Molecular-level understanding of oil–water separation is critical for designing high-performance superwettable materials. Herein, molecular dynamics (MD) simulations are employed to investigate the interfacial behavior of zinc stearate (ZnSt)–modified polyurethane (PU) surfaces. Quantitative contact angle analysis reveals a transition from moderate wettability on pristine PU (water contact angle ≈ 61° ± 2, oil contact angle ≈ 44° ± 2) to pronounced superhydrophobic–superoleophilic behavior after ZnSt modification, with a water contact angle of ≈ 169° ± 2 and an oil contact angle below 5°. Energy analyses show a substantial increase in oil–surface interaction energy (stabilizing near ≈ 115 kcal·mol−1) and a marked reduction in water adhesion. Radial distribution functions, mean square displacement, and density profiles confirm weakened water–surface interactions and enhanced lateral mobility and multilayer adsorption of oil on ZnSt-modified PU. The close agreement between simulated contact angles and reported experimental values validates the computational framework. These results elucidate the molecular mechanisms governing selective wettability and provide quantitative guidance for the design of advanced PU-based oil–water separation materials.
{"title":"Molecular insights into zinc stearate nanoparticle-modified polyurethane foam for efficient water–oil separation","authors":"Fatemeh Sadati , Yousef Tamsilian , Reza Mossayebi Behbahani","doi":"10.1016/j.molliq.2026.129287","DOIUrl":"10.1016/j.molliq.2026.129287","url":null,"abstract":"<div><div>Molecular-level understanding of oil–water separation is critical for designing high-performance superwettable materials. Herein, molecular dynamics (MD) simulations are employed to investigate the interfacial behavior of zinc stearate (ZnSt)–modified polyurethane (PU) surfaces. Quantitative contact angle analysis reveals a transition from moderate wettability on pristine PU (water contact angle ≈ 61° ± 2, oil contact angle ≈ 44° ± 2) to pronounced superhydrophobic–superoleophilic behavior after ZnSt modification, with a water contact angle of ≈ 169° ± 2 and an oil contact angle below 5°. Energy analyses show a substantial increase in oil–surface interaction energy (stabilizing near ≈ 115 kcal·mol<sup>−1</sup>) and a marked reduction in water adhesion. Radial distribution functions, mean square displacement, and density profiles confirm weakened water–surface interactions and enhanced lateral mobility and multilayer adsorption of oil on ZnSt-modified PU. The close agreement between simulated contact angles and reported experimental values validates the computational framework. These results elucidate the molecular mechanisms governing selective wettability and provide quantitative guidance for the design of advanced PU-based oil–water separation materials.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"446 ","pages":"Article 129287"},"PeriodicalIF":5.2,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035847","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 : 2026-03-15Epub Date: 2026-01-27DOI: 10.1016/j.molliq.2026.129292
Soma Keszei , Rita Skoda-Földes , György Lendvay
Sensing of weakly coordinating anions remains a significant challenge, due to their relatively low basicity. Our theoretical and experimental investigations show that a ferrocene moiety, incorporated into a receptor molecule not only serves as an electrochemical marker, but also able to participate in the binding of weakly coordinating anions, making possible their detection. Geometrical parameters of DFT-optimized structures of complexes, formed by the binding of [BF4]−, [OTf]− and [CF3CO2]− anions to the isomers of protonated 1-(4-ferrocenyl-6-phenylpyrimidin-2-yl)-3-phenylurea revealed the formation of C-H---anion hydrogen bonds between ferrocene and the O or F atoms of the coordinated anion, which is supported by bond order, QTAIM, NCI as well as chemical energy component analysis. Importantly, the computational predictions of hydrogen bond formation are corroborated by low-temperature 1H NMR titration experiments, highlighting the essential role of combined experimental and theoretical investigations in accurately characterizing anion recognition processes.
{"title":"Ferrocene as a non-innocent redox marker in sensors: Unveiling its role in anion binding by electronic structure calculations and experiments","authors":"Soma Keszei , Rita Skoda-Földes , György Lendvay","doi":"10.1016/j.molliq.2026.129292","DOIUrl":"10.1016/j.molliq.2026.129292","url":null,"abstract":"<div><div>Sensing of weakly coordinating anions remains a significant challenge, due to their relatively low basicity. Our theoretical and experimental investigations show that a ferrocene moiety, incorporated into a receptor molecule not only serves as an electrochemical marker, but also able to participate in the binding of weakly coordinating anions, making possible their detection. Geometrical parameters of DFT-optimized structures of complexes, formed by the binding of [BF<sub>4</sub>]<sup>−</sup>, [OTf]<sup>−</sup> and [CF<sub>3</sub>CO<sub>2</sub>]<sup>−</sup> anions to the isomers of protonated 1-(4-ferrocenyl-6-phenylpyrimidin-2-yl)-3-phenylurea revealed the formation of C-H---anion hydrogen bonds between ferrocene and the O or F atoms of the coordinated anion, which is supported by bond order, QTAIM, NCI as well as chemical energy component analysis. Importantly, the computational predictions of hydrogen bond formation are corroborated by low-temperature <sup>1</sup>H NMR titration experiments, highlighting the essential role of combined experimental and theoretical investigations in accurately characterizing anion recognition processes.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"446 ","pages":"Article 129292"},"PeriodicalIF":5.2,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074428","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}
1,2,4-oxadiazole is a heterocyclic compound rarely preferred as a main scaffold in the organic emitter literature due to its antisymmetric structure and restricted structural conjugation. To provide knowledge for designing new structures, it is essential to understand the emission mechanism of compounds comprising this member of the oxadiazole family as a scaffold. Herein, we report the syntheses and the photophysical properties of a new group of fluorescent small molecules with a 1,2,4-oxadiazole scaffold that features aryl and styryl moieties modified with donor and acceptor groups. The photophysical properties of the compounds, exhibiting fluorescence emission in both solution and solid-state, have been systematically studied, and their emission mechanism was also discussed considering the results. Analyzing steady-state photoluminescence (PL) measurements performed for the dilute solutions of compounds shows that only the donor-acceptor structured compounds exhibit strong fluorescence emission, shifting to the lower-energy side of the spectrum, accompanied by a decreasing PL quantum yield, as the solvent polarity increases. The results indicate that the main mechanism responsible for this strong positive solvatochromic behavior is the dipole-dipole coupling between the molecules of the synthesized compounds with intramolecular charge transfer (ICT) properties and the solvent molecules. The solvatochromic behavior of the compounds was also analyzed using five different solvatochromic shift methods. In addition, the results of the quantum chemical calculations performed for the synthesized molecules reveal a charge-separated distribution for the frontier molecular orbitals of the compounds, confirming their ICT nature. On the other hand, PL spectroscopy studies show that all compounds also exhibit PL emission in solid phases. The results indicate that the solid-state emission of the compounds can be tuned between the blue and red regions of the visible spectrum, depending on the position and type of functional groups attached to the oxadiazole scaffold, without significant changes in conjugation length. Furthermore, the analyses of time-resolved fluorescence measurements conducted to understand their emission kinetics reveal an ICT-driven emission model consisting of a radiative decay pathway from a locally excited (LE) state to an ICT state, then to the ground state.
{"title":"Solid-state emissive small molecules comprising 1,2,4-oxadiazole scaffold: intramolecular charge transfer-driven tunable photophysical properties","authors":"Murat Olutas , Farah I.A. Al-Hayali , Akın Sağırlı , Havva Acar","doi":"10.1016/j.molliq.2026.129324","DOIUrl":"10.1016/j.molliq.2026.129324","url":null,"abstract":"<div><div>1,2,4-oxadiazole is a heterocyclic compound rarely preferred as a main scaffold in the organic emitter literature due to its antisymmetric structure and restricted structural conjugation. To provide knowledge for designing new structures, it is essential to understand the emission mechanism of compounds comprising this member of the oxadiazole family as a scaffold. Herein, we report the syntheses and the photophysical properties of a new group of fluorescent small molecules with a 1,2,4-oxadiazole scaffold that features aryl and styryl moieties modified with donor and acceptor groups. The photophysical properties of the compounds, exhibiting fluorescence emission in both solution and solid-state, have been systematically studied, and their emission mechanism was also discussed considering the results. Analyzing steady-state photoluminescence (PL) measurements performed for the dilute solutions of compounds shows that only the donor-acceptor structured compounds exhibit strong fluorescence emission, shifting to the lower-energy side of the spectrum, accompanied by a decreasing PL quantum yield, as the solvent polarity increases. The results indicate that the main mechanism responsible for this strong positive solvatochromic behavior is the dipole-dipole coupling between the molecules of the synthesized compounds with intramolecular charge transfer (ICT) properties and the solvent molecules. The solvatochromic behavior of the compounds was also analyzed using five different solvatochromic shift methods. In addition, the results of the quantum chemical calculations performed for the synthesized molecules reveal a charge-separated distribution for the frontier molecular orbitals of the compounds, confirming their ICT nature. On the other hand, PL spectroscopy studies show that all compounds also exhibit PL emission in solid phases. The results indicate that the solid-state emission of the compounds can be tuned between the blue and red regions of the visible spectrum, depending on the position and type of functional groups attached to the oxadiazole scaffold, without significant changes in conjugation length. Furthermore, the analyses of time-resolved fluorescence measurements conducted to understand their emission kinetics reveal an ICT-driven emission model consisting of a radiative decay pathway from a locally excited (LE) state to an ICT state, then to the ground state.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"446 ","pages":"Article 129324"},"PeriodicalIF":5.2,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074514","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 : 2026-03-15Epub Date: 2026-01-14DOI: 10.1016/j.molliq.2026.129267
Julian Ticona-Chambi , Erivelton N. Carvalho , Edvaldo A. Almeida , Ana M.E. Santo , Lourdes Infantes , Silvia L. Cuffini
Solubility is a key physical chemical property of pharmaceutical compounds, relevant not only for research studies but also for industrial processes. Therefore, solvent selection represents a critical step in the development of new pharmaceutical formulations and in the manufacturing of pharmaceutical products. According to the International Conference on Harmonization (ICH), solvent selection in these processes must be carefully evaluated and scientifically justified, highlighting the requirement for efficient methods to assist in this process. The Hansen Solubility Parameters (HSP) and its corresponding solubility sphere provide a theoretical framework for understanding the solubility behavior of compounds in different solvents. Although HSP were originally developed for polymer systems, their application to small molecules often requires adjustments or complementary experimental validation to achieve accurate predictions. For this reason, this study aimed to develop and evaluate an optimized method based on the HSP theory and experimental measurements, applied in small molecules drug. A set of eighteen molecules, including APIs, bioactive molecules, and coformers, were analyzed. The theoretical HSP and Hansen solubility sphere values were calculated using the Group Contribution method through the HSPmol software. Then, qualitative solubility information of forty-five representative solvents commonly used in the pharmaceutical industry, was input into HSPmol software, to optimize the HSP and solubility sphere values, using a desirability function. The results demonstrated that the O-HSP-pharm method reduced the overall error and improved the representativeness of the dissolved sphere. The Total Error value obtained with the optimization method was lower than that of the theoretical model, indicating higher predictive accuracy. Moreover, the results indicate that it is necessary to provide qualitative solubility information for at least 25 solvents to HSPmol in order to obtain a robust and representative solubility sphere. The optimized method provided useful solubility data, clearly identifying the best solvents for dissolving small molecules. These findings underscore the strong potential of the O-HSP-pharm method as a robust and reliable tool to guide experimental procedures and formulation design within the pharmaceutical field.
{"title":"Optimized Hansen solubility parameters method for pharmaceutical solids: O-HSP-pharm","authors":"Julian Ticona-Chambi , Erivelton N. Carvalho , Edvaldo A. Almeida , Ana M.E. Santo , Lourdes Infantes , Silvia L. Cuffini","doi":"10.1016/j.molliq.2026.129267","DOIUrl":"10.1016/j.molliq.2026.129267","url":null,"abstract":"<div><div>Solubility is a key physical chemical property of pharmaceutical compounds, relevant not only for research studies but also for industrial processes. Therefore, solvent selection represents a critical step in the development of new pharmaceutical formulations and in the manufacturing of pharmaceutical products. According to the International Conference on Harmonization (ICH), solvent selection in these processes must be carefully evaluated and scientifically justified, highlighting the requirement for efficient methods to assist in this process. The Hansen Solubility Parameters (HSP) and its corresponding solubility sphere provide a theoretical framework for understanding the solubility behavior of compounds in different solvents. Although HSP were originally developed for polymer systems, their application to small molecules often requires adjustments or complementary experimental validation to achieve accurate predictions. For this reason, this study aimed to develop and evaluate an optimized method based on the HSP theory and experimental measurements, applied in small molecules drug. A set of eighteen molecules, including APIs, bioactive molecules, and coformers, were analyzed. The theoretical HSP and Hansen solubility sphere values were calculated using the Group Contribution method through the HSPmol software. Then, qualitative solubility information of forty-five representative solvents commonly used in the pharmaceutical industry, was input into HSPmol software, to optimize the HSP and solubility sphere values, using a desirability function. The results demonstrated that the O-HSP-pharm method reduced the overall error and improved the representativeness of the dissolved sphere. The Total Error value obtained with the optimization method was lower than that of the theoretical model, indicating higher predictive accuracy. Moreover, the results indicate that it is necessary to provide qualitative solubility information for at least 25 solvents to HSPmol in order to obtain a robust and representative solubility sphere. The optimized method provided useful solubility data, clearly identifying the best solvents for dissolving small molecules. These findings underscore the strong potential of the O-HSP-pharm method as a robust and reliable tool to guide experimental procedures and formulation design within the pharmaceutical field.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"446 ","pages":"Article 129267"},"PeriodicalIF":5.2,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035979","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 : 2026-03-15Epub Date: 2026-01-15DOI: 10.1016/j.molliq.2026.129266
Kata Szayly , Gergely Stankovits , András Szilágyi, Benjámin Gyarmati
Mucoadhesive formulations can improve the bioavailability of active ingredients in a patient-friendly manner compared to conventional, non-adhesive dosage forms. However, evaluating mucoadhesive performance is highly challenging on ex vivo samples due to the natural variability and storage difficulties of biological samples, thus mucosa-mimetic materials are becoming increasingly important for the robust, in vitro prediction of mucoadhesive properties. In this work, we prepared mucosa-mimetic hydrogels with closer resemblance in adhesive and viscoelastic properties to those of porcine small intestinal mucosa compared to previous models. To this end, we re-designed our previously developed mucin-containing poly(vinyl alcohol) (muc/PVA) hydrogel model, synthesized via the freeze-thaw method. Our approach has two key elements: minimizing the number of freeze-thaw cycles and tailoring the mechanical properties by the mucin content in the hydrogels. The adhesion on the mucosa-mimetic hydrogels was tested by using tablets of mucoadhesive excipients with highly dissimilar physicochemical properties: hydroxypropyl methylcellulose, slightly cross-linked poly(acrylic acid), and chitosan. The model hydrogels were able to differentiate the tablets in terms of their adhesion, and it was also possible to control the strength of adhesion by changing the mucin content of the hydrogels. Furthermore, muc/PVA hydrogels with a specific mucin content (6.5 wt%) displayed satisfactory similarity in viscoelasticity and adhesion towards all polymer tablets to small intestine, thus the studied range of muc/PVA hydrogels can be useful models in early development steps of novel mucoadhesive dosage forms.
{"title":"Engineering the viscoelastic and adhesive properties of mucosa-mimetic poly(vinyl alcohol)/mucin hydrogels to model the small intestinal mucosa","authors":"Kata Szayly , Gergely Stankovits , András Szilágyi, Benjámin Gyarmati","doi":"10.1016/j.molliq.2026.129266","DOIUrl":"10.1016/j.molliq.2026.129266","url":null,"abstract":"<div><div>Mucoadhesive formulations can improve the bioavailability of active ingredients in a patient-friendly manner compared to conventional, non-adhesive dosage forms. However, evaluating mucoadhesive performance is highly challenging on ex vivo samples due to the natural variability and storage difficulties of biological samples, thus mucosa-mimetic materials are becoming increasingly important for the robust, in vitro prediction of mucoadhesive properties. In this work, we prepared mucosa-mimetic hydrogels with closer resemblance in adhesive and viscoelastic properties to those of porcine small intestinal mucosa compared to previous models. To this end, we re-designed our previously developed mucin-containing poly(vinyl alcohol) (muc/PVA) hydrogel model, synthesized via the freeze-thaw method. Our approach has two key elements: minimizing the number of freeze-thaw cycles and tailoring the mechanical properties by the mucin content in the hydrogels. The adhesion on the mucosa-mimetic hydrogels was tested by using tablets of mucoadhesive excipients with highly dissimilar physicochemical properties: hydroxypropyl methylcellulose, slightly cross-linked poly(acrylic acid), and chitosan. The model hydrogels were able to differentiate the tablets in terms of their adhesion, and it was also possible to control the strength of adhesion by changing the mucin content of the hydrogels. Furthermore, muc/PVA hydrogels with a specific mucin content (6.5 wt%) displayed satisfactory similarity in viscoelasticity and adhesion towards all polymer tablets to small intestine, thus the studied range of muc/PVA hydrogels can be useful models in early development steps of novel mucoadhesive dosage forms.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"446 ","pages":"Article 129266"},"PeriodicalIF":5.2,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035962","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 : 2026-03-15Epub Date: 2026-01-15DOI: 10.1016/j.molliq.2026.129265
Nаtаlyа Sh. Lebedevа , Elenа S. Yurinа , Sаbir S. Guseinоv , Аleksey N. Kiselev , Mikhаil А. Lebedev , Irinа А. Skоrоbоgаtkinа , Sergey А. Syrbu
The prасtiсаl useful prоperties оf sulfо derivаtives оf pоrphyrins depend signifiсаntly оn pH. Fоr exаmple, саnсer сells hаve а mоre асidiс envirоnment (pH = 5.5) соmpаred tо nоrmаl сells (pH = 7.2). The effeсt оf pH (5.5 ≤ pH ≤ 6.5 аnd 7.4) оn the соmplexing аbility tоwаrds BSА аnd the phоtосаtаlytiс асtivity оf sulfо-substituted pоrphyrins соntаining а hydrоphоbiс peripherаl substituent (а residue оf benzоthiаzоle, benzimidаzоle аnd benzоxаzоle) wаs studied.
Ассоrding tо аbsоrptiоn аnd fluоresсenсe speсtrоsсоpy, it wаs fоund thаt аt pH = 7.4, pоrphyrins in mоnоmeriс fоrm bind tо prоtein. The lосаlizаtiоn оf pоrphyrins inside the prоtein glоbule wаs prоven by IR speсtrоsсоpy, thermосhemiсаl аnаlysis, stаtiоnаry аnd time-resоlved fluоrimetry. It wаs fоund thаt the соmplexаtiоn оf pоrphyrins with BSА leаds tо аn inсreаse in the prоpоrtiоn оf disоrdered struсtures аnd β-sheets аnd а deсreаse in the thermаl resistаnсe оf prоtein. Phоtоirrаdiаtiоn оf соmplexes оf BSА with pоrphyrins led tо оxidаtiоn оf prоtein struсtures.
In the rаnge оf 5.5 ≤ pH ≤ 6.5 pоrphyrins exist in the fоrm оf H-self-аssосiаtes thаt аre nоt destrоyed when interасting with BSА; pоrphyrins dо nоt саuse сhаnges in the seсоndаry struсture оf the prоtein, but inсreаse its thermаl resistаnсe by 10°С. Аnаlysis оf phоtосаtаlytiс асtivity shоwed thаt pоrphyrin lоses its аbility tо phоtо-оxidize prоteins in weаkly асidiс envirоnments.
Lead ions (Pb2+) are highly toxic, bioaccumulative, and non-biodegradable, making their removal from contaminated environments a critical global challenge. In this work, an integrated quantum–experimental framework was developed to investigate Pb2+ adsorption by two anionic surfactants N-lauroylsarcosine (LS) and sodium dodecyl sulfate (SDS) and a nonionic surfactant (Tween 80). Density Functional Theory (DFT) calculations of molecular electrostatic potential, Mulliken charge distribution, and adsorption energy (ΔEₐdₛ) revealed that LS exhibited the strongest affinity for Pb2+, followed by SDS, while Tween 80 showed negligible binding. Experimental validation through surface tension isotherms (Szyszkowski and Szyszkowski–Frumkin model fitting) and dynamic light scattering (DLS) measurements confirmed these trends. Pb2+ complexation significantly reduced micellar aggregation numbers (from 73 to 18 for LS and from 78 to 29 for SDS), while Tween 80 displayed minimal variation. The strong agreement between theoretical and experimental results demonstrates that Pb2+ ions destabilize micelles by reducing their aggregation capacity, with LS showing the most efficient Pb2+ removal. This study provides a systematic correlation between DFT-predicted adsorption energetics and experimental interfacial behavior in Pb2+–surfactant systems, establishing a predictive strategy for the rational design of eco-friendly, surfactant-assisted remediation technologies for heavy metal pollutants.
{"title":"Integrating DFT and experiments to elucidate Pb2+–surfactant interactions for micelle-enhanced water remediation","authors":"Abdelhakim Bourouba , Redha Alouaoui , Samira Ferhat , Tomasz Janek","doi":"10.1016/j.molliq.2026.129331","DOIUrl":"10.1016/j.molliq.2026.129331","url":null,"abstract":"<div><div>Lead ions (Pb<sup>2+</sup>) are highly toxic, bioaccumulative, and non-biodegradable, making their removal from contaminated environments a critical global challenge. In this work, an integrated quantum–experimental framework was developed to investigate Pb<sup>2+</sup> adsorption by two anionic surfactants N-lauroylsarcosine (LS) and sodium dodecyl sulfate (SDS) and a nonionic surfactant (Tween 80). Density Functional Theory (DFT) calculations of molecular electrostatic potential, Mulliken charge distribution, and adsorption energy (ΔEₐdₛ) revealed that LS exhibited the strongest affinity for Pb<sup>2+</sup>, followed by SDS, while Tween 80 showed negligible binding. Experimental validation through surface tension isotherms (Szyszkowski and Szyszkowski–Frumkin model fitting) and dynamic light scattering (DLS) measurements confirmed these trends. Pb<sup>2+</sup> complexation significantly reduced micellar aggregation numbers (from 73 to 18 for LS and from 78 to 29 for SDS), while Tween 80 displayed minimal variation. The strong agreement between theoretical and experimental results demonstrates that Pb<sup>2+</sup> ions destabilize micelles by reducing their aggregation capacity, with LS showing the most efficient Pb<sup>2+</sup> removal. This study provides a systematic correlation between DFT-predicted adsorption energetics and experimental interfacial behavior in Pb<sup>2+</sup>–surfactant systems, establishing a predictive strategy for the rational design of eco-friendly, surfactant-assisted remediation technologies for heavy metal pollutants.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"446 ","pages":"Article 129331"},"PeriodicalIF":5.2,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146185158","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 : 2026-03-15Epub Date: 2026-01-06DOI: 10.1016/j.molliq.2026.129237
Agnieszka Tomczyk-Nazarczuk , Olena Siryk , Marcin Kuśmierz , Iwona Komaniecka , Yurii Samchenko , Izabela Polowczyk , Katarzyna Szewczuk-Karpisz
Water and soil pollution with toxic substances can cause potent damage to natural ecosystems and human health. It is thus important to develop material that can effectively capture various impurities and facilitate environmental remediation. In this study, poly(acrylamide-co-acrylonitrile) hydrogel (HG) was fabricated and characterized by FTIR, XPS, thermal analysis, and swelling degree. Furthermore, systematic sorption studies were performed to evaluate hydrogel affinity for copper (Cu), cadmium (Cd), arsenic (As), selenium (Se), diuron (D), and glyphosate (G) in both mono- and bi-sorbate (with two different pollutants) systems. Sorption efficiency of the solid was also examined in the presence of water-soluble macromolecular compounds, that is, anionic polyacrylamide (AN), cationic polyacrylamide (CT), and bacterial exopolysaccharide (EPS). The performed analyses suggested that chelation/coordination, surface complexation, electrostatic attraction, hydrogen bonding, and van der Waals forces played a key role in the sorption of impurities. The examined hydrogel was of great capacity towards glyphosate, allowing for the binding of 99.99 % of this toxic plant protection product, especially in the bi-sorbate systems with metals and metalloids. The investigated material also bound great amounts of diuron, especially in the solutions with As or Se. Even 89.55 % were sorbed in such cases. Low desorption degrees in the range of 8.9–11.87 %, noted in the selected systems, confirmed the strong affinity of herbicides for HG. Therefore, the developed poly(acrylamide-co-acrylonitrile) hydrogel can be considered as an effective material for removing toxic plant protection products from water–soil environments.
{"title":"Development of new poly(acrylamide-co-acrylonitrile) hydrogel: physicochemical characteristics and affinity for metals/metalloids/herbicides in mono- and bi-sorbate aqueous systems","authors":"Agnieszka Tomczyk-Nazarczuk , Olena Siryk , Marcin Kuśmierz , Iwona Komaniecka , Yurii Samchenko , Izabela Polowczyk , Katarzyna Szewczuk-Karpisz","doi":"10.1016/j.molliq.2026.129237","DOIUrl":"10.1016/j.molliq.2026.129237","url":null,"abstract":"<div><div>Water and soil pollution with toxic substances can cause potent damage to natural ecosystems and human health. It is thus important to develop material that can effectively capture various impurities and facilitate environmental remediation. In this study, poly(acrylamide-<em>co</em>-acrylonitrile) hydrogel (HG) was fabricated and characterized by FTIR, XPS, thermal analysis, and swelling degree. Furthermore, systematic sorption studies were performed to evaluate hydrogel affinity for copper (Cu), cadmium (Cd), arsenic (As), selenium (Se), diuron (D), and glyphosate (G) in both mono- and bi-sorbate (with two different pollutants) systems. Sorption efficiency of the solid was also examined in the presence of water-soluble macromolecular compounds, that is, anionic polyacrylamide (AN), cationic polyacrylamide (CT), and bacterial exopolysaccharide (EPS). The performed analyses suggested that chelation/coordination, surface complexation, electrostatic attraction, hydrogen bonding, and van der Waals forces played a key role in the sorption of impurities. The examined hydrogel was of great capacity towards glyphosate, allowing for the binding of 99.99 % of this toxic plant protection product, especially in the bi-sorbate systems with metals and metalloids. The investigated material also bound great amounts of diuron, especially in the solutions with As or Se. Even 89.55 % were sorbed in such cases. Low desorption degrees in the range of 8.9–11.87 %, noted in the selected systems, confirmed the strong affinity of herbicides for HG. Therefore, the developed poly(acrylamide-<em>co</em>-acrylonitrile) hydrogel can be considered as an effective material for removing toxic plant protection products from water–soil environments.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"446 ","pages":"Article 129237"},"PeriodicalIF":5.2,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145975619","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-15Epub Date: 2026-01-26DOI: 10.1016/j.molliq.2026.129302
Aanchal Rathi , Mohammad Saddam Khan , Zehra , Saba Noor , Tanzeel Khan , Faheem Ahmad , Md. Imtaiyaz Hassan , Mohammad Mahfuzul Haque
Berberine chloride, a natural isoquinoline alkaloid, has been investigated as a potential inhibitor of PIM-1 kinase, an oncogenic target implicated in drug resistance and cancer progression. ADMET and bioactivity profiling demonstrated high gastrointestinal absorption, favorable physicochemical properties, adherence to the Lipinski rule of five, and a bioavailability score above 50%, supporting its drug-like potential. Molecular docking study revealed a strong binding of berberine chloride within the binding pocket of PIM-1, which possesses an affinity of −9.1 kcal/mol, stabilized by hydrogen bonds, van der Waals interactions, and pi contacts with key catalytic residues. Kinase inhibition assay confirmed activity with an IC₅₀ of 57.2 μM. Binding affinity was further validated through fluorescence quenching (Ka = 1.7 × 106 M−1) and isothermal titration calorimetry, which indicated spontaneous, enthalpy-driven interactions. A proliferation assay in MCF-7 breast cancer cells demonstrated concentration-dependent inhibition, with an IC₅₀ of 162.3 ± 17 μM, underscoring its anticancer potential. Molecular dynamics simulations over 200 ns showed minimal structural deviations, stable compactness, and consistent hydrogen-bond patterns in the PIM-1-berberine chloride complex. Secondary-structure dynamics and principal component analysis confirmed the preservation of structural integrity and stabilized conformational states. MMPBSA analysis further indicated a favorable binding free energy (−14.91 kJ/mol), reflecting stable and energetically favorable interactions. Together, these results demonstrate that berberine chloride exhibits consistent computational and experimental evidence of PIM-1 inhibition and anticancer activity, supporting its role as a promising scaffold for future drug development.
{"title":"Elucidating the inhibitory potential of berberine chloride against PIM-1 kinase for anticancer therapeutics","authors":"Aanchal Rathi , Mohammad Saddam Khan , Zehra , Saba Noor , Tanzeel Khan , Faheem Ahmad , Md. Imtaiyaz Hassan , Mohammad Mahfuzul Haque","doi":"10.1016/j.molliq.2026.129302","DOIUrl":"10.1016/j.molliq.2026.129302","url":null,"abstract":"<div><div>Berberine chloride, a natural isoquinoline alkaloid, has been investigated as a potential inhibitor of PIM-1 kinase, an oncogenic target implicated in drug resistance and cancer progression. ADMET and bioactivity profiling demonstrated high gastrointestinal absorption, favorable physicochemical properties, adherence to the Lipinski rule of five, and a bioavailability score above 50%, supporting its drug-like potential. Molecular docking study revealed a strong binding of berberine chloride within the binding pocket of PIM-1, which possesses an affinity of −9.1 kcal/mol, stabilized by hydrogen bonds, van der Waals interactions, and pi contacts with key catalytic residues. Kinase inhibition assay confirmed activity with an IC₅₀ of 57.2 μM. Binding affinity was further validated through fluorescence quenching (<em>Ka</em> = 1.7 × 10<sup>6</sup> M<sup>−1</sup>) and isothermal titration calorimetry, which indicated spontaneous, enthalpy-driven interactions. A proliferation assay in MCF-7 breast cancer cells demonstrated concentration-dependent inhibition, with an IC₅₀ of 162.3 ± 17 μM, underscoring its anticancer potential. Molecular dynamics simulations over 200 ns showed minimal structural deviations, stable compactness, and consistent hydrogen-bond patterns in the PIM-1-berberine chloride complex. Secondary-structure dynamics and principal component analysis confirmed the preservation of structural integrity and stabilized conformational states. MMPBSA analysis further indicated a favorable binding free energy (−14.91 kJ/mol), reflecting stable and energetically favorable interactions. Together, these results demonstrate that berberine chloride exhibits consistent computational and experimental evidence of PIM-1 inhibition and anticancer activity, supporting its role as a promising scaffold for future drug development.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"446 ","pages":"Article 129302"},"PeriodicalIF":5.2,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074433","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 : 2026-03-15Epub Date: 2026-01-22DOI: 10.1016/j.molliq.2026.129308
Kun Zhao , Jianxue Li , Ke Meng , Lei Tan , Zhimin Chen , Jiafu Chen , Shaohua Liu , Jianwei Fu
The presence of Pb2+ in water systems poses potential dangers to the environment and public health, and developing efficient adsorbents is a feasible solution to the predicament. Herein, a cross-linked poly(tricholorotriazine-tannic acid) (TCA) nanosphere has been facilely prepared through one-step precipitation polymerization. The microstructure of TCA was well analyzed by TEM, SEM, FT-IR, XRD, TGA and N2 sorption and its adsorption performance for aqueous Pb2+ was systematically evaluated. Results showed that TCA owned a hard spherical structure with size of about 250 nm and specific surface area of 22.3 m2 g−1. The adsorption capacity of TCA for Pb2+ in 50 mg L−1 lead nitrate solution could be up to 136.3 mg g−1 at pH = 5 and 298 K. The adsorption rate is extremely fast, completing 91% of the equilibrium adsorption capacity within one minute. After five cycles of adsorption-desorption, the TCA nanospheres still maintained a high adsorption capacity of 109 mg g−1 for Pb2+. Adsorption kinetics and isotherm analysis suggested that the removal of Pb2+ by TCA followed the pseudo-second-order dynamics model and the Langmuir isotherm model. Thermodynamic parameters revealed that the Pb2+ removal process was spontaneous and endothermic in nature. The plausible removal mechanism could be attributed to coordination, chemical bonding and ion exchange between TCA and Pb2+.
{"title":"Facile fabrication of poly(tricholorotriazine-tannic acid) nanosphere and its rapid removal feature towards lead ions","authors":"Kun Zhao , Jianxue Li , Ke Meng , Lei Tan , Zhimin Chen , Jiafu Chen , Shaohua Liu , Jianwei Fu","doi":"10.1016/j.molliq.2026.129308","DOIUrl":"10.1016/j.molliq.2026.129308","url":null,"abstract":"<div><div>The presence of Pb<sup>2+</sup> in water systems poses potential dangers to the environment and public health, and developing efficient adsorbents is a feasible solution to the predicament. Herein, a cross-linked poly(tricholorotriazine-tannic acid) (TCA) nanosphere has been facilely prepared through one-step precipitation polymerization. The microstructure of TCA was well analyzed by TEM, SEM, FT-IR, XRD, TGA and N<sub>2</sub> sorption and its adsorption performance for aqueous Pb<sup>2+</sup> was systematically evaluated. Results showed that TCA owned a hard spherical structure with size of about 250 nm and specific surface area of 22.3 m<sup>2</sup> g<sup>−1</sup>. The adsorption capacity of TCA for Pb<sup>2+</sup> in 50 mg L<sup>−1</sup> lead nitrate solution could be up to 136.3 mg g<sup>−1</sup> at pH = 5 and 298 K. The adsorption rate is extremely fast, completing 91% of the equilibrium adsorption capacity within one minute. After five cycles of adsorption-desorption, the TCA nanospheres still maintained a high adsorption capacity of 109 mg g<sup>−1</sup> for Pb<sup>2+</sup>. Adsorption kinetics and isotherm analysis suggested that the removal of Pb<sup>2+</sup> by TCA followed the pseudo-second-order dynamics model and the Langmuir isotherm model. Thermodynamic parameters revealed that the Pb<sup>2+</sup> removal process was spontaneous and endothermic in nature. The plausible removal mechanism could be attributed to coordination, chemical bonding and ion exchange between TCA and Pb<sup>2+</sup>.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"446 ","pages":"Article 129308"},"PeriodicalIF":5.2,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074527","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}
扫码关注我们
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号