Pub Date : 2026-02-02DOI: 10.1016/j.molliq.2026.129325
Zeliha Akçin, Tuğçe Emre, Orhan Gezici
Deep eutectic solvents (DESs) have recently attracted considerable attention as tunable liquid media capable of modulating the photophysical behavior of dissolved species. In this study, the fluorescence characteristics of Rhodamine B were systematically investigated in two model DESs—choline chloride/urea (DES-U) and choline chloride/ethylene glycol (DES-E)—and their aqueous mixtures. The results demonstrate that DES composition and water content exert a pronounced influence on fluorescence intensity, emission wavelength, detection limits, and dynamic linear ranges. Compared to water, DES-based systems generally enhance fluorescence response, induce bathochromic shifts, and provide lower limit of detection, albeit with narrower linear dynamic ranges. These effects are attributed primarily to solvent-controlled protonation–deprotonation equilibria and aggregate formation arising from the unique microenvironments of DESs. The findings highlight the potential of DESs as designable media for fluorescence-based analytical applications.
{"title":"Insights into spectrofluorimetric analysis in deep eutectic solvents","authors":"Zeliha Akçin, Tuğçe Emre, Orhan Gezici","doi":"10.1016/j.molliq.2026.129325","DOIUrl":"10.1016/j.molliq.2026.129325","url":null,"abstract":"<div><div>Deep eutectic solvents (DESs) have recently attracted considerable attention as tunable liquid media capable of modulating the photophysical behavior of dissolved species. In this study, the fluorescence characteristics of Rhodamine B were systematically investigated in two model DESs—choline chloride/urea (DES-U) and choline chloride/ethylene glycol (DES-E)—and their aqueous mixtures. The results demonstrate that DES composition and water content exert a pronounced influence on fluorescence intensity, emission wavelength, detection limits, and dynamic linear ranges. Compared to water, DES-based systems generally enhance fluorescence response, induce bathochromic shifts, and provide lower limit of detection, albeit with narrower linear dynamic ranges. These effects are attributed primarily to solvent-controlled protonation–deprotonation equilibria and aggregate formation arising from the unique microenvironments of DESs. The findings highlight the potential of DESs as designable media for fluorescence-based analytical applications.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"447 ","pages":"Article 129325"},"PeriodicalIF":5.2,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146102575","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 : 2026-02-02DOI: 10.1016/j.molliq.2026.129264
Jiahao Li , Shiwei Chen , Chennan Zheng , Yijin Chang , Dazhi Zhou , Fengming Li , Changchun Hao
This study investigates how ultrasound influences the interaction between trypsin (TRP) and enrofloxacin (ENRO) using integrated spectroscopic analysis and molecular simulations. The results show that ENRO quenches TRP fluorescence mainly through a static mechanism, with ultrasound enhancing the quenching effect and inducing more pronounced microenvironmental changes around Trp residues compared with thermal treatment. Circular dichroism analysis indicates that ultrasound leads to slight increases in β-sheet content and decreases in random coil, suggesting local structural ordering rather than unfolding. Molecular docking and dynamics simulations further confirm the stability of the TRP–ENRO complex and support the experimentally observed binding behavior. While the study provides molecular-level insight into how ultrasound modulates protein–ligand interactions, limitations remain, including the lack of enzymatic activity assays, cavitation characterization, and quantitative binding free-energy calculations. These findings establish a basis for future mechanistic and functional investigations.
{"title":"Ultrasound regulation of trypsin-enrofloxacin binding and conformational changes","authors":"Jiahao Li , Shiwei Chen , Chennan Zheng , Yijin Chang , Dazhi Zhou , Fengming Li , Changchun Hao","doi":"10.1016/j.molliq.2026.129264","DOIUrl":"10.1016/j.molliq.2026.129264","url":null,"abstract":"<div><div>This study investigates how ultrasound influences the interaction between trypsin (TRP) and enrofloxacin (ENRO) using integrated spectroscopic analysis and molecular simulations. The results show that ENRO quenches TRP fluorescence mainly through a static mechanism, with ultrasound enhancing the quenching effect and inducing more pronounced microenvironmental changes around Trp residues compared with thermal treatment. Circular dichroism analysis indicates that ultrasound leads to slight increases in β-sheet content and decreases in random coil, suggesting local structural ordering rather than unfolding. Molecular docking and dynamics simulations further confirm the stability of the TRP–ENRO complex and support the experimentally observed binding behavior. While the study provides molecular-level insight into how ultrasound modulates protein–ligand interactions, limitations remain, including the lack of enzymatic activity assays, cavitation characterization, and quantitative binding free-energy calculations. These findings establish a basis for future mechanistic and functional investigations.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"447 ","pages":"Article 129264"},"PeriodicalIF":5.2,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146102573","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}
Encapsulation of methyl salicylate (MS) within analogous cationic surfactant micelles provides a versatile platform for tuning soft matter assemblies with enhanced performance. The central objective of the current study is to elucidate the impact of MS on the aggregation behavior of cetyltrimethylammonium-based cationic surfactants having tosylate, chloride, and bromide counterions by an integrated suite of physicochemical methods. A combination of viscosity, small-angle neutron scattering (SANS), and cryogenic transmission electron microscopy (cryo-TEM) was employed to unveil the MS-driven morphological transitions of cationic micelles. The depth of partitioning of MS within cationic micelles, driven by concentration- and temperature-induced hydrophobicity, can be effectively explicated by pyrene steady-state fluorescence, through I1/I3 analysis. Complementary Density functional theory (DFT) calculations were also employed to gain a deeper understanding of the molecular-level interactions between MS and host micelles, thereby substantiating the experimental findings. It also assesses the bioactive properties of MS-loaded in cationic micelles. The outcomes of this study underscore the MS-surfactant interaction in the formulation of soft materials for possible applications in pharmaceuticals and nanostructured formulations.
{"title":"Structural remodeling of cationic micelles through methyl salicylate encapsulation: insights from SANS and cryo-TEM","authors":"Nikunj Patel , Kinal Patel , Sugam Kumar , Sharmistha Dutta Choudhury , Unnati Dani , Mayursing Girase , Ketan Kuperkar , Jagruti Barot , Mehul Khimani , Paresh Parekh , Jigisha K. Parikh , Vinod K. Aswal , Vijay I. Patel","doi":"10.1016/j.molliq.2026.129316","DOIUrl":"10.1016/j.molliq.2026.129316","url":null,"abstract":"<div><div>Encapsulation of methyl salicylate (MS) within analogous cationic surfactant micelles provides a versatile platform for tuning soft matter assemblies with enhanced performance. The central objective of the current study is to elucidate the impact of MS on the aggregation behavior of cetyltrimethylammonium-based cationic surfactants having tosylate, chloride, and bromide counterions by an integrated suite of physicochemical methods. A combination of viscosity, small-angle neutron scattering (SANS), and cryogenic transmission electron microscopy (cryo-TEM) was employed to unveil the MS-driven morphological transitions of cationic micelles. The depth of partitioning of MS within cationic micelles, driven by concentration- and temperature-induced hydrophobicity, can be effectively explicated by pyrene steady-state fluorescence, through <em>I</em><sub>1</sub>/<em>I</em><sub>3</sub> analysis. Complementary Density functional theory (DFT) calculations were also employed to gain a deeper understanding of the molecular-level interactions between MS and host micelles, thereby substantiating the experimental findings. It also assesses the bioactive properties of MS-loaded in cationic micelles. The outcomes of this study underscore the MS-surfactant interaction in the formulation of soft materials for possible applications in pharmaceuticals and nanostructured formulations.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"446 ","pages":"Article 129316"},"PeriodicalIF":5.2,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074575","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-29DOI: 10.1016/j.molliq.2026.129293
Rahmat Sadeghi, Soheyl Vaali
Deep eutectic solvent (DES)-based nanofluids have emerged as a promising class of versatile, sustainable, and highly functional materials that synergistically combine the unique physicochemical and environmentally benign properties of DESs with the enhanced thermal, electrical, and functional characteristics of nanoparticles. Furthermore, the three-dimensional network architecture formed by DES increases the stability of the homogeneous dispersion of nanoparticles and prevents their aggregation. This review provides a comprehensive overview of the current progress in the types, synthesis strategies, stability, thermophysical properties, and theoretical investigations of DES-based nanofluids. A complete database of different types of nanomaterials and DESs used to prepare DES-based nanofluids will be presented along with the characteristics of the resulting nanofluids in terms of preparation method, stability, and thermophysical properties. Various approaches for the preparation, stabilization, and homogeneous particle dispersion have been discussed, along with various factors affecting the stability of these types of nanofluids. The thermophysical properties of the nanofluids—such as thermal conductivity, heat capacity, viscosity, density, photothermal conversion—are examined, highlighting the influence of the type and concentration of nanoparticle, type and composition of DES and temperature. A variety of theoretical studies including theoretical and semi-empirical equations, molecular dynamics simulations, aspen plus simulations, and machine learning that have been conducted to study the properties, stability, structure, interactions, and thermophysical properties of the nanofluids will also be discussed. This review will critically examine all the various studies and works carried out so far, and while pointing out the existing weaknesses and challenges, it will also present future research directions needed to address the shortcomings. Finally, this review concludes with an analysis of the strengths, weaknesses, opportunities and threats in this area.
{"title":"Deep Eutectic Solvent-Based Nanofluids: A Comprehensive Overview of Types, Synthesis Strategies, Stability, Thermophysical Properties, and Theoretical Investigations","authors":"Rahmat Sadeghi, Soheyl Vaali","doi":"10.1016/j.molliq.2026.129293","DOIUrl":"10.1016/j.molliq.2026.129293","url":null,"abstract":"<div><div>Deep eutectic solvent (DES)-based nanofluids have emerged as a promising class of versatile, sustainable, and highly functional materials that synergistically combine the unique physicochemical and environmentally benign properties of DESs with the enhanced thermal, electrical, and functional characteristics of nanoparticles. Furthermore, the three-dimensional network architecture formed by DES increases the stability of the homogeneous dispersion of nanoparticles and prevents their aggregation. This review provides a comprehensive overview of the current progress in the types, synthesis strategies, stability, thermophysical properties, and theoretical investigations of DES-based nanofluids. A complete database of different types of nanomaterials and DESs used to prepare DES-based nanofluids will be presented along with the characteristics of the resulting nanofluids in terms of preparation method, stability, and thermophysical properties. Various approaches for the preparation, stabilization, and homogeneous particle dispersion have been discussed, along with various factors affecting the stability of these types of nanofluids. The thermophysical properties of the nanofluids—such as thermal conductivity, heat capacity, viscosity, density, photothermal conversion—are examined, highlighting the influence of the type and concentration of nanoparticle, type and composition of DES and temperature. A variety of theoretical studies including theoretical and semi-empirical equations, molecular dynamics simulations, aspen plus simulations, and machine learning that have been conducted to study the properties, stability, structure, interactions, and thermophysical properties of the nanofluids will also be discussed. This review will critically examine all the various studies and works carried out so far, and while pointing out the existing weaknesses and challenges, it will also present future research directions needed to address the shortcomings. Finally, this review concludes with an analysis of the strengths, weaknesses, opportunities and threats in this area.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"446 ","pages":"Article 129293"},"PeriodicalIF":5.2,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074569","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-29DOI: 10.1016/j.molliq.2026.129245
Francisco J. Arias
In the referenced article the authors employ a coarse-grained molecular dynamics approach to explore the influence of nanobubbles on the viscosity and surface tension of water. Surface tension is computed via the pressure-tensor method, and the simulations indicate that nanobubbles systematically reduce the surface-tension coefficient. A linear empirical correlation is proposed for the ratio , where is the surface tension of nanobubble water and is that of pure water under identical conditions. However, this linear relation is calibrated only within K, despite the pressure coefficients spanning up to bar, where liquid water remains stable at temperatures significantly above K. A direct extension of the linear form leads to unphysical predictions outside the calibration interval. In this Comment, by linking the molecular-dynamics results of Du et al. with classical interfacial thermodynamics—originating in Gibbs’ adsorption theory and later strengthened by Frenkel’s molecular-kinetic framework—it is demonstrated that the temperature dependence of should follow an exponential attenuation law. This form naturally reduces to the authors’ linear correlation via a first-order expansion, while remaining physically consistent at higher temperatures. Moreover, the resulting model predicts a molecular Gibbs free energy in excellent agreement with independent values reported in the literature, thus lending further confidence to the MD simulations of Du et al.
{"title":"Comment on “Effects of nanobubble on physical properties of water: A coarse-grained molecular dynamics analysis” by Yuhang Du, Fanqi Pei, Zhi Wen, and Guofeng Lou [J. Mol. Liq. 437 (2025) 128445]","authors":"Francisco J. Arias","doi":"10.1016/j.molliq.2026.129245","DOIUrl":"10.1016/j.molliq.2026.129245","url":null,"abstract":"<div><div>In the referenced article the authors employ a coarse-grained molecular dynamics approach to explore the influence of nanobubbles on the viscosity and surface tension of water. Surface tension is computed via the pressure-tensor method, and the simulations indicate that nanobubbles systematically reduce the surface-tension coefficient. A linear empirical correlation is proposed for the ratio <span><math><mi>γ</mi><mrow><mo>/</mo></mrow><msub><mi>γ</mi><mi>f</mi></msub></math></span>, where <span><math><mi>γ</mi></math></span> is the surface tension of nanobubble water and <span><math><msub><mi>γ</mi><mi>f</mi></msub></math></span> is that of pure water under identical conditions. However, this linear relation is calibrated only within <span><math><mi>T</mi><mo>∈</mo><mo>[</mo><mn>300</mn><mo>,</mo><mn>350</mn><mo>]</mo></math></span> K, despite the pressure coefficients spanning up to <span><math><mn>100</mn></math></span> bar, where liquid water remains stable at temperatures significantly above <span><math><mn>350</mn></math></span> K. A direct extension of the linear form leads to unphysical predictions outside the calibration interval. In this Comment, by linking the molecular-dynamics results of Du et al. with classical interfacial thermodynamics—originating in Gibbs’ adsorption theory and later strengthened by Frenkel’s molecular-kinetic framework—it is demonstrated that the temperature dependence of <span><math><mi>γ</mi><mrow><mo>/</mo></mrow><msub><mi>γ</mi><mi>f</mi></msub></math></span> should follow an exponential attenuation law. This form naturally reduces to the authors’ linear correlation via a first-order expansion, while remaining physically consistent at higher temperatures. Moreover, the resulting model predicts a molecular Gibbs free energy in excellent agreement with independent values reported in the literature, thus lending further confidence to the MD simulations of Du et al.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"446 ","pages":"Article 129245"},"PeriodicalIF":5.2,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074572","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-28DOI: 10.1016/j.molliq.2026.129327
Shivani Daksh , Shashank Deep , Anupama Datta
The aggregation of the Aβ42 protein and its interaction with metal ions are key contributors to the progression of neurodegenerative diseases, presenting significant challenges in developing effective therapeutic strategies. This study evaluated the triazole-chalcone conjugate, (E)-3-(4-(dimethylamino)phenyl)-1-(4-((1-(2-(4-((E)-3-(4(dimethylamino)phenyl) acryloyl)phenoxy)ethyl)-1H-1,2,3-triazol-4-yl)methoxy)phenyl)prop-2-en-1-one (L1), as a multi-target-directed ligand by assessing its Aβ42 aggregation inhibition and disaggregation efficiency, metal-chelating ability, and its potential to attenuate metal-induced oxidative stress. Molecular docking studies revealed that L1 has a greater binding affinity towards Aβ42 protofibril than the monomeric counterpart. Here, the two chalcone moieties were conjugated via click chemistry, employing a triazole linker known for its metal chelation properties and biological activity enhancement. In vitro thioflavin-T fluorescence assays demonstrated that L1 effectively inhibited self-induced Aβ42 aggregation, achieving a maximum inhibition of 72.4 ± 2.3% at a 1:2 (Aβ42:L1) molar ratio, with an IC₅₀ value of 3.19 ± 0.07 μM. Furthermore, L1 exhibited strong copper-chelating ability with a 2:1 (L1:Cu2+) stoichiometry and significantly attenuated Cu2+-induced Aβ42 aggregation, displaying an IC₅₀ value of 5.41 ± 0.13 μM. In a Cu-ascorbate redox system, L1 markedly suppressed hydroxyl radical generation, indicating effective mitigation of metal-induced oxidative stress. Cellular studies using SH-SY5Y neuroblastoma cells confirmed the non-toxic nature of L1 and demonstrated substantial protection against Aβ42-induced cytotoxicity. Collectively, these findings establish L1 as a promising multifunctional candidate that simultaneously inhibits Aβ42 aggregation, disrupts preformed fibrils, chelates metal ions, and reduces oxidative stress, highlighting the therapeutic potential of dimeric triazole–chalcone conjugates for neurodegenerative disease intervention.
{"title":"Dimeric triazole-chalcone conjugate as multi-target directed β-amyloid inhibitor","authors":"Shivani Daksh , Shashank Deep , Anupama Datta","doi":"10.1016/j.molliq.2026.129327","DOIUrl":"10.1016/j.molliq.2026.129327","url":null,"abstract":"<div><div>The aggregation of the Aβ<sub>42</sub> protein and its interaction with metal ions are key contributors to the progression of neurodegenerative diseases, presenting significant challenges in developing effective therapeutic strategies. This study evaluated the triazole-chalcone conjugate, (<em>E</em>)-3-(4-(dimethylamino)phenyl)-1-(4-((1-(2-(4-((E)-3-(4(dimethylamino)phenyl) acryloyl)phenoxy)ethyl)-1H-1,2,3-triazol-4-yl)methoxy)phenyl)prop-2-en-1-one (L1), as a multi-target-directed ligand by assessing its Aβ<sub>42</sub> aggregation inhibition and disaggregation efficiency, metal-chelating ability, and its potential to attenuate metal-induced oxidative stress. Molecular docking studies revealed that L1 has a greater binding affinity towards Aβ<sub>42</sub> protofibril than the monomeric counterpart. Here, the two chalcone moieties were conjugated via click chemistry, employing a triazole linker known for its metal chelation properties and biological activity enhancement. In vitro thioflavin-T fluorescence assays demonstrated that L1 effectively inhibited self-induced Aβ<sub>42</sub> aggregation, achieving a maximum inhibition of 72.4 ± 2.3% at a 1:2 (Aβ<sub>42</sub>:L1) molar ratio, with an IC₅₀ value of 3.19 ± 0.07 μM. Furthermore, L1 exhibited strong copper-chelating ability with a 2:1 (L1:Cu<sup>2+</sup>) stoichiometry and significantly attenuated Cu<sup>2+</sup>-induced Aβ<sub>42</sub> aggregation, displaying an IC₅₀ value of 5.41 ± 0.13 μM. In a Cu-ascorbate redox system, L1 markedly suppressed hydroxyl radical generation, indicating effective mitigation of metal-induced oxidative stress. Cellular studies using SH-SY5Y neuroblastoma cells confirmed the non-toxic nature of L1 and demonstrated substantial protection against Aβ<sub>42</sub>-induced cytotoxicity. Collectively, these findings establish L1 as a promising multifunctional candidate that simultaneously inhibits Aβ<sub>42</sub> aggregation, disrupts preformed fibrils, chelates metal ions, and reduces oxidative stress, highlighting the therapeutic potential of dimeric triazole–chalcone conjugates for neurodegenerative disease intervention.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"447 ","pages":"Article 129327"},"PeriodicalIF":5.2,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146102574","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":"2026-01-27","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 : 2026-01-27DOI: 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":"2026-01-27","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}
Pub 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":"2026-01-26","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 : 2026-01-26DOI: 10.1016/j.molliq.2026.129321
Mstislav V. Kirillov, Anastasia A. Sizova, Vladimir V. Sizov
Molecular dynamics simulations were performed to study the influence of a series of α,ω-dicarboxylic acids on the behavior of n-decane–water systems in hydrophobic confinement. Acids with a cyclic backbone (benzene-1,4-dicarboxylic and cyclohexane-1,4-dicarboxylic) did not succeed in altering the shapes of the liquid phases. The acid with the longest hydrocarbon chain (1,10-decanedioic) demonstrates some surfactant-like properties along with the ability to consistently alter the shape of the interface between the two immiscible liquids. Two acids with shorter hydrocarbon chains (1,8-octanedioic and 1,6-hexanedioic) can be viewed as an intermediate case, since both one- and two-cylinder morphologies of the liquid–liquid interface occur for these additives. The acid with the shortest hydrocarbon chain (1,4-butanedioic) does not have a significant effect on the shapes of the liquid phases. The ability to alter the morphology of the liquid–liquid interface might be related to the structural features of the aggregates formed by molecules of dicarboxylic acids.
{"title":"Immiscible oil/water systems in hydrophobic porous media in the presence of dicarboxylic acids","authors":"Mstislav V. Kirillov, Anastasia A. Sizova, Vladimir V. Sizov","doi":"10.1016/j.molliq.2026.129321","DOIUrl":"10.1016/j.molliq.2026.129321","url":null,"abstract":"<div><div>Molecular dynamics simulations were performed to study the influence of a series of α,ω-dicarboxylic acids on the behavior of <em>n</em>-decane–water systems in hydrophobic confinement. Acids with a cyclic backbone (benzene-1,4-dicarboxylic and cyclohexane-1,4-dicarboxylic) did not succeed in altering the shapes of the liquid phases. The acid with the longest hydrocarbon chain (1,10-decanedioic) demonstrates some surfactant-like properties along with the ability to consistently alter the shape of the interface between the two immiscible liquids. Two acids with shorter hydrocarbon chains (1,8-octanedioic and 1,6-hexanedioic) can be viewed as an intermediate case, since both one- and two-cylinder morphologies of the liquid–liquid interface occur for these additives. The acid with the shortest hydrocarbon chain (1,4-butanedioic) does not have a significant effect on the shapes of the liquid phases. The ability to alter the morphology of the liquid–liquid interface might be related to the structural features of the aggregates formed by molecules of dicarboxylic acids.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"446 ","pages":"Article 129321"},"PeriodicalIF":5.2,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074587","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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