Microplastics (MPs) are synthetic polymers which have potentially emerged as one of the persistent, mobile pollutants in both terrestrial and aquatic environments. The polymer specific physicochemical properties, ageing, surface functional groups and hydrogen bonded structure lead to strong interactions and affinity towards a wide range of emerging pollutants co-existing the ecosystem. This review primarily focuses on the recent advances in understanding microplastic and emerging pollutant-based interactions at the molecular level, highlighting hydrophobic partitioning, electrostatic interactions, π–π stacking, and water-mediated hydrogen bonding. Here we light the contribution of the said mechanism in the generation of MPs-emerging pollutant associated complex pollutants and also illustrates the efficiency, scalability, environmental sustainability, and potential limitations of various removal methods. The complex pollutants comprise microplastics and other co-contaminants adsorbed onto the surface of the microplastics. These complex pollutants possess enhanced ecotoxicological implications, enhanced bioavailability as well as remedial challenges. Furthermore, it also focusses on the identification of key mechanistic research gaps and helps articulate research design principles for liquid-phase remediation strategies. Thus, the integration of the interaction dynamics, removal methodologies, and related challenges could provide potential mitigation measures to address the challenges imposed by microplastics and their co-contaminants in the environment.
{"title":"When microplastics meet emerging pollutants: Key insights on mechanistic features for environmental remediations","authors":"Susmita Singha Roy , Narayanamoorthy Bhuvanendran , Saravanan Pichiah , Aneek Kuila , Nirmalendu Sekhar Mishra","doi":"10.1016/j.molliq.2025.129227","DOIUrl":"10.1016/j.molliq.2025.129227","url":null,"abstract":"<div><div>Microplastics (MPs) are synthetic polymers which have potentially emerged as one of the persistent, mobile pollutants in both terrestrial and aquatic environments. The polymer specific physicochemical properties, ageing, surface functional groups and hydrogen bonded structure lead to strong interactions and affinity towards a wide range of emerging pollutants co-existing the ecosystem. This review primarily focuses on the recent advances in understanding microplastic and emerging pollutant-based interactions at the molecular level, highlighting hydrophobic partitioning, electrostatic interactions, π–π stacking, and water-mediated hydrogen bonding. Here we light the contribution of the said mechanism in the generation of MPs-emerging pollutant associated complex pollutants and also illustrates the efficiency, scalability, environmental sustainability, and potential limitations of various removal methods. The complex pollutants comprise microplastics and other co-contaminants adsorbed onto the surface of the microplastics. These complex pollutants possess enhanced ecotoxicological implications, enhanced bioavailability as well as remedial challenges. Furthermore, it also focusses on the identification of key mechanistic research gaps and helps articulate research design principles for liquid-phase remediation strategies. Thus, the integration of the interaction dynamics, removal methodologies, and related challenges could provide potential mitigation measures to address the challenges imposed by microplastics and their co-contaminants in the environment.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"444 ","pages":"Article 129227"},"PeriodicalIF":5.2,"publicationDate":"2025-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145922202","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 : 2025-12-30DOI: 10.1016/j.molliq.2025.129223
Liwen Li , Muzhi Guo , Yifan Zhang , Jie Zhong
The research on hydrate nucleation holds great significance for gas storage and transportation. Given the diversity of guest molecules, numerous studies have separately explored the nucleation properties of each individual guest molecule. Although many studies provide valuable insights, this case-by-case method obscures relationships among different guests and impedes the establishment of generalizable principles. Here, we introduce “ideal-model guest molecules” to enable system-level control of guest-molecular dipole and conduct extensive molecular simulations using Forward Flux Sampling to study hydrate nucleation. By investigating critical nuclei, nucleation probability, the interface structures and dynamic properties of hydrate nuclei, we find that there is a competitive relationship between the polarity and solubility of guest molecules during hydrate nucleation. When the polarity of guest molecules is below a critical value, it promotes hydrate nucleation; once the polarity of guest molecules exceeds this critical state, it significantly inhibits hydrate nucleation. We believe that these findings uncover universal nucleation principles and can guide the molecular design of hydrate additives.
{"title":"Influence of guest-molecule dipole on hydrate nucleation via molecule dynamics simulation","authors":"Liwen Li , Muzhi Guo , Yifan Zhang , Jie Zhong","doi":"10.1016/j.molliq.2025.129223","DOIUrl":"10.1016/j.molliq.2025.129223","url":null,"abstract":"<div><div>The research on hydrate nucleation holds great significance for gas storage and transportation. Given the diversity of guest molecules, numerous studies have separately explored the nucleation properties of each individual guest molecule. Although many studies provide valuable insights, this case-by-case method obscures relationships among different guests and impedes the establishment of generalizable principles. Here, we introduce “ideal-model guest molecules” to enable system-level control of guest-molecular dipole and conduct extensive molecular simulations using Forward Flux Sampling to study hydrate nucleation. By investigating critical nuclei, nucleation probability, the interface structures and dynamic properties of hydrate nuclei, we find that there is a competitive relationship between the polarity and solubility of guest molecules during hydrate nucleation. When the polarity of guest molecules is below a critical value, it promotes hydrate nucleation; once the polarity of guest molecules exceeds this critical state, it significantly inhibits hydrate nucleation. We believe that these findings uncover universal nucleation principles and can guide the molecular design of hydrate additives.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"445 ","pages":"Article 129223"},"PeriodicalIF":5.2,"publicationDate":"2025-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145923083","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}
Localized liquid-liquid phase separation (LLPS) can unexpectedly occur during the crystallization of fine chemicals, even within one-phase regions of phase diagrams when antisolvent is introduced. This study investigates how initial solute concentration and antisolvent addition rate influence localized LLPS in a water/ethanol/butylparaben system. Cloud point measurements under non-equilibrium conditions reveal that both higher antisolvent addition rates and elevated initial solute concentrations significantly increase the likelihood of LLPS. Rapid antisolvent addition induces local spinodal regions, triggering spontaneous phase separation, while high solute concentrations suppress mass transfer by slowing antisolvent diffusion. This suppression leads to phase separation before local supersaturation is resolved, resulting in solute-rich and solute-poor domains. The constructed phase diagram based on cloud points offers practical insights for controlling LLPS, enabling the design of efficient and scalable crystallization processes that minimize LLPS and improve product quality in fine chemical manufacturing.
{"title":"Non-equilibrium phase behavior of localized LLPS driven by solute concentration and antisolvent addition rate","authors":"Naoya Matsushima , Yuhei Tsugawa , Kazunori Kadota , Mikio Yoshida , Yoshiyuki Shirakawa","doi":"10.1016/j.molliq.2025.129224","DOIUrl":"10.1016/j.molliq.2025.129224","url":null,"abstract":"<div><div>Localized liquid-liquid phase separation (LLPS) can unexpectedly occur during the crystallization of fine chemicals, even within one-phase regions of phase diagrams when antisolvent is introduced. This study investigates how initial solute concentration and antisolvent addition rate influence localized LLPS in a water/ethanol/butylparaben system. Cloud point measurements under non-equilibrium conditions reveal that both higher antisolvent addition rates and elevated initial solute concentrations significantly increase the likelihood of LLPS. Rapid antisolvent addition induces local spinodal regions, triggering spontaneous phase separation, while high solute concentrations suppress mass transfer by slowing antisolvent diffusion. This suppression leads to phase separation before local supersaturation is resolved, resulting in solute-rich and solute-poor domains. The constructed phase diagram based on cloud points offers practical insights for controlling LLPS, enabling the design of efficient and scalable crystallization processes that minimize LLPS and improve product quality in fine chemical manufacturing.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"444 ","pages":"Article 129224"},"PeriodicalIF":5.2,"publicationDate":"2025-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145881873","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 : 2025-12-30DOI: 10.1016/j.molliq.2025.129221
Prasanna Kulkarni
The design of functional liquids like Deep Eutectic Solvents (DES) is hindered by an incomplete understanding of the link between molecular components and the physical properties of the resulting mixture. Traditional metrics like binding energy () fail to explain why some strongly bound pairs form low-viscosity liquids while others form glassy solids. This work introduces a holistic, multi-scale computational framework, built upon a validated quantum chemical method, to deconstruct supramolecular stability into two distinct, orthogonal physical phenomena: local bonding quality and global electrostatic neutralization. This study develops two novel descriptors: the topological Non-Covalent Interaction Score (), which quantifies localized interaction strength, and the electrostatic COSMO Dimer Interaction Score (), which measures the homogeneity of the complex’s surface potential. By applying this framework to nearly 3000 DES complexes, a “Stability Phase Space” is constructed that classifies pairs into distinct archetypes, such as rigidly bound “Local Champions” and flexibly packed “Global Stabilizers.” This classification provides a new, physically-grounded rationale for designing complex liquids and offers a powerful, scalable methodology for screening candidates.
{"title":"Predicting supramolecular stability: A validated framework combining orthogonal topological and electrostatic descriptors","authors":"Prasanna Kulkarni","doi":"10.1016/j.molliq.2025.129221","DOIUrl":"10.1016/j.molliq.2025.129221","url":null,"abstract":"<div><div>The design of functional liquids like Deep Eutectic Solvents (DES) is hindered by an incomplete understanding of the link between molecular components and the physical properties of the resulting mixture. Traditional metrics like binding energy (<span><math><mi>Δ</mi><mi>E</mi></math></span>) fail to explain why some strongly bound pairs form low-viscosity liquids while others form glassy solids. This work introduces a holistic, multi-scale computational framework, built upon a validated quantum chemical method, to deconstruct supramolecular stability into two distinct, orthogonal physical phenomena: <em>local bonding quality</em> and <em>global electrostatic neutralization</em>. This study develops two novel descriptors: the topological Non-Covalent Interaction Score (<span><math><msub><mi>S</mi><mrow><mtext>NCI</mtext></mrow></msub></math></span>), which quantifies localized interaction strength, and the electrostatic COSMO Dimer Interaction Score (<span><math><msub><mi>S</mi><mrow><mtext>CDI</mtext></mrow></msub></math></span>), which measures the homogeneity of the complex’s surface potential. By applying this framework to nearly 3000 DES complexes, a “Stability Phase Space” is constructed that classifies pairs into distinct archetypes, such as rigidly bound “Local Champions” and flexibly packed “Global Stabilizers.” This classification provides a new, physically-grounded rationale for designing complex liquids and offers a powerful, scalable methodology for screening candidates.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"444 ","pages":"Article 129221"},"PeriodicalIF":5.2,"publicationDate":"2025-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882288","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 : 2025-12-30DOI: 10.1016/j.molliq.2025.129222
Muhammad Kashif Javed , Biao Xu , Asma Sani , Tao Liu
Ultra-dry CO2 foams stabilized by surfactant/polymer mixtures are attractive for CO2 flooding and storage, yet the molecular mechanisms that control their thermal stability remain unclear. Here, we combine atomistic molecular dynamics (MD) and dissipative particle dynamics (DPD) to elucidate how cocamidopropyl betaine (CAPB) and poly(vinyl alcohol) (PVA) stabilize CO2/water interfaces at 12 MPa and 298–398 K. MD simulations reveal the formation of a compact interfacial scaffold in which CAPB headgroups and PVA hydroxyl groups are strongly associated, while CAPB tails extend into the CO2-rich phase. Binding-energy and radial distribution analyses show that CAPB-PVA and CAPB-CO2 interactions dominate over PVA-water and CO2-water interactions, explaining the strong affinity of the mixed layer for the interface. Mean-square displacement and velocity analyses demonstrate a pronounced mobility contrast between the highly mobile CO2/water molecules and the dynamically constrained CAPB/PVA network, consistent with enhanced interfacial rigidity and Marangoni-type stabilization. Coarse-grained DPD simulations, parameterized from the MD-derived Flory-Huggins χ-parameters, reproduce the interfacial density profiles and extend the analysis to larger length and time scales, confirming the persistence of the CAPB/PVA scaffold under ultra-dry foam compositions. These multiscale insights clarify the distinct role of PVA compared to previously studied oxygen-rich polymers and provide molecular-level guidance for designing thermally robust CO2 foam formulations.
{"title":"Synergistic stabilization mechanism of ultra-dry CO2/water foams by Zwitterionic surfactant and polyvinyl alcohol: Insights from mesoscopic and molecular dynamics simulations","authors":"Muhammad Kashif Javed , Biao Xu , Asma Sani , Tao Liu","doi":"10.1016/j.molliq.2025.129222","DOIUrl":"10.1016/j.molliq.2025.129222","url":null,"abstract":"<div><div>Ultra-dry CO<sub>2</sub> foams stabilized by surfactant/polymer mixtures are attractive for CO<sub>2</sub> flooding and storage, yet the molecular mechanisms that control their thermal stability remain unclear. Here, we combine atomistic molecular dynamics (MD) and dissipative particle dynamics (DPD) to elucidate how cocamidopropyl betaine (CAPB) and poly(vinyl alcohol) (PVA) stabilize CO<sub>2</sub>/water interfaces at 12 MPa and 298–398 K. MD simulations reveal the formation of a compact interfacial scaffold in which CAPB headgroups and PVA hydroxyl groups are strongly associated, while CAPB tails extend into the CO<sub>2</sub>-rich phase. Binding-energy and radial distribution analyses show that CAPB-PVA and CAPB-CO<sub>2</sub> interactions dominate over PVA-water and CO<sub>2</sub>-water interactions, explaining the strong affinity of the mixed layer for the interface. Mean-square displacement and velocity analyses demonstrate a pronounced mobility contrast between the highly mobile CO<sub>2</sub>/water molecules and the dynamically constrained CAPB/PVA network, consistent with enhanced interfacial rigidity and Marangoni-type stabilization. Coarse-grained DPD simulations, parameterized from the MD-derived Flory-Huggins χ-parameters, reproduce the interfacial density profiles and extend the analysis to larger length and time scales, confirming the persistence of the CAPB/PVA scaffold under ultra-dry foam compositions. These multiscale insights clarify the distinct role of PVA compared to previously studied oxygen-rich polymers and provide molecular-level guidance for designing thermally robust CO<sub>2</sub> foam formulations.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"444 ","pages":"Article 129222"},"PeriodicalIF":5.2,"publicationDate":"2025-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882292","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 : 2025-12-30DOI: 10.1016/j.molliq.2025.129220
Gabriel J. Olguin-Orellana , María B. Camarada , German J. Soldano , Jans Alzate-Morales , Marcelo M. Mariscal
We present a molecular dynamics study on the thermal conductivity () of graphene-based nanofluids, examining monolayer (mG), bilayer (bG), and trilayer (tG) graphene immersed in liquid argon. At 300 K, pristine mG displayed the highest = 2700 W/mK, confirming its outstanding phonon transport capacity. Introducing 5% centralized vacancies (mG5C) reduced to 2257 W/mK, whereas decentralized defects (mG5D) caused a steeper decline to 2080 W/mK. The random-defect configuration (mG5R) exhibited an even stronger suppression, reaching only 1824 W/mK, which highlights the disruptive effect of stochastic defect topology on phonon propagation. Increasing the vacancy concentration to 15% further reduced the thermal response: dropped to 1847 W/mK for mG15C and to 1647 W/mK for mG15D. This systematic reduction demonstrates that both defect density and spatial distribution critically modulate phonon scattering. The same tendency was maintained throughout the 100–800 K range and was reproduced in the bG and tG models.
To elucidate the underlying mechanisms, we computed the vibrational density of states (VDOS) from velocity autocorrelation functions. Defective models exhibited the suppression of high-frequency phonon modes ( 50 THz) and an enhancement of low-frequency localized vibrations ( 30 THz), indicating increased phonon scattering and confinement of vibrational modes. Radial distribution function (RDF) analysis revealed that centralized defects promote more ordered argon layering near the graphene surface, enhancing interfacial thermal coupling. In contrast, decentralized vacancies reduced this structural order and likely increased interfacial resistance.
These findings demonstrate that thermal conductivity in graphene nanofluids can be tuned through defect engineering, balancing intrinsic phonon transport with interfacial coupling. This provides valuable guidance for optimizing nanofluids in thermal management technologies.
{"title":"Thermal conductivity of graphene nanofluids via defect engineering: a computational approach","authors":"Gabriel J. Olguin-Orellana , María B. Camarada , German J. Soldano , Jans Alzate-Morales , Marcelo M. Mariscal","doi":"10.1016/j.molliq.2025.129220","DOIUrl":"10.1016/j.molliq.2025.129220","url":null,"abstract":"<div><div>We present a molecular dynamics study on the thermal conductivity (<span><math><mi>κ</mi></math></span>) of graphene-based nanofluids, examining monolayer (mG), bilayer (bG), and trilayer (tG) graphene immersed in liquid argon. At 300 K, pristine mG displayed the highest <span><math><mi>κ</mi></math></span> = 2700 W/mK, confirming its outstanding phonon transport capacity. Introducing 5% centralized vacancies (mG5C) reduced <span><math><mi>κ</mi></math></span> to 2257 W/mK, whereas decentralized defects (mG5D) caused a steeper decline to 2080 W/mK. The random-defect configuration (mG5R) exhibited an even stronger suppression, reaching only 1824 W/mK, which highlights the disruptive effect of stochastic defect topology on phonon propagation. Increasing the vacancy concentration to 15% further reduced the thermal response: <span><math><mi>κ</mi></math></span> dropped to 1847 W/mK for mG15C and to 1647 W/mK for mG15D. This systematic reduction demonstrates that both defect density and spatial distribution critically modulate phonon scattering. The same tendency was maintained throughout the 100–800 K range and was reproduced in the bG and tG models.</div><div>To elucidate the underlying mechanisms, we computed the vibrational density of states (VDOS) from velocity autocorrelation functions. Defective models exhibited the suppression of high-frequency phonon modes ( 50 THz) and an enhancement of low-frequency localized vibrations (<span><math><mo><</mo></math></span> 30 THz), indicating increased phonon scattering and confinement of vibrational modes. Radial distribution function (RDF) analysis revealed that centralized defects promote more ordered argon layering near the graphene surface, enhancing interfacial thermal coupling. In contrast, decentralized vacancies reduced this structural order and likely increased interfacial resistance.</div><div>These findings demonstrate that thermal conductivity in graphene nanofluids can be tuned through defect engineering, balancing intrinsic phonon transport with interfacial coupling. This provides valuable guidance for optimizing nanofluids in thermal management technologies.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"445 ","pages":"Article 129220"},"PeriodicalIF":5.2,"publicationDate":"2025-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145923375","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 : 2025-12-30DOI: 10.1016/j.molliq.2025.129178
Jin Long Xu , Zhao Hua Ren , Ying Peng , Yu Bai , Zhou Wen Lu , Wen Di Yang
The micellization behavior of mixture of two coconut oil based surfactants (zwitterionic amidopropyl hydroxysultaine and anionic polyoxyethylenated sulfate) was investigated using three techniques of the surface tension, the conductivity and the fluorescence spectra in two aqueous solutions containing glycerol and glycol, and the effect of alcohol on the interaction between two surfactants was discussed. Some thermodynamic models (including the pseudophase separation model, the Clint's model, the Rubingh's model, etc.) were adopted to estimate the related micellization parameters. In presence of glycerol or glycol, the synergistic and nonideal interaction between two surfactants depends largely on the composition in bulk solution. The steric hindrance, electrostatic interaction between two surfactants and the hydration of molecular chain, etc. are used to account for the intermolecular behavior. Alcohols with different dielectric constants induce the change of cohesive energy density of bulk solution and then influence the conformation and the hydration behavior of surfactant molecule, consequently changing the micellization process. In comparison to the case of glycol, the presence of glycerol promotes the incorporation of zwitterionic surfactant into mixed micelle in solutions enriched in anionic surfactant and while the reverse tendency appears in other solutions. Consequently, the optimum mixing ratio is about 0.63 in presence of glycerol and while it is delayed to about 0.70 on adding glycol. The fluorescence probing also is adopted to discuss the micellization process based on the aggregation number and the pyrene 1:3 ratio. The excess free energy change indicates a spontaneous process of micellization and again confirms the more advantage in presence of glycerol relative to that in water-glycol. These findings are to understand the micellization process and further to provide some foundational data for the design of surfactant formulations.
{"title":"Mixture of zwitterionic sulfobetaine and anionic polyoxyethylenated sulfate derived from coconut oil: Difference in micellization behavior induced by glycerol and glycol","authors":"Jin Long Xu , Zhao Hua Ren , Ying Peng , Yu Bai , Zhou Wen Lu , Wen Di Yang","doi":"10.1016/j.molliq.2025.129178","DOIUrl":"10.1016/j.molliq.2025.129178","url":null,"abstract":"<div><div>The micellization behavior of mixture of two coconut oil based surfactants (zwitterionic amidopropyl hydroxysultaine and anionic polyoxyethylenated sulfate) was investigated using three techniques of the surface tension, the conductivity and the fluorescence spectra in two aqueous solutions containing glycerol and glycol, and the effect of alcohol on the interaction between two surfactants was discussed. Some thermodynamic models (including the pseudophase separation model, the Clint's model, the Rubingh's model, etc.) were adopted to estimate the related micellization parameters. In presence of glycerol or glycol, the synergistic and nonideal interaction between two surfactants depends largely on the composition in bulk solution. The steric hindrance, electrostatic interaction between two surfactants and the hydration of molecular chain, etc. are used to account for the intermolecular behavior. Alcohols with different dielectric constants induce the change of cohesive energy density of bulk solution and then influence the conformation and the hydration behavior of surfactant molecule, consequently changing the micellization process. In comparison to the case of glycol, the presence of glycerol promotes the incorporation of zwitterionic surfactant into mixed micelle in solutions enriched in anionic surfactant and while the reverse tendency appears in other solutions. Consequently, the optimum mixing ratio is about 0.63 in presence of glycerol and while it is delayed to about 0.70 on adding glycol. The fluorescence probing also is adopted to discuss the micellization process based on the aggregation number and the pyrene 1:3 ratio. The excess free energy change indicates a spontaneous process of micellization and again confirms the more advantage in presence of glycerol relative to that in water-glycol. These findings are to understand the micellization process and further to provide some foundational data for the design of surfactant formulations.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"445 ","pages":"Article 129178"},"PeriodicalIF":5.2,"publicationDate":"2025-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145923381","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 : 2025-12-30DOI: 10.1016/j.molliq.2025.129209
Brij Mohan , Richu , Anil Kumar , Ashwani Kumar
Herein, the current research is concerned with the appraisal of physicochemical behavior of l-ascorbic acid in H2O as well as (0.05, 0.10 and 0.15 mol.kg−1) [Bmim][Cl]/[Bmim][BF4] + H2O media at distinct temperatures commencing 293.15 K to 313.15 K and investigational pressure, P = 0.1 MPa. The physicochemical properties have been studied for the interpretation of various probable interactions prepondering in the premeditated mixtures. For all the investigated solutions, the insinuated density, velocity of sound and dynamic viscosity values have been employed for the determination of several parameters like apparent molar volume (Vφ), apparent molar isentropic compression (Kφ,s), limiting apparent molar volume (V0φ), limiting apparent molar isentropic compression (K0φ,s), limiting apparent molar volume of transfer (∆trV0φ), limiting apparent molar isentropic compression of transfer (∆trK0φ,s), limiting apparent molar expansibility (E0φ), viscosity A, B-coefficients, (∂2V0φ/∂T2), and thermodynamic properties (, , T) at distinct temperatures. From the obtained results, it has been manifested that there is a progression in solute-IL interactions with increase in concentration of IL. Further, on evaluation of the results of and (∂2V0φ/∂T2), it has been figured out that l-ascorbic acid shows structure breaking behavior in the chosen solvent media. Additionally, via UV-vis spectral examination, it has been conceded that there is supremacy of effective hydrophilic interactions amid l-ascorbic acid and [Bmim][Cl]/[Bmim][BF4] in the prepared mixtures which is in synchronization with the outcomes of other physicochemical studies.
{"title":"Physicochemical, ultrasonic, transport and UV spectral investigations of l-ascorbic acid in aqueous [Bmim][Cl]/[Bmim][BF4] media at several temperatures and concentrations","authors":"Brij Mohan , Richu , Anil Kumar , Ashwani Kumar","doi":"10.1016/j.molliq.2025.129209","DOIUrl":"10.1016/j.molliq.2025.129209","url":null,"abstract":"<div><div>Herein, the current research is concerned with the appraisal of physicochemical behavior of <span>l</span>-ascorbic acid in H<sub>2</sub>O as well as (0.05, 0.10 and 0.15 mol.kg<sup>−1</sup>) [Bmim][Cl]/[Bmim][BF<sub>4</sub>] + H<sub>2</sub>O media at distinct temperatures commencing 293.15 K to 313.15 K and investigational pressure, <em>P</em> = 0.1 MPa. The physicochemical properties have been studied for the interpretation of various probable interactions prepondering in the premeditated mixtures. For all the investigated solutions, the insinuated density, velocity of sound and dynamic viscosity values have been employed for the determination of several parameters like apparent molar volume (<em>V</em><sub><em>φ</em></sub>), apparent molar isentropic compression (<em>K</em><sub><em>φ,s</em></sub>), limiting apparent molar volume (<em>V</em><sup><em>0</em></sup><sub><em>φ</em></sub>), limiting apparent molar isentropic compression (<em>K</em><sup><em>0</em></sup><sub><em>φ,s</em></sub>), limiting apparent molar volume of transfer <em>(∆</em><sub><em>tr</em></sub><em>V</em><sup><em>0</em></sup><sub><em>φ</em></sub>), limiting apparent molar isentropic compression of transfer (<em>∆</em><sub><em>tr</em></sub><em>K</em><sup><em>0</em></sup><sub><em>φ,s</em></sub>), limiting apparent molar expansibility (<em>E</em><sup><em>0</em></sup><sub><em>φ</em></sub>), viscosity <em>A</em>, <em>B</em>-coefficients, (<em>∂</em><sup><em>2</em></sup><em>V</em><sup><em>0</em></sup><sub><em>φ</em></sub><em>/∂T</em><sup><em>2</em></sup>), <span><math><mrow><mfrac><mi>dB</mi><mrow><mspace></mspace><mi>dT</mi></mrow></mfrac></mrow></math></span> and thermodynamic properties (<span><math><mrow><msubsup><mi>Δμ</mi><mn>1</mn><mn>0</mn></msubsup><mo>,</mo><msubsup><mi>Δμ</mi><mn>2</mn><mn>0</mn></msubsup></mrow></math></span>, <span><math><mrow><msubsup><mi>ΔH</mi><mn>2</mn><mn>0</mn></msubsup></mrow></math></span>, <em>T</em><span><math><mrow><msubsup><mi>ΔS</mi><mn>2</mn><mn>0</mn></msubsup></mrow></math></span>) at distinct temperatures. From the obtained results, it has been manifested that there is a progression in solute-IL interactions with increase in concentration of IL. Further, on evaluation of the results of <span><math><mrow><mfrac><mi>dB</mi><mrow><mspace></mspace><mi>dT</mi></mrow></mfrac></mrow></math></span> and (<em>∂</em><sup><em>2</em></sup><em>V</em><sup><em>0</em></sup><sub><em>φ</em></sub><em>/∂T</em><sup><em>2</em></sup>), it has been figured out that <span>l</span>-ascorbic acid shows structure breaking behavior in the chosen solvent media. Additionally, via UV-vis spectral examination, it has been conceded that there is supremacy of effective hydrophilic interactions amid <span>l</span>-ascorbic acid and [Bmim][Cl]/[Bmim][BF<sub>4</sub>] in the prepared mixtures which is in synchronization with the outcomes of other physicochemical studies.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"445 ","pages":"Article 129209"},"PeriodicalIF":5.2,"publicationDate":"2025-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145895845","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}
Cholesteric liquid crystals with long pitch and externally controlled conditions present unique opportunities for manipulating the polarization state of the light. In this paper, the optical properties of long-pitch cholesterics with homeotropic boundary conditions have been investigated theoretically and experimentally. A translationally invariant helical configuration has been obtained for less than critical thicknesses, where the molecular alignment is fully homeotropic, by applying an electric field. It has been shown that at certain discrete values of the applied voltages, the rotation of the polarization plane of incident linearly polarized light does not depend on either the polarization angle of the incident light or the wavelength of the light, at least in the 400–600 nm range and in the 172.5 × 172.5 μm cell area. We investigate how spatial variations within a liquid-crystal cell can influence the polarization of transmitted light and explore the possibility of achieving controllable polarization states using a single cell. These results highlight the potential of such systems for use in tunable photonic elements and advanced polarization control devices.
{"title":"Light polarization control properties of long-pitch translationally invariant cholesterics with homeotropic boundary conditions","authors":"Tatevik Sarukhanyan , Mushegh Rafayelyan , Andrey Malinchenko , Ashot Gevorgyan , Anushavan Makaryan , Roma Alaverdyan , Rafik Hakobyan","doi":"10.1016/j.molliq.2025.129218","DOIUrl":"10.1016/j.molliq.2025.129218","url":null,"abstract":"<div><div>Cholesteric liquid crystals with long pitch and externally controlled conditions present unique opportunities for manipulating the polarization state of the light. In this paper, the optical properties of long-pitch cholesterics with homeotropic boundary conditions have been investigated theoretically and experimentally. A translationally invariant helical configuration has been obtained for less than critical thicknesses, where the molecular alignment is fully homeotropic, by applying an electric field. It has been shown that at certain discrete values of the applied voltages, the rotation of the polarization plane of incident linearly polarized light does not depend on either the polarization angle of the incident light or the wavelength of the light, at least in the 400–600 nm range and in the 172.5 × 172.5 μm cell area. We investigate how spatial variations within a liquid-crystal cell can influence the polarization of transmitted light and explore the possibility of achieving controllable polarization states using a single cell. These results highlight the potential of such systems for use in tunable photonic elements and advanced polarization control devices.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"445 ","pages":"Article 129218"},"PeriodicalIF":5.2,"publicationDate":"2025-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145923509","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 : 2025-12-30DOI: 10.1016/j.molliq.2025.129217
Md. Nurannabi Miah , Muhammad Rizwanur Rahman , Mohammad Nasim Hasan
Phase-change heat transfer in liquids has gained significant importance with the growing demand for efficient thermal management in compact, high-heat-flux devices. Nanochannel boiling offers a promising approach to overcoming the limitations imposed by reduced dimensions and elevated heat densities. In this study, molecular dynamics simulations are used to examine the influence of heater length (Hlength) and solid-fluid interaction potentials (Wphi/Wpho) on the phase-change heat transfer characteristics of bubble-induced nanochannel flow. The results reveal that bubble nucleation initiates when the local kinetic energy surpasses the potential energy, effectively reducing the total energy to zero at that location. A surrounding region of particles in the liquid phase with elevated potential energy is observed near the bubble nucleus, which promotes both nucleation and subsequent heat transfer. Among the considered configurations, the longest heater (H200) under hydrophilic wetting conditions (Wphi) enables the earliest bubble nucleation, attributed to its enhanced ability to overcome energy barriers due to higher thermal efficiency. As the heater surface area increases, more fluid molecules interact directly with the heated surface, leading to heat accumulation at multiple sites, contrasting with the localized accumulation observed in shorter heaters. This spatial distribution results in a transition from a smooth, well-structured bubble propagation pattern for the shortest heater to a more chaotic and random propagation behavior as heater length increases. Under hydrophilic conditions, a distinct nonevaporating layer, characterized by fluid atoms with minimal potential energy, is consistently identified at the heater surface. This layer significantly enhances both energy transfer and bubble propagation. In contrast, hydrophobic surfaces exhibit delayed nucleation, and a pronounced vapor shielding effect, especially in case of longer heater lengths, which markedly hampers heat transfer. This study offers a molecular-scale understanding of the involved interplay between heater geometry and wetting behavior in bubble-induced nanochannel flows, providing valuable guidance for the design of efficient nanoscale thermal management systems.
{"title":"Wettability-driven boiling transitions in nanochannels from molecular dynamics study","authors":"Md. Nurannabi Miah , Muhammad Rizwanur Rahman , Mohammad Nasim Hasan","doi":"10.1016/j.molliq.2025.129217","DOIUrl":"10.1016/j.molliq.2025.129217","url":null,"abstract":"<div><div>Phase-change heat transfer in liquids has gained significant importance with the growing demand for efficient thermal management in compact, high-heat-flux devices. Nanochannel boiling offers a promising approach to overcoming the limitations imposed by reduced dimensions and elevated heat densities. In this study, molecular dynamics simulations are used to examine the influence of heater length (<em>H</em><sub><em>length</em></sub>) and solid-fluid interaction potentials (<em>W</em><sub><em>phi</em></sub>/<em>W</em><sub><em>pho</em></sub>) on the phase-change heat transfer characteristics of bubble-induced nanochannel flow. The results reveal that bubble nucleation initiates when the local kinetic energy surpasses the potential energy, effectively reducing the total energy to zero at that location. A surrounding region of particles in the liquid phase with elevated potential energy is observed near the bubble nucleus, which promotes both nucleation and subsequent heat transfer. Among the considered configurations, the longest heater (<em>H</em><sub><em>200</em></sub>) under hydrophilic wetting conditions (<em>W</em><sub><em>phi</em></sub>) enables the earliest bubble nucleation, attributed to its enhanced ability to overcome energy barriers due to higher thermal efficiency. As the heater surface area increases, more fluid molecules interact directly with the heated surface, leading to heat accumulation at multiple sites, contrasting with the localized accumulation observed in shorter heaters. This spatial distribution results in a transition from a smooth, well-structured bubble propagation pattern for the shortest heater to a more chaotic and random propagation behavior as heater length increases. Under hydrophilic conditions, a distinct nonevaporating layer, characterized by fluid atoms with minimal potential energy, is consistently identified at the heater surface. This layer significantly enhances both energy transfer and bubble propagation. In contrast, hydrophobic surfaces exhibit delayed nucleation, and a pronounced vapor shielding effect, especially in case of longer heater lengths, which markedly hampers heat transfer. This study offers a molecular-scale understanding of the involved interplay between heater geometry and wetting behavior in bubble-induced nanochannel flows, providing valuable guidance for the design of efficient nanoscale thermal management systems.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"445 ","pages":"Article 129217"},"PeriodicalIF":5.2,"publicationDate":"2025-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145923510","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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