Pub Date : 2025-12-03DOI: 10.1016/j.molliq.2025.129090
Tsogtbilegt Boldoo , Veerakumar Chinnasamy , Honghyun Cho
The enhancement of phase change materials (PCMs) by adding nanoparticles presents a potential option for improving thermal energy storage (TES) systems. This study investigated the thermal performance of eicosane PCM nanoemulsions improved with multi-walled carbon nanotube (MWCNT) introduced at different stages of the preparation process. Besides, the research examines the impact of MWCNT addition timing on the thermal properties and dispersion stability of the resulting nanoemulsions. As a result, the optimal composition was determined to be MWCNT@PCM-ED, with MWCNT and PCM concentrations of 0.2 wt% and 50 wt%, respectively. The results show that the timing of MWCNT addition significantly impacts the thermal characteristics of the PCM nanoemulsions. PCM emulsions with MWCNTs added during pre-emulsification exhibited the highest improvement in thermal characteristics, while those with post-emulsification addition showed relatively lower enhancement. The degree of supercooling in MWCNT@PCM-ED, consisting of 0.2 wt% MWCNT and 50 wt% eicosane, was reduced from 8 to 0.4 °C compared to pure eicosane PCM. However, the latent heat of fusion for MWCNT@PCM-ED decreased from 251.3 to 138.5 J/g relative to pure eicosane PCM. These results are crucial for developing high-performance PCM nanoemulsions for TES applications.
{"title":"Comparative analysis of thermal behavior and formulation of phase change nanoemulsion: Influence of MWCNT loading at different emulsification stages","authors":"Tsogtbilegt Boldoo , Veerakumar Chinnasamy , Honghyun Cho","doi":"10.1016/j.molliq.2025.129090","DOIUrl":"10.1016/j.molliq.2025.129090","url":null,"abstract":"<div><div>The enhancement of phase change materials (PCMs) by adding nanoparticles presents a potential option for improving thermal energy storage (TES) systems. This study investigated the thermal performance of eicosane PCM nanoemulsions improved with multi-walled carbon nanotube (MWCNT) introduced at different stages of the preparation process. Besides, the research examines the impact of MWCNT addition timing on the thermal properties and dispersion stability of the resulting nanoemulsions. As a result, the optimal composition was determined to be MWCNT@PCM-ED, with MWCNT and PCM concentrations of 0.2 wt% and 50 wt%, respectively. The results show that the timing of MWCNT addition significantly impacts the thermal characteristics of the PCM nanoemulsions. PCM emulsions with MWCNTs added during pre-emulsification exhibited the highest improvement in thermal characteristics, while those with post-emulsification addition showed relatively lower enhancement. The degree of supercooling in MWCNT@PCM-ED, consisting of 0.2 wt% MWCNT and 50 wt% eicosane, was reduced from 8 to 0.4 °C compared to pure eicosane PCM. However, the latent heat of fusion for MWCNT@PCM-ED decreased from 251.3 to 138.5 J/g relative to pure eicosane PCM. These results are crucial for developing high-performance PCM nanoemulsions for TES applications.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"441 ","pages":"Article 129090"},"PeriodicalIF":5.2,"publicationDate":"2025-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145692223","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 : 2025-12-03DOI: 10.1016/j.molliq.2025.129023
Sakineh Mizani , Martin Oettel , Péter Gurin , Szabolcs Varga
We report the discovery of a mixed orientational structure in the quasi-one-dimensional fluid of hard non-spherical bodies with the exact calculation of the thermodynamic and structural quantities using the transfer operator method. The mixed arrangement, which is spatially uniform, but orientationally ordered, cannot be identified with conventional mesophases such as tetratic, cubatic and nematic. It is found that the particles form a mixed orientational arrangement with preferred parallel and perpendicular orientations in a channel, where the number of parallel and perpendicularly oriented particles is not equal even at the close-packing density. The mixed structure can be stabilized with hard bodies having equal side lengths in parallel and perpendicular orientations along the channel. These conditions can be realized with colloidal superdisks (superballs) if the curvature of neighboring sides (faces) is different. We show that even a small stretching of the superparticle destabilizes mixed ordering due to perfect nematic order evolving upon approaching close packing.
{"title":"Emergence of mixed orientational ordering in quasi-one-dimensional superdisk and superball fluids","authors":"Sakineh Mizani , Martin Oettel , Péter Gurin , Szabolcs Varga","doi":"10.1016/j.molliq.2025.129023","DOIUrl":"10.1016/j.molliq.2025.129023","url":null,"abstract":"<div><div>We report the discovery of a mixed orientational structure in the quasi-one-dimensional fluid of hard non-spherical bodies with the exact calculation of the thermodynamic and structural quantities using the transfer operator method. The mixed arrangement, which is spatially uniform, but orientationally ordered, cannot be identified with conventional mesophases such as tetratic, cubatic and nematic. It is found that the particles form a mixed orientational arrangement with preferred parallel and perpendicular orientations in a channel, where the number of parallel and perpendicularly oriented particles is not equal even at the close-packing density. The mixed structure can be stabilized with hard bodies having equal side lengths in parallel and perpendicular orientations along the channel. These conditions can be realized with colloidal superdisks (superballs) if the curvature of neighboring sides (faces) is different. We show that even a small stretching of the superparticle destabilizes mixed ordering due to perfect nematic order evolving upon approaching close packing.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"442 ","pages":"Article 129023"},"PeriodicalIF":5.2,"publicationDate":"2025-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145735994","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}
Keratin, a structurally resilient protein abundant in wool, remains underutilized due to challenges in its efficient extraction and regeneration. In this study, density functional theory (DFT) calculations were employed to investigate four molar ratios of lactic acid (LA) to sodium acetate (NaOAc) in a natural deep eutectic solvent (NADES) system. Computational descriptors, including interaction energies, topological, and electron localization analyses, indicated that the 2:1 LA:NaOAc ratio provides the most favorable environment for disrupting keratin disulfide bonds through cooperative hydrogen and chalcogen bonding. Guided by these predictions, experimental extractions conducted at 110 °C for 4 h with a fiber-to-liquid ratio of 2.5 % yielded the highest keratin recovery (21.83 %), significantly surpassing other formulations. Spectroscopic (FTIR, EDX), thermal (TGA/DSC), morphological (SEM), and crystallographic (XRD) analyses confirmed that the regenerated keratin retained its structural integrity and characteristic features. Furthermore, the NADES exhibited excellent recyclability over five extraction cycles with only a 15 % decrease in performance. This integrated computational-experimental approach establishes a cost-effective and environmentally benign strategy for keratin valorization, highlighting the potential of NADES-based systems for sustainable biopolymer processing.
{"title":"Integrating DFT-guided design and green natural deep eutectic solvent chemistry for efficient keratin dissolution and recovery from wool waste","authors":"Mohamed Belhajja , Omar Cherkaoui , Khalid Bougrin","doi":"10.1016/j.molliq.2025.129084","DOIUrl":"10.1016/j.molliq.2025.129084","url":null,"abstract":"<div><div>Keratin, a structurally resilient protein abundant in wool, remains underutilized due to challenges in its efficient extraction and regeneration. In this study, density functional theory (DFT) calculations were employed to investigate four molar ratios of lactic acid (LA) to sodium acetate (NaOAc) in a natural deep eutectic solvent (NADES) system. Computational descriptors, including interaction energies, topological, and electron localization analyses, indicated that the 2:1 LA:NaOAc ratio provides the most favorable environment for disrupting keratin disulfide bonds through cooperative hydrogen and chalcogen bonding. Guided by these predictions, experimental extractions conducted at 110 °C for 4 h with a fiber-to-liquid ratio of 2.5 % yielded the highest keratin recovery (21.83 %), significantly surpassing other formulations. Spectroscopic (FTIR, EDX), thermal (TGA/DSC), morphological (SEM), and crystallographic (XRD) analyses confirmed that the regenerated keratin retained its structural integrity and characteristic features. Furthermore, the NADES exhibited excellent recyclability over five extraction cycles with only a 15 % decrease in performance. This integrated computational-experimental approach establishes a cost-effective and environmentally benign strategy for keratin valorization, highlighting the potential of NADES-based systems for sustainable biopolymer processing.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"442 ","pages":"Article 129084"},"PeriodicalIF":5.2,"publicationDate":"2025-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145735941","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 : 2025-12-03DOI: 10.1016/j.molliq.2025.129087
Ayesha Hossain , Priyanka Roy , Ajit Tudu , Pranish Bomzan , Subarna Thapa , Taniya Dey , Sangita Dey , Md Abbasuddin Sk , Sanchita Sil , Anoop Kumar , Mahendra Nath Roy
Food colorant Azorubine (AzB) plays a vital role in improving the aesthetic quotient, reinstating the natural look, and maintaining homogeneity of processed foods. Nevertheless this study is straight forward of β-cyclodextrin (β-CD)-induced inclusion complexation (IC) with Azorubine, was obtained to enhance its physicochemical and biological characteristics. The encapsulation of Azorubine inside the β-CD cavity was confirmed by nuclear magnetic resonance (1H NMR), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA). The inclusion complex's 1:1 stoichiometry was confirmed using Job's plot with significant affinity for AzB with β-CD, having a binding constant (Ka = 2.96 × 104 M−1) that suggests the thermodynamic feasibility of reversible encapsulation. The results of molecular docking studies highlighting strong favourable host–guest interaction with specific optimum binding energy (−6.1 kcal) denoting formation of stable complex. Encapsulation of AzB with β-CD immensely boost its degradation by Fenton like mechanism catalyzed by CuO NPs which impact the environmental safety concern of the AzB toxicity. In addition, the antioxidant, anti-fungal activity of AzB, enhanced its intrinsic property, this implies its potential for dual-use as a food additive, making external preservatives unnecessary. The in vitro cytotoxicity assays on liver cell lines showed low cytotoxic effect, which emphasized the complex safety in its potential application as food. The present study reinforce the impact of β-CD encapsulating the food colorant AzB with not only improving the properties also addressing the toxicity and environmental issues. Hope this study pave a new avenue with the toxicity concern of food colorant.
{"title":"Insights into the formation of host–guest complexation based on Azorubine and β-cyclodextrin system for augmenting the bioactive potential assessment","authors":"Ayesha Hossain , Priyanka Roy , Ajit Tudu , Pranish Bomzan , Subarna Thapa , Taniya Dey , Sangita Dey , Md Abbasuddin Sk , Sanchita Sil , Anoop Kumar , Mahendra Nath Roy","doi":"10.1016/j.molliq.2025.129087","DOIUrl":"10.1016/j.molliq.2025.129087","url":null,"abstract":"<div><div>Food colorant Azorubine (AzB) plays a vital role in improving the aesthetic quotient, reinstating the natural look, and maintaining homogeneity of processed foods. Nevertheless this study is straight forward of β-cyclodextrin (β-CD)-induced inclusion complexation (IC) with Azorubine, was obtained to enhance its physicochemical and biological characteristics. The encapsulation of Azorubine inside the β-CD cavity was confirmed by nuclear magnetic resonance (<sup>1</sup>H NMR), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA). The inclusion complex's 1:1 stoichiometry was confirmed using Job's plot with significant affinity for AzB with β-CD, having a binding constant (Ka = 2.96 × 10<sup>4</sup> M<sup>−1</sup>) that suggests the thermodynamic feasibility of reversible encapsulation. The results of molecular docking studies highlighting strong favourable host–guest interaction with specific optimum binding energy (−6.1 kcal) denoting formation of stable complex. Encapsulation of AzB with β-CD immensely boost its degradation by Fenton like mechanism catalyzed by CuO NPs which impact the environmental safety concern of the AzB toxicity. In addition, the antioxidant, anti-fungal<!--> <!-->activity of AzB, enhanced its intrinsic property, this implies its potential<!--> <!-->for dual-use as a food additive, making external preservatives unnecessary. The in vitro cytotoxicity assays on liver cell lines showed low cytotoxic effect, which emphasized the complex safety in its potential application<!--> <!-->as food. The present study reinforce the impact of β-CD encapsulating the food colorant AzB with not only improving the properties also addressing the toxicity and environmental issues. Hope this study pave a new avenue with the toxicity concern of food colorant.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"442 ","pages":"Article 129087"},"PeriodicalIF":5.2,"publicationDate":"2025-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145735538","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 : 2025-12-03DOI: 10.1016/j.molliq.2025.129045
Furkan Burak Şen
Black cumin (BC) is a plant species that contains essential oils in different compositions along with bioactive compounds and has properties such as antioxidant, antimicrobial, antidiabetic, anticancer, anti-asthmatic, antihypertensive, cytotoxic. In this study, a green extraction approach was established by integrating both MAE and NADES, aiming to promote sustainability through the valorization of agro-industrial waste. For the purpose, four different NADES formulations were prepared, and the most effective system (choline chloride, urea, and water (1:2:1, mol/mol)) was selected based on extraction efficiency. Optimization of MAE parameters was carried out using response surface methodology. Antioxidant activities of the BCSC extracts, including ABTS radical scavenging capacity, DPPH free radical scavenging activity, and total antioxidant capacity, were evaluated and compared with extracts obtained using conventional solvents. The antioxidant constituents were further characterized by HPLC-PDA analysis. Results demonstrated that DES-based MAE exhibited superior performance over traditional extraction methods, underlining the potential of BCSC as a sustainable source of natural antioxidants.
{"title":"Modeling of microwave extraction parameters of black cumin seed cake using green solvent","authors":"Furkan Burak Şen","doi":"10.1016/j.molliq.2025.129045","DOIUrl":"10.1016/j.molliq.2025.129045","url":null,"abstract":"<div><div>Black cumin (BC) is a plant species that contains essential oils in different compositions along with bioactive compounds and has properties such as antioxidant, antimicrobial, antidiabetic, anticancer, anti-asthmatic, antihypertensive, cytotoxic. In this study, a green extraction approach was established by integrating both MAE and NADES, aiming to promote sustainability through the valorization of agro-industrial waste. For the purpose, four different NADES formulations were prepared, and the most effective system (choline chloride, urea, and water (1:2:1, mol/mol)) was selected based on extraction efficiency. Optimization of MAE parameters was carried out using response surface methodology. Antioxidant activities of the BCSC extracts, including ABTS radical scavenging capacity, DPPH free radical scavenging activity, and total antioxidant capacity, were evaluated and compared with extracts obtained using conventional solvents. The antioxidant constituents were further characterized by HPLC-PDA analysis. Results demonstrated that DES-based MAE exhibited superior performance over traditional extraction methods, underlining the potential of BCSC as a sustainable source of natural antioxidants.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"442 ","pages":"Article 129045"},"PeriodicalIF":5.2,"publicationDate":"2025-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145735991","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 : 2025-12-03DOI: 10.1016/j.molliq.2025.129073
Ellora Priscille Ndia Ntone , Sunarti Abdul Rahman , Maya Sarah , Mohd Hafiz Dzarfan Othman , Azam Taufik Mohd Din , Afifi Zainal
Mixed matrix membranes (MMMs) have emerged as a promising technology for CO₂ capture and CO₂/CH₄ separation, offering a balance of efficiency, operational flexibility, and cost-effectiveness. Nonetheless, fabricating defect-free membranes that simultaneously achieve high permeability and selectivity remains a critical challenge. This review provides a comprehensive overview of recent advances in incorporating functionalized fillers, including metal oxides (zeolites, metal-organic frameworks, silica), carbon-based nanomaterials (graphene oxide, carbon nanotubes), and biomass-derived nanomaterials in polymer matrices to enhance separation performance. These fillers improve gas transport by introducing selective adsorption sites, tailoring pore structures, and enhancing interfacial compatibility, while biomass-based fillers present sustainable and low-cost alternatives. Functionalization further promotes uniform dispersion and stronger polymer-filler interactions, resulting in higher CO₂ permeability and CO₂/CH₄ selectivity. Comparative analyses reveal that many functionalized MMMs outperform conventional polymeric membranes. Additionally, this review highlights progress in fabrication techniques, characterization methods, and future directions, including hybrid filler systems, surface engineering, scalable membrane production, and techno-economic assessments. With continued innovation, functionalized filler-based MMMs hold strong potential to deliver energy-efficient and environmentally sustainable solutions for next-generation gas separation technologies.
{"title":"Sustainable and functionalized nanofillers to improve CO₂ capture and methane purification in mixed matrix membranes","authors":"Ellora Priscille Ndia Ntone , Sunarti Abdul Rahman , Maya Sarah , Mohd Hafiz Dzarfan Othman , Azam Taufik Mohd Din , Afifi Zainal","doi":"10.1016/j.molliq.2025.129073","DOIUrl":"10.1016/j.molliq.2025.129073","url":null,"abstract":"<div><div>Mixed matrix membranes (MMMs) have emerged as a promising technology for CO₂ capture and CO₂/CH₄ separation, offering a balance of efficiency, operational flexibility, and cost-effectiveness. Nonetheless, fabricating defect-free membranes that simultaneously achieve high permeability and selectivity remains a critical challenge. This review provides a comprehensive overview of recent advances in incorporating functionalized fillers, including metal oxides (zeolites, metal-organic frameworks, silica), carbon-based nanomaterials (graphene oxide, carbon nanotubes), and biomass-derived nanomaterials in polymer matrices to enhance separation performance. These fillers improve gas transport by introducing selective adsorption sites, tailoring pore structures, and enhancing interfacial compatibility, while biomass-based fillers present sustainable and low-cost alternatives. Functionalization further promotes uniform dispersion and stronger polymer-filler interactions, resulting in higher CO₂ permeability and CO₂/CH₄ selectivity. Comparative analyses reveal that many functionalized MMMs outperform conventional polymeric membranes. Additionally, this review highlights progress in fabrication techniques, characterization methods, and future directions, including hybrid filler systems, surface engineering, scalable membrane production, and techno-economic assessments. With continued innovation, functionalized filler-based MMMs hold strong potential to deliver energy-efficient and environmentally sustainable solutions for next-generation gas separation technologies.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"441 ","pages":"Article 129073"},"PeriodicalIF":5.2,"publicationDate":"2025-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145691813","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 widespread presence of Citalopram (CIT), a selective serotonin reuptake inhibitor (SSRI), in water resources raises environmental concerns due to its resistance to conventional treatment processes. In this work, a novel nanomesoporous magnetic metal–organic framework (Meso-MMOF) was fabricated by integrating MIL-100(Fe) with SBA-3 mesostructured silica-coated Fe3O4 nanoparticles, followed by surface functionalization with sulfonic acid groups (Fe3O4@SiO2–SBA-3–MIL-100(Fe)/SO3H). Structural and morphological analyses (FT-IR, XRD, FESEM, EDX, N2 adsorption-desorption isotherm, VSM, and Zeta potential) confirmed the successful synthesis of uniform nanoparticles with a diameter of 40 nm, featuring a surface area of 7.37 m2 g−1 and a pore volume of 0.0674 cm3 g−1. The adsorption efficiency of the synthesized material toward CIT was evaluated and optimized through central composite design under the response surface methodology. Under optimal conditions (pH 2, 0.1 g adsorbent, 25 min contact time, and 25 mL solution), the CIT removal efficiency exceeded 95 %. Kinetic modelling revealed that the process follows linear pseudo-second order behavior (R2 = 0.9957). Adsorption isotherms were examined using various linear and non-linear of two- and three-parametric isotherm models. Complementary density functional theory (DFT) calculations were performed to assess the reactivity of CIT and compare it with structurally similar antidepressants. Analysis of molecular descriptors such as electrophilicity index, chemical potential, and chemical hardness, along with electrostatic potential mapping, demonstrated the high reactivity of CIT and its strong affinity for interaction with the Meso-MMOF surface. These findings highlight the Meso-MMOF's potential as a robust adsorbent for CIT contaminants in water treatment applications.
{"title":"Synthesis of nanomesoporous magnetic metal–organic framework of Fe3O4@SiO2-SBA-3-MIL-100(Fe)/SO3H for citalopram adsorption from aqueous phase: experimental and DFT studies","authors":"Abolfazl Chinehvari , Shahab Shariati , Mahmoudreza Sohrabi , Naghmeh Dalili Mansour","doi":"10.1016/j.molliq.2025.129062","DOIUrl":"10.1016/j.molliq.2025.129062","url":null,"abstract":"<div><div>The widespread presence of Citalopram (CIT), a selective serotonin reuptake inhibitor (SSRI), in water resources raises environmental concerns due to its resistance to conventional treatment processes. In this work, a novel nanomesoporous magnetic metal–organic framework (Meso-MMOF) was fabricated by integrating MIL-100(Fe) with SBA-3 mesostructured silica-coated Fe<sub>3</sub>O<sub>4</sub> nanoparticles, followed by surface functionalization with sulfonic acid groups (Fe<sub>3</sub>O<sub>4</sub>@SiO<sub>2</sub>–SBA-3–MIL-100(Fe)/SO<sub>3</sub>H). Structural and morphological analyses (FT-IR, XRD, FESEM, EDX, N<sub>2</sub> adsorption-desorption isotherm, VSM, and Zeta potential) confirmed the successful synthesis of uniform nanoparticles with a diameter of 40 nm, featuring a surface area of 7.37 m<sup>2</sup> g<sup>−1</sup> and a pore volume of 0.0674 cm<sup>3</sup> g<sup>−1</sup>. The adsorption efficiency of the synthesized material toward CIT was evaluated and optimized through central composite design under the response surface methodology. Under optimal conditions (pH 2, 0.1 g adsorbent, 25 min contact time, and 25 mL solution), the CIT removal efficiency exceeded 95 %. Kinetic modelling revealed that the process follows linear pseudo-second order behavior (R<sup>2</sup> = 0.9957). Adsorption isotherms were examined using various linear and non-linear of two- and three-parametric isotherm models. Complementary density functional theory (DFT) calculations were performed to assess the reactivity of CIT and compare it with structurally similar antidepressants. Analysis of molecular descriptors such as electrophilicity index, chemical potential, and chemical hardness, along with electrostatic potential mapping, demonstrated the high reactivity of CIT and its strong affinity for interaction with the Meso-MMOF surface. These findings highlight the Meso-MMOF's potential as a robust adsorbent for CIT contaminants in water treatment applications.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"442 ","pages":"Article 129062"},"PeriodicalIF":5.2,"publicationDate":"2025-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145693223","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}
5-Fluorouracil (5-FU) is an anticancer agent that has constraints of poor permeability and low bioavailability. To improve the bioavailability of 5-FU and its cytotoxicity potential in the breast cancer cell line (MCF-7), a 5-FU-phospholipid complex (5-FUPLC) embedded in basil oil (BO) based self-nanoemulsifying drug delivery system (SNEDDS) was developed. 5-FUPLC (1:1) complexation was prepared and physically characterized using TLC, NMR and partition coefficient. Risk assessment identified the critical factors assigned in the design of experimentation (DoE) of 5-FUPLC-SNEDDS, optimized using central-composite design (CCD) modelling. Previously, the phase dynamic of BO was explored in Tween20/PEG400, selected as a surfactant/co-surfactant mix (Smix). Five pre-concentrate SNEDDS formulations were drawn from CCD modelling, exhibiting fully dilutable potential via transitioning of nanostructure domains via a bi-continuous system, as characterized via FTIR characterization. Interestingly, 5-FU loading turned pre-concentrate SNEDDS to coarse dispersion across the dilution line (85/15). Meanwhile, 5-FUPLC loading favours nano-emulsification of BO. 5-FUPLC-loaded SNEDDS formulations were physically characterized for droplet size, polydispersity index, and zeta potential. Additionally, their conductivity, refractive index, dilution and %transmittance were assessed. 5-FUPLC-SNEDDS had a sustained release pattern contrary to the immediate releasing character of 5-FU, ascribed to the hydrophobic nature of the complex. Antioxidant potential of SNEDDS was attributed to the possession of BO in the nano-emulsified form. Phospholipid complexation physically transforms the 5-FU (hydrophilic) into 5-FUPLC (hydrophobic), as confirmed from log P values. As a result, 5-FUPLC facilitated the nano-emulsification of BO, and itself was embedded in the dispersed phase (BO) of SNEDDS; its affinity towards the lipophilic phase was confirmed from LogD (of 5-FUPLC). 5-FUPLC-SNEDDS modulated the drug permeability, investigated using the rat ileum method. Pharmacokinetic assessment ofoptimized formulation (F1) produced a 2.2-fold increase in the area under the curve [AUC]0-12h compared to the 5-FU solution. Cytotoxicity assessment of the optimized system (F1) in MCF-7 cell lines exhibited a significant difference in %inhibition of cell growth when compared with 5-FU-loaded SNEDDS as well as 5-FU solution. 5-FUPLC complex embedded in BO nano-emulsified SNEDDS framework optimized using CCD modelling, improved bioavailability and cytotoxicity potential of 5-FU.
{"title":"Cytotoxicity potential of basil oil embedded 5-fluorouracil-phospholipid complex loaded self-nanoemulsifying system: Design expert® endorsed approach for bioavailability enhancement","authors":"Piyush Kumar Singh Arya , Amulya Jindal , Anoop Kumar","doi":"10.1016/j.molliq.2025.129021","DOIUrl":"10.1016/j.molliq.2025.129021","url":null,"abstract":"<div><div>5-Fluorouracil (5-FU) is an anticancer agent that has constraints of poor permeability and low bioavailability. To improve the bioavailability of 5-FU and its cytotoxicity potential in the breast cancer cell line (MCF-7), a 5-FU-phospholipid complex (5-FUPLC) embedded in basil oil (BO) based self-nanoemulsifying drug delivery system (SNEDDS) was developed. 5-FUPLC (1:1) complexation was prepared and physically characterized using TLC, NMR and partition coefficient. Risk assessment identified the critical factors assigned in the design of experimentation (DoE) of 5-FUPLC-SNEDDS, optimized using central-composite design (CCD) modelling. Previously, the phase dynamic of BO was explored in Tween20/PEG400, selected as a surfactant/co-surfactant mix (S<sub>mix</sub>). Five pre-concentrate SNEDDS formulations were drawn from CCD modelling, exhibiting fully dilutable potential via transitioning of nanostructure domains via a bi-continuous system, as characterized via FTIR characterization. Interestingly, 5-FU loading turned pre-concentrate SNEDDS to coarse dispersion across the dilution line (85/15). Meanwhile, 5-FUPLC loading favours nano-emulsification of BO. 5-FUPLC-loaded SNEDDS formulations were physically characterized for droplet size, polydispersity index, and zeta potential. Additionally, their conductivity, refractive index, dilution and %transmittance were assessed. 5-FUPLC-SNEDDS had a sustained release pattern contrary to the immediate releasing character of 5-FU, ascribed to the hydrophobic nature of the complex. Antioxidant potential of SNEDDS was attributed to the possession of BO in the nano-emulsified form. Phospholipid complexation physically transforms the 5-FU (hydrophilic) into 5-FUPLC (hydrophobic), as confirmed from log <em>P</em> values. As a result, 5-FUPLC facilitated the nano-emulsification of BO, and itself was embedded in the dispersed phase (BO) of SNEDDS; its affinity towards the lipophilic phase was confirmed from LogD (of 5-FUPLC). 5-FUPLC-SNEDDS modulated the drug permeability, investigated using the rat ileum method. Pharmacokinetic assessment ofoptimized formulation (F1) produced a 2.2-fold increase in the area under the curve [AUC]<sub>0-12h</sub> compared to the 5-FU solution. Cytotoxicity assessment of the optimized system (F1) in MCF-7 cell lines exhibited a significant difference in %inhibition of cell growth when compared with 5-FU-loaded SNEDDS as well as 5-FU solution. 5-FUPLC complex embedded in BO nano-emulsified SNEDDS framework optimized using CCD modelling, improved bioavailability and cytotoxicity potential of 5-FU.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"441 ","pages":"Article 129021"},"PeriodicalIF":5.2,"publicationDate":"2025-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145691839","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 : 2025-12-02DOI: 10.1016/j.molliq.2025.129071
Niko Prasetyo , Yuniawan Hidayat
The solvation structure and dynamics of alkaline-earth dications (Mg2+, Sr2+, and Ba2+) in liquid ammonia were investigated using quantum mechanical charge field molecular dynamics (QMCF MD) simulations. Radial, angular, and coordination number distributions (RDF, ADF, CND) were evaluated to characterize the structural features, while mean residence times (MRTs) were used to analyze ligand exchange dynamics. The simulations reproduced experimental structural data with good accuracy. A rigid first solvation shell with no ligand exchange was found for Mg2+, whereas Sr2+ and Ba2+ exhibited more flexible and labile solvation shells. These trends reflect the increase in ionic radius and the concomitant decrease in charge density along the series, demonstrating the capability of QMCF MD to capture periodic variations in ion–solvent interactions.
{"title":"Hybrid forces molecular dynamics on the structure and dynamics of solvated alkaline-earth ions in liquid ammonia","authors":"Niko Prasetyo , Yuniawan Hidayat","doi":"10.1016/j.molliq.2025.129071","DOIUrl":"10.1016/j.molliq.2025.129071","url":null,"abstract":"<div><div>The solvation structure and dynamics of alkaline-earth dications (Mg<sup>2+</sup>, Sr<sup>2+</sup>, and Ba<sup>2+</sup>) in liquid ammonia were investigated using quantum mechanical charge field molecular dynamics (QMCF MD) simulations. Radial, angular, and coordination number distributions (RDF, ADF, CND) were evaluated to characterize the structural features, while mean residence times (MRTs) were used to analyze ligand exchange dynamics. The simulations reproduced experimental structural data with good accuracy. A rigid first solvation shell with no ligand exchange was found for Mg<sup>2+</sup>, whereas Sr<sup>2+</sup> and Ba<sup>2+</sup> exhibited more flexible and labile solvation shells. These trends reflect the increase in ionic radius and the concomitant decrease in charge density along the series, demonstrating the capability of QMCF MD to capture periodic variations in ion–solvent interactions.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"441 ","pages":"Article 129071"},"PeriodicalIF":5.2,"publicationDate":"2025-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145691812","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 : 2025-12-02DOI: 10.1016/j.molliq.2025.129063
Fen Wang , Daowei Liu , Pengli Yin, Hongxing Deng, Ruixue Li, Fuqiong Wang, Xiaohong Cheng
Carbazole-salicylaldehyde Schiff base based hexacaternars BP/n, DE/n, DS/n and DM/n, (n = 12, 16), featuring with biphenyl, diphenyl ether, diphenyl sulfide, and diphenyl methane as central core respectively, were successfully synthesized. Their self-assembly, photophysical, as well as chemical sensing properties were systematically investigated. Except for short-chain compounds DS/12 and DM/12, all the other compounds (BP/n, DE/n (n = 12, 16), DS/16, and DM/16) formed luminescent columnar liquid crystal phases and exhibited rare positive birefringence characteristics. Linear core compounds BP/n (n = 12, 16) can self-assemble into a Colrec/p2mm phase, whereas bent core compounds DE/n (n = 12, 16), DS/16, and DM/16. DS/16 form Colhex/p6mm phase. DS/16 exhibited only a monotropic mesophase upon cooling. In addition, linear core compound BP/12 was able to form organogels with three-dimensional porous network morphologies, while bent core compounds DE/12, DS/12 and DM/12 formed organogels with fibrous nanoribbon morphologies. Furthermore, compared to DP, these compounds exhibit turn-on fluorescence response, as along with good sensing selectivity and low detection limits towards Al3+. Additionally, white light emission was achieved by doping each of these compounds with the blue light emitting compound DP.
{"title":"Linear vs. bent-core carbazole-Schiff base based hexacatenars: synthesis, mesomorphism, and applications as WLEDs and “turn-on” fluorescence sensors towards Al3+","authors":"Fen Wang , Daowei Liu , Pengli Yin, Hongxing Deng, Ruixue Li, Fuqiong Wang, Xiaohong Cheng","doi":"10.1016/j.molliq.2025.129063","DOIUrl":"10.1016/j.molliq.2025.129063","url":null,"abstract":"<div><div>Carbazole-salicylaldehyde Schiff base based hexacaternars <strong>BP/<em>n</em></strong>, <strong>DE/<em>n</em></strong>, <strong>DS/<em>n</em></strong> and <strong>DM/<em>n</em>,</strong> (<strong><em>n</em></strong> = <strong>12</strong>, <strong>16</strong>), featuring with biphenyl, diphenyl ether, diphenyl sulfide, and diphenyl methane as central core respectively, were successfully synthesized. Their self-assembly, photophysical, as well as chemical sensing properties were systematically investigated. Except for short-chain compounds <strong>DS/12</strong> and <strong>DM/12</strong>, all the other compounds (<strong>BP/<em>n</em></strong>, <strong>DE/<em>n</em></strong> (<strong><em>n</em></strong> = <strong>12</strong>, <strong>16</strong>), <strong>DS/16</strong>, and <strong>DM/16</strong>) formed luminescent columnar liquid crystal phases and exhibited rare positive birefringence characteristics. Linear core compounds <strong>BP/<em>n</em></strong> (<strong><em>n</em></strong> = <strong>12</strong>, <strong>16</strong>) can self-assemble into a Col<sub>rec</sub>/<em>p</em>2<em>mm</em> phase, whereas bent core compounds <strong>DE/<em>n</em></strong> (<strong><em>n</em></strong> = <strong>12</strong>, <strong>16</strong>), <strong>DS/16</strong>, and <strong>DM/16</strong>. <strong>DS/16</strong> form Col<sub>hex</sub>/<em>p</em>6<em>mm</em> phase. <strong>DS/16</strong> exhibited only a monotropic mesophase upon cooling. In addition, linear core compound <strong>BP/12</strong> was able to form organogels with three-dimensional porous network morphologies, while bent core compounds <strong>DE/12</strong>, <strong>DS/12</strong> and <strong>DM/12</strong> formed organogels with fibrous nanoribbon morphologies. Furthermore, compared to <strong>DP</strong>, these compounds exhibit turn-on fluorescence response, as along with good sensing selectivity and low detection limits towards Al<sup>3+</sup>. Additionally, white light emission was achieved by doping each of these compounds with the blue light emitting compound <strong>DP</strong>.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"441 ","pages":"Article 129063"},"PeriodicalIF":5.2,"publicationDate":"2025-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145691816","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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