Pub Date : 2025-02-04DOI: 10.1016/j.molliq.2025.126978
Ming-Yu Jin , Yun-Bo Yu , Zheng-Cai Liu , Le-Yi Pan , Tong-Xin Liang , Long-Qing Li , Yahui Yu , Lin Li , Jing-Kun Yan
In this study, an anionic C6-carboxylic curdlan (C6-Cc) was selected to prepare complex coacervates with nisin and examined their phase behavior, microstructure, and interaction mechanisms. The results revealed that the characteristic pH values (pHc, pHφ1, pHopt, pHφ2) of the nisin/C6-Cc complexes were highly dependent on the mass ratio of C6-Cc to nisin within the phase diagram. As the mass ratio of C6-Cc to nisin decreased, the characteristic pH shifted toward higher values. The complex coacervates of nisin/C6-Cc at different phase states displayed significantly distinct microstructural properties, with the maximum complex coacervates formed at pHopt showing large particle aggregates and compact microstructures. The primary driving force behind complex coacervation between nisin and C6-Cc was electrostatic attraction, with hydrophobic interactions and hydrogen bonding also contributing to the complexation process. Moreover, the complex coacervates formed at pHφ1 exhibited notable viscoelastic behavior, dominated by elasticity due to strong electrostatic interactions.
{"title":"Phase behavior and interaction mechanism of complex coacervation between nisin and carboxylic curdlan","authors":"Ming-Yu Jin , Yun-Bo Yu , Zheng-Cai Liu , Le-Yi Pan , Tong-Xin Liang , Long-Qing Li , Yahui Yu , Lin Li , Jing-Kun Yan","doi":"10.1016/j.molliq.2025.126978","DOIUrl":"10.1016/j.molliq.2025.126978","url":null,"abstract":"<div><div>In this study, an anionic C6-carboxylic curdlan (C6-Cc) was selected to prepare complex coacervates with nisin and examined their phase behavior, microstructure, and interaction mechanisms. The results revealed that the characteristic pH values (pH<sub>c</sub>, pH<sub>φ1</sub>, pH<sub>opt</sub>, pH<sub>φ2</sub>) of the nisin/C6-Cc complexes were highly dependent on the mass ratio of C6-Cc to nisin within the phase diagram. As the mass ratio of C6-Cc to nisin decreased, the characteristic pH shifted toward higher values. The complex coacervates of nisin/C6-Cc at different phase states displayed significantly distinct microstructural properties, with the maximum complex coacervates formed at pH<sub>opt</sub> showing large particle aggregates and compact microstructures. The primary driving force behind complex coacervation between nisin and C6-Cc was electrostatic attraction, with hydrophobic interactions and hydrogen bonding also contributing to the complexation process. Moreover, the complex coacervates formed at pH<sub>φ1</sub> exhibited notable viscoelastic behavior, dominated by elasticity due to strong electrostatic interactions.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"424 ","pages":"Article 126978"},"PeriodicalIF":5.3,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143350772","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}
An experimental study of the volumetric properties of the ternary system Li–K–Pb in the liquid state was carried out. The density (ρ) and volumetric thermal expansion coefficient (β) were measured for alloys of the following stoichiometric compositions: Li3KPb4, LiKPb2, LiK3Pb4, LiKPb, Li4K3Pb4, Li4KPb2, Li16K3Pb7 and Li5KPb3. The experiments employed a contactless method of irradiating samples with a narrow beam of gamma quanta in the range from the liquidus temperatures of the alloys to 1000 K with an uncertainty of ρ and β values of 0.6–0.9 % and 4–7 %, respectively. Based on the obtained results, recommended temperature dependences of the studied properties were compiled and the relative excess molar volume was calculated. The latter was found to be negative for all alloys and anomalously large in absolute value, about 20–30 %. According to experimental studies of binary Li–Pb and K–Pb alloys, such significant volumetric compression may indicate the presence of short-range chemical order in the form of ionic complexes in the liquid Li–K–Pb system.
{"title":"Ionic complexes in liquid Li–K–Pb alloys","authors":"A.Sh. Agazhanov, R.A. Khairulin, R.N. Abdullaev, A.R. Khairulin, S.V. Stankus","doi":"10.1016/j.molliq.2025.127090","DOIUrl":"10.1016/j.molliq.2025.127090","url":null,"abstract":"<div><div>An experimental study of the volumetric properties of the ternary system Li–K–Pb in the liquid state was carried out. The density (ρ) and volumetric thermal expansion coefficient (β) were measured for alloys of the following stoichiometric compositions: Li<sub>3</sub>KPb<sub>4</sub>, LiKPb<sub>2</sub>, LiK<sub>3</sub>Pb<sub>4</sub>, LiKPb, Li<sub>4</sub>K<sub>3</sub>Pb<sub>4</sub>, Li<sub>4</sub>KPb<sub>2</sub>, Li<sub>16</sub>K<sub>3</sub>Pb<sub>7</sub> and Li<sub>5</sub>KPb<sub>3</sub>. The experiments employed a contactless method of irradiating samples with a narrow beam of gamma quanta in the range from the liquidus temperatures of the alloys to 1000 K with an uncertainty of ρ and β values of 0.6–0.9 % and 4–7 %, respectively. Based on the obtained results, recommended temperature dependences of the studied properties were compiled and the relative excess molar volume was calculated. The latter was found to be negative for all alloys and anomalously large in absolute value, about 20–30 %. According to experimental studies of binary Li–Pb and K–Pb alloys, such significant volumetric compression may indicate the presence of short-range chemical order in the form of ionic complexes in the liquid Li–K–Pb system.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"424 ","pages":"Article 127090"},"PeriodicalIF":5.3,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143388352","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-04DOI: 10.1016/j.molliq.2025.127080
Zhixue Huang , Yefei Wang , Mingchen Ding , Jing Wang , Huan Yang , Xiaorong Yu , Wuhua Chen
To investigate the potential of amphiphilic nanomaterials in enhancing oil recovery, a novel BN-NH2 nanosheets were prepared and evaluated. The proposed preparation method for BN-NH2 nanosheets involved activating BN (boron nitride) surface by sodium hydroxide and subsequently modifying BN using APTES ((3-aminopropyl)triethoxysilane). The successful synthesis of BN-NH2 nanosheets with a size of 280 nm was confirmed using FT-IR, TGA, SEM, and particle size analysis. The BN-NH2 nanofluid (1000 mg/L) exhibited excellent stability, maintaining minimal particle size changes after 5 days of standing. At 60 °C, the BN-NH2 nanofluid (1000 mg/L) maintained an interfacial tension of 10.1 mN/m, highlighting its ability to reduce interfacial tension. At 60 °C, the BN-NH2 nanofluid (1000 mg/L) achieved an emulsification index of 0.28 after 240 h, demonstrating its excellent emulsification performance. The BN-NH2 nanofluid (1000 mg/L) effectively altered reservoir wettability, reducing the contact angle from 108.8° to 46.8°. Displacement experiments revealed that BN-NH2 nanofluid flooding could enhance oil recovery by 16.2 % compared to water flooding. The mechanism of enhanced oil recovery by BN-NH2 nanofluid was analyzed via microscopic displacement experiments.
{"title":"Preparation and enhanced oil recovery evaluation of amphiphilic boron nitride nanosheets","authors":"Zhixue Huang , Yefei Wang , Mingchen Ding , Jing Wang , Huan Yang , Xiaorong Yu , Wuhua Chen","doi":"10.1016/j.molliq.2025.127080","DOIUrl":"10.1016/j.molliq.2025.127080","url":null,"abstract":"<div><div>To investigate the potential of amphiphilic nanomaterials in enhancing oil recovery, a novel BN-NH<sub>2</sub> nanosheets were prepared and evaluated. The proposed preparation method for BN-NH<sub>2</sub> nanosheets involved activating BN (boron nitride) surface by sodium hydroxide and subsequently modifying BN using APTES ((3-aminopropyl)triethoxysilane). The successful synthesis of BN-NH<sub>2</sub> nanosheets with a size of 280 nm was confirmed using FT-IR, TGA, SEM, and particle size analysis. The BN-NH<sub>2</sub> nanofluid (1000 mg/L) exhibited excellent stability, maintaining minimal particle size changes after 5 days of standing. At 60 °C, the BN-NH<sub>2</sub> nanofluid (1000 mg/L) maintained an interfacial tension of 10.1 mN/m, highlighting its ability to reduce interfacial tension. At 60 °C, the BN-NH<sub>2</sub> nanofluid (1000 mg/L) achieved an emulsification index of 0.28 after 240 h, demonstrating its excellent emulsification performance. The BN-NH<sub>2</sub> nanofluid (1000 mg/L) effectively altered reservoir wettability, reducing the contact angle from 108.8° to 46.8°. Displacement experiments revealed that BN-NH<sub>2</sub> nanofluid flooding could enhance oil recovery by 16.2 % compared to water flooding. The mechanism of enhanced oil recovery by BN-NH<sub>2</sub> nanofluid was analyzed via microscopic displacement experiments.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"424 ","pages":"Article 127080"},"PeriodicalIF":5.3,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143350773","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-03DOI: 10.1016/j.molliq.2025.127077
Meijun Chen , Changjun Zou , Wenyue Tang , Japan Trivedi
A supramolecular deep eutectic solvent (SUPRADES) was synthesized by cyclodextrin and lactic acid, and its synergistic effect on fuel desulfurization performance with carbon nanotubes (CNTs) was also explored. The stability of CNTs in SUPRADES and the effect of CNTs on the viscosity of SUPRADES were investigated. The results indicate that adding CNTs can enhance the desulfurization efficiency of supramolecular deep eutectic solvents, and can achieve a better desulfurization effect in a shorter timeframe. The desulfurization rates were examined under varying conditions, including different CNTs contents, temperatures, O/S ratios, initial sulfur concentrations, and SUPRADES-to-simulated oil volume ratios. The desulfurization rate can reach 90.32 % at a temperature of 80 °C and a mass fraction of CNTs of 0.1 wt%. An increase in desulfurization rate of 19.47 % at 80 °C was observed for HL-β-CD/CNT compared to HL-β-CD. By characterizing the desulfurized SUPRADES, it was found that its structure remained stable after desulfurization. This SUPRADES synergized CNTs provide a novel approach for fuel desulfurization.
{"title":"Supramolecular-based preparation of deep eutectic solvents synergized with carbon nanotubes for oxidative desulfurization of fuels","authors":"Meijun Chen , Changjun Zou , Wenyue Tang , Japan Trivedi","doi":"10.1016/j.molliq.2025.127077","DOIUrl":"10.1016/j.molliq.2025.127077","url":null,"abstract":"<div><div>A supramolecular deep eutectic solvent (SUPRADES) was synthesized by cyclodextrin and lactic acid, and its synergistic effect on fuel desulfurization performance with carbon nanotubes (CNTs) was also explored. The stability of CNTs in SUPRADES and the effect of CNTs on the viscosity of SUPRADES were investigated. The results indicate that adding CNTs can enhance the desulfurization efficiency of supramolecular deep eutectic solvents, and can achieve a better desulfurization effect in a shorter timeframe. The desulfurization rates were examined under varying conditions, including different CNTs contents, temperatures, O/S ratios, initial sulfur concentrations, and SUPRADES-to-simulated oil volume ratios. The desulfurization rate can reach 90.32 % at a temperature of 80 °C and a mass fraction of CNTs of 0.1 wt%. An increase in desulfurization rate of 19.47 % at 80 °C was observed for HL-β-CD/CNT compared to HL-β-CD. By characterizing the desulfurized SUPRADES, it was found that its structure remained stable after desulfurization. This SUPRADES synergized CNTs provide a novel approach for fuel desulfurization.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"424 ","pages":"Article 127077"},"PeriodicalIF":5.3,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143377308","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-03DOI: 10.1016/j.molliq.2025.127024
Carlos A. Franco , Oscar E. Medina , Dahiana Galeano-Caro , Lina M. Salinas , Luis G. Alzate , Daniela Molina , Gabriel J. Rendón , Cristian C. Obregón , Sergio H. Lopera , Farid B. Cortes , Camilo A. Franco
This study introduced a novel nanofluid injection method to enhance heavy crude oil recovery in steam-impacted wells, offering an alternative to traditional steam injection techniques. This research focuses on improving oil mobility by disrupting the viscoelastic network of asphaltenes through silica nanoparticle adsorption. Comprehensive experimental evaluations included nanoparticle characterization, reservoir fluid analysis, and dynamic core-flooding tests under reservoir conditions. Three carrier fluids, surfactant-based (SB), diesel-based (DT), and light hydrocarbon with surfactant (LHC + S), were tested with silica nanoparticles to identify the most effective combination. Key findings demonstrated that a concentration of 300 mg L−1 of silica nanoparticles dispersed in LHC + S reduced oil viscosity by 57 % at 25 °C, lowered the contact angle from 47° to 15°, and decreased interfacial tension by 38.0 %. Core flooding revealed that nanofluid injection increased the recovery factor from 89 % to 92 %, confirming enhanced crude oil displacement. Field trials in two mature wells subjected to four prior steam cycles showed oil production increases of 32 % and 56 % during the first-month post-treatment, with cumulative gains of 11,148 Bbl and 2240 Bbl, respectively. Additionally, viscosity reductions of 60 % were sustained over 12 months, validating the long-term efficacy of nanofluid injection as a nonthermal Enhanced Oil Recovery (EOR) method. By eliminating the need for steam and significantly improving the oil displacement efficiency, this study demonstrates the potential of nanofluid injection to reduce the operational costs and environmental impact in heavy oil fields undergoing thermal depletion.
{"title":"Enhancing heavy crude oil mobility at reservoir conditions by nanofluid injection in wells with previous steam stimulation cycles: Experimental evaluation and field trial implementation","authors":"Carlos A. Franco , Oscar E. Medina , Dahiana Galeano-Caro , Lina M. Salinas , Luis G. Alzate , Daniela Molina , Gabriel J. Rendón , Cristian C. Obregón , Sergio H. Lopera , Farid B. Cortes , Camilo A. Franco","doi":"10.1016/j.molliq.2025.127024","DOIUrl":"10.1016/j.molliq.2025.127024","url":null,"abstract":"<div><div>This study introduced a novel nanofluid injection method to enhance heavy crude oil recovery in steam-impacted wells, offering an alternative to traditional steam injection techniques. This research focuses on improving oil mobility by disrupting the viscoelastic network of asphaltenes through silica nanoparticle adsorption. Comprehensive experimental evaluations included nanoparticle characterization, reservoir fluid analysis, and dynamic core-flooding tests under reservoir conditions. Three carrier fluids, surfactant-based (SB), diesel-based (DT), and light hydrocarbon with surfactant (LHC + S), were tested with silica nanoparticles to identify the most effective combination. Key findings demonstrated that a concentration of 300 mg L<sup>−1</sup> of silica nanoparticles dispersed in LHC + S reduced oil viscosity by 57 % at 25 °C, lowered the contact angle from 47° to 15°, and decreased interfacial tension by 38.0 %. Core flooding revealed that nanofluid injection increased the recovery factor from 89 % to 92 %, confirming enhanced crude oil displacement. Field trials in two mature wells subjected to four prior steam cycles showed oil production increases of 32 % and 56 % during the first-month post-treatment, with cumulative gains of 11,148 Bbl and 2240 Bbl, respectively. Additionally, viscosity reductions of 60 % were sustained over 12 months, validating the long-term efficacy of nanofluid injection as a nonthermal Enhanced Oil Recovery (EOR) method. By eliminating the need for steam and significantly improving the oil displacement efficiency, this study demonstrates the potential of nanofluid injection to reduce the operational costs and environmental impact in heavy oil fields undergoing thermal depletion.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"424 ","pages":"Article 127024"},"PeriodicalIF":5.3,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143387761","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}
Pub Date : 2025-02-03DOI: 10.1016/j.molliq.2025.127076
Kaipeng Lin , Zishi Chen , Ruifeng Shen , Sirong Long , Yicheng Huang , Minyi Zeng , Xuedan Hou , Shilin Cao , Hongxia Zhao , Jason P. Hallett
Keratin, as a natural biopolymer, holds great promise for industrial applications. In this work, a series of renewable urea-polyol solvents were designed for keratin extraction from waste chicken feathers. Urea-ethylene glycol (U-EG) exhibited the highest solubility of 18.1 % (181 mg feather/g solvent) for feather keratin at 120 °C, with a significant enhancement to 29.4 % achieved by adding 5 wt% arginine (Arg). Structural analysis indicates that the extracted keratin mostly maintained its original primary structure. These solvents substantially disrupted the disulfide bonds, affecting the secondary structure by converting some α-helix to β-sheet and amorphous structures like random coils. Molecular dynamics simulations revealed that U-EG could act as molecular scissors, synergistically reinforced by Arg, by disrupting the intermolecular interactions of solvents. This disruption liberated more free solvent molecules to interact with keratin via van der Waals forces, Coulomb forces, and hydrogen bonding interactions. U-EG exhibited excellent recyclability, maintaining high solubility of 86 % after five cycles of reuse.
{"title":"Recyclable urea-polyols solvents as molecular scissors for extracting keratin from waste feather","authors":"Kaipeng Lin , Zishi Chen , Ruifeng Shen , Sirong Long , Yicheng Huang , Minyi Zeng , Xuedan Hou , Shilin Cao , Hongxia Zhao , Jason P. Hallett","doi":"10.1016/j.molliq.2025.127076","DOIUrl":"10.1016/j.molliq.2025.127076","url":null,"abstract":"<div><div>Keratin, as a natural biopolymer, holds great promise for industrial applications. In this work, a series of renewable urea-polyol solvents were designed for keratin extraction from waste chicken feathers. Urea-ethylene glycol (U-EG) exhibited the highest solubility of 18.1 % (181 mg feather/g solvent) for feather keratin at 120 °C, with a significant enhancement to 29.4 % achieved by adding 5 wt% arginine (Arg). Structural analysis indicates that the extracted keratin mostly maintained its original primary structure. These solvents substantially disrupted the disulfide bonds, affecting the secondary structure by converting some α-helix to β-sheet and amorphous structures like random coils. Molecular dynamics simulations revealed that U-EG could act as molecular scissors, synergistically reinforced by Arg, by disrupting the intermolecular interactions of solvents. This disruption liberated more free solvent molecules to interact with keratin via van der Waals forces, Coulomb forces, and hydrogen bonding interactions. U-EG exhibited excellent recyclability, maintaining high solubility of 86 % after five cycles of reuse.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"424 ","pages":"Article 127076"},"PeriodicalIF":5.3,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143346630","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-03DOI: 10.1016/j.molliq.2025.127074
Andrey A. Sokolov, Boris N. Solomonov, Mikhail I. Yagofarov
The search for the relationship between thermochemical and structural parameters of matter has been a relevant direction of investigations in the field of thermodynamics of organic compounds for many decades. Future research in this direction is essential for the development of fundamental theories and predictive schemes. In this work, we investigated the relationship between the shape of the molecule and the thermodynamic properties of melting for non-associated organic compounds. The sphericity parameter was introduced, and a Python script for its calculation was written for the quantitative characterization of the molecular shape. Analysis of a large amount of literature data revealed a linear correlation between the ratio of fusion enthalpy to molar volume change during melting and the sphericity parameter. The relationships found provide a deeper insight into the melting process. They may serve as a basis for further studies of the influence of molecular structure on its mechanism. In addition, it opens up the possibility of estimating the ratio of the enthalpy of fusion to the molar volume change during melting from the shape of the molecule, which may be useful in predicting melting curve slopes on phase diagrams.
{"title":"Influence of molecular shape on the melting thermodynamics of non-associated organic compounds","authors":"Andrey A. Sokolov, Boris N. Solomonov, Mikhail I. Yagofarov","doi":"10.1016/j.molliq.2025.127074","DOIUrl":"10.1016/j.molliq.2025.127074","url":null,"abstract":"<div><div>The search for the relationship between thermochemical and structural parameters of matter has been a relevant direction of investigations in the field of thermodynamics of organic compounds for many decades. Future research in this direction is essential for the development of fundamental theories and predictive schemes. In this work, we investigated the relationship between the shape of the molecule and the thermodynamic properties of melting for non-associated organic compounds. The sphericity parameter was introduced, and a Python script for its calculation was written for the quantitative characterization of the molecular shape. Analysis of a large amount of literature data revealed a linear correlation between the ratio of fusion enthalpy to molar volume change during melting and the sphericity parameter. The relationships found provide a deeper insight into the melting process. They may serve as a basis for further studies of the influence of molecular structure on its mechanism. In addition, it opens up the possibility of estimating the ratio of the enthalpy of fusion to the molar volume change during melting from the shape of the molecule, which may be useful in predicting melting curve slopes on phase diagrams.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"424 ","pages":"Article 127074"},"PeriodicalIF":5.3,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143372405","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-03DOI: 10.1016/j.molliq.2025.127075
Erdal Dinç , Asiye Üçer , Muhammed Elgasi
A novel spectrofluorimetric multiway analysis method was introduced to estimate the interaction between maprotiline hydrochloride (MAP) and calf thymus deoxyribonucleic acid (DNA) and quantify the binding constant of the MAP-DNA complex. This innovative approach combines the high sensitivity and specificity of spectrofluorimetry with an advanced multiway data analysis algorithm, enabling detailed characterization of the binding process in this study. This exemplary application is to elucidate MAP-DNA interactions using a multiway data analysis model applied to fluorescence excitation-emission measurements. After the reaction between MAP and DNA fluorescence spectra were recorded to generate a three-dimensional data tensor. This tensor was decomposed using parallel factor analysis (PARAFAC) to extract distinct excitation spectra, emission spectra, and concentration profiles. This PARAFAC decomposition effectively isolated the individual fluorescence signals of free MAP and the MAP-DNA complex. In the PARAFAC application, the binding constants were calculated at 288, 298, and 310 K as (10.64 ± 0.025) × 104, 1.90 ± 0.050) × 104, and (0.42 ± 0.004) × 104 M−1, respectively. Thermodynamic parameters (ΔS0 = −282.19 J mol−1 K−1, ΔH0 = −108.83 kJ/mol and ΔG0 = −27.70, −24.40, and −21.49 kJ/mol at 288, 298, and 310 K, respectively) were calculated. Negative ΔG° values indicated that, under standard conditions, the binding process was thermodynamically favorable at equilibrium. The negative ΔS° and ΔH° values revealed that van der Waals forces and hydrogen bonding were the primary contributors to MAP-DNA binding. This comprehensive analysis demonstrated the utility of the PARAFAC approach in distinguishing free drug (MAP) from the MAP-DNA complex and elucidating the binding mechanisms. Compared to traditional techniques, the multiway data analysis approach has high potential as an alternative and powerful tool to evidence the drug-DNA interaction even in complex reaction mixtures.
{"title":"An introduction to multiway modeling of fluorescence excitation-emission measurements to estimate the interaction of maprotiline hydrochloride and DNA, and quantify the drug-DNA binding constant","authors":"Erdal Dinç , Asiye Üçer , Muhammed Elgasi","doi":"10.1016/j.molliq.2025.127075","DOIUrl":"10.1016/j.molliq.2025.127075","url":null,"abstract":"<div><div>A novel spectrofluorimetric multiway analysis method was introduced to estimate the interaction between maprotiline hydrochloride (MAP) and calf thymus deoxyribonucleic acid (DNA) and quantify the binding constant of the MAP-DNA complex. This innovative approach combines the high sensitivity and specificity of spectrofluorimetry with an advanced multiway data analysis algorithm, enabling detailed characterization of the binding process in this study. This exemplary application is to elucidate MAP-DNA interactions using a multiway data analysis model applied to fluorescence excitation-emission measurements. After the reaction between MAP and DNA fluorescence spectra were recorded to generate a three-dimensional data tensor. This tensor was decomposed using parallel factor analysis (PARAFAC) to extract distinct excitation spectra, emission spectra, and concentration profiles. This PARAFAC decomposition effectively isolated the individual fluorescence signals of free MAP and the MAP-DNA complex. In the PARAFAC application, the binding constants were calculated at 288, 298, and 310 K as (10.64 ± 0.025) × 10<sup>4</sup>, 1.90 ± 0.050) × 10<sup>4</sup>, and (0.42 ± 0.004) × 10<sup>4</sup> M<sup>−1</sup>, respectively. Thermodynamic parameters (<em>ΔS<sup>0</sup></em> = −282.19 J mol<sup>−1</sup> K<sup>−1</sup>, <em>ΔH<sup>0</sup></em> = −108.83 kJ/mol and <em>ΔG<sup>0</sup></em> = −27.70, −24.40, and −21.49 kJ/mol at 288, 298, and 310 K, respectively) were calculated. Negative ΔG° values indicated that, under standard conditions, the binding process was thermodynamically favorable at equilibrium. The negative ΔS° and ΔH° values revealed that van der Waals forces and hydrogen bonding were the primary contributors to MAP-DNA binding. This comprehensive analysis demonstrated the utility of the PARAFAC approach in distinguishing free drug (MAP) from the MAP-DNA complex and elucidating the binding mechanisms. Compared to traditional techniques, the multiway data analysis approach has high potential as an alternative and powerful tool to evidence the drug-DNA interaction even in complex reaction mixtures.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"424 ","pages":"Article 127075"},"PeriodicalIF":5.3,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143379280","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-02DOI: 10.1016/j.molliq.2025.127073
Andrew C. Strzelecki , S. Scott Parker , Shane C. Mann , David C. Arellano , Sarah M. Hickam , S. Douglas Ware , Nathan A. Conroy , Hakim Boukhalfa , Titus Y.P. De Jong , David A. Andersson , J. Matt Jackson , Jeremy Mitchell , Marisa Monreal , Hongwu Xu
Despite more than 70 years of research on the thermodynamic properties of molten salts, there are still limited experimental data towards understanding the phase stability relations of molten mixtures containing PuCl3. While recent thermodynamic measurements of PuCl3-NaCl yielded some data, there have been significant differences in the reported values of heat capacity of PuCl3-NaCl in the liquid, or molten state. In this work, we conducted transpose temperature drop calorimetry of the PuCl3-NaCl eutectic using a commercial Tian-Calvet twin microcalorimeter and the Ni encapsulation technique developed by us previously. The transpose temperature drop enthalpy (ΔHttd) was measured to be 155.31 ± 8.03 kJ∙mol−1 at a temperature of 975.77 ± 0.08 K. To verify this value, a critical assessment of the literature was performed to determine that the enthalpy increment, ΔHT-726, of molten PuCl3-NaCl eutectic is 101.5 ± 8.1 kJ∙mol−1, which agrees well with the heat capacity (Cp) derived by Karlsson et al. [26] using differential scanning calorimetry. The original Cp equation of Karlsson et al. was then extended with confidence to 993 K (Cp = 101.9 ± 2.1 J∙mol−1∙K−1). In addition, the excess heat capacity () of molten PuCl3-NaCl eutectic was determined to be 4.2 ± 2.1 J∙mol−1∙K−1, which was then used to determine the enthalpy of mixing (ΔHmix) to be –5.3 kJ∙mol−1. These results provide the basis for modeling the thermodynamic stability of molten PuCl3-bearing chlorides for nuclear energy and other applications.
{"title":"Determination of thermochemical properties of the molten PuCl3-NaCl eutectic mixture by high-temperature drop calorimetry","authors":"Andrew C. Strzelecki , S. Scott Parker , Shane C. Mann , David C. Arellano , Sarah M. Hickam , S. Douglas Ware , Nathan A. Conroy , Hakim Boukhalfa , Titus Y.P. De Jong , David A. Andersson , J. Matt Jackson , Jeremy Mitchell , Marisa Monreal , Hongwu Xu","doi":"10.1016/j.molliq.2025.127073","DOIUrl":"10.1016/j.molliq.2025.127073","url":null,"abstract":"<div><div>Despite more than 70 years of research on the thermodynamic properties of molten salts, there are still limited experimental data towards understanding the phase stability relations of molten mixtures containing PuCl<sub>3</sub>. While recent thermodynamic measurements of PuCl<sub>3</sub>-NaCl yielded some data, there have been significant differences in the reported values of heat capacity of PuCl<sub>3</sub>-NaCl in the liquid, or molten state. In this work, we conducted transpose temperature drop calorimetry of the PuCl<sub>3</sub>-NaCl eutectic using a commercial Tian-Calvet twin microcalorimeter and the Ni encapsulation technique developed by us previously. The transpose temperature drop enthalpy (<em>ΔH</em><sub><em>ttd</em></sub>) was measured to be 155.31 ± 8.03 kJ∙mol<sup>−1</sup> at a temperature of 975.77 ± 0.08 K. To verify this value, a critical assessment of the literature was performed to determine that the enthalpy increment, <em>ΔH</em><sub><em>T-</em></sub><sub><em>726</em></sub>, of molten PuCl<sub>3</sub>-NaCl eutectic is 101.5 ± 8.1 kJ∙mol<sup>−1</sup>, which agrees well with the heat capacity (C<sub>p</sub>) derived by Karlsson et al. <span><span>[26]</span></span> using differential scanning calorimetry. The original C<sub>p</sub> equation of Karlsson et al. was then extended with confidence to 993 K (C<sub>p</sub> = 101.9 ± 2.1 J∙mol<sup>−1</sup>∙K<sup>−1</sup>). In addition, the excess heat capacity (<span><math><msubsup><mi>C</mi><mrow><mi>p</mi></mrow><mrow><mi>ex</mi></mrow></msubsup></math></span>) of molten PuCl<sub>3</sub>-NaCl eutectic was determined to be 4.2 ± 2.1 J∙mol<sup>−1</sup>∙K<sup>−1</sup>, which was then used to determine the enthalpy of mixing (<em>ΔH</em><sub><em>mix</em></sub>) to be –5.3 kJ∙mol<sup>−1</sup>. These results provide the basis for modeling the thermodynamic stability of molten PuCl<sub>3</sub>-bearing chlorides for nuclear energy and other applications.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"424 ","pages":"Article 127073"},"PeriodicalIF":5.3,"publicationDate":"2025-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143350775","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-02DOI: 10.1016/j.molliq.2025.127071
Krzysztof Nowacki , Marcin Wysokowski , Maciej Galiński
Lately, deep eutectic solvents (DESs) have been taken into detailed consideration as potential electrolytes for use in various electrochemical devices. This study reports a successful synthesis of three novel natural deep eutectic solvents (NADESs) based on betaine hydrochloride as the hydrogen bond acceptor and glycerol, glycolic acid, and ethylene glycol as hydrogen bond donors. Comprehensive research, including ATR-FTIR, surface tension, rheological properties, and ionic conductivity, revealed that the betaine hydrochloride–ethylene glycol (BETCl−:MEG) system exhibited superior physicochemical characteristics. This NADES was subsequently evaluated as an electrolyte in an electric double-layer capacitor (EDLC), demonstrating excellent electrochemical performance with a specific capacitance of 94 F g−1 (0.5 A g−1) and excellent electrochemical stability. Notably, this study represents the first successful application of a betaine hydrochloride-based NADES as a liquid electrolyte in an energy storage device, highlighting its potential as a sustainable alternative to other innovative electrolyte systems, such as deep eutectic solvents based on choline chloride. These findings suggest that betaine-based NADESs hold significant promise for future applications in energy storage technologies.
{"title":"Synthesis and characterization of betaine-based natural deep eutectic solvents for electrochemical application","authors":"Krzysztof Nowacki , Marcin Wysokowski , Maciej Galiński","doi":"10.1016/j.molliq.2025.127071","DOIUrl":"10.1016/j.molliq.2025.127071","url":null,"abstract":"<div><div>Lately, deep eutectic solvents (DESs) have been taken into detailed consideration as potential electrolytes for use in various electrochemical devices. This study reports a successful synthesis of three novel natural deep eutectic solvents (NADESs) based on betaine hydrochloride as the hydrogen bond acceptor and glycerol, glycolic acid, and ethylene glycol as hydrogen bond donors. Comprehensive research, including ATR-FTIR, surface tension, rheological properties, and ionic conductivity, revealed that the betaine hydrochloride–ethylene glycol (BETCl<sup>−</sup>:MEG) system exhibited superior physicochemical characteristics. This NADES was subsequently evaluated as an electrolyte in an electric double-layer capacitor (EDLC), demonstrating excellent electrochemical performance with a specific capacitance of 94 F g<sup>−1</sup> (0.5 A g<sup>−1</sup>) and excellent electrochemical stability. Notably, this study represents the first successful application of a betaine hydrochloride-based NADES as a liquid electrolyte in an energy storage device, highlighting its potential as a sustainable alternative to other innovative electrolyte systems, such as deep eutectic solvents based on choline chloride. These findings suggest that betaine-based NADESs hold significant promise for future applications in energy storage technologies.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"424 ","pages":"Article 127071"},"PeriodicalIF":5.3,"publicationDate":"2025-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143346627","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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