Journal of Molecular Liquids最新文献_第10页

Cobalt(II) complexes of tri-dentate S,N,S-thiophenyl Schiff base ligand for prospective biological studies and ct-DNA interaction. Catalytic benzyl alcohol oxidative performance 三齿 S,N,S-噻吩希夫碱配体的钴(II)配合物，用于前瞻性生物研究和 ct-DNA 相互作用。催化苯甲醇氧化性能

IF 5.3 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2025-03-03 DOI: 10.1016/j.molliq.2025.127269

Zakaria S. Bakhuraisa , Ahmed Khalil , Mustafa J. Abdelmageed Abualreish , Ahmed Desoky M. Mohamad , Mamdouh A. Mohamed , Mohamed Shaker S. Adam

The condensing reaction of thiophene-2-carbaldehyde with 2-aminobenzenethiol yielded S,N,S-thiophenyl Schiff base ligand (HLNS). In various molar ratios, the coordination behavior of HLNS towards cobalt(II) ions was studied within 1 and 2: 1 equivalents, resulting in the formation of two diverse structural complexes, [CoLNSCl(H₂O)₂] and [Co(LNS)₂], respectively. Their structural elucidation was achieved using various spectroscopic methods, which involved thermogravimetric assessments, elemental analysis, magnetic characteristics, and conductivity measurements.

The inhibitory influence of HLNS (as an unbonded ligand) and its cobalt(II)-chelating agents on the restrained proliferation of three particular microbes of bacterial and fungal strains, and three recognized cell lines of human cancer were assessed assigning the structural effect on the reactivity of [CoLNSCl(H₂O)₂] and [Co(LNS)₂] versus their free ligand (HLNS). The study sought to ascertain the predominant role of Co(II) ions in the two chelates on the binding strength of HLNS, [CoLNSCl(H₂O)₂], and [Co(LNS)₂] towards calf thymus DNA (ct-DNA), which was evaluated by examining the changes in their viscometric and spectrophotometric characteristics. The evaluation of binding constants (K_b), Gibbs free energy

Δ G_{b}^{\neq}

, and chromism modes was utilized to analyze the interaction modes of the current compounds with ct-DNA compared to that action of HLNS.

[CoLNSCl(H₂O)₂] and [Co(LNS)₂] represented high catalytic oxidative performance for benzyl alcohol with hydrogen peroxide homogeneously. At 80 °C, the yielding percentage of the selective-product (benzaldehyde) was 85 % after 4 h and 82 % after 5 h with [CoLNSCl(H₂O)₂] and [Co(LNS)₂], respectively. The variation in the optimal atmosphere for both catalysts referred to their molecular structure differences.

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引用次数: 0

Phase behaviour of primitive models of room temperature ionic liquids in porous media: Effects of cation shape, ion association and disordered confinement

IF 5.3 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2025-03-03 DOI: 10.1016/j.molliq.2025.127240

T. Hvozd , T. Patsahan , O. Patsahan , Yu. Kalyuzhnyi , M. Holovko

The vapour–liquid phase behaviour of room temperature ionic liquids (RTILs) confined in disordered porous media is studied using a theoretical approach that combines an extension of scaled particle theory, Wertheim's thermodynamic perturbation theory, and the associative mean spherical approximation. Two models, differing in the shape of the molecular cation, are considered: one with cations formed as charged flexible chains and the other with cations modelled as charged hard spherocylinders. Each model is described by a mixture of dimerized and free ions, while the porous medium is represented as a disordered matrix of hard spheres. We focus on the effects of the molecular cation shape, partial ion association, and disordered confinement on the vapour–liquid-like phase behaviour of the model RTILs. In the approximation considered, we find that both the critical temperature

T_{c r}^{⁎}

and critical density

ρ_{c r}^{⁎}

in the model with spherocylinder cations are lower than those in the model with chain cations, and the phase coexistence region is narrower. This is the first theoretical attempt to describe an RTIL model with molecular ions shaped as spherocylinders, particularly in a disordered porous medium.

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引用次数: 0

Initial stage aggregation of colloidal particles induced by the deposition of oppositely charged particles using standardized colloid mixing

IF 5.3 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2025-03-03 DOI: 10.1016/j.molliq.2025.127271

Marita Wulandari , Santanu Saha , Takuya Sugimoto , Yuji Yamashita , Yasuhisa Adachi

This research examines the flocculation behavior of negatively charged polystyrene sulfate latex (PSL) particles induced by the deposition of positively charged amidine latex (AL) particles under a standardized colloid mixing protocol across various particle concentrations and ionic strengths. In contrast to polymer-induced flocculation, the AL particles form a rigid monolayer on PSL surfaces, as verified through scanning electron microscopy (SEM) and hydrodynamic layer-thickness measurements. This monolayer configuration stabilizes the effective collision radius, resulting in a consistent initial flocculation rate that remains largely unaffected by changes in AL concentration. The enhancement factor increases as the ionic strength decreases. This study validates the applicability of standardized colloid mixing method with oppositely charged particle as flocculants and also proposes a non-unity correction factor derived from hydrodynamic and ionic interactions. Furthermore, by extending our experiments to include AL particles of different diameters and varying ionic strengths, we provide insights for estimating the correction factor, thereby enhancing the accuracy of flocculation rate predictions.

{"title":"Initial stage aggregation of colloidal particles induced by the deposition of oppositely charged particles using standardized colloid mixing","authors":"Marita Wulandari , Santanu Saha , Takuya Sugimoto , Yuji Yamashita , Yasuhisa Adachi","doi":"10.1016/j.molliq.2025.127271","DOIUrl":"10.1016/j.molliq.2025.127271","url":null,"abstract":"<div><div>This research examines the flocculation behavior of negatively charged polystyrene sulfate latex (PSL) particles induced by the deposition of positively charged amidine latex (AL) particles under a standardized colloid mixing protocol across various particle concentrations and ionic strengths. In contrast to polymer-induced flocculation, the AL particles form a rigid monolayer on PSL surfaces, as verified through scanning electron microscopy (SEM) and hydrodynamic layer-thickness measurements. This monolayer configuration stabilizes the effective collision radius, resulting in a consistent initial flocculation rate that remains largely unaffected by changes in AL concentration. The enhancement factor increases as the ionic strength decreases. This study validates the applicability of standardized colloid mixing method with oppositely charged particle as flocculants and also proposes a non-unity correction factor derived from hydrodynamic and ionic interactions. Furthermore, by extending our experiments to include AL particles of different diameters and varying ionic strengths, we provide insights for estimating the correction factor, thereby enhancing the accuracy of flocculation rate predictions.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"425 ","pages":"Article 127271"},"PeriodicalIF":5.3,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143548550","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

Comparative analysis of drug deposition patterns among three commercial nasal spray brands: A computational and experimental study 三种商用鼻腔喷雾品牌药物沉积模式的比较分析：计算与实验研究

IF 5.3 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2025-03-02 DOI: 10.1016/j.molliq.2025.127276

Guiliang Liu , Mohammad Hossein Doranehgard , Xuan Ruan , Bingkai Chen , Brent Senior , Adam Kimple , Rui Ni , Zheng Li

This study investigates drug deposition patterns in nasal drug delivery by combining experimental measurements with computational fluid dynamics simulations. We analyzed three, over the counter, mometasone nasal spray devices, experimentally characterizing particle diameter (dp), spray velocity (up), and spray angle (α). Unlike previous studies that relied on assumed parameters or single-brand analyses, we conducted comparative analyses using measured parameters integrated into COMSOL Multiphysics simulations. The study optimized the Line of Sight (LOS) method by exploring various spray positions and instructions to avoid anterior loss of medication in the anterior nasal cavity. Results revealed that Brand 3, with its narrow spray angle, achieved superior drug delivery efficiency when properly aligned with the target region. However, its performance decreased significantly when misaligned due to its smaller spray cone angle. Our findings show that sprays with narrower cone angles delivered medicine more effectively to the ostiomeatal complex (OMC) with up to 44% higher efficiency using the LOS method. Additionally, in cases with septal deviation, we observed a 14–20% higher drug deposition rate in the right nasal cavity compared to the left. The LOS method significantly improved drug deposition by 2.86–3 times, while the Deep Spray method further enhanced it by 38–50%. This integrated experimental-computational approach provides practical insights for optimizing nasal spray device design and administration techniques, particularly considering anatomical variations.

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引用次数: 0

Enhancing thermal stability of preformed particle gels (PPGs) under high temperature: The role of crosslinkers

IF 5.3 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2025-03-02 DOI: 10.1016/j.molliq.2025.127208

Zhiyi Wei, Jinze Zhang, Jiayin Liu, Liuyang Yang, Lingkeer Zhang, Jiexiang Wang, Haiming Fan

In response to the challenges posed by high-temperature reservoirs to gel treatment, this study investigates the impact of crosslinkers on the thermal stability of preformed particle gels (PPGs). By replacing the N, N′-methylene-bis-acrylamide (MBA) in conventional PPGs (M-PPGs) with triallylamine (TAA), the high-temperature resistant PPGs (T-PPGs) were successfully prepared and their properties were systematically evaluated. The study found that the thermal ageing process of T-PPGs at different temperatures can be classified into three types. T-PPGs remain stable over a long period below 70 °C. Between 70 and 140 °C, the hydrolysis of the side groups on the polymer backbones of T-PPGs leads to an increase in the swelling ratio, but the gel network structure and the maximum equilibrium swelling ratio remain stable. When the temperature exceeds 150 °C, the polymer backbones undergo oxidative degradation and damage, resulting in a continuous increase in the swelling ratio and ultimately transforming into a sol. T-PPGs exhibit higher thermal stability compared to M-PPGs. Fractured core experiments indicate that T-PPGs can maintain a certain degree of fracture core plugging effect even after ageing for 60 h at 140 °C. This study reveals the key role of crosslinker in the thermal stability of PPGs, specifically that the TAA does not undergo hydrolysis at high temperatures, effectively preventing the destruction of the gel network structure. The successful preparation of T-PPGs and the understanding of their thermal stability mechanism will inspire the development of high-temperature-resistant PPGs.

{"title":"Enhancing thermal stability of preformed particle gels (PPGs) under high temperature: The role of crosslinkers","authors":"Zhiyi Wei, Jinze Zhang, Jiayin Liu, Liuyang Yang, Lingkeer Zhang, Jiexiang Wang, Haiming Fan","doi":"10.1016/j.molliq.2025.127208","DOIUrl":"10.1016/j.molliq.2025.127208","url":null,"abstract":"<div><div>In response to the challenges posed by high-temperature reservoirs to gel treatment, this study investigates the impact of crosslinkers on the thermal stability of preformed particle gels (PPGs). By replacing the N, N′-methylene-bis-acrylamide (MBA) in conventional PPGs (M-PPGs) with triallylamine (TAA), the high-temperature resistant PPGs (T-PPGs) were successfully prepared and their properties were systematically evaluated. The study found that the thermal ageing process of T-PPGs at different temperatures can be classified into three types. T-PPGs remain stable over a long period below 70 °C. Between 70 and 140 °C, the hydrolysis of the side groups on the polymer backbones of T-PPGs leads to an increase in the swelling ratio, but the gel network structure and the maximum equilibrium swelling ratio remain stable. When the temperature exceeds 150 °C, the polymer backbones undergo oxidative degradation and damage, resulting in a continuous increase in the swelling ratio and ultimately transforming into a sol. T-PPGs exhibit higher thermal stability compared to M-PPGs. Fractured core experiments indicate that T-PPGs can maintain a certain degree of fracture core plugging effect even after ageing for 60 h at 140 °C. This study reveals the key role of crosslinker in the thermal stability of PPGs, specifically that the TAA does not undergo hydrolysis at high temperatures, effectively preventing the destruction of the gel network structure. The successful preparation of T-PPGs and the understanding of their thermal stability mechanism will inspire the development of high-temperature-resistant PPGs.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"425 ","pages":"Article 127208"},"PeriodicalIF":5.3,"publicationDate":"2025-03-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547882","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

CuO/Al2O3/carbomer as a new hybrid agent for wettability alteration and oil recovery in carbonate reservoirs

IF 5.3 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2025-03-01 DOI: 10.1016/j.molliq.2025.127270

Ehsan Jafarbeigi, Mohammad Shahini Nia, Mohsen Mansouri, Tavan Kikhavani, Naimeh Setareshenas

Generally, nanoparticles are used in enhanced oil recovery (EOR) methods to improve surface activity at the oil/rock/fluid interface. The goal of this literature is the development of a new nano-composite for use as a hybrid agent for EOR. In this regard, synthetic nano-composite was synthesized using a multi-step approach. In order to confirm the synthetic structure of nano-composite, FTIR, XRD, BET, SEM and EDX tests were used. In this regard, tests such as contact angle (CA), stability and compatibility of nano-composite, interfacial tension (IFT), zeta (ζ) potential, and core flooding were done. XRD analysis confirmed the crystal structure of nano-composite (CuO/Al₂O₃/carbomer). Also, the EDX analysis showed the purity of nano-particles for both samples. On the other hand, BET analysis of surface area for CuO/Al₂O₃ and CuO/Al₂O₃/Carbomer showed 67.34 m²/g and 14.63 m²/g, respectively. This synthetic CuO/Al₂O₃/carbomer nano-composite was able to provide superhydrophilic wettability for core rock. The results of CA tests in the presence of hybrid agent (400 ppm) showed that superhydrophilic wetting (CA = 32°) was obtained. Also, the IFT decreased to the lowest required value (IFT = 7.8 mN/m). In the presence of hybrid agent (400 ppm), oil recovery (OR) increased by 26 % (core 1) and 21 % (core 2), respectively.

{"title":"CuO/Al2O3/carbomer as a new hybrid agent for wettability alteration and oil recovery in carbonate reservoirs","authors":"Ehsan Jafarbeigi, Mohammad Shahini Nia, Mohsen Mansouri, Tavan Kikhavani, Naimeh Setareshenas","doi":"10.1016/j.molliq.2025.127270","DOIUrl":"10.1016/j.molliq.2025.127270","url":null,"abstract":"<div><div>Generally, nanoparticles are used in enhanced oil recovery (EOR) methods to improve surface activity at the oil/rock/fluid interface. The goal of this literature is the development of a new nano-composite for use as a hybrid agent for EOR. In this regard, synthetic nano-composite was synthesized using a multi-step approach. In order to confirm the synthetic structure of nano-composite, FTIR, XRD, BET, SEM and EDX tests were used. In this regard, tests such as contact angle (CA), stability and compatibility of nano-composite, interfacial tension (IFT), zeta (ζ) potential, and core flooding were done. XRD analysis confirmed the crystal structure of nano-composite (CuO/Al<sub>2</sub>O<sub>3</sub>/carbomer). Also, the EDX analysis showed the purity of nano-particles for both samples. On the other hand, BET analysis of surface area for CuO/Al<sub>2</sub>O<sub>3</sub> and CuO/Al<sub>2</sub>O<sub>3</sub>/Carbomer showed 67.34 m<sup>2</sup>/g and 14.63 m<sup>2</sup>/g, respectively. This synthetic CuO/Al<sub>2</sub>O<sub>3</sub>/carbomer nano-composite was able to provide superhydrophilic wettability for core rock. The results of CA tests in the presence of hybrid agent (400 ppm) showed that superhydrophilic wetting (CA = 32°) was obtained. Also, the IFT decreased to the lowest required value (IFT = 7.8 mN/m). In the presence of hybrid agent (400 ppm), oil recovery (OR) increased by 26 % (core 1) and 21 % (core 2), respectively.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"425 ","pages":"Article 127270"},"PeriodicalIF":5.3,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547880","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

Solubility measurements and thermodynamic correlation of bis(imino)pyridine-based Cu and Ni complexes in pure solvents

IF 5.3 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2025-03-01 DOI: 10.1016/j.molliq.2025.127268

Talha Baig , Ziyuan Pang , Mubashar Ilyas , Muhammad Abbas , Sheza Tahir , Xiaoli Ma

In this work, the solubility of a bis(imino)pyridine-based ligand L = 2,6-Bis[1-(cyclohexylimino)ethyl]pyridine and its two metal complexes LCuCl₂ and LNiCl₂ is measured by static equilibrium method in four selected solvents. These complexes are widely used in catalysis, polymerization, cycloaddition reactions, anticancer drugs, and in optoelectronic materials where the solvation process has a critical impact on their properties. The solubility data is vital for improving the crystallization process and the efficiency of homogeneous catalysis. Six thermodynamic models (Apelblat, Polynomial, Yaws, Vant’s Hoff, λh, and NRTL) are applied to analyze the solubility values of LH and four models (Apelblat, Polynomial, Yaws, Vant’s Hoff) are applied for both metal complexes LCuCl₂ and LNiCl₂. To ensure the precision of experimental data, the ARD and RMSD values are calculated for accuracy evaluation. The solubility data of L indicates that dichloromethane is the best reaction solvent having its highest solubility value 7.515 × 10² x at 298.15 K and absolute ethanol is the best solvent for its crystallization. Similarly, the solubility data collected for LCuCl₂ and LNiCl₂ reveals that trichloromethane is the best reaction solvent having highest solubility values 4.188 × 10³ x and 4.279 × 10³ x respectively at 298.15 K and acetone is the crystallization solvent for both of these metal complexes. The polynomial model represents the optimal choice for accurately fitting the solubility data related to all three examined compounds having average ARD values less than 1 %. Hirshfeld surface analysis show that H⋯H contacts are the most significant interactions, about 68.2 % in the compound LCuCl₂. Moreover, molecular electrostatic potential indicates that the N atom and the metal centers of the two compounds exhibit distinct electronegativity. In addition, functions related to apparent thermodynamics were obtained. The dissolution process proved endothermic and entropy rose in the experimental settings, with spontaneous energy accounting for the variation in solubility.

{"title":"Solubility measurements and thermodynamic correlation of bis(imino)pyridine-based Cu and Ni complexes in pure solvents","authors":"Talha Baig , Ziyuan Pang , Mubashar Ilyas , Muhammad Abbas , Sheza Tahir , Xiaoli Ma","doi":"10.1016/j.molliq.2025.127268","DOIUrl":"10.1016/j.molliq.2025.127268","url":null,"abstract":"<div><div>In this work, the solubility of a bis(imino)pyridine-based ligand <strong>L</strong> = 2,6-Bis[1-(cyclohexylimino)ethyl]pyridine and its two metal complexes <strong>LCuCl<sub>2</sub></strong> and <strong>LNiCl<sub>2</sub></strong> is measured by static equilibrium method in four selected solvents. These complexes are widely used in catalysis, polymerization, cycloaddition reactions, anticancer drugs, and in optoelectronic materials where the solvation process has a critical impact on their properties. The solubility data is vital for improving the crystallization process and the efficiency of homogeneous catalysis. Six thermodynamic models (Apelblat, Polynomial, Yaws, Vant’s Hoff, λh, and NRTL) are applied to analyze the solubility values of LH and four models (Apelblat, Polynomial, Yaws, Vant’s Hoff) are applied for both metal complexes <strong>LCuCl<sub>2</sub></strong> and <strong>LNiCl<sub>2</sub></strong>. To ensure the precision of experimental data, the ARD and RMSD values are calculated for accuracy evaluation. The solubility data of L indicates that dichloromethane is the best reaction solvent having its highest solubility value 7.515 × 10<sup>2</sup> x at 298.15 K and absolute ethanol is the best solvent for its crystallization. Similarly, the solubility data collected for <strong>LCuCl<sub>2</sub></strong> and <strong>LNiCl<sub>2</sub></strong> reveals that trichloromethane is the best reaction solvent having highest solubility values 4.188 × 10<sup>3</sup> x and 4.279 × 10<sup>3</sup> x respectively at 298.15 K and acetone is the crystallization solvent for both of these metal complexes. The polynomial model represents the optimal choice for accurately fitting the solubility data related to all three examined compounds having average ARD values less than 1 %. Hirshfeld surface analysis show that H⋯H contacts are the most significant interactions, about 68.2 % in the compound <strong>LCuCl<sub>2</sub></strong>. Moreover, molecular electrostatic potential indicates that the N atom and the metal centers of the two compounds exhibit distinct electronegativity. In addition, functions related to apparent thermodynamics were obtained. The dissolution process proved endothermic and entropy rose in the experimental settings, with spontaneous energy accounting for the variation in solubility.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"425 ","pages":"Article 127268"},"PeriodicalIF":5.3,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547875","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

Mechanism, kinetic, and thermodynamic studies on the leaching of Mo, Fe, and Zn oxides from ferromolybdenum furnace dusts using choline chloride/fructose deep eutectic solvent (DES)

IF 5.3 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2025-03-01 DOI: 10.1016/j.molliq.2025.127266

Mahdi Sadigh, Mahdi Gharabaghi, Sied Ziaedin Shafaei Tonkaboni

In the present study, the mechanisms, kinetics and thermodynamics of the dissolution of Mo, Zn, and Fe oxides from ferromolybdenum furnace dust in a choline chloride/fructose Deep Eutectic Solvent (DES) with the mole ratio of 1:1 were investigated. Several mechanisms have been proposed for the dissolution of metal oxides in DESs, and the most probable mechanism was studied. Water was also added to reduce the viscosity (in 10:1 mol ratio of water to DES). Therefore, leaching in pure water was investigated to obtain the mole ratios of dissolved metals to water. The kinetic studies indicated the process was a diffusion-controlled mechanism, while the high apparent activation energy values for Mo and Fe were due to multi-stage complex formation and distortion of ligand geometry. The proposed mechanism for iron complexation reaction was confirmed because of the similarity in calculated and reported equilibrium constants (K_eq). This method was used to calculate the K_eq, ΔH°, ΔS°, and ΔG° for molybdenum complexation mechanism. It was concluded that, in the presence of Fe³⁺ ions, Zn did not participate in the complexation reaction because DES did not increase Zn extraction. XRD analysis was performed to determine the phases in the dust sample. XPS and FTIR analysis confirmed the formation of Mo-fructose complexes in the leaching residues. FTIR analysis of the leaching residues showed the disappearance of MoO bonds in MoO₃ due to leaching, and the appearance of bridging bonds (MoOMo) related to Mo-fructose complexes.

{"title":"Mechanism, kinetic, and thermodynamic studies on the leaching of Mo, Fe, and Zn oxides from ferromolybdenum furnace dusts using choline chloride/fructose deep eutectic solvent (DES)","authors":"Mahdi Sadigh, Mahdi Gharabaghi, Sied Ziaedin Shafaei Tonkaboni","doi":"10.1016/j.molliq.2025.127266","DOIUrl":"10.1016/j.molliq.2025.127266","url":null,"abstract":"<div><div>In the present study, the mechanisms, kinetics and thermodynamics of the dissolution of Mo, Zn, and Fe oxides from ferromolybdenum furnace dust in a choline chloride/fructose Deep Eutectic Solvent (DES) with the mole ratio of 1:1 were investigated. Several mechanisms have been proposed for the dissolution of metal oxides in DESs, and the most probable mechanism was studied. Water was also added to reduce the viscosity (in 10:1 mol ratio of water to DES). Therefore, leaching in pure water was investigated to obtain the mole ratios of dissolved metals to water. The kinetic studies indicated the process was a diffusion-controlled mechanism, while the high apparent activation energy values for Mo and Fe were due to multi-stage complex formation and distortion of ligand geometry. The proposed mechanism for iron complexation reaction was confirmed because of the similarity in calculated and reported equilibrium constants (K<sub>eq</sub>). This method was used to calculate the K<sub>eq</sub>, ΔH°, ΔS°, and ΔG° for molybdenum complexation mechanism. It was concluded that, in the presence of Fe<sup>3+</sup> ions, Zn did not participate in the complexation reaction because DES did not increase Zn extraction. XRD analysis was performed to determine the phases in the dust sample. XPS and FTIR analysis confirmed the formation of Mo-fructose complexes in the leaching residues. FTIR analysis of the leaching residues showed the disappearance of Mo<img>O bonds in MoO<sub>3</sub> due to leaching, and the appearance of bridging bonds (Mo<img>O<img>Mo) related to Mo-fructose complexes.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"425 ","pages":"Article 127266"},"PeriodicalIF":5.3,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547878","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

Effect of encapsulation in cyclodextrin nanocavities on the photophysical properties of bithiophene-5-carboxamidine derivatives

IF 5.3 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2025-03-01 DOI: 10.1016/j.molliq.2025.127275

Mai N.A. Mahmoud , Maha M. Khaled , Mohamed A. Ismail , Hesham A.A. Medien , Hesham S. Abdel-Samad , Ayman A. Abdel-Shafi

The objective of this work is to investigate the impact of encapsulation on the photophysical characteristics of the hydrochloride salt of 5-(5-(4-methoxyphenyl)thiophen-2-yl)thiophene-2-carboxamidine (I) and 5-(5-(3,5-dimethoxyphenyl)thiophen-2-yl)thiophene-2-carboxamidine (II) compounds in neutral aqueous solution and when added to different cyclodextrin derivatives (CDs) such as α-cyclodextrin (α-CD), β-cyclodextrin (β-CD), methyl-β-cyclodextrin (Mβ-CD) and 2-(hydroxypropyl) β-cyclodextrin (HPβ-CD) investigated by steady-state absorption, fluorescence emission, and time-resolved fluorescence emission techniques. Significant changes in fluorescence quantum yield were detected, accompanied by a blue shift similar to what occurs when the solvent is switched from aqueous to non-aqueous media. The observed changes in the fluorescence emission spectra indicate that both (I) and (II) form 1:1 inclusion complex with the cyclodextrin derivatives under study. Fluorescence decay measurements show that the contribution of the ICT state (a₁) decreases while the contribution of the LE state (a₂) increases with added concentrations of α-CD, β-CD, Mβ-CD and HPβ-CD. ¹H NMR measurements show noticeable chemical shifts in the cyclodextrin interior protons only in the case of β-CD and small or distorted shifts in other types of CDs. In contrast, changes in the chemical shift of I or II protons were very pronounced despite their very low solubility in D₂O. This study highlights how cavity size and surface functionalization influence excited-state behaviour. The results indicate that larger and more functionalized cyclodextrins (Mβ-CD and HPβ-CD) exhibit different stabilization effects compared to smaller, unmodified α-CD and β-CD.

{"title":"Effect of encapsulation in cyclodextrin nanocavities on the photophysical properties of bithiophene-5-carboxamidine derivatives","authors":"Mai N.A. Mahmoud , Maha M. Khaled , Mohamed A. Ismail , Hesham A.A. Medien , Hesham S. Abdel-Samad , Ayman A. Abdel-Shafi","doi":"10.1016/j.molliq.2025.127275","DOIUrl":"10.1016/j.molliq.2025.127275","url":null,"abstract":"<div><div>The objective of this work is to investigate the impact of encapsulation on the photophysical characteristics of the hydrochloride salt of 5-(5-(4-methoxyphenyl)thiophen-2-yl)thiophene-2-carboxamidine (I) and 5-(5-(3,5-dimethoxyphenyl)thiophen-2-yl)thiophene-2-carboxamidine (II) compounds in neutral aqueous solution and when added to different cyclodextrin derivatives (CDs) such as α-cyclodextrin (α-CD), β-cyclodextrin (β-CD), methyl-β-cyclodextrin (Mβ-CD) and 2-(hydroxypropyl) β-cyclodextrin (HPβ-CD) investigated by steady-state absorption, fluorescence emission, and time-resolved fluorescence emission techniques. Significant changes in fluorescence quantum yield were detected, accompanied by a blue shift similar to what occurs when the solvent is switched from aqueous to non-aqueous media. The observed changes in the fluorescence emission spectra indicate that both (I) and (II) form 1:1 inclusion complex with the cyclodextrin derivatives under study. Fluorescence decay measurements show that the contribution of the ICT state (a<sub>1</sub>) decreases while the contribution of the LE state (a<sub>2</sub>) increases with added concentrations of α-CD, β-CD, Mβ-CD and HPβ-CD. <sup>1</sup>H NMR measurements show noticeable chemical shifts in the cyclodextrin interior protons only in the case of β-CD and small or distorted shifts in other types of CDs. In contrast, changes in the chemical shift of I or II protons were very pronounced despite their very low solubility in D<sub>2</sub>O. This study highlights how cavity size and surface functionalization influence excited-state behaviour. The results indicate that larger and more functionalized cyclodextrins (Mβ-CD and HPβ-CD) exhibit different stabilization effects compared to smaller, unmodified α-CD and β-CD.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"425 ","pages":"Article 127275"},"PeriodicalIF":5.3,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547873","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

Hybrid adsorbents for pollutants removal: A comprehensive review of chitosan, glycidyl methacrylate and their composites

IF 5.3 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2025-03-01 DOI: 10.1016/j.molliq.2025.127262

Khalid Z. Elwakeel , Rihab M. Mohammad , Huda M. Alghamdi , Ahmed M. Elgarahy

Adsorption is widely recognized as a superior pollutant removal technique due to its minimal chemical requirements, reducing toxicity, and simplifying handling compared to other methods. A variety of adsorbents, including natural polymers like chitosan and synthetic polymers such as glycidyl methacrylate (GMA), have demonstrated effective pollutant remediation capabilities. While these materials were initially employed in their natural forms, recent advancements have shifted toward the development of composite materials to enhance performance. This review provides a comprehensive examination of chitosan (CS), GMA, and their hybrids and nanocomposites as adsorbents, focusing on their availability, stability, sorption capacity, and durability. Characterization techniques for evaluating surface modifications and their impact on adsorption mechanisms are discussed in detail. Furthermore, the review explores various modifications of CS and GMA with functional materials, emphasizing their adsorption mechanisms and effectiveness in removing metal ions and dyes. Key factors affecting adsorption efficiency, such as pH, temperature, adsorbent dosage, and contaminant concentration, are critically analyzed. The key kinetic, equilibrium, and thermodynamic studies essential for understanding adsorption efficiency were assessed. A comparative analysis of different adsorbents and their variants is presented, along with insights into specific functionalization techniques aimed at enhancing adsorption capacities. This review aims to guide readers in selecting adsorbents that provide the highest return on investment. Additionally, it addresses the challenges and future directions of adsorption technology, emphasizing the need for continued research, particularly in scaling up applications with real-world water samples and advancing polymer performance through innovative modifications.

{"title":"Hybrid adsorbents for pollutants removal: A comprehensive review of chitosan, glycidyl methacrylate and their composites","authors":"Khalid Z. Elwakeel , Rihab M. Mohammad , Huda M. Alghamdi , Ahmed M. Elgarahy","doi":"10.1016/j.molliq.2025.127262","DOIUrl":"10.1016/j.molliq.2025.127262","url":null,"abstract":"<div><div>Adsorption is widely recognized as a superior pollutant removal technique due to its minimal chemical requirements, reducing toxicity, and simplifying handling compared to other methods. A variety of adsorbents, including natural polymers like chitosan and synthetic polymers such as glycidyl methacrylate (GMA), have demonstrated effective pollutant remediation capabilities. While these materials were initially employed in their natural forms, recent advancements have shifted toward the development of composite materials to enhance performance. This review provides a comprehensive examination of chitosan (CS), GMA, and their hybrids and nanocomposites as adsorbents, focusing on their availability, stability, sorption capacity, and durability. Characterization techniques for evaluating surface modifications and their impact on adsorption mechanisms are discussed in detail. Furthermore, the review explores various modifications of CS and GMA with functional materials, emphasizing their adsorption mechanisms and effectiveness in removing metal ions and dyes. Key factors affecting adsorption efficiency, such as pH, temperature, adsorbent dosage, and contaminant concentration, are critically analyzed. The key kinetic, equilibrium, and thermodynamic studies essential for understanding adsorption efficiency were assessed. A comparative analysis of different adsorbents and their variants is presented, along with insights into specific functionalization techniques aimed at enhancing adsorption capacities. This review aims to guide readers in selecting adsorbents that provide the highest return on investment. Additionally, it addresses the challenges and future directions of adsorption technology, emphasizing the need for continued research, particularly in scaling up applications with real-world water samples and advancing polymer performance through innovative modifications.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"426 ","pages":"Article 127262"},"PeriodicalIF":5.3,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143577081","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