Journal of Molecular Liquids最新文献

Physicochemical properties of triethylamine hydrochloride-based chloroaluminate ionic liquid

IF 5.3 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2025-03-17 DOI: 10.1016/j.molliq.2025.127411

V.A. Elterman, A.V. Borozdin, E.A. Il’ina, L.A. Yolshina

The use of chloroaluminate ionic liquids (ILs) based on triethylamine hydrochloride as electrolytes for aluminum ion batteries (AIBs) can reduce the cost of the device, while at the same time preserving its performance characteristics. However, the ionic composition of the system and the physicochemical properties required for the optimization of the electrolyte composition have not been systematically studied in literature. The present paper reports on the studies into the ionic composition, viscosity, density and melting temperatures of the IL across wide temperature and concentration ranges. Raman spectroscopy revealed the presence of AlCl₄⁻, Al₂Cl₇⁻ and Et₃NH⁺ ions in the electrolyte, and the trends of their concentration changes are similar to the behaviors reported for other chloroaluminate ILs. Visual polythermal method and differential scanning calorimetry (DSC) were used to obtain the phase diagram of the electrolyte. The melting temperature of the system increases with the ratio of aluminum chloride to the organic salt (N) and reaches its maximum at N = 1.0 followed by its decrease down to 234 K at N = 1.7. The IL with N = 1.95 displays only glass transition at cooling. The shape of the DSC curves for the ILs is similar to that of the DSC curves obtained at heating isothermally crystallized polymers. The temperature and concentration dependences of density are described by a linear function; however, the concentration dependences contain a bend at N = 1.0. The viscosity of the ILs decreases with the growth of temperature and aluminum chloride concentration. The temperature dependence of viscosity is non-linear and can be described by the Vogel-Fulcher-Tammann equation. The results obtained indicate that the ILs with N > 1 undergo a structural change due to the formation of Al₂Cl₇⁻ ion. ILs with a high content of Al₂Cl₇⁻ anion (N > 1.5) are the most viable choice for electrolytes of AIBs, since they offer a relatively low melting temperature and their viscosity is comparable with that of other chloroaluminate ILs.

{"title":"Physicochemical properties of triethylamine hydrochloride-based chloroaluminate ionic liquid","authors":"V.A. Elterman, A.V. Borozdin, E.A. Il’ina, L.A. Yolshina","doi":"10.1016/j.molliq.2025.127411","DOIUrl":"10.1016/j.molliq.2025.127411","url":null,"abstract":"<div><div>The use of chloroaluminate ionic liquids (ILs) based on triethylamine hydrochloride as electrolytes for aluminum ion batteries (AIBs) can reduce the cost of the device, while at the same time preserving its performance characteristics. However, the ionic composition of the system and the physicochemical properties required for the optimization of the electrolyte composition have not been systematically studied in literature. The present paper reports on the studies into the ionic composition, viscosity, density and melting temperatures of the IL across wide temperature and concentration ranges. Raman spectroscopy revealed the presence of AlCl<sub>4</sub><sup>−</sup>, Al<sub>2</sub>Cl<sub>7</sub><sup>−</sup> and Et<sub>3</sub>NH<sup>+</sup> ions in the electrolyte, and the trends of their concentration changes are similar to the behaviors reported for other chloroaluminate ILs. Visual polythermal method and differential scanning calorimetry (DSC) were used to obtain the phase diagram of the electrolyte. The melting temperature of the system increases with the ratio of aluminum chloride to the organic salt (N) and reaches its maximum at N = 1.0 followed by its decrease down to 234 K at N = 1.7. The IL with N = 1.95 displays only glass transition at cooling. The shape of the DSC curves for the ILs is similar to that of the DSC curves obtained at heating isothermally crystallized polymers. The temperature and concentration dependences of density are described by a linear function; however, the concentration dependences contain a bend at N = 1.0. The viscosity of the ILs decreases with the growth of temperature and aluminum chloride concentration. The temperature dependence of viscosity is non-linear and can be described by the Vogel-Fulcher-Tammann equation. The results obtained indicate that the ILs with N > 1 undergo a structural change due to the formation of Al<sub>2</sub>Cl<sub>7</sub><sup>−</sup> ion. ILs with a high content of Al<sub>2</sub>Cl<sub>7</sub><sup>−</sup> anion (N > 1.5) are the most viable choice for electrolytes of AIBs, since they offer a relatively low melting temperature and their viscosity is comparable with that of other chloroaluminate ILs.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"427 ","pages":"Article 127411"},"PeriodicalIF":5.3,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143643886","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

A multichannel fluorescent sensor for solid and vapor phase detection of 4-nitroaniline and salicylaldehyde with latent fingerprint and an invisible ink analysis: Extensive experimental and DFT studies

IF 5.3 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2025-03-16 DOI: 10.1016/j.molliq.2025.127399

Muqadas , Alam Shabbir , Mohammed A. Assiri , Muazzama Khan , Sohail Anjum Shahzad

Organic fluorophores with extensive aromaticity are crucial while designing sensors with outstanding optical characteristics. Herein, we synthesized a novel fluorescein based organic fluorophore 2-((anthracen-9-ylmethylene) amino)-3′,6′-dihydroxyspiro[isoindoline-1,9′-xanthen]-3-one (ADX) demonstrating exceptional photophysical properties. We conducted a comprehensive examination of fluorescence properties of the sensor ADX, exploring various aspects including aggregation, solvatochromism, solid and vapor phase studies using fluorescence emission, UV Vis. and other spectroscopic analysis. Notably, fluorophore exhibits aggregation induced emission (AIE) character, marked by a substantial Stokes shift of 78 nm. This characteristic was comprehensively evaluated in a water/DMF (9:1, v/v) binary solvent system, which facilitated the designing of latent fingerprint detection and an invisible ink. Furthermore, admirable optical properties of sensor ADX were utilized for efficient and selective sensing of 4-nitroaniline (4-NA) with “Turn Off” and salicylaldehyde (SA) with “Turn On” fluorescence in real water samples. Calculated limit of detection (LOD) was 165 nM and limit of quantification (LOQ) was 549 nM for 4-NA while 31.4 nM and 104.6 nM for SA, respectively. To further enhance practical applications, we developed a portable paper-based strip for on-site sensing of 4-NA and SA. Additionally, we thoroughly evaluated the mechanistic approach for the detection of 4-NA and SA through NMR, ultraviolet–visible (UV–Vis.) and photoluminescence spectroscopic techniques along with DFT studies. DFT studies include the calculation of reduced density gradient (RDG), thermodynamic stability, charge transfer and QTAIM analysis. Collectively, our experimental and theoretical investigations support the existence of weak intermolecular interactions among sensor ADX and analytes (4-NA and SA).

{"title":"A multichannel fluorescent sensor for solid and vapor phase detection of 4-nitroaniline and salicylaldehyde with latent fingerprint and an invisible ink analysis: Extensive experimental and DFT studies","authors":"Muqadas , Alam Shabbir , Mohammed A. Assiri , Muazzama Khan , Sohail Anjum Shahzad","doi":"10.1016/j.molliq.2025.127399","DOIUrl":"10.1016/j.molliq.2025.127399","url":null,"abstract":"<div><div>Organic fluorophores with extensive aromaticity are crucial while designing sensors with outstanding optical characteristics. Herein, we synthesized a novel fluorescein based organic fluorophore 2-((anthracen-9-ylmethylene) amino)-3′,6′-dihydroxyspiro[isoindoline-1,9′-xanthen]-3-one (<strong>ADX</strong>) demonstrating exceptional photophysical properties. We conducted a comprehensive examination of fluorescence properties of the sensor <strong>ADX</strong>, exploring various aspects including aggregation, solvatochromism, solid and vapor phase studies using fluorescence emission, UV Vis. and other spectroscopic analysis. Notably, fluorophore exhibits aggregation induced emission (AIE) character, marked by a substantial Stokes shift of 78 nm. This characteristic was comprehensively evaluated in a water/DMF (9:1, v/v) binary solvent system, which facilitated the designing of latent fingerprint detection and an invisible ink. Furthermore, admirable optical properties of sensor <strong>ADX</strong> were utilized for efficient and selective sensing of 4-nitroaniline (4-NA) with “Turn Off” and salicylaldehyde (SA) with “Turn On” fluorescence in real water samples. Calculated limit of detection (LOD) was 165 nM and limit of quantification (LOQ) was 549 nM for 4-NA while 31.4 nM and 104.6 nM for SA, respectively. To further enhance practical applications, we developed a portable paper-based strip for on-site sensing of 4-NA and SA. Additionally, we thoroughly evaluated the mechanistic approach for the detection of 4-NA and SA through NMR, ultraviolet–visible (UV–Vis.) and photoluminescence spectroscopic techniques along with DFT studies. DFT studies include the calculation of reduced density gradient (RDG), thermodynamic stability, charge transfer and QTAIM analysis. Collectively, our experimental and theoretical investigations support the existence of weak intermolecular interactions among sensor <strong>ADX</strong> and analytes (4-NA and SA).</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"427 ","pages":"Article 127399"},"PeriodicalIF":5.3,"publicationDate":"2025-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143643882","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

Local field and deformation of droplets in emulsions

IF 5.3 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2025-03-15 DOI: 10.1016/j.molliq.2025.127406

Arthur Zakinyan , Ali M. Ahmed , Daria Kononenko

The deformation of individual liquid droplets in an applied electric or magnetic field is a traditional subject of research. Deformation processes in the system of droplets of the dispersed phase of an emulsion are of fundamental and applied interest but are currently poorly understood. Such processes must depend on the interaction of the droplets with each other. In this work, emulsions of ideal dielectric fluids in an electric field or ferrofluids in a magnetic field are considered. As a result of computer simulations and experimental studies, it is shown that the imposition of an external field on the system of droplets leads to their stretching along the field, accompanied by a slower process of formation of chain structures from droplets. At the initial stage of the system evolution, long-range interactions of polarized droplets can influence the degree of their deformation differently depending on the ratio of permeabilities of the dispersed phase and the dispersion medium. The subsequent formation of chain structures of droplets leads to the manifestation of short-range interactions of neighboring droplets in chains. These interactions, caused by the attraction of the droplets to each other, lead to the compression of the droplets in the field direction, which reduces the resulting degree of elongation of the droplets, regardless of the ratio of the properties of the droplets and the medium.

{"title":"Local field and deformation of droplets in emulsions","authors":"Arthur Zakinyan , Ali M. Ahmed , Daria Kononenko","doi":"10.1016/j.molliq.2025.127406","DOIUrl":"10.1016/j.molliq.2025.127406","url":null,"abstract":"<div><div>The deformation of individual liquid droplets in an applied electric or magnetic field is a traditional subject of research. Deformation processes in the system of droplets of the dispersed phase of an emulsion are of fundamental and applied interest but are currently poorly understood. Such processes must depend on the interaction of the droplets with each other. In this work, emulsions of ideal dielectric fluids in an electric field or ferrofluids in a magnetic field are considered. As a result of computer simulations and experimental studies, it is shown that the imposition of an external field on the system of droplets leads to their stretching along the field, accompanied by a slower process of formation of chain structures from droplets. At the initial stage of the system evolution, long-range interactions of polarized droplets can influence the degree of their deformation differently depending on the ratio of permeabilities of the dispersed phase and the dispersion medium. The subsequent formation of chain structures of droplets leads to the manifestation of short-range interactions of neighboring droplets in chains. These interactions, caused by the attraction of the droplets to each other, lead to the compression of the droplets in the field direction, which reduces the resulting degree of elongation of the droplets, regardless of the ratio of the properties of the droplets and the medium.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"427 ","pages":"Article 127406"},"PeriodicalIF":5.3,"publicationDate":"2025-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143643888","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

Ice-responsive Coatings: Evaluating the effect of Hydrogen bond donors on Deep eutectic solvents/Ionic liquids Anti-icing efficiency 冰响应涂料：评估氢键供体对深共晶溶剂/离子液体抗冰效率的影响

IF 5.3 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2025-03-14 DOI: 10.1016/j.molliq.2025.127389

Saba Goharshenas Moghadam, Gelareh Momen, Reza Jafari

Although there has been pioneering research on the anti-icing properties of Ionic liquids (ILs) and Deep Eutectic Solvents (DESs), coatings based on these materials are still in the early stages of development. Given the limited understanding of DESs in anti-icing applications, we investigated the role of hydrogen bond donors (HBDs) within DESs, focusing on their hydrophilicity and hydrophobicity. After conducting a comprehensive study using advanced characterization techniques, including ATR-FTIR, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) analysis, and wettability measurements, our findings demonstrate that DESs can be effectively introduced as ice-responsive components on a surface, significantly improving their anti-icing performance. Our comparative analysis showed that the introduction of hydrophobic HBDs into DES-based coatings reduced ice adhesion strength to 13 kPa, while maintaining an ice formation temperature of −35 °C. Despite plasticising characteristic of DESs, notably, the mechanical properties, including tensile strength, remained consistent with the neat coating, though with enhanced elongation at break. Solid-state NMR spectroscopy revealed the formation of a thicker quasi-liquid layer (QLL) on the surface of coatings containing hydrophobic HBDs, which was further confirmed by low-temperature ATR-FTIR analysis. Moreover, these coatings exhibited modified frost formation patterns, leading to increased resistance to frost buildup over multiple cycles. Ice adhesion strength of coatings was examined against accelerated weathering, icing/de-icing cycles, as well. This study presents a novel approach for designing sustainable, high-performance icephobic coatings, emphasizing the potential of DESs as effective ice-responsive components in achieving superior anti-icing and anti-frosting capabilities.

{"title":"Ice-responsive Coatings: Evaluating the effect of Hydrogen bond donors on Deep eutectic solvents/Ionic liquids Anti-icing efficiency","authors":"Saba Goharshenas Moghadam, Gelareh Momen, Reza Jafari","doi":"10.1016/j.molliq.2025.127389","DOIUrl":"10.1016/j.molliq.2025.127389","url":null,"abstract":"<div><div>Although there has been pioneering research on the anti-icing properties of Ionic liquids (ILs) and Deep Eutectic Solvents (DESs), coatings based on these materials are still in the early stages of development. Given the limited understanding of DESs in anti-icing applications, we investigated the role of hydrogen bond donors (HBDs) within DESs, focusing on their hydrophilicity and hydrophobicity. After conducting a comprehensive study using advanced characterization techniques, including ATR-FTIR, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) analysis, and wettability measurements, our findings demonstrate that DESs can be effectively introduced as ice-responsive components on a surface, significantly improving their anti-icing performance. Our comparative analysis showed that the introduction of hydrophobic HBDs into DES-based coatings reduced ice adhesion strength to 13 kPa, while maintaining an ice formation temperature of −35 °C. Despite plasticising characteristic of DESs, notably, the mechanical properties, including tensile strength, remained consistent with the neat coating, though with enhanced elongation at break. Solid-state NMR spectroscopy revealed the formation of a thicker quasi-liquid layer (QLL) on the surface of coatings containing hydrophobic HBDs, which was further confirmed by low-temperature ATR-FTIR analysis. Moreover, these coatings exhibited modified frost formation patterns, leading to increased resistance to frost buildup over multiple cycles. Ice adhesion strength of coatings was examined against accelerated weathering, icing/de-icing cycles, as well. This study presents a novel approach for designing sustainable, high-performance icephobic coatings, emphasizing the potential of DESs as effective ice-responsive components in achieving superior anti-icing and anti-frosting capabilities.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"427 ","pages":"Article 127389"},"PeriodicalIF":5.3,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143637532","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

Lignin nanoparticles as sustainable stabilizers for pickering emulsions

IF 5.3 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2025-03-14 DOI: 10.1016/j.molliq.2025.127393

Joslaine Jacumazo, Lilian Fernanda Martins do Amaral, Pierina Alexandra Martinez Huamani, Natalia Mello da Silva, Natalia Brasil Posselt Costa, Rilton Alves de Freitas

Lignin is an abundant aromatic biopolymer known for its low toxicity, biodegradability, and renewable sourcing. In this manuscript, lignin was processed into nanoparticles to exploit its emulsifying potential. The antisolvent precipitation method was used to synthesize lignin nanoparticles (LigNPs), which were characterized for their size, morphology, stability, and cytotoxicity. The chemical structure of lignin was confirmed through HSQC-NMR, revealing no significant changes after fractionation. LigNPs exhibited colloidal stability over 90 days, maintaining stable apparent hydrodynamic diameters and negative zeta potentials, indicating stability due to electrostatic repulsion. Macroscopic and microscopic analyses confirmed their effectiveness in stabilizing emulsions, with densely packed interfaces at higher nanoparticles concentrations (0.100 % w v⁻¹). The addition of salt destabilized the emulsions, highlighting the role of electrostatic interactions in stabilization. Confocal microscopy revealed complete particle coverage at the oil droplet interface, forming a stable barrier against coalescence. The emulsions exhibited promising long-term stability, minimal creaming, and good biocompatibility. These findings underscore the potential of LigNPs as cost-effective, eco-friendly alternatives in various industries, including pharmaceuticals, cosmetics, and food, supporting lignin valorization within a circular economy framework.

{"title":"Lignin nanoparticles as sustainable stabilizers for pickering emulsions","authors":"Joslaine Jacumazo, Lilian Fernanda Martins do Amaral, Pierina Alexandra Martinez Huamani, Natalia Mello da Silva, Natalia Brasil Posselt Costa, Rilton Alves de Freitas","doi":"10.1016/j.molliq.2025.127393","DOIUrl":"10.1016/j.molliq.2025.127393","url":null,"abstract":"<div><div>Lignin is an abundant aromatic biopolymer known for its low toxicity, biodegradability, and renewable sourcing. In this manuscript, lignin was processed into nanoparticles to exploit its emulsifying potential. The antisolvent precipitation method was used to synthesize lignin nanoparticles (LigNPs), which were characterized for their size, morphology, stability, and cytotoxicity. The chemical structure of lignin was confirmed through HSQC-NMR, revealing no significant changes after fractionation. LigNPs exhibited colloidal stability over 90 days, maintaining stable apparent hydrodynamic diameters and negative zeta potentials, indicating stability due to electrostatic repulsion. Macroscopic and microscopic analyses confirmed their effectiveness in stabilizing emulsions, with densely packed interfaces at higher nanoparticles concentrations (0.100 % w v<sup>−1</sup>). The addition of salt destabilized the emulsions, highlighting the role of electrostatic interactions in stabilization. Confocal microscopy revealed complete particle coverage at the oil droplet interface, forming a stable barrier against coalescence. The emulsions exhibited promising long-term stability, minimal creaming, and good biocompatibility. These findings underscore the potential of LigNPs as cost-effective, eco-friendly alternatives in various industries, including pharmaceuticals, cosmetics, and food, supporting lignin valorization within a circular economy framework.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"427 ","pages":"Article 127393"},"PeriodicalIF":5.3,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143643885","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

Faraday effect of imidazole and pyrrolidine and their N-alkyl derivatives

IF 5.3 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2025-03-14 DOI: 10.1016/j.molliq.2025.127398

Marceli Koralewski, Małgorzata Paprzycka, Mikołaj Baranowski

Ionic liquids (ILs) are of great interest because of their spectacular physicochemical properties and applications. Recent research suggests the possible application of magnetic ILs (MILs) in photonics. That fact motivated us to start with magnetooptical (MO) studies on the precursor compounds of most known ILs based on imidazolium and pyrrolidinium cations to gain information allowed tailoring the magnitude of the Faraday effect (FE) in this kind of materials. Herein, we present results of the magnetooptical rotatory dispersion (MORD) and refractive index (RI). The MORD spectrum was described by the Faraday B-terms according to the Serber theory. The respective parameters describing the FE and RI were evaluated and correlated with the position of the experimentally observed optical edge for the compounds studied. The Verdet constant varies very slightly with temperature as expected for diamagnetic materials. Comparison measurements for other precursors of heterocyclic ring compounds of cations of Ils, i.e. pyridine, piperidine, pyrazole, and pyrrole, as well as their methyl derivatives, were also made. The results obtained allow to establish the empirical relation between the Verdet constant and the N-alkyl chain length, as well as the diamagnetic susceptibility and optical polarizability, which were evaluated for studied materials. Comparison of the obtained results with the data for benzene and cyclohexane allowed for the correlation of the V constant with the degree of aromaticity of the studied compounds. RI was also correlated with the N-alkyl chain length. The developed relations will be useful for designing new MILs and tailoring their MO properties.

{"title":"Faraday effect of imidazole and pyrrolidine and their N-alkyl derivatives","authors":"Marceli Koralewski, Małgorzata Paprzycka, Mikołaj Baranowski","doi":"10.1016/j.molliq.2025.127398","DOIUrl":"10.1016/j.molliq.2025.127398","url":null,"abstract":"<div><div>Ionic liquids (ILs) are of great interest because of their spectacular physicochemical properties and applications. Recent research suggests the possible application of magnetic ILs (MILs) in photonics. That fact motivated us to start with magnetooptical (MO) studies on the precursor compounds of most known ILs based on imidazolium and pyrrolidinium cations to gain information allowed tailoring the magnitude of the Faraday effect (FE) in this kind of materials. Herein, we present results of the magnetooptical rotatory dispersion (MORD) and refractive index (RI). The MORD spectrum was described by the Faraday B-terms according to the Serber theory. The respective parameters describing the FE and RI were evaluated and correlated with the position of the experimentally observed optical edge for the compounds studied. The Verdet constant varies very slightly with temperature as expected for diamagnetic materials. Comparison measurements for other precursors of heterocyclic ring compounds of cations of Ils, i.e. pyridine, piperidine, pyrazole, and pyrrole, as well as their methyl derivatives, were also made. The results obtained allow to establish the empirical relation between the Verdet constant and the N-alkyl chain length, as well as the diamagnetic susceptibility and optical polarizability, which were evaluated for studied materials. Comparison of the obtained results with the data for benzene and cyclohexane allowed for the correlation of the V constant with the degree of aromaticity of the studied compounds. RI was also correlated with the N-alkyl chain length. The developed relations will be useful for designing new MILs and tailoring their MO properties.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"427 ","pages":"Article 127398"},"PeriodicalIF":5.3,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143643976","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

Correlation of thermochemical and spectral characteristics as a method for determining the type of binding of porphyrins to nucleic acids

IF 5.3 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2025-03-14 DOI: 10.1016/j.molliq.2025.127387

Sabir S. Guseinov, Elena S. Yurina, Natalya Sh. Lebedeva

The work is devoted to the analysis and generalization of the thermochemical and spectral characteristics of complexes of porphyrins with synthetic oligonucleotides poly[d(AT)₂], poly[d(GC)₂] and calf thymus DNA of solutions, studied in our laboratory. The interactions of nucleic acids (NA) with cationic porphyrins containing indole (PorIn), caffeine (PorCofe), adenine (PorAd) and guanine (PorGu) residues as substituents were studied by spectrophotometric titration. The calorimetric method was used for measuring the temperature dependences of the heat capacity of solutions of cationic porphyrins, NA, as well as complexes. A correlation relationship was obtained for the temperature dependence of the specific heat capacity of NA-porphyrin-buffer. It was found that there is a correlation between the heat capacity of solutions of the complexes at 25 °C, the ratio of hypochromic effect to the shift of the maximum of absorption of the band Sore and the way of binding of NA to cationic porphyrins. Spectral methods for recording changes in the photophysical properties of chromophore ligands made it possible in most cases to reveal the mechanism of binding of porphyrins to NA. Thermochemical studies provided the evaluation of the structural consequences of the complexation process and clarification of the method of porphyrins binding to NA. The perspectives of joint application of the results of thermochemical and spectral studies to elucidate the structural aspects of the formation of complexes NA-porphyrin are discussed in this paper.

{"title":"Correlation of thermochemical and spectral characteristics as a method for determining the type of binding of porphyrins to nucleic acids","authors":"Sabir S. Guseinov, Elena S. Yurina, Natalya Sh. Lebedeva","doi":"10.1016/j.molliq.2025.127387","DOIUrl":"10.1016/j.molliq.2025.127387","url":null,"abstract":"<div><div>The work is devoted to the analysis and generalization of the thermochemical and spectral characteristics of complexes of porphyrins with synthetic oligonucleotides poly[d(AT)<sub>2</sub>], poly[d(GC)<sub>2</sub>] and calf thymus DNA of solutions, studied in our laboratory. The interactions of nucleic acids (NA) with cationic porphyrins containing indole (PorIn), caffeine (PorCofe), adenine (PorAd) and guanine (PorGu) residues as substituents were studied by spectrophotometric titration. The calorimetric method was used for measuring the temperature dependences of the heat capacity of solutions of cationic porphyrins, NA, as well as complexes. A correlation relationship was obtained for the temperature dependence of the specific heat capacity of NA-porphyrin-buffer. It was found that there is a correlation between the heat capacity of solutions of the complexes at 25 °C, the ratio of hypochromic effect to the shift of the maximum of absorption of the band Sore and the way of binding of NA to cationic porphyrins. Spectral methods for recording changes in the photophysical properties of chromophore ligands made it possible in most cases to reveal the mechanism of binding of porphyrins to NA. Thermochemical studies provided the evaluation of the structural consequences of the complexation process and clarification of the method of porphyrins binding to NA. The perspectives of joint application of the results of thermochemical and spectral studies to elucidate the structural aspects of the formation of complexes NA-porphyrin are discussed in this paper.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"426 ","pages":"Article 127387"},"PeriodicalIF":5.3,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143629353","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

NaCl solution crystallization progress on graphene surface induced by cation-π interaction

IF 5.3 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2025-03-13 DOI: 10.1016/j.molliq.2025.127395

Xiaohu Zhang, Guosheng Shi, Xing Liu

By using molecular dynamics simulations, we researched the NaCl solution crystallization progress with different concentrations on the graphene surface and found that the ions will quickly be adsorbed to the graphene surface due to the cation-π interaction between Na⁺ and graphene, accompanied by ion dehydration and electrostatic interaction between positive and negative ions, the small cluster formed. Gradually the smaller clusters gather to form the bigger two-dimensional crystal on the graphene surface, rather than forming the three-dimensional bulk-like NaCl crystal without the cation-π interaction. As the increase of concentration, the size of clusters increases, but the morphology remains the same. Moreover, the abnormal NaCl stoichiometric ratio crystal appears during the crystallization progress in the two-dimensional clusters, especially at lower concentrations. The number of abnormal NaCl clusters increases significantly as the concentration decreases from 2.7 M to 1.0 M. The normal Na-Cl ratio is predominant when the concentration approaches saturation levels. This work is beneficial to understanding the crystallization process from the molecular level and helps design new material development and valuable resource recovery and utilization.

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引用次数: 0

Progress in the design of molecular structure of amino acid corrosion inhibitors based on molecular orbital theory and their mechanisms: A review

IF 5.3 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2025-03-13 DOI: 10.1016/j.molliq.2025.127374

Xin Sun , Hongxiang Xu , Yijun Cao , Jiushuai Deng , Yuntao Kang , Jingzheng Wang , Jiahua Cui

With the growing emphasis on green chemistry and sustainability, environmentally friendly corrosion inhibitors have gained significant interest. Amino acids, due to their natural origin and strong interactions with metal surfaces via amino and carboxyl groups, are promising alternatives. They offer superior corrosion inhibition efficiency (90%–95% vs. 70%–85%), higher biodegradability (80%–95% vs. 30%–50%), and cost-effectiveness compared to traditional inhibitors. Additionally, they perform well across a broad pH range (3–11) and at elevated temperatures. This review summarizes recent advances in amino acid-based corrosion inhibitors, highlighting their advantages, limitations, structural modifications, and insights from DFT and molecular simulations.

引用次数: 0

Proton-transfer reaction thermodynamics in highly concentrated electrolytes for advanced aqueous lithium-ion batteries

IF 5.3 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2025-03-13 DOI: 10.1016/j.molliq.2025.127388

Ryo Kanzaki , Tomoya Hidaka , Hitoshi Kodamatani , Takashi Tomiyasu , Kenta Fujii

We have studied proton-transfer reactions in highly concentrated aqueous electrolytes focusing on lithium bis(trifluoromethanesulfonyl)amide (LiTf₂N) for potential applications in advanced aqueous lithium-ion batteries. In 20 mol kg⁻¹ LiTf₂N aqueous solution, the autoprotolysis constant pK_W increased significantly to 16.2, indicating a reduction in ionization compared to bulk water (pK_W = 14 at infinite dilution), and the H⁺ concentration is lower than in dilute aqueous solutions. This was mainly attributed to the increase in the activity coefficient of H⁺ (γ_H) with increasing LiTf₂N concentration. Calorimetric measurements revealed that the increase in pK_W is driven by an increase in the autoprotolysis enthalpy, suggesting that H⁺ is enthalpically unfavorable in concentrated LiTf₂N solutions. In contrast, the autoprotolysis entropy showed no significant contribution to the pK_W variation. We extended this study to the acid-base reaction of acetic acid as a model system in highly concentrated electrolyte solutions. The pK_a value of acetic acid (or the corresponding ionization Gibbs energy) showed little dependence on the LiTf₂N concentration. In contrast, the corresponding ionization enthalpy and entropy increased significantly with increasing LiTf₂N concentration. Due to the enthalpy–entropy compensation effect, the pK_a value resulted in limited variation even under highly concentrated conditions. The obtained enthalpy values for the ionization processes support that proton carriers lie in an enthalpically unstable state. These findings provide new insights into the fundamental behavior of protons in highly concentrated aqueous electrolytes, which is critical for the design and optimization of aqueous lithium-ion batteries and other electrochemical systems.

{"title":"Proton-transfer reaction thermodynamics in highly concentrated electrolytes for advanced aqueous lithium-ion batteries","authors":"Ryo Kanzaki , Tomoya Hidaka , Hitoshi Kodamatani , Takashi Tomiyasu , Kenta Fujii","doi":"10.1016/j.molliq.2025.127388","DOIUrl":"10.1016/j.molliq.2025.127388","url":null,"abstract":"<div><div>We have studied proton-transfer reactions in highly concentrated aqueous electrolytes focusing on lithium bis(trifluoromethanesulfonyl)amide (LiTf<sub>2</sub>N) for potential applications in advanced aqueous lithium-ion batteries. In 20 mol kg<sup>−1</sup> LiTf<sub>2</sub>N aqueous solution, the autoprotolysis constant p<em>K</em><sub>W</sub> increased significantly to 16.2, indicating a reduction in ionization compared to bulk water (p<em>K</em><sub>W</sub> = 14 at infinite dilution), and the H<sup>+</sup> concentration is lower than in dilute aqueous solutions. This was mainly attributed to the increase in the activity coefficient of H<sup>+</sup> (<em>γ</em><sub>H</sub>) with increasing LiTf<sub>2</sub>N concentration. Calorimetric measurements revealed that the increase in p<em>K</em><sub>W</sub> is driven by an increase in the autoprotolysis enthalpy, suggesting that H<sup>+</sup> is enthalpically unfavorable in concentrated LiTf<sub>2</sub>N solutions. In contrast, the autoprotolysis entropy showed no significant contribution to the p<em>K</em><sub>W</sub> variation. We extended this study to the acid-base reaction of acetic acid as a model system in highly concentrated electrolyte solutions. The p<em>K</em><sub>a</sub> value of acetic acid (or the corresponding ionization Gibbs energy) showed little dependence on the LiTf<sub>2</sub>N concentration. In contrast, the corresponding ionization enthalpy and entropy increased significantly with increasing LiTf<sub>2</sub>N concentration. Due to the enthalpy–entropy compensation effect, the p<em>K</em><sub>a</sub> value resulted in limited variation even under highly concentrated conditions. The obtained enthalpy values for the ionization processes support that proton carriers lie in an enthalpically unstable state. These findings provide new insights into the fundamental behavior of protons in highly concentrated aqueous electrolytes, which is critical for the design and optimization of aqueous lithium-ion batteries and other electrochemical systems.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"427 ","pages":"Article 127388"},"PeriodicalIF":5.3,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143643975","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