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Solubilization of carboxyl derivatives of porphyrin molecules by micelles of cationic surfactants: Solubilization capacity and localization sites
IF 5.3 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-02-10 DOI: 10.1016/j.molliq.2025.127124
Elena Yu. Kaigorodova, Galina M. Mamardashvili, Nugzar Zh. Mamardashvili
The article is dedicated to the processes of solubilization of virtually insoluble carboxy-substituted tetraphenylporphyrin macrocycles by micelles of cationic surfactants (CTAB, CPC, and MTAB) to enhance their solubility in water. The influence of various structural parameters on the efficiency of the solubilization process is discussed, specifically the nature of the surfactant’s polar group (trimethylammonium group, +N(CH3)3, and pyridinium group, +NC5H5), the length of the surfactant’s hydrocarbon tail (−C16H31 and −C14H29), and the position of the functional group (–COOH) in the phenyl rings of 5,10,15,20-tetraphenylporphyrin. The ability of two carboxy-substituted porphyrin isomers to localize within the micelles of CTAB, CPC, and MTAB was determined using UV–visible, fluorescence, and 1H NMR spectroscopy, as well as dynamic light scattering. The data indicate that the hydrodynamic radii of empty surfactant micelles increase in the order: MTAB < CPC < CTAB, with the size of MTAB being comparable to the dimensions of the porphyrin macrocycles. The solubilization of carboxy-substituted tetraphenylporphyrins by the studied surfactants in all cases leads to a decrease in the critical micelle concentration (CMC) and an increase in the hydrodynamic radius of the micelles by 12–30 %. The maximum increase is observed for MTAB micelles. The calculated solubilization capacity of CTAB, CPC, and MTAB micelles for these porphyrin molecules ranges from 1 to 18 porphyrin macrocycles per 10 micelles, depending on the surfactant and porphyrin. Using NMR spectroscopy, the most likely localization sites of porphyrin isomers within the micelles were analyzed. In terms of porphyrin positioning, the data suggest that porphyrins with –COOH groups in para-positions are localized in the hydrophobic core of all three ionic micelles, while the –COOH groups themselves occupy more polar domains of the cationic micelles—specifically, the Stern layer. This arrangement is energetically favorable, as the macrocycle is retained within the micelle through a combination of electrostatic and hydrophobic interactions. In contrast, porphyrins with –COOH groups in the ortho-positions localize either predominantly or exclusively in the hydrophobic core or in the polar region and are retained within the micelles solely by one type of interaction. The results can be used to develop therapeutic drugs with increased solubility and bioavailability (for example, photosensitizers for PDT or antimicrobial photodynamic therapy of localized infections).
{"title":"Solubilization of carboxyl derivatives of porphyrin molecules by micelles of cationic surfactants: Solubilization capacity and localization sites","authors":"Elena Yu. Kaigorodova,&nbsp;Galina M. Mamardashvili,&nbsp;Nugzar Zh. Mamardashvili","doi":"10.1016/j.molliq.2025.127124","DOIUrl":"10.1016/j.molliq.2025.127124","url":null,"abstract":"<div><div>The article is dedicated to the processes of solubilization of virtually insoluble carboxy-substituted tetraphenylporphyrin macrocycles by micelles of cationic surfactants (CTAB, CPC, and MTAB) to enhance their solubility in water. The influence of various structural parameters on the efficiency of the solubilization process is discussed, specifically the nature of the surfactant’s polar group (trimethylammonium group, <sup>+</sup>N(CH<sub>3</sub>)<sub>3</sub>, and pyridinium group, <sup>+</sup>NC<sub>5</sub>H<sub>5</sub>), the length of the surfactant’s hydrocarbon tail (−C<sub>16</sub>H<sub>31</sub> and −C<sub>14</sub>H<sub>29</sub>), and the position of the functional group (–COOH) in the phenyl rings of 5,10,15,20-tetraphenylporphyrin. The ability of two carboxy-substituted porphyrin isomers to localize within the micelles of CTAB, CPC, and MTAB was determined using UV–visible, fluorescence, and <sup>1</sup>H NMR spectroscopy, as well as dynamic light scattering. The data indicate that the hydrodynamic radii of empty surfactant micelles increase in the order: MTAB &lt; CPC &lt; CTAB, with the size of MTAB being comparable to the dimensions of the porphyrin macrocycles. The solubilization of carboxy-substituted tetraphenylporphyrins by the studied surfactants in all cases leads to a decrease in the critical micelle concentration (CMC) and an increase in the hydrodynamic radius of the micelles by 12–30 %. The maximum increase is observed for MTAB micelles. The calculated solubilization capacity of CTAB, CPC, and MTAB micelles for these porphyrin molecules ranges from 1 to 18 porphyrin macrocycles per 10 micelles, depending on the surfactant and porphyrin. Using NMR spectroscopy, the most likely localization sites of porphyrin isomers within the micelles were analyzed. In terms of porphyrin positioning, the data suggest that porphyrins with –COOH groups in <em>para</em>-positions are localized in the hydrophobic core of all three ionic micelles, while the –COOH groups themselves occupy more polar domains of the cationic micelles—specifically, the Stern layer. This arrangement is energetically favorable, as the macrocycle is retained within the micelle through a combination of electrostatic and hydrophobic interactions. In contrast, porphyrins with –COOH groups in the <em>ortho</em>-positions localize either predominantly or exclusively in the hydrophobic core or in the polar region and are retained within the micelles solely by one type of interaction. The results can be used to develop therapeutic drugs with increased solubility and bioavailability (for example, photosensitizers for PDT or antimicrobial photodynamic therapy of localized infections).</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"424 ","pages":"Article 127124"},"PeriodicalIF":5.3,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143388349","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}
引用次数: 0
Experimental and theoretical exploration of intermolecular interactions in butyl acrylate + benzene, + toluene, + o-xylene, + m-xylene, + p-xylene, and + mesitylene binary mixtures at ambient temperatures: Ultrasonic and viscometric methods
IF 5.3 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-02-10 DOI: 10.1016/j.molliq.2025.127117
Anil Kumar Nain
The speeds of sound, u and viscosities, η of the binary mixtures of butyl acrylate with benzene, toluene, o-xylene, m-xylene, p-xylene, and mesitylene across the full mole fraction range were measured at ambient temperatures and pressure, p = 100 kPa. The experimental data are correlated by means of Jouyban-Acree model to represents the composition and temperature dependence of these physical properties. Using the measured data, various parameters, viz., excess isentropic compressibilities, excess speeds of sound, excess molar isentropic compressibilities, and deviations in viscosity were evaluated. The partial molar isentropic compressibilities and excess partial molar isentropic compressibilities of the constituents over whole composition range; and at infinite dilution are calculated. The variation of these parameters has been interpreted in relation to the intermolecular interactions in these mixtures. The results specified the presence of weak interactions between unlike molecules, the interactions follow the order: benzene > toluene > p-xylene > m-xylene > o-xylene > mesitylene. The extent of interactions depends on the number and position of the methyl groups substituted to benzene ring in these aromatic hydrocarbons. The speeds of sound were theoretically calculated by means of various theories/relations and the viscosities of these mixtures were correlated by means of several empirical and semi-empirical models and the outcomes are compared with experimental data. The relative applicability of these theories/relations has been discussed.
{"title":"Experimental and theoretical exploration of intermolecular interactions in butyl acrylate + benzene, + toluene, + o-xylene, + m-xylene, + p-xylene, and + mesitylene binary mixtures at ambient temperatures: Ultrasonic and viscometric methods","authors":"Anil Kumar Nain","doi":"10.1016/j.molliq.2025.127117","DOIUrl":"10.1016/j.molliq.2025.127117","url":null,"abstract":"<div><div>The speeds of sound, <em>u</em> and viscosities, <em>η</em> of the binary mixtures of butyl acrylate with benzene, toluene, <em>o</em>-xylene, <em>m</em>-xylene, <em>p</em>-xylene, and mesitylene across the full mole fraction range were measured at ambient temperatures and pressure, <em>p</em> = 100 kPa. The experimental data are correlated by means of Jouyban-Acree model to represents the composition and temperature dependence of these physical properties. Using the measured data, various parameters, <em>viz.</em>, excess isentropic compressibilities, excess speeds of sound, excess molar isentropic compressibilities, and deviations in viscosity were evaluated. The partial molar isentropic compressibilities and excess partial molar isentropic compressibilities of the constituents over whole composition range; and at infinite dilution are calculated. The variation of these parameters has been interpreted in relation to the intermolecular interactions in these mixtures. The results specified the presence of weak interactions between unlike molecules, the interactions follow the order: benzene &gt; toluene &gt; <em>p</em>-xylene &gt; <em>m</em>-xylene &gt; <em>o</em>-xylene &gt; mesitylene. The extent of interactions depends on the number and position of the methyl groups substituted to benzene ring in these aromatic hydrocarbons. The speeds of sound were theoretically calculated by means of various theories/relations and the viscosities of these mixtures were correlated by means of several empirical and semi-empirical models and the outcomes are compared with experimental data. The relative applicability of these theories/relations has been discussed.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"424 ","pages":"Article 127117"},"PeriodicalIF":5.3,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143422319","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}
引用次数: 0
Novel anticancer agents, Pt complex with 1-pyrrolidineacetic acid ligand: Synthesis, biological activity, DNA interaction, molecular docking, and dynamic study
IF 5.3 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-02-10 DOI: 10.1016/j.molliq.2025.127126
Diba Kadivar , Mahboube Eslami Moghadam , Morteza Rezaeisadat
New aliphatic cyclic N-substituted glycine derivative, as asymmetric N, O donate bidentate ligand, and its new Pt complex, [Pt(NH3)2(pyrro-gly)]NO3, where pyrro-gly is 1-Pyrrolidineacetic acid were synthesized and characterized. To investigate the hydrolytic properties, solubility, lipophilicity, and stability of both ligand and Pt complex were analyzed. The cytotoxic properties of both compounds were ascertained on normal and cancerous cell lines in comparison with carboplatin. An apoptosis assay was used to follow the mechanism of cell death in cancerous cells. Regarding isothermal titration, hypochromic absorption was seen during DNA-complex interaction. Fluorescence data illustrated that static quenching occurred. Also, binding constants in EtBr and Hoechst systems showed that groove binding accrues during DNA interaction. Based on circular dichroism studies, electrostatic approaches to DNA and then groove binding interaction were proved which are in agreement with viscosity data. In the docking study, the estimated free binding energy for the Pt complex system is more negative than the ligand system in DNA interaction. The molecular dynamics investigation revealed that the system attained equilibrium after a duration of 100 ns, as determined through the analysis of RMSD, RMSF, and Rg. The findings of the RMSF analysis demonstrated that the majority of residues experienced notable shifts from their starting positions. The computed binding free energy of the complex with DNA was found, which suggested a thermodynamically favorable interaction. The analysis of RDF at equilibrium revealed that Thymine and Guanine residues exhibited the most pronounced and least complex distributions, respectively.
{"title":"Novel anticancer agents, Pt complex with 1-pyrrolidineacetic acid ligand: Synthesis, biological activity, DNA interaction, molecular docking, and dynamic study","authors":"Diba Kadivar ,&nbsp;Mahboube Eslami Moghadam ,&nbsp;Morteza Rezaeisadat","doi":"10.1016/j.molliq.2025.127126","DOIUrl":"10.1016/j.molliq.2025.127126","url":null,"abstract":"<div><div>New aliphatic cyclic N-substituted glycine derivative, as asymmetric N, O donate bidentate ligand, and its new Pt complex, [Pt(NH<sub>3</sub>)<sub>2</sub>(pyrro-gly)]NO<sub>3</sub>, where pyrro-gly is 1-Pyrrolidineacetic acid were synthesized and characterized. To investigate the hydrolytic properties, solubility, lipophilicity, and stability of both ligand and Pt complex were analyzed. The cytotoxic properties of both compounds were ascertained on normal and cancerous cell lines in comparison with carboplatin. An apoptosis assay was used to follow the mechanism of cell death in cancerous cells. Regarding isothermal titration, hypochromic absorption was seen during DNA-complex interaction. Fluorescence data illustrated that static quenching occurred. Also, binding constants in EtBr and Hoechst systems showed that groove binding accrues during DNA interaction. Based on circular dichroism studies, electrostatic approaches to DNA and then groove binding interaction were proved which are in agreement with viscosity data. In the docking study, the estimated free binding energy for the Pt complex system is more negative than the ligand system in DNA interaction. The molecular dynamics investigation revealed that the system attained equilibrium after a duration of 100 ns, as determined through the analysis of RMSD, RMSF, and Rg. The findings of the RMSF analysis demonstrated that the majority of residues experienced notable shifts from their starting positions. The computed binding free energy of the complex with DNA was found, which suggested a thermodynamically favorable interaction. The analysis of RDF at equilibrium revealed that Thymine and Guanine residues exhibited the most pronounced and least complex distributions, respectively.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"424 ","pages":"Article 127126"},"PeriodicalIF":5.3,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143402979","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}
引用次数: 0
Efficiency of magnetite decorated with carbon quantum dot nanocomposites for the adsorptive removal of methylene blue from wastewater: Kinetic and modeling studies
IF 5.3 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-02-10 DOI: 10.1016/j.molliq.2025.127128
Sanae El Ghacham , Youssef Aoulad El Hadj Ali , Lamia Hejji , Nouha El Mail , Abdelmonaim Azzouz , Anas Chraka , Luis Pérez-Villarejo , Pedro J. Sánchez-Soto , Badredine Souhail , Christian Sonne
In this study, a green and straightforward hydrothermal approach was employed to synthesize magnetite decorated with carbon quantum dots (Fe3O4@CQDs) nanocomposites for the effective removal of excess methylene blue (MB) from contaminated water. The textural and chemical proprieties of the Fe3O4@CQDs nanocomposites were comprehensively characterized using various techniques, including FTIR, XRD, SEM, UV–visible, and nitrogen adsorption–desorption analysis. Batch experiments were conducted to optimize process parameters, such as contact time, initial concentration, adsorbent dosage, initial pH, and temperature. The maximum monolayer adsorption capacity was found to be 83.51 mg/g within 45 min. Isotherm and kinetic studies indicated that the adsorption process followed Langmuir and pseudo-second-order models. Detailed analysis revealed that the adsorption mechanism of MB onto Fe3O4@CQDs nanocomposites involves hydrogen bonding, electrostatic interactions, and chemical binding between the adsorbent and adsorbate. The reusability of Fe3O4@CQDs was assessed, showing no significant decline in adsorption capacity over four regeneration cycles. These findings highlight the remarkable potential of Fe3O4@CQDs nanocomposites as efficient adsorbents for dyes removal and provide valuable insights for developing advanced strategies to eliminate cationic dye pollutants from wastewater.
{"title":"Efficiency of magnetite decorated with carbon quantum dot nanocomposites for the adsorptive removal of methylene blue from wastewater: Kinetic and modeling studies","authors":"Sanae El Ghacham ,&nbsp;Youssef Aoulad El Hadj Ali ,&nbsp;Lamia Hejji ,&nbsp;Nouha El Mail ,&nbsp;Abdelmonaim Azzouz ,&nbsp;Anas Chraka ,&nbsp;Luis Pérez-Villarejo ,&nbsp;Pedro J. Sánchez-Soto ,&nbsp;Badredine Souhail ,&nbsp;Christian Sonne","doi":"10.1016/j.molliq.2025.127128","DOIUrl":"10.1016/j.molliq.2025.127128","url":null,"abstract":"<div><div>In this study, a green and straightforward hydrothermal approach was employed to synthesize magnetite decorated with carbon quantum dots (Fe<sub>3</sub>O<sub>4</sub>@CQDs) nanocomposites for the effective removal of excess methylene blue (MB) from contaminated water. The textural and chemical proprieties of the Fe<sub>3</sub>O<sub>4</sub>@CQDs nanocomposites were comprehensively characterized using various techniques, including FTIR, XRD, SEM, UV–visible, and nitrogen adsorption–desorption analysis. Batch experiments were conducted to optimize process parameters, such as contact time, initial concentration, adsorbent dosage, initial pH, and temperature. The maximum monolayer adsorption capacity was found to be 83.51 mg/g within 45 min. Isotherm and kinetic studies indicated that the adsorption process followed Langmuir and pseudo-second-order models. Detailed analysis revealed that the adsorption mechanism of MB onto Fe<sub>3</sub>O<sub>4</sub>@CQDs nanocomposites involves hydrogen bonding, electrostatic interactions, and chemical binding between the adsorbent and adsorbate. The reusability of Fe<sub>3</sub>O<sub>4</sub>@CQDs was assessed, showing no significant decline in adsorption capacity over four regeneration cycles. These findings highlight the remarkable potential of Fe<sub>3</sub>O<sub>4</sub>@CQDs nanocomposites as efficient adsorbents for dyes removal and provide valuable insights for developing advanced strategies to eliminate cationic dye pollutants from wastewater.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"424 ","pages":"Article 127128"},"PeriodicalIF":5.3,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143421804","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}
引用次数: 0
Synthesis, structural characterization and inhibition effects of new bicatenar surfactants based of phenolphtalein on the corrosion of carbon steel in 1 M HCl: Experimental and computational insights
IF 5.3 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-02-10 DOI: 10.1016/j.molliq.2025.127116
Hicham Zgueni , Mohammed El Mesky , Rahime Eshaghi Malekshah , Fatima Ennafaa , Mohamed Znini , El Houssine Mabrouk , Driss Chebabe
The objective of this work is the synthesis of new surfactants with polar head phenolphtalein and their inhibitive effect against carbon steel corrosion in acidic medium. Indeed, These compounds were synthesized by the action of the phénolphtalein on différents alkyl halides such as decyl bromide, undecyl bromide and dodecyl bromide. IR, 1H NMR, 13C NMRand mass spectra have confirmed the structure of the obtained surfactants PHC10, PHC11 and PHC12. Electrochemical techniques such as potentiodynamic polarization and electrochemical impedance spectroscopy, as well as the SEM/EDX surface analysis are used to evaluate the corrosion resistance of these surfactants. In addition, theoretical methods including molecular dynamics simulations and density functional theory are used to understand the mechanisms of interaction between surfactants and metal surface. The obtained results show that the synthesized surfactants significantly reduce corrosion rate, suggesting their potential application in industrial environments. This study contributes to the advancement of corrosion prevention strategies by integrating synthetic chemistry with electrochemical and theoretical analyses.
{"title":"Synthesis, structural characterization and inhibition effects of new bicatenar surfactants based of phenolphtalein on the corrosion of carbon steel in 1 M HCl: Experimental and computational insights","authors":"Hicham Zgueni ,&nbsp;Mohammed El Mesky ,&nbsp;Rahime Eshaghi Malekshah ,&nbsp;Fatima Ennafaa ,&nbsp;Mohamed Znini ,&nbsp;El Houssine Mabrouk ,&nbsp;Driss Chebabe","doi":"10.1016/j.molliq.2025.127116","DOIUrl":"10.1016/j.molliq.2025.127116","url":null,"abstract":"<div><div>The objective of this work is the synthesis of new surfactants with polar head phenolphtalein and their inhibitive effect against carbon steel corrosion in acidic medium. Indeed, These compounds were synthesized by the action of the phénolphtalein on différents alkyl halides such as decyl bromide, undecyl bromide and dodecyl bromide. IR, <sup>1</sup>H NMR, <sup>13</sup>C NMRand mass spectra have confirmed the structure of the obtained surfactants PHC10, PHC11 and PHC12. Electrochemical techniques such as potentiodynamic polarization and electrochemical impedance spectroscopy, as well as the SEM/EDX surface analysis are used to evaluate the corrosion resistance of these surfactants. In addition, theoretical methods including molecular dynamics simulations and density functional theory are used to understand the mechanisms of interaction between surfactants and metal surface. The obtained results show that the synthesized surfactants significantly reduce corrosion rate, suggesting their potential application in industrial environments. This study contributes to the advancement of corrosion prevention strategies by integrating synthetic chemistry with electrochemical and theoretical analyses.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"424 ","pages":"Article 127116"},"PeriodicalIF":5.3,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143421789","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}
引用次数: 0
Thermodynamic Assessment for Rivaroxaban Nanoparticle Production Using Gas Anti-solvent (GAS) Process: Synthesis and Characterization
IF 5.3 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-02-10 DOI: 10.1016/j.molliq.2025.127125
Mahshid Askarizadeh , Nadia Esfandiari , Bizhan Honarvar , Seyed Ali Sajadian , Amin Azdarpour
Nanoparticles of Rivaroxaban were successfully created using the supercritical gas antisolvent method. The study focused on the effects of pressure, temperature, and initial solute concentration on the size and shape of the nanoparticles, utilizing the Box-Behnken design approach. The optimal conditions were determined to be an initial Rivaroxaban concentration of 25 mg/ml, a pressure of 160 bar and a temperature of 318 K. These parameters resulted in nanoparticles of 340.1 ± 10.7 nm, significantly smaller than the original sample (45 μm). Different analytical methods, including XRD, DLS, DSC, FTIR and FESEM were used to study the Rivaroxaban nanoparticles. The findings indicated that the nanoparticles produced through the GAS antisolvent method had lower crystallinity. The FESEM and DLS data confirmed the nanometer size and narrow distribution of the Rivaroxaban particles obtained through this method.
{"title":"Thermodynamic Assessment for Rivaroxaban Nanoparticle Production Using Gas Anti-solvent (GAS) Process: Synthesis and Characterization","authors":"Mahshid Askarizadeh ,&nbsp;Nadia Esfandiari ,&nbsp;Bizhan Honarvar ,&nbsp;Seyed Ali Sajadian ,&nbsp;Amin Azdarpour","doi":"10.1016/j.molliq.2025.127125","DOIUrl":"10.1016/j.molliq.2025.127125","url":null,"abstract":"<div><div>Nanoparticles of Rivaroxaban were successfully created using the supercritical gas antisolvent method. The study focused on the effects of pressure, temperature, and initial solute concentration on the size and shape of the nanoparticles, utilizing the Box-Behnken design approach. The optimal conditions were determined to be an initial Rivaroxaban concentration of 25 mg/ml, a pressure of 160 bar and a temperature of 318 K. These parameters resulted in nanoparticles of 340.1 ± 10.7 nm, significantly smaller than the original sample (45 μm). Different analytical methods, including XRD, DLS, DSC, FTIR and FESEM were used to study the Rivaroxaban nanoparticles. The findings indicated that the nanoparticles produced through the GAS antisolvent method had lower crystallinity. The FESEM and DLS data confirmed the nanometer size and narrow distribution of the Rivaroxaban particles obtained through this method.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"424 ","pages":"Article 127125"},"PeriodicalIF":5.3,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143422323","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}
引用次数: 0
Advancements in photocatalytic systems for ciprofloxacin degradation, efficiency, mechanisms, and environmental considerations
IF 5.3 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-02-10 DOI: 10.1016/j.molliq.2025.127115
Muhammad Idrees , Zia Ul Haq Khan , Sana Sabahat , Jingyu Sun , Noor Samad Shah , Jibran Iqbal
In aquatic ecosystems, the presence of ciprofloxacin (CIP) causes substantial environmental and public health risks, which require advanced water treatment procedures beyond conventional methods. This review emphasizes on the recent advances in the photocatalytic degradation of CIP, exploring the efficiency and mechanisms of various photocatalysts, covering 11 categories of metal-based, carbon-based, and hybrid nanostructures. The review underlines the major importance of photocatalyst morphology, surface area, doping, and the construction of heterojunctions in improving photocatalytic activity. Moreover, it addresses the causes of CIP pollution, the environmental repercussions of CIP, and its role in antibiotic resistance. The review offers a comprehensive overview of recent papers emphasizing the potential of photocatalysis driven by ultraviolet, visible, UV–visible, and solar light irradiation. Several studies underline the relevance of immobilizing photocatalysts for large-scale water treatment applications. The review concludes by identifying the significant obstacles and future approaches for developing more effective, sustainable, and large-scale photocatalytic systems for CIP degradation in wastewater.
{"title":"Advancements in photocatalytic systems for ciprofloxacin degradation, efficiency, mechanisms, and environmental considerations","authors":"Muhammad Idrees ,&nbsp;Zia Ul Haq Khan ,&nbsp;Sana Sabahat ,&nbsp;Jingyu Sun ,&nbsp;Noor Samad Shah ,&nbsp;Jibran Iqbal","doi":"10.1016/j.molliq.2025.127115","DOIUrl":"10.1016/j.molliq.2025.127115","url":null,"abstract":"<div><div>In aquatic ecosystems, the presence of ciprofloxacin (CIP) causes substantial environmental and public health risks, which require advanced water treatment procedures beyond conventional methods. This review emphasizes on the recent advances in the photocatalytic degradation of CIP, exploring the efficiency and mechanisms of various photocatalysts, covering 11 categories of metal-based, carbon-based, and hybrid nanostructures. The review underlines the major importance of photocatalyst morphology, surface area, doping, and the construction of heterojunctions in improving photocatalytic activity. Moreover, it addresses the causes of CIP pollution, the environmental repercussions of CIP, and its role in antibiotic resistance. The review offers a comprehensive overview of recent papers emphasizing the potential of photocatalysis driven by ultraviolet, visible, UV–visible, and solar light irradiation. Several studies underline the relevance of immobilizing photocatalysts for large-scale water treatment applications. The review concludes by identifying the significant obstacles and future approaches for developing more effective, sustainable, and large-scale photocatalytic systems for CIP degradation in wastewater.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"424 ","pages":"Article 127115"},"PeriodicalIF":5.3,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143403668","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}
引用次数: 0
An overview on advancements in hydrogels for effective wastewater treatment
IF 5.3 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-02-10 DOI: 10.1016/j.molliq.2025.127120
Amruta Pattnaik, Prabir Ghosh, Anil Kumar Poonia
Hydrogels, three-dimensional networks of polymers with excellent water retention properties, have emerged as adaptable wastewater treatment materials. This mini-review discusses current advances in hydrogel technology. These possess a large surface area, porosity, and functional diversity that enable them to efficiently absorb and eliminate contaminants through a variety of physical and chemical interactions. Hydrogel synthesis innovations, such as free radical polymerisation, ionic gelation, and interpenetrating polymer networks (IPNs), have resulted in the production of hydrogels that are strong, long-lasting, and selective for certain pollutants. The integration of antibacterial agents, surface functionalisation, and the development of composite hydrogels with materials has considerably increased their efficiency. This review also looks at the regenerative and reusable properties of hydrogels, emphasizing their cost-effectiveness and sustainability. By reviewing these achievements, this article aims to provide a thorough knowledge of hydrogel-based technologies and their potential to revolutionize wastewater treatment, providing effective and environmentally friendly solutions for environmental cleanup.
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引用次数: 0
Innovative fluorescent nanocomposite eutectogels: Design and characterization towards biosensing applications
IF 5.3 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-02-10 DOI: 10.1016/j.molliq.2025.127123
Yolanda Alacid , Raúl Martínez-Baquero , Rocío Esquembre , Francisco Montilla , María José Martínez-Tomé , C. Reyes Mateo
Recent advancements in materials science have led to the creation of innovative gel formulations like eutectogels, which exploit the distinctive characteristics of deep eutectic solvents (DES) to enhance the functionality and versatility of traditional gel systems. By incorporating fluorescent nanoparticles, eutectogels gain luminescent properties, significantly increasing their performance. In this study, we have developed and characterized a novel nanocomposite eutectogel by integrating conjugated polymer-based nanoparticles (CPNs) with varying emission bands, derived from either polyfluorene or poly(phenylenevinylene). Before synthesizing the fluorescent eutectogels, it was confirmed that the nanoparticles maintained the same fluorescent properties in both DES and aqueous solution. The results show that the incorporation of CPNs inside the eutectogels provides fluorescent materials with good properties in terms of integrity, thermal stability, homogeneity and reproducibility allowing their preservation during weeks. The fluorescent nanocomposite eutectogels were tested as sensing platforms by immobilizing enzymes. In particular, the capability of these materials to act as fluorescent biosensors for detecting hydrolase activity was successfully demonstrated, with alkaline phosphatase entrapped in the nanocomposite eutectogel serving as the model enzyme. This finding is one of the first demonstrations of the functioning of an enzyme in an eutectogel.
{"title":"Innovative fluorescent nanocomposite eutectogels: Design and characterization towards biosensing applications","authors":"Yolanda Alacid ,&nbsp;Raúl Martínez-Baquero ,&nbsp;Rocío Esquembre ,&nbsp;Francisco Montilla ,&nbsp;María José Martínez-Tomé ,&nbsp;C. Reyes Mateo","doi":"10.1016/j.molliq.2025.127123","DOIUrl":"10.1016/j.molliq.2025.127123","url":null,"abstract":"<div><div>Recent advancements in materials science have led to the creation of innovative gel formulations like eutectogels, which exploit the distinctive characteristics of deep eutectic solvents (DES) to enhance the functionality and versatility of traditional gel systems. By incorporating fluorescent nanoparticles, eutectogels gain luminescent properties, significantly increasing their performance. In this study, we have developed and characterized a novel nanocomposite eutectogel by integrating conjugated polymer-based nanoparticles (CPNs) with varying emission bands, derived from either polyfluorene or poly(phenylenevinylene). Before synthesizing the fluorescent eutectogels, it was confirmed that the nanoparticles maintained the same fluorescent properties in both DES and aqueous solution. The results show that the incorporation of CPNs inside the eutectogels provides fluorescent materials with good properties in terms of integrity, thermal stability, homogeneity and reproducibility allowing their preservation during weeks. The fluorescent nanocomposite eutectogels were tested as sensing platforms by immobilizing enzymes. In particular, the capability of these materials to act as fluorescent biosensors for detecting hydrolase activity was successfully demonstrated, with alkaline phosphatase entrapped in the nanocomposite eutectogel serving as the model enzyme. This finding is one of the first demonstrations of the functioning of an enzyme in an eutectogel.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"424 ","pages":"Article 127123"},"PeriodicalIF":5.3,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143388351","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Mechanical activation improves green depressant starch for the flotation separation of pyrite from chalcopyrite via molecular structure optimization
IF 5.3 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-02-10 DOI: 10.1016/j.molliq.2025.127122
Lixinran Zhao , Keyao Li , Sokhibjon Turdalievich Matkarimov , Cheng Liu , Shenxu Bao , Siyuan Yang
For the first time, the present study uses the mechanically activating method to enhance the depression selectivity of natural polymers, which applies the mechanically activated starch (MAS) for the flotation depression of pyrite from chalcopyrite. After the addition of MAS prepared in an appropriate condition, the flotation recovery of pyrite decreased by 72 % while the chalcopyrite recovery remained nearly unaffected. Adsorption tests, Zeta potential measurements and X-ray photoelectron spectroscopy (XPS) analysis show that MAS primarily chemisorbed onto the pyrite surface by forming covalent bonds with surface iron atoms, thereby reducing its hydrophobicity. Proton nuclear magnetic resonance (1HNMR) test results indicate that mechanical activation can alter the internal structure of MAS, thereby increasing its activity. Frontier orbital analysis and molecular dynamics simulations further confirm the chemisorption of MAS on the pyrite surface and the MAS prepared under different intensities of mechanical activations have different adsorption abilities on the pyrite surface. The MAS prepared under moderate mechanical activation has the best adsorption and depression abilities, which is attributed to the exposure of more interacting sites and remains of relatively large molecular weight. This research highlights the potential of MAS as an environmentally friendly alternative to traditional macromolecular depressants, offering a sustainable approach that can reduce environmental impact. It also provides valuable insights into the novel application of mechanically activated polymers in the field of mineral flotation.
{"title":"Mechanical activation improves green depressant starch for the flotation separation of pyrite from chalcopyrite via molecular structure optimization","authors":"Lixinran Zhao ,&nbsp;Keyao Li ,&nbsp;Sokhibjon Turdalievich Matkarimov ,&nbsp;Cheng Liu ,&nbsp;Shenxu Bao ,&nbsp;Siyuan Yang","doi":"10.1016/j.molliq.2025.127122","DOIUrl":"10.1016/j.molliq.2025.127122","url":null,"abstract":"<div><div>For the first time, the present study uses the mechanically activating method to enhance the depression selectivity of natural polymers, which applies the mechanically activated starch (MAS) for the flotation depression of pyrite from chalcopyrite. After the addition of MAS prepared in an appropriate condition, the flotation recovery of pyrite decreased by 72 % while the chalcopyrite recovery remained nearly unaffected. Adsorption tests, Zeta potential measurements and X-ray photoelectron spectroscopy (XPS) analysis show that MAS primarily chemisorbed onto the pyrite surface by forming covalent bonds with surface iron atoms, thereby reducing its hydrophobicity. Proton nuclear magnetic resonance (<sup>1</sup>HNMR) test results indicate that mechanical activation can alter the internal structure of MAS, thereby increasing its activity. Frontier orbital analysis and molecular dynamics simulations further confirm the chemisorption of MAS on the pyrite surface and the MAS prepared under different intensities of mechanical activations have different adsorption abilities on the pyrite surface. The MAS prepared under moderate mechanical activation has the best adsorption and depression abilities, which is attributed to the exposure of more interacting sites and remains of relatively large molecular weight. This research highlights the potential of MAS as an environmentally friendly alternative to traditional macromolecular depressants, offering a sustainable approach that can reduce environmental impact. It also provides valuable insights into the novel application of mechanically activated polymers in the field of mineral flotation.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"424 ","pages":"Article 127122"},"PeriodicalIF":5.3,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143387920","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}
引用次数: 0
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Journal of Molecular Liquids
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