofluid paradox. This review critically examines the transition from laboratory-scale demonstrations to industrial implementation and highlights the persistent gap between predicted and actual performance of nanofluids. The study highlights advancements in 2D nanomaterials, hybrid formulations, surface-engineered structures, and emerging base fluids, reflecting ongoing innovation in nanofluid design. These developments also reveal a critical balance between improved heat-transfer performance and challenges related to stability, synthesis complexity, and sustainability. The review further addresses the major commercialization barriers such as poor reproducibility, lack of standardization, and dispersion instability. Classical heat transfer frameworks are reassessed because new nanoscale processes including phonon mediated interfacial heat transport and size dependent convective behaviour highlight fundamental limits in traditional continuum-based models. Additionally, it evaluates recent applications in renewable energy systems, electronics cooling, and biomedical devices, highlighting both their potential and practical limitations. Furthermore, the concept of smart nanofluids, including magnetic, photothermal, and stimuli-responsive fluids, is discussed as an emerging frontier for tunable thermal systems. Finally, future perspectives underscore the urgent need for standardized synthesis and testing protocols, AI-driven predictive modeling to optimize nanoparticle stability and thermal performance, the development of Metastable-By-Design (MBD) nanofluids for adaptive thermal management, stronger academia–industry collaboration, and robust regulatory frameworks to enable safe, scalable, and practical implementation. This comprehensive assessment provides a roadmap to bridge the gap between scientific innovation and technological realization in nanofluid-based sustainable energy systems.
{"title":"Next-generation nanofluids: Smart materials, hybrid composites, and the path to sustainable thermal management","authors":"Ubaid Ur Rehman , Kashaf Ul Sahar , Chun-Ming Wang","doi":"10.1016/j.molliq.2025.129148","DOIUrl":"10.1016/j.molliq.2025.129148","url":null,"abstract":"<div><div>Nanofluids, which are colloidal suspensions of nanoparticles in base fluids, have been extensively explored for advanced heat transfer and thermal management. Despite their promising thermal conductivities in laboratory studies, their large-scale adoption remains limited, giving rise to the nanofluid paradox. This review critically examines the transition from laboratory-scale demonstrations to industrial implementation and highlights the persistent gap between predicted and actual performance of nanofluids. The study highlights advancements in 2D nanomaterials, hybrid formulations, surface-engineered structures, and emerging base fluids, reflecting ongoing innovation in nanofluid design. These developments also reveal a critical balance between improved heat-transfer performance and challenges related to stability, synthesis complexity, and sustainability. The review further addresses the major commercialization barriers such as poor reproducibility, lack of standardization, and dispersion instability. Classical heat transfer frameworks are reassessed because new nanoscale processes including phonon mediated interfacial heat transport and size dependent convective behaviour highlight fundamental limits in traditional continuum-based models. Additionally, it evaluates recent applications in renewable energy systems, electronics cooling, and biomedical devices, highlighting both their potential and practical limitations. Furthermore, the concept of smart nanofluids, including magnetic, photothermal, and stimuli-responsive fluids, is discussed as an emerging frontier for tunable thermal systems. Finally, future perspectives underscore the urgent need for standardized synthesis and testing protocols, AI-driven predictive modeling to optimize nanoparticle stability and thermal performance, the development of Metastable-By-Design (MBD) nanofluids for adaptive thermal management, stronger academia–industry collaboration, and robust regulatory frameworks to enable safe, scalable, and practical implementation. This comprehensive assessment provides a roadmap to bridge the gap between scientific innovation and technological realization in nanofluid-based sustainable energy systems.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"443 ","pages":"Article 129148"},"PeriodicalIF":5.2,"publicationDate":"2025-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145799222","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Sulfolane is a groundwater pollutant used to remove acidic components from petroleum. Phenolic compounds such as phenol, m-cresol, p-cresol and dimethylphenol can be found as co-pollutants because they are present in petroleum. Sulfolane is freely miscible in pure water, but phenolic compounds decrease its miscibility. Depending on the composition of the mixture, either larger droplets or molecular clusters form. Clusters are visible by small angle neutron scattering. Demixing occurs because sulfolane has higher affinity for phenols than water, as evident from activity coefficients estimated by COnductor like Screening MOdel for Realistic Solvents, COSMO-RS. Attenuated total reflectance – Fourier transform infrared spectroscopy reveals interactions between the -OH groups of phenols and the -SO groups of sulfolane. Sulfolane interacts more strongly with phenols than water, as seen by computer simulations. Demixing of sulfolane by phenols leads to entrapment into varying mineral substrates, potentially attenuating its migration in groundwater. It also enables its removal from ternary mixtures by polyurethane sponges, onto which sulfolane alone does not sorb in binary aqueous mixtures.
亚砜是一种地下水污染物，用于去除石油中的酸性成分。苯酚、间甲酚、对甲酚和二甲酚等酚类化合物可以被发现为共同污染物，因为它们存在于石油中。亚砜在纯水中可自由混溶，但酚类化合物会降低其混溶性。根据混合物的组成，形成较大的液滴或分子团簇。通过小角度中子散射可以看到星团。从COnductor like Screening MOdel for Realistic solvent （cosmos - rs）估计的活度系数可以看出，发生脱混是因为亚砜对酚类的亲和力比水高。衰减全反射-傅里叶变换红外光谱揭示了酚的- oh基团和亚砜的- so基团之间的相互作用。计算机模拟显示，与水相比，硫代烷与酚的相互作用更强。磺胺砜被酚类分解后会被困在不同的矿物基质中，从而潜在地减弱其在地下水中的迁移。它还可以通过聚氨酯海绵将其从三元混合物中去除，因为在二元水混合物中，单在三元混合物上不吸附环己烷。
{"title":"Environmental implications of sulfolane demixing from water by phenolic co-contaminants","authors":"Erica Pensini , Nour Kashlan , Jaime Vickery , Alejandro G. Marangoni , Kenneth Truong , Sylvain Prévost","doi":"10.1016/j.molliq.2025.129143","DOIUrl":"10.1016/j.molliq.2025.129143","url":null,"abstract":"<div><div>Sulfolane is a groundwater pollutant used to remove acidic components from petroleum. Phenolic compounds such as phenol, m-cresol, p-cresol and dimethylphenol can be found as co-pollutants because they are present in petroleum. Sulfolane is freely miscible in pure water, but phenolic compounds decrease its miscibility. Depending on the composition of the mixture, either larger droplets or molecular clusters form. Clusters are visible by small angle neutron scattering. Demixing occurs because sulfolane has higher affinity for phenols than water, as evident from activity coefficients estimated by COnductor like Screening MOdel for Realistic Solvents, COSMO-RS. Attenuated total reflectance – Fourier transform infrared spectroscopy reveals interactions between the -OH groups of phenols and the -SO groups of sulfolane. Sulfolane interacts more strongly with phenols than water, as seen by computer simulations. Demixing of sulfolane by phenols leads to entrapment into varying mineral substrates, potentially attenuating its migration in groundwater. It also enables its removal from ternary mixtures by polyurethane sponges, onto which sulfolane alone does not sorb in binary aqueous mixtures.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"443 ","pages":"Article 129143"},"PeriodicalIF":5.2,"publicationDate":"2025-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145799215","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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