Pub Date : 2026-01-09DOI: 10.1016/j.molliq.2025.129210
Oksana Bilous , Kirill A. Okrugin , Ali Lakkis , Reinhard Richter , Sofia Kantorovich
We present a systematic numerical study of a quasi-two-dimensional mixed system composed of Stockmayer-type dipolar particles and purely repulsive non-polar particles. By combining detailed cluster analysis with a quantitative evaluation of self-diffusion, we demonstrate how the interplay between particle area fraction, dipolar interactions, and an out-of-plane magnetic induction governs the structural organisation and dynamical behaviour of the mixture. We show that, in the absence of induction, isolated magnetic particles diffuse essentially in a Gaussian manner across all concentrations. At longer time scales, by contrast, the system enters a crowding-dominated diffusive regime, in which both the diffusion exponent and the non-Gaussianity vary monotonically with area fraction. Our findings provide a framework for interpreting diffusion phenomena in ferrogranular materials and pave the way for future experimental verification, particularly regarding induction-controlled cooling of non-magnetic components.
{"title":"Self-diffusion in ferrogranulates: Stockmayer model revisited","authors":"Oksana Bilous , Kirill A. Okrugin , Ali Lakkis , Reinhard Richter , Sofia Kantorovich","doi":"10.1016/j.molliq.2025.129210","DOIUrl":"10.1016/j.molliq.2025.129210","url":null,"abstract":"<div><div>We present a systematic numerical study of a quasi-two-dimensional mixed system composed of Stockmayer-type dipolar particles and purely repulsive non-polar particles. By combining detailed cluster analysis with a quantitative evaluation of self-diffusion, we demonstrate how the interplay between particle area fraction, dipolar interactions, and an out-of-plane magnetic induction governs the structural organisation and dynamical behaviour of the mixture. We show that, in the absence of induction, isolated magnetic particles diffuse essentially in a Gaussian manner across all concentrations. At longer time scales, by contrast, the system enters a crowding-dominated diffusive regime, in which both the diffusion exponent and the non-Gaussianity vary monotonically with area fraction. Our findings provide a framework for interpreting diffusion phenomena in ferrogranular materials and pave the way for future experimental verification, particularly regarding induction-controlled cooling of non-magnetic components.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"446 ","pages":"Article 129210"},"PeriodicalIF":5.2,"publicationDate":"2026-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035904","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 : 2026-01-08DOI: 10.1016/j.molliq.2026.129244
Zhexian Mao , Rong Zhou , Jiangyang Mei , Jiuming Wang , Junxi Xia , Hongyu Jin , Wang Zhong , Yong Jin
Phosphate surfactants with short fluorocarbon chains have attracted extensive attention due to their advantages of less toxicity, easy biodegradation and high thermal stability, which are suitable alternatives to long fluoroalkyl chain surfactants. The industrial mass production of phosphate surfactants usually uses the phosphorus pentoxide (P2O5) method together with one-pot technique, which is more environmentally friendly and has no by-products or purification required. Nevertheless, the products generated by the P2O5 method are usually mixtures of monoester and diester, and the such influence of phosphate monoester to diester ratios on the properties of phosphate surfactants with short fluorocarbon chains prepared based on all synthetic methods has not been systematically studied, which greatly restricts the large-scale industrialized production and application. Herein, a series of phosphate surfactants with short fluorocarbon chains (PFnSm) containing different ratios of monoester to diester were prepared using fluorinated alcohols with different fluorocarbon chain lengths (n = 2, 4, 6) and P2O5. The results showed that as the ratio of monoester to diester of PF6Sm decreases, the surface activity, emulsification performance, wettability and antibacterial property of PF6Sm will increase, but the critical micelle concentration (CMC) will decrease. The lowest surface tension of PF6Sm can be reduced to 17.9 mN/m at a very low concentration (0.32 mM), and all of these surfactants exhibit good wettability on polytetrafluoroethylene (PTFE) plate and excellent emulsification performance for liquid paraffin. Interestingly, antibacterial property of PF6Sm is positively affected to a certain extent as the ratio of monoester to diester decreases. The antibacterial rates can be significantly increased by 48.7 % and 25.2 % for Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus), respectively. This enhancement is likely attributable to a stronger hydrophobic drive for penetrating the peptidoglycan layer and enhanced membrane penetration by enlarging membrane defects. This study provides valuable insights into the large-scale industrialized production and the development in future of phosphate surfactants with short fluorocarbon chains exhibiting lower toxicity.
{"title":"Surface activity, wettability, emulsification and antibacterial property of phosphate surfactants with short fluorocarbon chains prepared by one-pot technique","authors":"Zhexian Mao , Rong Zhou , Jiangyang Mei , Jiuming Wang , Junxi Xia , Hongyu Jin , Wang Zhong , Yong Jin","doi":"10.1016/j.molliq.2026.129244","DOIUrl":"10.1016/j.molliq.2026.129244","url":null,"abstract":"<div><div>Phosphate surfactants with short fluorocarbon chains have attracted extensive attention due to their advantages of less toxicity, easy biodegradation and high thermal stability, which are suitable alternatives to long fluoroalkyl chain surfactants. The industrial mass production of phosphate surfactants usually uses the phosphorus pentoxide (P<sub>2</sub>O<sub>5</sub>) method together with one-pot technique, which is more environmentally friendly and has no by-products or purification required. Nevertheless, the products generated by the P<sub>2</sub>O<sub>5</sub> method are usually mixtures of monoester and diester, and the such influence of phosphate monoester to diester ratios on the properties of phosphate surfactants with short fluorocarbon chains prepared based on all synthetic methods has not been systematically studied, which greatly restricts the large-scale industrialized production and application. Herein, a series of phosphate surfactants with short fluorocarbon chains (PF<sub>n</sub>S<sub>m</sub>) containing different ratios of monoester to diester were prepared using fluorinated alcohols with different fluorocarbon chain lengths (<em>n</em> = 2, 4, 6) and P<sub>2</sub>O<sub>5</sub>. The results showed that as the ratio of monoester to diester of PF<sub>6</sub>S<sub>m</sub> decreases, the surface activity, emulsification performance, wettability and antibacterial property of PF<sub>6</sub>S<sub>m</sub> will increase, but the critical micelle concentration (CMC) will decrease. The lowest surface tension of PF<sub>6</sub>S<sub>m</sub> can be reduced to 17.9 mN/m at a very low concentration (0.32 mM), and all of these surfactants exhibit good wettability on polytetrafluoroethylene (PTFE) plate and excellent emulsification performance for liquid paraffin. Interestingly, antibacterial property of PF<sub>6</sub>S<sub>m</sub> is positively affected to a certain extent as the ratio of monoester to diester decreases. The antibacterial rates can be significantly increased by 48.7 % and 25.2 % for <em>Escherichia coli</em> (<em>E. coli</em>) and <em>Staphylococcus aureus</em> (<em>S. aureus</em>), respectively. This enhancement is likely attributable to a stronger hydrophobic drive for penetrating the peptidoglycan layer and enhanced membrane penetration by enlarging membrane defects. This study provides valuable insights into the large-scale industrialized production and the development in future of phosphate surfactants with short fluorocarbon chains exhibiting lower toxicity.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"445 ","pages":"Article 129244"},"PeriodicalIF":5.2,"publicationDate":"2026-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145923374","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 : 2026-01-07DOI: 10.1016/j.molliq.2026.129246
Sajda. S. Affat , Denys Snigur
A novel, eco-friendly approach for the preconcentration and quantification of trace thallium(III) ions in environmental samples was developed using micelle-mediated ionic liquid-based vortex-assisted dispersive liquid–liquid microextraction (MM-IL-VA-DLLME) coupled with flame atomic absorption spectroscopy (FAAS). The method introduces C-Phycocyanin as a green complexing reagent for Tl(III). The method demonstrated linearity up to 400 μg L−1 under the optimized conditions. The LOD and LOQ were 0.02 μg L−1 and 0.05 μg L−1, respectively. The proposed MM-IL-VA-DLLME method was successfully applied to the determination of thallium(III) in water, soil, and industrial dust samples. The Analytical Greenness Metric Approach (AGREE) was applied to assess the environmental impact of the proposed method.
{"title":"A novel micelle-mediated ionic liquid-based vortex-assisted dispersive liquid-liquid microextraction for preconcentration and FAAS determination of thallium (III)","authors":"Sajda. S. Affat , Denys Snigur","doi":"10.1016/j.molliq.2026.129246","DOIUrl":"10.1016/j.molliq.2026.129246","url":null,"abstract":"<div><div>A novel, eco-friendly approach for the preconcentration and quantification of trace thallium(III) ions in environmental samples was developed using micelle-mediated ionic liquid-based vortex-assisted dispersive liquid–liquid microextraction (MM-IL-VA-DLLME) coupled with flame atomic absorption spectroscopy (FAAS). The method introduces C-Phycocyanin as a green complexing reagent for Tl(III). The method demonstrated linearity up to 400 μg L<sup>−1</sup> under the optimized conditions. The LOD and LOQ were 0.02 μg L<sup>−1</sup> and 0.05 μg L<sup>−1</sup>, respectively. The proposed MM-IL-VA-DLLME method was successfully applied to the determination of thallium(III) in water, soil, and industrial dust samples. The Analytical Greenness Metric Approach (AGREE) was applied to assess the environmental impact of the proposed method.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"445 ","pages":"Article 129246"},"PeriodicalIF":5.2,"publicationDate":"2026-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145923502","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 : 2026-01-07DOI: 10.1016/j.molliq.2026.129241
Naveenkumar V. Hiremath , Shruti S. Malunavar , Rajesh G. Kalkhambkar , Manohar R. Rathod , Ravikumar Kapavarapu , Mohammad Arshad
A microwave-assisted (MW), ionic-liquid (IL)–mediated green synthesis of 3-trifluoromethylpyrazoles was achieved via multicomponent coupling of various substituted aldehydes, 2-bromo-3,3,3-trifluoropropene, and sulfonyl hydrazides in an ionic-liquid solvent system. The ionic-liquid solvent could be recycled and reused effectively for up to seven cycles without any loss of performance. The study demonstrates the antimicrobial potential of pyrazole-based derivatives through in silico molecular docking against bacterial (MDD) and fungal (CYP51) protein targets. The results showed that compounds 2, 4, 7, and 12 exhibited strong binding affinities (−8.3 to −9.2 kcal/mol for MDD; −8.0 to −8.5 kcal/mol for CYP51), surpassing VT1 (−7.8 kcal/mol) and approaching 2P0 (−10.0 kcal/mol), with compound 7 emerging as the most promising candidate across both targets. ADMET (absorption, distribution, metabolism, excretion, and toxicity) analysis indicated favorable solubility, high gastrointestinal absorption, and a favorable toxicity profile. These results show that these derivatives are promising broad-spectrum antimicrobial agents. Additionally, density functional theory (DFT) computations at the B3LYP/6-31G(d) level and theoretical/experimental photophysical evaluations were carried out for compounds 2, 6, 10, and 11. In biological assay, the synthesized compounds showed potent antibacterial activity against Gram-positive bacteria. In particular, compounds 2, 4, 5, 7, 8, 10, 12, and 13 were the most active. Compounds 2, 4, and 7 displayed minimum inhibitory concentration (MIC) values of approximately 2–4 μg/mL against S. aureus and B. cereus. In antifungal testing, compounds 2, 4, 7, 10, 12, and 13 showed strong activity with MIC of approximately 2–8 μg/mL against yeasts such as C. albicans, while only compound 12 exhibited moderate efficacy against filamentous fungi. Structure-activity analysis revealed that the compounds with electron-withdrawing and lipophilic substituents (e.g., 4-F, 4-CF₃) such as compounds 4 and 7, enhance potency, whereas weaker or heteroaryl substituents reduce efficacy against both bacterial and fungal strains.
{"title":"Microwave-assisted ionic liquid-mediated regioselective synthesis of 3-trifluoromethylpyrazoles: molecular docking, DFT, and biological studies","authors":"Naveenkumar V. Hiremath , Shruti S. Malunavar , Rajesh G. Kalkhambkar , Manohar R. Rathod , Ravikumar Kapavarapu , Mohammad Arshad","doi":"10.1016/j.molliq.2026.129241","DOIUrl":"10.1016/j.molliq.2026.129241","url":null,"abstract":"<div><div>A microwave-assisted (MW), ionic-liquid (IL)–mediated green synthesis of 3-trifluoromethylpyrazoles was achieved via multicomponent coupling of various substituted aldehydes, 2-bromo-3,3,3-trifluoropropene, and sulfonyl hydrazides in an ionic-liquid solvent system. The ionic-liquid solvent could be recycled and reused effectively for up to seven cycles without any loss of performance. The study demonstrates the antimicrobial potential of pyrazole-based derivatives through in silico molecular docking against bacterial (MDD) and fungal (CYP51) protein targets. The results showed that compounds <strong>2, 4, 7,</strong> and <strong>12</strong> exhibited strong binding affinities (−8.3 to −9.2 kcal/mol for MDD; −8.0 to −8.5 kcal/mol for CYP51), surpassing VT1 (−7.8 kcal/mol) and approaching 2P0 (−10.0 kcal/mol), with compound <strong>7</strong> emerging as the most promising candidate across both targets. ADMET (absorption, distribution, metabolism, excretion, and toxicity) analysis indicated favorable solubility, high gastrointestinal absorption, and a favorable toxicity profile. These results show that these derivatives are promising broad-spectrum antimicrobial agents. Additionally, density functional theory (DFT) computations at the B3LYP/6-31G(d) level and theoretical/experimental photophysical evaluations were carried out for compounds <strong>2</strong>, <strong>6</strong>, <strong>10</strong>, and <strong>11</strong>. In biological assay, the synthesized compounds showed potent antibacterial activity against Gram-positive bacteria. In particular, compounds 2, 4, 5, 7, 8, 10, 12, and 13 were the most active. Compounds <strong>2</strong>, <strong>4</strong>, and <strong>7</strong> displayed minimum inhibitory concentration (MIC) values of approximately 2–4 μg/mL against <em>S. aureus</em> and <em>B. cereus</em>. In antifungal testing, compounds 2, 4, 7, 10, 12, and 13 showed strong activity with MIC of approximately 2–8 μg/mL against yeasts such as <em>C. albicans</em>, while only compound <strong>12</strong> exhibited moderate efficacy against filamentous fungi. Structure-activity analysis revealed that the compounds with electron-withdrawing and lipophilic substituents (e.g., 4-F, 4-CF₃) such as compounds <strong>4</strong> and <strong>7</strong>, enhance potency, whereas weaker or heteroaryl substituents reduce efficacy against both bacterial and fungal strains.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"445 ","pages":"Article 129241"},"PeriodicalIF":5.2,"publicationDate":"2026-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145974007","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 : 2026-01-06DOI: 10.1016/j.molliq.2026.129243
Eman.I. Ali , Y.H. Kotp , I.M. Ali , F.A. Elsaid , H.A. Shawky
A soft-templated approach based on multilamellar vesicle (MLV) formation was developed for the synthesis of multi-shelled hollow mesoporous silica (MHMS) spheres with precisely tunable morphology and exceptional porosity. By systematically varying the concentrations of CTAB, 1-pentanol, and ammonia, we achieved precise control over particle size, shell number, specific surface area, and pore structure. The optimized synthesis yielded highly uniform MHMS particles with a surface area ranging from 455 to 1085 m2 g−1 and pore volumes up to 1.54 cm3/g, among the highest reported for similar silica nanostructures.
Comprehensive characterization via XRD, FTIR, DTG, TEM, SEM, and nitrogen sorption techniques confirmed the formation of highly uniform MHMS with 4–5 concentric wrinkled shells and well-developed mesopores.
Kinetic and isotherm modeling revealed that the adsorption process followed a pseudo-second-order mechanism and Freundlich behavior, suggesting multilayer adsorption on a heterogeneous surface, while the Langmuir monolayer capacity (qmax) was 161.2 mg g−1. Thermodynamic analysis revealed a spontaneous and endothermic nature of adsorption, characterized by ΔG° = −3.97 kJ mol−1, ΔH° = 8.06 kJ mol−1, and ΔS° = 0.054 kJ mol−1 K−1, indicating increased randomness at the solid–liquid interface. These findings highlight the effectiveness of vesicle-directed soft templating in constructing multi-shell hierarchical silica adsorbents with high specific surface area, and tailored accessible mesopores, offering strong potential for dye removal and other environmental remediation applications.
{"title":"Morphology control of multi-shelled hollow mesoporous silica via soft-templating for enhanced methylene blue adsorption","authors":"Eman.I. Ali , Y.H. Kotp , I.M. Ali , F.A. Elsaid , H.A. Shawky","doi":"10.1016/j.molliq.2026.129243","DOIUrl":"10.1016/j.molliq.2026.129243","url":null,"abstract":"<div><div>A soft-templated approach based on multilamellar vesicle (MLV) formation was developed for the synthesis of multi-shelled hollow mesoporous silica (MHMS) spheres with precisely tunable morphology and exceptional porosity. By systematically varying the concentrations of CTAB, 1-pentanol, and ammonia, we achieved precise control over particle size, shell number, specific surface area, and pore structure. The optimized synthesis yielded highly uniform MHMS particles with a surface area ranging from 455 to 1085 m<sup>2</sup> g<sup>−1</sup> and pore volumes up to 1.54 cm<sup>3</sup>/g, among the highest reported for similar silica nanostructures.</div><div>Comprehensive characterization via XRD, FTIR, DTG, TEM, SEM, and nitrogen sorption techniques confirmed the formation of highly uniform MHMS with 4–5 concentric wrinkled shells and well-developed mesopores.</div><div>Kinetic and isotherm modeling revealed that the adsorption process followed a pseudo-second-order mechanism and Freundlich behavior, suggesting multilayer adsorption on a heterogeneous surface, while the Langmuir monolayer capacity (q<sub>max</sub>) was 161.2 mg g<sup>−1</sup>. Thermodynamic analysis revealed a spontaneous and endothermic nature of adsorption, characterized by ΔG° = −3.97 kJ mol<sup>−1</sup>, ΔH° = 8.06 kJ mol<sup>−1</sup>, and ΔS° = 0.054 kJ mol<sup>−1</sup> K<sup>−1</sup>, indicating increased randomness at the solid–liquid interface. These findings highlight the effectiveness of vesicle-directed soft templating in constructing multi-shell hierarchical silica adsorbents with high specific surface area, and tailored accessible mesopores, offering strong potential for dye removal and other environmental remediation applications.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"445 ","pages":"Article 129243"},"PeriodicalIF":5.2,"publicationDate":"2026-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145923081","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 : 2026-01-06DOI: 10.1016/j.molliq.2026.129240
Dongyang Li , Ning Zhou , Yuqing Chen , Yuting Guo , Zheng Huang , Zhifeng Dai , Xiaodong Huang , Yubing Xiong
Aqueous two-phase systems (ATPSs) represent an environmentally benign platform for liquid–liquid separation, yet precise and reversible control over their phase behavior remains underexplored. In this work, we design and construct a dual-responsive ATPS using poly(ionic liquid)s (PILs) functionalized with benzyl (Bn) and spiropyran (SP) groups via a facile post-synthetic modification strategy. The resulting system exhibits reversible switching between biphasic and monophasic states upon exposure to pH or thermal stimuli. Detailed investigations reveal that these transitions are governed by stimulus-induced changes in the hydration capacity and intermolecular interactions of PILs, modulated by SP isomerization and protonation processes. Furthermore, increasing the degree of Bn substitution enhances the hydrophobicity and promotes the phase separation, while acidic conditions or elevated temperatures favor the dissolution and suppress the phase segregation. This study not only demonstrates a versatile molecular design principle for responsive ATPSs but also opens new opportunities for tunable separation technologies, intelligent extraction, and stimuli-regulated delivery systems.
{"title":"Thermo- and pH-responsive phase separation behaviors of aqueous two-phase systems enabled by spiropyran-functionalized poly(ionic liquid)","authors":"Dongyang Li , Ning Zhou , Yuqing Chen , Yuting Guo , Zheng Huang , Zhifeng Dai , Xiaodong Huang , Yubing Xiong","doi":"10.1016/j.molliq.2026.129240","DOIUrl":"10.1016/j.molliq.2026.129240","url":null,"abstract":"<div><div>Aqueous two-phase systems (ATPSs) represent an environmentally benign platform for liquid–liquid separation, yet precise and reversible control over their phase behavior remains underexplored. In this work, we design and construct a dual-responsive ATPS using poly(ionic liquid)s (PILs) functionalized with benzyl (Bn) and spiropyran (SP) groups via a facile post-synthetic modification strategy. The resulting system exhibits reversible switching between biphasic and monophasic states upon exposure to pH or thermal stimuli. Detailed investigations reveal that these transitions are governed by stimulus-induced changes in the hydration capacity and intermolecular interactions of PILs, modulated by SP isomerization and protonation processes. Furthermore, increasing the degree of Bn substitution enhances the hydrophobicity and promotes the phase separation, while acidic conditions or elevated temperatures favor the dissolution and suppress the phase segregation. This study not only demonstrates a versatile molecular design principle for responsive ATPSs but also opens new opportunities for tunable separation technologies, intelligent extraction, and stimuli-regulated delivery systems.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"445 ","pages":"Article 129240"},"PeriodicalIF":5.2,"publicationDate":"2026-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145923082","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 : 2026-01-06DOI: 10.1016/j.molliq.2026.129237
Agnieszka Tomczyk-Nazarczuk , Olena Siryk , Marcin Kuśmierz , Iwona Komaniecka , Yurii Samchenko , Izabela Polowczyk , Katarzyna Szewczuk-Karpisz
Water and soil pollution with toxic substances can cause potent damage to natural ecosystems and human health. It is thus important to develop material that can effectively capture various impurities and facilitate environmental remediation. In this study, poly(acrylamide-co-acrylonitrile) hydrogel (HG) was fabricated and characterized by FTIR, XPS, thermal analysis, and swelling degree. Furthermore, systematic sorption studies were performed to evaluate hydrogel affinity for copper (Cu), cadmium (Cd), arsenic (As), selenium (Se), diuron (D), and glyphosate (G) in both mono- and bi-sorbate (with two different pollutants) systems. Sorption efficiency of the solid was also examined in the presence of water-soluble macromolecular compounds, that is, anionic polyacrylamide (AN), cationic polyacrylamide (CT), and bacterial exopolysaccharide (EPS). The performed analyses suggested that chelation/coordination, surface complexation, electrostatic attraction, hydrogen bonding, and van der Waals forces played a key role in the sorption of impurities. The examined hydrogel was of great capacity towards glyphosate, allowing for the binding of 99.99 % of this toxic plant protection product, especially in the bi-sorbate systems with metals and metalloids. The investigated material also bound great amounts of diuron, especially in the solutions with As or Se. Even 89.55 % were sorbed in such cases. Low desorption degrees in the range of 8.9–11.87 %, noted in the selected systems, confirmed the strong affinity of herbicides for HG. Therefore, the developed poly(acrylamide-co-acrylonitrile) hydrogel can be considered as an effective material for removing toxic plant protection products from water–soil environments.
{"title":"Development of new poly(acrylamide-co-acrylonitrile) hydrogel: physicochemical characteristics and affinity for metals/metalloids/herbicides in mono- and bi-sorbate aqueous systems","authors":"Agnieszka Tomczyk-Nazarczuk , Olena Siryk , Marcin Kuśmierz , Iwona Komaniecka , Yurii Samchenko , Izabela Polowczyk , Katarzyna Szewczuk-Karpisz","doi":"10.1016/j.molliq.2026.129237","DOIUrl":"10.1016/j.molliq.2026.129237","url":null,"abstract":"<div><div>Water and soil pollution with toxic substances can cause potent damage to natural ecosystems and human health. It is thus important to develop material that can effectively capture various impurities and facilitate environmental remediation. In this study, poly(acrylamide-<em>co</em>-acrylonitrile) hydrogel (HG) was fabricated and characterized by FTIR, XPS, thermal analysis, and swelling degree. Furthermore, systematic sorption studies were performed to evaluate hydrogel affinity for copper (Cu), cadmium (Cd), arsenic (As), selenium (Se), diuron (D), and glyphosate (G) in both mono- and bi-sorbate (with two different pollutants) systems. Sorption efficiency of the solid was also examined in the presence of water-soluble macromolecular compounds, that is, anionic polyacrylamide (AN), cationic polyacrylamide (CT), and bacterial exopolysaccharide (EPS). The performed analyses suggested that chelation/coordination, surface complexation, electrostatic attraction, hydrogen bonding, and van der Waals forces played a key role in the sorption of impurities. The examined hydrogel was of great capacity towards glyphosate, allowing for the binding of 99.99 % of this toxic plant protection product, especially in the bi-sorbate systems with metals and metalloids. The investigated material also bound great amounts of diuron, especially in the solutions with As or Se. Even 89.55 % were sorbed in such cases. Low desorption degrees in the range of 8.9–11.87 %, noted in the selected systems, confirmed the strong affinity of herbicides for HG. Therefore, the developed poly(acrylamide-<em>co</em>-acrylonitrile) hydrogel can be considered as an effective material for removing toxic plant protection products from water–soil environments.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"446 ","pages":"Article 129237"},"PeriodicalIF":5.2,"publicationDate":"2026-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145975619","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 : 2026-01-06DOI: 10.1016/j.molliq.2026.129239
Ksenia A. Romanova , Nikolay M. Chtchelkatchev , Yuriy G. Galyametdinov
Quantum-chemical simulations of the lanthanide(III) (Ln(III)) complexes with unique structural, liquid-crystalline (LC), optical, and magnetic properties are conducted to identify the optimal components of polyfunctional materials. However, the intricate correlations among their structure, composition, and behavior, along with their dependence on external factors, hinder their practical application. In this work, we investigated the structural properties and LC organization of Ln(III) complexes with substituted β-diketones and Lewis bases using density functional theory, machine learning models, and molecular dynamics simulations. Ten Ln(III) complexes with several ions (La, Nd, Sm, Eu, Gd, Tb, Ho, Er, Yb, Lu) were simulated to study correlations between their structural properties and LC behavior. For the first time, machine learning models were employed to enhance molecular dynamics simulations of LC Ln(III) complexes, and the computational results were compared with experimental data. This complex approach demonstrates that the ionic radius of Ln(III) primarily controls the thermodynamic parameters and temperatures of phase transitions, whereas the ligand environment and geometric anisotropy determine the emergence of LC properties. Additionally, the Voronoi-Dirichlet polyhedral approach was applied to analyze the first coordination sphere and intermolecular interaction forces. The volumes and radii of these polyhedra were found to correlate with LC phase transition parameters. The developed computational protocol provides a robust predictive tool for the multiscale simulation of complex structures and polyatomic systems for materials science, the rational design and discovery of novel lanthanide-based functional materials with controlled supramolecular organization, the next-generation luminescent materials for displays, sensors, lasers and other optoelectronic devices.
{"title":"Multiscale computational design and experimental validation of mesogenic lanthanide(III) complexes for advanced optoelectronic materials","authors":"Ksenia A. Romanova , Nikolay M. Chtchelkatchev , Yuriy G. Galyametdinov","doi":"10.1016/j.molliq.2026.129239","DOIUrl":"10.1016/j.molliq.2026.129239","url":null,"abstract":"<div><div>Quantum-chemical simulations of the lanthanide(III) (Ln(III)) complexes with unique structural, liquid-crystalline (LC), optical, and magnetic properties are conducted to identify the optimal components of polyfunctional materials. However, the intricate correlations among their structure, composition, and behavior, along with their dependence on external factors, hinder their practical application. In this work, we investigated the structural properties and LC organization of Ln(III) complexes with substituted β-diketones and Lewis bases using density functional theory, machine learning models, and molecular dynamics simulations. Ten Ln(III) complexes with several ions (La, Nd, Sm, Eu, Gd, Tb, Ho, Er, Yb, Lu) were simulated to study correlations between their structural properties and LC behavior. For the first time, machine learning models were employed to enhance molecular dynamics simulations of LC Ln(III) complexes, and the computational results were compared with experimental data. This complex approach demonstrates that the ionic radius of Ln(III) primarily controls the thermodynamic parameters and temperatures of phase transitions, whereas the ligand environment and geometric anisotropy determine the emergence of LC properties. Additionally, the Voronoi-Dirichlet polyhedral approach was applied to analyze the first coordination sphere and intermolecular interaction forces. The volumes and radii of these polyhedra were found to correlate with LC phase transition parameters. The developed computational protocol provides a robust predictive tool for the multiscale simulation of complex structures and polyatomic systems for materials science, the rational design and discovery of novel lanthanide-based functional materials with controlled supramolecular organization, the next-generation luminescent materials for displays, sensors, lasers and other optoelectronic devices.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"446 ","pages":"Article 129239"},"PeriodicalIF":5.2,"publicationDate":"2026-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145950417","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 : 2026-01-05DOI: 10.1016/j.molliq.2026.129238
Haiyan Fan , Utkirjon Holikulov , Bekzod Khudaykulov , Zarina Yelemessova , Ali Ghanadzadeh Gilani , Enrico Benassi
Polyaniline is one of the most promising conducting polymers, and its synthesis demands a detailed understanding of aniline's (ANL) interactions with solvents. Herein, the intermolecular interactions formed between ANL and a series of n-alkanols (AlkOH) — viz. methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, and 1-octanol — were investigated using vibrational spectroscopy (FT-IR and Raman) and UV–Vis fluorescence spectroscopy, quantum mechanical calculations, and morphological characterisation. These systems exhibit considerable complexity due to the potential coexistence of ANL-ANL dimers in multiple configurations, both with and without alcohol participation. Spectroscopic analyses confirmed the formation of tri-molecular [ANL·(AlkOH)₂] clusters, with methanol (MeOH) displaying unique behaviour compared to longer-chain alkanols. In the [ANL·(MeOH)₂] cluster, one MeOH molecule adopts a perpendicular orientation of its OH group relative to the aniline phenyl ring, while the second MeOH forms a Me–O(H)⋯HNH–C₆H₅ hydrogen bond. For other alkanols, a different [ANL·(AlkOH)₂] configuration was identified, wherein aniline bonds simultaneously to two alcohol molecules via its amino hydrogen atoms. Although alternative clusters (e.g., [ANL₂·AlkOH] or [ANL₂·(AlkOH)₂]) could theoretically exist, vibrational spectroscopy data did not provide sufficient evidence for their significant populations. Both [ANL·(AlkOH)₂] cluster types exhibited distinct molecular electrostatic potentials (positive and negative regions), likely promoting inter-cluster interactions and subsequent aggregation. SEM imaging revealed a predominant circular morphology (ranging from hundreds of nanometers to several micrometers) across all six systems. A secondary morphological feature was observed in all cases except the ANL-MeOH system. Moreover, the aggregation was characterised by the fluorescence of all six binary mixtures at xANL = 0.1, corroborating the hypothesis of aggregation and heterogeneity/anisotropy of the binary systems. This study provides the first molecular-level model, revealing two distinct structural classes of trimolecular [ANL·(AlkOH)₂] clusters that explain the observed macroscopic aggregation and morphological features.
{"title":"Following the footprints of aggregation in aniline and normal alkanols","authors":"Haiyan Fan , Utkirjon Holikulov , Bekzod Khudaykulov , Zarina Yelemessova , Ali Ghanadzadeh Gilani , Enrico Benassi","doi":"10.1016/j.molliq.2026.129238","DOIUrl":"10.1016/j.molliq.2026.129238","url":null,"abstract":"<div><div>Polyaniline is one of the most promising conducting polymers, and its synthesis demands a detailed understanding of aniline's (ANL) interactions with solvents. Herein, the intermolecular interactions formed between ANL and a series of <em>n</em>-alkanols (AlkOH) — <em>viz.</em> methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, and 1-octanol — were investigated using vibrational spectroscopy (FT-IR and Raman) and UV–Vis fluorescence spectroscopy, quantum mechanical calculations, and morphological characterisation. These systems exhibit considerable complexity due to the potential coexistence of ANL-ANL dimers in multiple configurations, both with and without alcohol participation. Spectroscopic analyses confirmed the formation of tri-molecular <strong>[ANL·(AlkOH)₂]</strong> clusters, with methanol (MeOH) displaying unique behaviour compared to longer-chain alkanols. In the <strong>[ANL·(MeOH)₂]</strong> cluster, one MeOH molecule adopts a perpendicular orientation of its OH group relative to the aniline phenyl ring, while the second MeOH forms a Me–O(H)⋯HNH–C₆H₅ hydrogen bond. For other alkanols, a different <strong>[ANL·(AlkOH)₂]</strong> configuration was identified, wherein aniline bonds simultaneously to two alcohol molecules <em>via</em> its amino hydrogen atoms. Although alternative clusters (<em>e.g.</em>, <strong>[ANL₂·AlkOH]</strong> or <strong>[ANL₂·(AlkOH)₂]</strong>) could theoretically exist, vibrational spectroscopy data did not provide sufficient evidence for their significant populations. Both <strong>[ANL·(AlkOH)₂]</strong> cluster types exhibited distinct molecular electrostatic potentials (positive and negative regions), likely promoting inter-cluster interactions and subsequent aggregation. SEM imaging revealed a predominant circular morphology (ranging from hundreds of nanometers to several micrometers) across all six systems. A secondary morphological feature was observed in all cases except the ANL-MeOH system. Moreover, the aggregation was characterised by the fluorescence of all six binary mixtures at <em>x</em><sub>ANL</sub> = 0.1, corroborating the hypothesis of aggregation and heterogeneity/anisotropy of the binary systems. This study provides the first molecular-level model, revealing two distinct structural classes of trimolecular <strong>[ANL·(AlkOH)₂]</strong> clusters that explain the observed macroscopic aggregation and morphological features.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"445 ","pages":"Article 129238"},"PeriodicalIF":5.2,"publicationDate":"2026-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145923513","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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