Pub Date : 2026-10-15Epub Date: 2026-09-15DOI: 10.1016/j.molliq.2026.129918
Murtaza Sayed, Aranda Arooj, Noor S. Shah, Javed Ali Khan, Luqman Ali Shah, Faiza Rehman, Hamidreza Arandiyan, Asad M. Khan, Abdur Rahman Khan
{"title":"Corrigendum to “Narrowing the band gap of TiO2 by co-doping with Mn2+ and Co2+ for efficient photocatalytic degradation of enoxacin and its additional peroxidase like activity: A mechanistic approach” [J. Mol. Liquids 272 (2018) 403–412]","authors":"Murtaza Sayed, Aranda Arooj, Noor S. Shah, Javed Ali Khan, Luqman Ali Shah, Faiza Rehman, Hamidreza Arandiyan, Asad M. Khan, Abdur Rahman Khan","doi":"10.1016/j.molliq.2026.129918","DOIUrl":"10.1016/j.molliq.2026.129918","url":null,"abstract":"","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"460 ","pages":"Article 129918"},"PeriodicalIF":5.2,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149211651","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-10-15Epub Date: 2026-09-29DOI: 10.1016/j.molliq.2026.129946
Pramodt Srinivasula
Conventional rheodielectric studies of dipolar suspensions primarily examine flow-induced variations in the principal permittivity components. In contrast, an asymptotic solution of the perturbed Fokker–Planck equation for orientable Brownian dipoles under weak flow predicts the emergence of off-diagonal permittivity components that are linear in the relative flow strength. For planar shear flow, these terms exceed the corresponding higher-order diagonal corrections, leading to a rotation of the principal dielectric axes. This previously unrecognized rheodielectric response motivates future experimental validation and suggests new possibilities for flow-controlled dielectric and rheo-optic functionalities.
{"title":"Weak-flow induced dielectric axes rotation in dipolar suspensions","authors":"Pramodt Srinivasula","doi":"10.1016/j.molliq.2026.129946","DOIUrl":"10.1016/j.molliq.2026.129946","url":null,"abstract":"<div><div>Conventional rheodielectric studies of dipolar suspensions primarily examine flow-induced variations in the principal permittivity components. In contrast, an asymptotic solution of the perturbed Fokker–Planck equation for orientable Brownian dipoles under weak flow predicts the emergence of off-diagonal permittivity components that are linear in the relative flow strength. For planar shear flow, these terms exceed the corresponding higher-order diagonal corrections, leading to a rotation of the principal dielectric axes. This previously unrecognized rheodielectric response motivates future experimental validation and suggests new possibilities for flow-controlled dielectric and rheo-optic functionalities.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"460 ","pages":"Article 129946"},"PeriodicalIF":5.2,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149154622","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 : 2026-10-15Epub Date: 2026-10-01DOI: 10.1016/j.molliq.2026.129953
Vinicius Carneiro Ferraz, Sophia Assunção de Castro Rocha, Luminita Marin, Elizabete Fernandes Lucas
One of the main operational challenges in the oil industry is the formation of inorganic scales, which can lead to significant economic losses. Synthetic chemical additives are already used to control scale formation, and their efficiency is related to their chemical structure and molar mass. However, there is a growing demand for efficient and environmentally friendly scale inhibitors. This work aimed to modify and characterize chitosan, as well as evaluate its performance as an inorganic scale inhibitor. For this purpose, chitosan was oxidatively degraded using sodium nitrite to obtain samples with different molar masses and subsequently modified by phosphonomethylation. The samples were characterized using spectroscopic, thermal, and viscometric techniques. Solubility tests were conducted as a function of pH (1−10). Static performance tests using carbonate and sulfate containing brines were carried out at two temperature conditions to evaluate inhibitory efficiency. Scanning electron microscopy analyses were performed on the precipitates generated during the static tests. A significant reduction in chitosan molar mass was achieved without altering its backbone structure. The characterization analyses provided evidence for the possible occurrence of phosphonomethylation, resulting in increased solubility over a broad pH range. The modified chitosan samples exhibited inhibitory efficiency, with the best performance at 90 °C observed for the oxidatively degraded sample treated with approximately 5.4 v/v% sodium nitrite for 3 h and subsequently phosphonomethylated. Morphological analyses indicated modification of the crystal surface and possible inhibition of nucleation sites. The combination of oxidative degradation and phosphonomethylation proved to be a promising strategy for developing efficient and environmentally friendly inorganic scale inhibitors.
{"title":"Phosphonomethylated chitosan oligomers: synthesis, characterization, and performance as green inorganic scale inhibitors","authors":"Vinicius Carneiro Ferraz, Sophia Assunção de Castro Rocha, Luminita Marin, Elizabete Fernandes Lucas","doi":"10.1016/j.molliq.2026.129953","DOIUrl":"10.1016/j.molliq.2026.129953","url":null,"abstract":"<div><div>One of the main operational challenges in the oil industry is the formation of inorganic scales, which can lead to significant economic losses. Synthetic chemical additives are already used to control scale formation, and their efficiency is related to their chemical structure and molar mass. However, there is a growing demand for efficient and environmentally friendly scale inhibitors. This work aimed to modify and characterize chitosan, as well as evaluate its performance as an inorganic scale inhibitor. For this purpose, chitosan was oxidatively degraded using sodium nitrite to obtain samples with different molar masses and subsequently modified by phosphonomethylation. The samples were characterized using spectroscopic, thermal, and viscometric techniques. Solubility tests were conducted as a function of pH (1−10). Static performance tests using carbonate and sulfate containing brines were carried out at two temperature conditions to evaluate inhibitory efficiency. Scanning electron microscopy analyses were performed on the precipitates generated during the static tests. A significant reduction in chitosan molar mass was achieved without altering its backbone structure. The characterization analyses provided evidence for the possible occurrence of phosphonomethylation, resulting in increased solubility over a broad pH range. The modified chitosan samples exhibited inhibitory efficiency, with the best performance at 90 °C observed for the oxidatively degraded sample treated with approximately 5.4 <em>v</em>/v% sodium nitrite for 3 h and subsequently phosphonomethylated. Morphological analyses indicated modification of the crystal surface and possible inhibition of nucleation sites. The combination of oxidative degradation and phosphonomethylation proved to be a promising strategy for developing efficient and environmentally friendly inorganic scale inhibitors.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"460 ","pages":"Article 129953"},"PeriodicalIF":5.2,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149154623","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-10-15Epub Date: 2026-09-29DOI: 10.1016/j.molliq.2026.129948
Samuel Guillot, Sandrine Delpeux, Aude Gagner, Cyrine Mejri, Hamidréza Ramézani, Fabienne Méducin, Louis Hennet
This study investigates the mechanisms governing Bisphenol A (BPA) uptake from water in squalane-based dispersed systems, deliberately chosen as a poor solvent for BPA to decouple bulk partitioning effects from interfacial and self-assembly-driven processes. The objective is to determine how formulation parameters control BPA localization across the different compartments of complex liquid systems. In the absence of lipids, interfacial tension measurements reveal that BPA exhibits interfacial activity at squalane-water interfaces at low emulsifier concentrations. However, this interfacial adsorption does not control the overall uptake. Instead, BPA uptake is primarily governed by the concentration-dependent self-assembly of the triblock copolymer F127 in the aqueous phase. Above the critical aggregation concentration, micelles dominate and act as the main uptake domains, as confirmed by kinetic measurements. Notably, identical uptake behavior is observed for F127 aqueous solutions and squalane-based emulsions when expressed as a function of emulsifier concentration, demonstrating that the presence of oil droplets does not introduce an additional uptake mechanism. A fundamentally different behavior emerges upon the introduction of monolinolein within the droplets, leading to the formation of internally structured L2 mesophases. This structural transition generates additional internal lipid-water interfaces and results in a marked enhancement of BPA uptake at constant emulsifier concentration. Small-angle X-ray scattering reveals that BPA incorporation induces measurable structural changes within the mesophase, indicating that BPA is not merely adsorbed but confined within the internal lipid-water architecture. Overall, this work demonstrates that BPA uptake in dispersed systems is governed by a transition from bulk micellar solubilization to confinement within internally structured interfaces. These findings provide a molecular-level understanding of solute partitioning in complex liquids and highlight the importance of designing hierarchical interfacial architectures.
{"title":"Interfacial and self-assembly controlled uptake of Bisphenol A in squalane-based dispersions: From micellar solubilization to mesophase confinement","authors":"Samuel Guillot, Sandrine Delpeux, Aude Gagner, Cyrine Mejri, Hamidréza Ramézani, Fabienne Méducin, Louis Hennet","doi":"10.1016/j.molliq.2026.129948","DOIUrl":"10.1016/j.molliq.2026.129948","url":null,"abstract":"<div><div>This study investigates the mechanisms governing Bisphenol A (BPA) uptake from water in squalane-based dispersed systems, deliberately chosen as a poor solvent for BPA to decouple bulk partitioning effects from interfacial and self-assembly-driven processes. The objective is to determine how formulation parameters control BPA localization across the different compartments of complex liquid systems. In the absence of lipids, interfacial tension measurements reveal that BPA exhibits interfacial activity at squalane-water interfaces at low emulsifier concentrations. However, this interfacial adsorption does not control the overall uptake. Instead, BPA uptake is primarily governed by the concentration-dependent self-assembly of the triblock copolymer F127 in the aqueous phase. Above the critical aggregation concentration, micelles dominate and act as the main uptake domains, as confirmed by kinetic measurements. Notably, identical uptake behavior is observed for F127 aqueous solutions and squalane-based emulsions when expressed as a function of emulsifier concentration, demonstrating that the presence of oil droplets does not introduce an additional uptake mechanism. A fundamentally different behavior emerges upon the introduction of monolinolein within the droplets, leading to the formation of internally structured L<sub>2</sub> mesophases. This structural transition generates additional internal lipid-water interfaces and results in a marked enhancement of BPA uptake at constant emulsifier concentration. Small-angle X-ray scattering reveals that BPA incorporation induces measurable structural changes within the mesophase, indicating that BPA is not merely adsorbed but confined within the internal lipid-water architecture. Overall, this work demonstrates that BPA uptake in dispersed systems is governed by a transition from bulk micellar solubilization to confinement within internally structured interfaces. These findings provide a molecular-level understanding of solute partitioning in complex liquids and highlight the importance of designing hierarchical interfacial architectures.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"460 ","pages":"Article 129948"},"PeriodicalIF":5.2,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149154624","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-10-15Epub Date: 2026-10-02DOI: 10.1016/j.molliq.2026.129954
Ramadan Eljamal, Gulsum Yilmaz, Osama Eljamal
Nanoscale zero-valent iron (nZVI) has emerged as a promising nanomaterial for enhancing anaerobic digestion (AD) owing to its strong reducing capacity and potential to stimulate microbial activity. However, its effects on methane production remain inconsistent, with both enhanced and inhibited performance reported. These contradictory findings mainly arise from the uncontrolled corrosion of bare nZVI, which causes the rapid release of electrons, Fe2+/Fe3+, hydrogen, and reactive oxygen species, together with nanoparticle aggregation and surface passivation. Surface modification has therefore emerged as an effective strategy for regulating nZVI corrosion. To the best of our knowledge, this is the first review to specifically examine surface modification of nZVI as a strategy for controlled corrosion and enhanced AD performance. The review evaluates carbon-supported materials, polymer coatings, inorganic shells, transition-metal modifications, and bio-inspired surface engineering. Particular attention is given to how surface properties, including dispersion, surface accessibility, coating permeability, conductivity, and coating thickness, influence corrosion kinetics, electron release, microbial interactions, and methane production. Individual studies have reported substantial improvements in methane production following the application of surface-modified nZVI, including a 120% increase under semi-continuous operation. These improvements were associated with enhanced microbial interactions, regulated electron transfer and redox processes, and improved substrate degradation. Finally, future research priorities are discussed, including adaptive dosing, multifunctional surface coatings, green synthesis, predictive corrosion engineering, and techno-economic and environmental assessments. Overall, controlled corrosion is proposed as a central design principle for developing stable, efficient, and sustainable surface-modified nZVI systems for AD.
{"title":"Surface modification of nanoscale zero-valent iron for controlled corrosion and enhanced anaerobic digestion: mechanisms, modification strategies, and future perspectives","authors":"Ramadan Eljamal, Gulsum Yilmaz, Osama Eljamal","doi":"10.1016/j.molliq.2026.129954","DOIUrl":"10.1016/j.molliq.2026.129954","url":null,"abstract":"<div><div>Nanoscale zero-valent iron (nZVI) has emerged as a promising nanomaterial for enhancing anaerobic digestion (AD) owing to its strong reducing capacity and potential to stimulate microbial activity. However, its effects on methane production remain inconsistent, with both enhanced and inhibited performance reported. These contradictory findings mainly arise from the uncontrolled corrosion of bare nZVI, which causes the rapid release of electrons, Fe<sup>2+</sup>/Fe<sup>3+</sup>, hydrogen, and reactive oxygen species, together with nanoparticle aggregation and surface passivation. Surface modification has therefore emerged as an effective strategy for regulating nZVI corrosion. To the best of our knowledge, this is the first review to specifically examine surface modification of nZVI as a strategy for controlled corrosion and enhanced AD performance. The review evaluates carbon-supported materials, polymer coatings, inorganic shells, transition-metal modifications, and bio-inspired surface engineering. Particular attention is given to how surface properties, including dispersion, surface accessibility, coating permeability, conductivity, and coating thickness, influence corrosion kinetics, electron release, microbial interactions, and methane production. Individual studies have reported substantial improvements in methane production following the application of surface-modified nZVI, including a 120% increase under semi-continuous operation. These improvements were associated with enhanced microbial interactions, regulated electron transfer and redox processes, and improved substrate degradation. Finally, future research priorities are discussed, including adaptive dosing, multifunctional surface coatings, green synthesis, predictive corrosion engineering, and techno-economic and environmental assessments. Overall, controlled corrosion is proposed as a central design principle for developing stable, efficient, and sustainable surface-modified nZVI systems for AD.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"460 ","pages":"Article 129954"},"PeriodicalIF":5.2,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149154625","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 : 2026-05-19DOI: 10.1016/j.molliq.2026.129676
Mohammad Mahdi Assaf , Philippe Marchal , Florentin Michaux , Véronique Sadtler , Sophie Beaubier , Romain Kapel , Tayssir Hamieh , Thibault Roques-Carmes
This paper addresses the interfacial dilatational properties and foaming behavior of three plant protein isolates obtained from rapeseed, sunflower, and linseed meals, at concentrations ranging from 1 to 60 g/L. The goal of this study was to highlight the link and the correlations between the interfacial storage elasticity modulus (E′) and foaming properties through both experimental values and statistical methods. The nature and the concentration of proteins have a strong impact on the interfacial and foam properties. Rapeseed albumin isolate exhibits improved properties with increasing protein concentration, displaying higher interfacial dilatational elasticity and leading to the higher foamability, foam elastic modulus G′Foam, and moderate foam stability. In contrast, linseed and sunflower protein isolates behave differently. Both show an enhancement in interfacial elasticity and foam properties up to a critical concentration, which indicates the presence of protein aggregates. This induces an antifoaming effect rather than foam stabilization, leading to a simultaneous decrease in the elastic interfacial modulus and inhibition of the foam characteristics. A clear correlation between E′ and several foam properties, including foamability, foam elastic modulus, half-life stability t1/2, and the foam stability after 1 h, was highlighted. The relationships are statistically significant with p-values substantially lower than 0.05. Positive correlations are confirmed between E′ and all the foam properties, indicating that the enhancement of E′ induces better foam properties.
{"title":"Role of interfacial elasticity (E′) as an indicator for the foam characteristics of plant proteins","authors":"Mohammad Mahdi Assaf , Philippe Marchal , Florentin Michaux , Véronique Sadtler , Sophie Beaubier , Romain Kapel , Tayssir Hamieh , Thibault Roques-Carmes","doi":"10.1016/j.molliq.2026.129676","DOIUrl":"10.1016/j.molliq.2026.129676","url":null,"abstract":"<div><div>This paper addresses the interfacial dilatational properties and foaming behavior of three plant protein isolates obtained from rapeseed, sunflower, and linseed meals, at concentrations ranging from 1 to 60 g/L. The goal of this study was to highlight the link and the correlations between the interfacial storage elasticity modulus (E′) and foaming properties through both experimental values and statistical methods. The nature and the concentration of proteins have a strong impact on the interfacial and foam properties. Rapeseed albumin isolate exhibits improved properties with increasing protein concentration, displaying higher interfacial dilatational elasticity and leading to the higher foamability, foam elastic modulus G′<sub>Foam</sub>, and moderate foam stability. In contrast, linseed and sunflower protein isolates behave differently. Both show an enhancement in interfacial elasticity and foam properties up to a critical concentration, which indicates the presence of protein aggregates. This induces an antifoaming effect rather than foam stabilization, leading to a simultaneous decrease in the elastic interfacial modulus and inhibition of the foam characteristics. A clear correlation between E′ and several foam properties, including foamability, foam elastic modulus, half-life stability t1/2, and the foam stability after 1 h, was highlighted. The relationships are statistically significant with <em>p</em>-values substantially lower than 0.05. Positive correlations are confirmed between E′ and all the foam properties, indicating that the enhancement of E′ induces better foam properties.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"456 ","pages":"Article 129676"},"PeriodicalIF":5.2,"publicationDate":"2026-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148001935","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}
The reaction rate of the Cu-catalyzed azide-alkyne cycloaddition (CuAAC) exhibits a unique solvent dependence that cannot be rationalized by solvent polarity alone; the reaction proceeds faster in glycerol, followed by water, and then CH2Cl2. In the present study, this characteristic solvent dependence is elucidated in detail using the three-dimensional reference interaction site model self-consistent field (3D-RISM-SCF) method, which combines quantum chemical calculation of the solute and statistical mechanical description of the solvent molecules. It is found that the calculated free energy profiles in the three solvents are consistent with the experimental results. A decomposition analysis of the relative solvation free energy in the rate-determining step reveals that the energetic contribution arising from solute-solvent electrostatic interactions is substantial in water, whereas the entropic contribution caused by associative reaction plays a dominant role in glycerol. The latter attenuates the destabilization of solute electronic energy, resulting in the greatest stabilization of the transition state in glycerol.
{"title":"Analysis of solvent effects on the Cu-catalyzed azide-alkyne cycloaddition reaction via three-dimensional reference interaction site model self-consistent field method and solvation free energy decomposition","authors":"Hikaru Oshimo , Yuki Nukumi , Leonardo Sabattini , Kanami Sugiyama , Hirofumi Sato , Masahiro Higashi","doi":"10.1016/j.molliq.2026.129355","DOIUrl":"10.1016/j.molliq.2026.129355","url":null,"abstract":"<div><div>The reaction rate of the Cu-catalyzed azide-alkyne cycloaddition (CuAAC) exhibits a unique solvent dependence that cannot be rationalized by solvent polarity alone; the reaction proceeds faster in glycerol, followed by water, and then CH<sub>2</sub>Cl<sub>2</sub>. In the present study, this characteristic solvent dependence is elucidated in detail using the three-dimensional reference interaction site model self-consistent field (3D-RISM-SCF) method, which combines quantum chemical calculation of the solute and statistical mechanical description of the solvent molecules. It is found that the calculated free energy profiles in the three solvents are consistent with the experimental results. A decomposition analysis of the relative solvation free energy in the rate-determining step reveals that the energetic contribution arising from solute-solvent electrostatic interactions is substantial in water, whereas the entropic contribution caused by associative reaction plays a dominant role in glycerol. The latter attenuates the destabilization of solute electronic energy, resulting in the greatest stabilization of the transition state in glycerol.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"448 ","pages":"Article 129355"},"PeriodicalIF":5.2,"publicationDate":"2026-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146187239","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 : 2026-04-15Epub Date: 2026-02-10DOI: 10.1016/j.molliq.2026.129361
Shiqi Zhou, Qianqian Wang
Study of multi-component hard-sphere fluid behaviour in confined environments represents a fundamental problem in statistical mechanics and condensed matter physics, where accurately describing particle distributions near solid surfaces and effective interactions between surfaces are crucial for understanding phenomena such as wetting, adsorption, and programmable assembly. This study employs Grand Canonical Monte Carlo simulations to re-examine accuracy of Fundamental Measure Theory in ultra-multicomponent (up to seven components) hard-sphere fluid mixtures, circumventing the limitations of softened potential approximation and ensemble mismatch inherent in prior molecular dynamics studies. We systematically investigated density distributions of three- to seven-component hard-sphere fluid mixtures confined between hard and soft walls, and calculated effective interactions between parallel hard plates. Results demonstrate that the White Bear approximation of the FMT consistently outperforms the Oleksy-Hansen dimensional crossover approximation across a wide range of packing fractions, with the agreement between theoretical predictions and simulation results validating the reliability of the FMT White Bear functional in ultra-multicomponent hard sphere fluids, while the Oleksy-Hansen functional shows unexpectedly diminished precision in low effective dimensionality scenarios—particularly at lower packing fractions where the crossover correction becomes dominated by smaller species rather than reflecting the true confinement experienced by large particles. Force curve analysis reveals the correspondence between oscillation characteristics and the diameter of the larger components, as well as the distortion effect of smaller particles on oscillation patterns. Solvation force studies reveal multiple repulsive potential barriers and wells (depending on the number of larger-sized components) when slit width becomes smaller than the maximum particle diameter, with barrier heights and well depths closely correlated with total packing fraction and mole fractions of the larger-sized components involved. These findings provide a theoretical foundation for designing smart colloidal systems with specific functionalities and suggest directions for improving fluid-state crossover functionals through additional constraints such as extra sum rules, tensorial contributions, or species-sensitive crossover diagnostics—offering significant application prospects in microfluidics, soft matter science, and advanced materials design.
密闭环境中多组分硬球流体行为的研究代表了统计力学和凝聚态物理中的一个基本问题，其中准确描述固体表面附近的颗粒分布以及表面之间的有效相互作用对于理解润湿，吸附和可编程组装等现象至关重要。本研究采用大规范蒙特卡罗模拟重新检验了基本测量理论在超多组分（多达7组分）硬球流体混合物中的准确性，绕过了先前分子动力学研究中固有的软化势近似和系集失配的局限性。系统地研究了三至七组分硬球流体混合物的密度分布，并计算了平行硬板之间的有效相互作用。结果表明，在广泛的填料分数范围内，FMT的White Bear近似始终优于Oleksy-Hansen维度交叉近似，理论预测和模拟结果之间的一致性验证了FMT White Bear功能在超多组分硬球流体中的可靠性。而Oleksy-Hansen泛函数在低有效维数情况下显示出意想不到的精度下降，特别是在较低的堆积分数下，交叉校正由较小的物种主导，而不是反映大颗粒所经历的真正限制。力曲线分析揭示了振荡特性与较大颗粒直径的对应关系，以及较小颗粒的畸变对振荡模式的影响。溶剂化力研究表明，当狭缝宽度小于最大颗粒直径时，存在多个排斥性势垒和井（取决于大尺寸组分的数量），势垒高度和井深与所涉及的大尺寸组分的总堆积分数和摩尔分数密切相关。这些发现为设计具有特定功能的智能胶体系统提供了理论基础，并为通过附加约束（如额外和规则、张量贡献或物种敏感交叉诊断）改进流体状态交叉功能提供了方向，在微流体、软物质科学和先进材料设计中提供了重要的应用前景。
{"title":"Monte-Carlo and Fundamental Measure Theory Insights into Structure of Ultra-Multicomponent Hard-Sphere Fluid Mixtures in Highly Confined Environments and Effective Interaction","authors":"Shiqi Zhou, Qianqian Wang","doi":"10.1016/j.molliq.2026.129361","DOIUrl":"10.1016/j.molliq.2026.129361","url":null,"abstract":"<div><div>Study of multi-component hard-sphere fluid behaviour in confined environments represents a fundamental problem in statistical mechanics and condensed matter physics, where accurately describing particle distributions near solid surfaces and effective interactions between surfaces are crucial for understanding phenomena such as wetting, adsorption, and programmable assembly. This study employs Grand Canonical Monte Carlo simulations to re-examine accuracy of Fundamental Measure Theory in ultra-multicomponent (up to seven components) hard-sphere fluid mixtures, circumventing the limitations of softened potential approximation and ensemble mismatch inherent in prior molecular dynamics studies. We systematically investigated density distributions of three- to seven-component hard-sphere fluid mixtures confined between hard and soft walls, and calculated effective interactions between parallel hard plates. Results demonstrate that the White Bear approximation of the FMT consistently outperforms the Oleksy-Hansen dimensional crossover approximation across a wide range of packing fractions, with the agreement between theoretical predictions and simulation results validating the reliability of the FMT White Bear functional in ultra-multicomponent hard sphere fluids, while the Oleksy-Hansen functional shows unexpectedly diminished precision in low effective dimensionality scenarios—particularly at lower packing fractions where the crossover correction becomes dominated by smaller species rather than reflecting the true confinement experienced by large particles. Force curve analysis reveals the correspondence between oscillation characteristics and the diameter of the larger components, as well as the distortion effect of smaller particles on oscillation patterns. Solvation force studies reveal multiple repulsive potential barriers and wells (depending on the number of larger-sized components) when slit width becomes smaller than the maximum particle diameter, with barrier heights and well depths closely correlated with total packing fraction and mole fractions of the larger-sized components involved. These findings provide a theoretical foundation for designing smart colloidal systems with specific functionalities and suggest directions for improving fluid-state crossover functionals through additional constraints such as extra sum rules, tensorial contributions, or species-sensitive crossover diagnostics—offering significant application prospects in microfluidics, soft matter science, and advanced materials design.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"448 ","pages":"Article 129361"},"PeriodicalIF":5.2,"publicationDate":"2026-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146187162","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 : 2026-04-15Epub Date: 2026-02-09DOI: 10.1016/j.molliq.2026.129368
Kinjal Solanki , Deep Bhalani , Olga Yu. Milyaeva , Ketan Kuperkar , Sugam Kumar , Vinod K. Aswal , Sadafara A. Pillai
This study systematically investigates the influence of alcohols and diols of varying chain lengths on the micellization, structural characteristics, and interfacial behavior of the nonionic surfactant Solutol® HS15. Using a comprehensive experimental approach that integrates cloud point analysis, dynamic light scattering (DLS), small-angle neutron scattering (SANS), 1H-nuclear magnetic resonance (1H NMR) spectroscopy, and surface tensiometry, the work elucidates how the molecular structure, hydrophobicity, and hydrogen-bonding capability of these additives modulate micellar stability and morphology. Short-chain alcohols such as ethanol and propanol increase cloud point and reduce micellar size by enhancing hydration of polyoxyethylene segments, whereas mid- and long-chain alcohols, including butanol, isobutanol, hexanol, and octanol, penetrate the hydrophobic core, promoting micellar swelling and lowering cloud point through enhanced hydrophobic interactions. In contrast, diols exhibit strong stabilizing effects, forming extensive hydrogen bond networks with polyethylene glycol (PEG) units, thereby reducing micellar size, increasing cloud point, and significantly enhancing surface elasticity. Temperature further amplifies these trends, inducing a transition from spherical to prolate ellipsoidal micelles due to dehydration of PEG headgroups and an increase in the packing parameter. 1H NMR results confirm differential partitioning of alcohols and diols within the micellar environment, while surface tension and compression isotherms reveal synergistic interfacial structuring, particularly in diol-containing systems. Collectively, the findings provide molecular-level insights into how alcohol and diol cosolvents govern Solutol® HS15 self-assembly, offering a robust framework for designing surfactant-based formulations with optimized solubilization, stability, and interfacial properties for pharmaceutical, cosmetic, and industrial applications.
{"title":"Effects of alcohols and diols on the micellization and interfacial behavior of Solutol® HS15 in industrial formulation engineering","authors":"Kinjal Solanki , Deep Bhalani , Olga Yu. Milyaeva , Ketan Kuperkar , Sugam Kumar , Vinod K. Aswal , Sadafara A. Pillai","doi":"10.1016/j.molliq.2026.129368","DOIUrl":"10.1016/j.molliq.2026.129368","url":null,"abstract":"<div><div>This study systematically investigates the influence of alcohols and diols of varying chain lengths on the micellization, structural characteristics, and interfacial behavior of the nonionic surfactant Solutol® HS15. Using a comprehensive experimental approach that integrates cloud point analysis, dynamic light scattering (DLS), small-angle neutron scattering (SANS), <sup>1</sup>H-nuclear magnetic resonance (<sup>1</sup>H NMR) spectroscopy, and surface tensiometry, the work elucidates how the molecular structure, hydrophobicity, and hydrogen-bonding capability of these additives modulate micellar stability and morphology. Short-chain alcohols such as ethanol and propanol increase cloud point and reduce micellar size by enhancing hydration of polyoxyethylene segments, whereas mid- and long-chain alcohols, including butanol, isobutanol, hexanol, and octanol, penetrate the hydrophobic core, promoting micellar swelling and lowering cloud point through enhanced hydrophobic interactions. In contrast, diols exhibit strong stabilizing effects, forming extensive hydrogen bond networks with polyethylene glycol (PEG) units, thereby reducing micellar size, increasing cloud point, and significantly enhancing surface elasticity. Temperature further amplifies these trends, inducing a transition from spherical to prolate ellipsoidal micelles due to dehydration of PEG headgroups and an increase in the packing parameter. <sup>1</sup>H NMR results confirm differential partitioning of alcohols and diols within the micellar environment, while surface tension and compression isotherms reveal synergistic interfacial structuring, particularly in diol-containing systems. Collectively, the findings provide molecular-level insights into how alcohol and diol cosolvents govern Solutol® HS15 self-assembly, offering a robust framework for designing surfactant-based formulations with optimized solubilization, stability, and interfacial properties for pharmaceutical, cosmetic, and industrial applications.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"448 ","pages":"Article 129368"},"PeriodicalIF":5.2,"publicationDate":"2026-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146187237","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}
RP-3 aviation kerosene features a highly complex composition. The use of representative surrogate fuels offers a viable alternative for the accurate prediction of key thermophysical parameters. In this study, a ternary mixture of n-dodecane, n-propylcyclohexane, and n-propylbenzene was formulated to create a high-fidelity thermophysical property surrogate model for RP-3 aviation kerosene via machine learning-augmented molecular dynamics (MD-ML) simulations. MD simulation accurately predicts the thermophysical properties of pure components and their three-component models, showing close agreement with experimental data in terms of density, thermal conductivity, and viscosity. Through Gaussian process regression (GPR) optimization, an optimal surrogate formulation was identified, consisting of 60.65 wt% n-dodecane, 29.03 wt% n-propylcyclohexane, and 10.32 wt% n-propylbenzene. This approach enables precise prediction of thermophysical properties for RP-3 kerosene, providing important theoretical frameworks and technical tools for advanced aviation fuel design and combustion performance analysis.
{"title":"Construction of a three-component thermophysical property surrogate model for RP-3 aviation kerosene via machine learning-augmented molecular dynamics","authors":"Qiuhui Gong , Lingxian Liao , Yuyue Gao , Longhui Cheng , Haisheng Ren","doi":"10.1016/j.molliq.2026.129336","DOIUrl":"10.1016/j.molliq.2026.129336","url":null,"abstract":"<div><div>RP-3 aviation kerosene features a highly complex composition. The use of representative surrogate fuels offers a viable alternative for the accurate prediction of key thermophysical parameters. In this study, a ternary mixture of n-dodecane, n-propylcyclohexane, and n-propylbenzene was formulated to create a high-fidelity thermophysical property surrogate model for RP-3 aviation kerosene via machine learning-augmented molecular dynamics (MD-ML) simulations. MD simulation accurately predicts the thermophysical properties of pure components and their three-component models, showing close agreement with experimental data in terms of density, thermal conductivity, and viscosity. Through Gaussian process regression (GPR) optimization, an optimal surrogate formulation was identified, consisting of 60.65 wt% n-dodecane, 29.03 wt% n-propylcyclohexane, and 10.32 wt% n-propylbenzene. This approach enables precise prediction of thermophysical properties for RP-3 kerosene, providing important theoretical frameworks and technical tools for advanced aviation fuel design and combustion performance analysis.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"448 ","pages":"Article 129336"},"PeriodicalIF":5.2,"publicationDate":"2026-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146187236","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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