Pub Date : 2025-04-19DOI: 10.1016/j.molliq.2025.127628
Swathi Thottathil , Yashoda Malgar Puttaiahgowda , Raja Selvaraj , Jayasree G. Elambalassery , Ramesh Vinayagam , Thivaharan Varadavenkatesan
Water pollution has become a widespread issue for both the environment and human health. The need for novel materials that can function as both adsorbent and disinfectant in wastewater treatment is vital. In this work, the porous organic polymer such as a triazine-based adsorbent (CC-ODA POP) was developed by the reaction among cyanuric chloride and 4,4′-oxydianiline. CC-ODA POP features a moderate surface area and a tunable porous structure, with a maximum adsorption capacity of 149 mg/g and 103 mg/g for Acid Blue 113 (AB 113) and Congo Red (CR) respectively. The adsorption of AB 113 and CR onto CC-ODA POP was effectively described by the Langmuir isotherm and pseudo-second-order kinetic models. The mechanism involves electrostatic attractions and hydrogen bonding and exhibits good recyclability. The interactions involving the polymer and dye molecules were explained using DFT studies based on the various quantum parameters, electrostatic potential diagram, and binding energy values. The calculated adsorption or complexation energy is more favorable for AB 113 (−19.68 kcal/mol) than CR (−18.17 kcal/mol). The CC-ODA POP demonstrated a disinfection efficiency of 99.64 % against E. coli. This triazine-based adsorbent, characterized by its high adsorption efficiency, excellent disinfection capabilities, and recyclability, holds significant potential for practical applications in wastewater treatment.
{"title":"Experimental and DFT studies of Congo red and AB 113 dyes removal by adsorption and disinfection using novel triazine-based porous organic polymer","authors":"Swathi Thottathil , Yashoda Malgar Puttaiahgowda , Raja Selvaraj , Jayasree G. Elambalassery , Ramesh Vinayagam , Thivaharan Varadavenkatesan","doi":"10.1016/j.molliq.2025.127628","DOIUrl":"10.1016/j.molliq.2025.127628","url":null,"abstract":"<div><div>Water pollution has become a widespread issue for both the environment and human health. The need for novel materials that can function as both adsorbent and disinfectant in wastewater treatment is vital. In this work, the porous organic polymer such as a triazine-based adsorbent (CC-ODA POP) was developed by the reaction among cyanuric chloride and 4,4′-oxydianiline. CC-ODA POP features a moderate surface area and a tunable porous structure, with a maximum adsorption capacity of 149 mg/g and 103 mg/g for Acid Blue 113 (AB 113) and Congo Red (CR) respectively. The adsorption of AB 113 and CR onto CC-ODA POP was effectively described by the Langmuir isotherm and pseudo-second-order kinetic models. The mechanism involves electrostatic attractions and hydrogen bonding and exhibits good recyclability. The interactions involving the polymer and dye molecules were explained using DFT studies based on the various quantum parameters, electrostatic potential diagram, and binding energy values. The calculated adsorption or complexation energy is more favorable for AB 113 (−19.68 kcal/mol) than CR (−18.17 kcal/mol). The CC-ODA POP demonstrated a disinfection efficiency of 99.64 % against <em>E. coli</em>. This triazine-based adsorbent, characterized by its high adsorption efficiency, excellent disinfection capabilities, and recyclability, holds significant potential for practical applications in wastewater treatment.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"429 ","pages":"Article 127628"},"PeriodicalIF":5.3,"publicationDate":"2025-04-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143856076","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 : 2025-04-19DOI: 10.1016/j.molliq.2025.127620
Zakaria Hafidi , María Teresa García , Ramon Pons , Francisco Fábio Oliveira de Sousa , María Elena Bautista , Sergio Vázquez , Lourdes Pérez
Antimicrobial resistance (AR) has become a global threat to public health systems and biofilm development plays a key role in this issue; it is estimated that 80 % of microbial infections in humans are caused by biofilms. So, there is an urgent need to explore efficient broad-spectrum antimicrobial compounds that can prevent and eradicate biofilms. In this work, we propose the use of simple, economical, and low molecular weight amino acid-based surfactants to fight against AR. These compounds consist of one amino acid (phenylalanine or tryptophan) linked through an amide bond to one C8–C14 alkyl chain. Surface tension measurements and SAXS analysis show the formation of prolate ellipsoidal micelles at low critical micelle concentration (CMC around 0.2–11 mM). These compounds exhibit antifungal activity against a broad-spectrum Candida strain, with the C14 derivatives being the most efficient agents with MIC values of 16–32 µM. They can disrupt mature C. albicans biofilms at very low concentrations, and the long-chain derivatives can easily condense DNA. Interestingly, these surfactants exhibited lower aquatic toxicity and better biodegradability than the widely used quaternary ammonium cationic surfactants (QACS). This is an important property given that non-biodegradable compounds lead to persistence in the environment, increasing the proliferation of antimicrobial resistance. The results obtained in this work allow for establishing a structure–activity relationship that can help in designing new biodegradable and biocompatible antimicrobial surfactants. Moreover, given their biological and physicochemical properties, these surfactants can be an interesting alternative to the existing antimicrobials for medical and industrial applications.
{"title":"Green cationic phenylalanine and tryptophan-based surfactants: Influence of the polar head amino acids and hydrophobic character on the self-aggregation, antimicrobial activity, and environmental behavior","authors":"Zakaria Hafidi , María Teresa García , Ramon Pons , Francisco Fábio Oliveira de Sousa , María Elena Bautista , Sergio Vázquez , Lourdes Pérez","doi":"10.1016/j.molliq.2025.127620","DOIUrl":"10.1016/j.molliq.2025.127620","url":null,"abstract":"<div><div>Antimicrobial resistance (AR) has become a global threat to public health systems and biofilm development plays a key role in this issue; it is estimated that 80 % of microbial infections in humans are caused by biofilms. So, there is an urgent need to explore efficient broad-spectrum antimicrobial compounds that can prevent and eradicate biofilms. In this work, we propose the use of simple, economical, and low molecular weight amino acid-based surfactants to fight against AR. These compounds consist of one amino acid (phenylalanine or tryptophan) linked through an amide bond to one C<sub>8</sub>–C<sub>14</sub> alkyl chain. Surface tension measurements and SAXS analysis show the formation of prolate ellipsoidal micelles at low critical micelle concentration (CMC around 0.2–11 mM). These compounds exhibit antifungal activity against a broad-spectrum Candida strain, with the C<sub>14</sub> derivatives being the most efficient agents with MIC values of 16–32 µM. They can disrupt mature <em>C. albicans</em> biofilms at very low concentrations, and the long-chain derivatives can easily condense DNA. Interestingly, these surfactants exhibited lower aquatic toxicity and better biodegradability than the widely used quaternary ammonium cationic surfactants (QAC<sub>S</sub>). This is an important property given that non-biodegradable compounds lead to persistence in the environment, increasing the proliferation of antimicrobial resistance. The results obtained in this work allow for establishing a structure–activity relationship that can help in designing new biodegradable and biocompatible antimicrobial surfactants. Moreover, given their biological and physicochemical properties, these surfactants can be an interesting alternative to the existing antimicrobials for medical and industrial applications.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"429 ","pages":"Article 127620"},"PeriodicalIF":5.3,"publicationDate":"2025-04-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143869420","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 : 2025-04-19DOI: 10.1016/j.molliq.2025.127601
Somaye Ghasemy, Alireza Fattahi
Ionic liquids (ILs) are a remarkable compound class consisting entirely of ions (cations and anions) with a melting point below 100 °C. In ILs, the cation’s positive charge and the anion’s negative charge are distributed through induction and resonance effects. This distribution reduces attraction between ion pairs and balances the energy between them, facilitating the formation of an IL. In this work, we designed the ILs containing the natural anions and cations. In the designed ILs, the anions contain various amino acids and sugars, and the cation contains methylated DNA base adenine. Our study has focused on intramolecular hydrogen bonding (H-bond) within the anion and intermolecular H-bond between methylated adenine cation and the various anions. Our objective in creating these structures is to investigate H-bonds’ influence on the negative charge distribution in the anion and to explore the anomeric effect on the stability of the cation in the designed ILs. In particular, using quantum mechanics (QM) calculations, we examined how intermolecular H-bonds affect the interaction energy between the ions in our newly designed ILs. At the same time, molecular dynamics (MD) simulations were utilized to validate the QM results. The QM average interaction energy (ΔEint) between the anion and cation of the designed ILs is −73.39 kcal/mol, consistent with the ΔEint typically reported for the common ILs. This approach may lead to developing more efficient and environmentally friendly ILs for various applications.
{"title":"Design and characterization of novel ionic liquids (ILs) containing natural compounds such as tryptophan, fructose, and adenine; the ILs stabilized via H-bonds and anomeric effect","authors":"Somaye Ghasemy, Alireza Fattahi","doi":"10.1016/j.molliq.2025.127601","DOIUrl":"10.1016/j.molliq.2025.127601","url":null,"abstract":"<div><div>Ionic liquids (ILs) are a remarkable compound class consisting entirely of ions (cations and anions) with a melting point below 100 °C. In ILs, the cation’s positive charge and the anion’s negative charge are distributed through induction and resonance effects. This distribution reduces attraction between ion pairs and balances the energy between them, facilitating the formation of an IL. In this work, we designed the ILs containing the natural anions and cations. In the designed ILs, the anions contain various amino acids and sugars, and the cation contains methylated DNA base adenine. Our study has focused on intramolecular hydrogen bonding (H-bond) within the anion and intermolecular H-bond between methylated adenine cation and the various anions. Our objective in creating these structures is to investigate H-bonds’ influence on the negative charge distribution in the anion and to explore the anomeric effect on the stability of the cation in the designed ILs. In particular, using quantum mechanics (QM) calculations, we examined how intermolecular H-bonds affect the interaction energy between the ions in our newly designed ILs. At the same time, molecular dynamics (MD) simulations were utilized to validate the QM results. The QM average interaction energy (Δ<em>E<sub>int</sub></em>) between the anion and cation of the designed ILs is −73.39 kcal/mol, consistent with the Δ<em>E<sub>int</sub></em> typically reported for the common ILs. This approach may lead to developing more efficient and environmentally friendly ILs for various applications.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"429 ","pages":"Article 127601"},"PeriodicalIF":5.3,"publicationDate":"2025-04-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143847649","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 : 2025-04-19DOI: 10.1016/j.molliq.2025.127570
Sadegh Salimi , Gholamreza Motalleb , Hossein Dehghani , Abbas Rahdar , Kazem Dastjerdi , Brenda Velasco , Pablo Taboada
This work examined whether co-administration of tamoxifen (TAM) and Fe3O4@SiO2@Cu hybrid NPs to MCF-7 cancer cells may have an impact in cell cytotoxicity by increasing IC50 and apoptosis. NPs were produced using an electrochemical process and showed a negative surface charge (−35 ± 2 mV) and average hydrodynamic diameter and particle size of ca. 83 ± 1 nm and 60 ± 4 nm as derived from dynamic light scattering and electron microscopy images, respectively, and being colloidally stable in physiological conditions to long term. The particles were also shown to be non-toxic to cells in a wide range of concentrations. Notably, the co-administration of TAM (15 μg/mL) with Fe3O4@SiO2@Cu nanocomposite (125 μg/mL) significantly reduced the IC50 of TAM from 15.1 μg/mL to 7.8 μg/mL (P < 000.1) after 72 h of incubation. Moreover, alterations in p53, MDM2, and MDM4 gene expressions were determined using quantitative reverse-transcriptase polymerase chain reaction (qRT-PCR) directly related to the cell-death apoptotic pathway. The expression level of p53 increased 2.1 times upon the co-administration of TAM with Fe3O4@SiO2@Cu NPs nanoparticles compared with untreated MCF-7 cancer cells as the control group (P < 0.001); conversely, expression of MDM2 and MDM4 genes were 2.6 and 2.9 times lower compared to control cancerous cells (P < 0.001). On the other hand, fluorescence microscopy analysis showed that co-administration of TAM (15 µg/mL) with Fe3O4@SiO2@Cu NPs (125 µg/mL) caused cell nuclei to break up. This was accompanied by changes in the cell shape, which proved that the nanoparticle-drug combination was highly cytostatic. Therefore, TAM co-administrated with Fe3O4@SiO2@Cu NPs could be a promising and possible way to deliver TAM in breast cancer chemotherapy and enhanced its therapeutic effect.
{"title":"Anticancer effect of tamoxifen and Fe3O4@SiO2@Cu hybrid NPs on malignant human breast cancer cell (MCF-7)","authors":"Sadegh Salimi , Gholamreza Motalleb , Hossein Dehghani , Abbas Rahdar , Kazem Dastjerdi , Brenda Velasco , Pablo Taboada","doi":"10.1016/j.molliq.2025.127570","DOIUrl":"10.1016/j.molliq.2025.127570","url":null,"abstract":"<div><div>This work examined whether co-administration of tamoxifen (TAM) and Fe<sub>3</sub>O<sub>4</sub>@SiO<sub>2</sub>@Cu hybrid NPs to MCF-7 cancer cells may have an impact in cell cytotoxicity by increasing IC<sub>50</sub> and apoptosis. NPs were produced using an electrochemical process and showed a negative surface charge (−35 ± 2 mV) and average hydrodynamic diameter and particle size of ca. 83 ± 1 nm and 60 ± 4 nm as derived from dynamic light scattering and electron microscopy images, respectively, and being colloidally stable in physiological conditions to long term. The particles were also shown to be non-toxic to cells in a wide range of concentrations. Notably, the co-administration of TAM (15 μg/mL) with Fe<sub>3</sub>O<sub>4</sub>@SiO<sub>2</sub>@Cu nanocomposite (125 μg/mL) significantly reduced the IC<sub>50</sub> of TAM from 15.1 μg/mL to 7.8 μg/mL (P < 000.1) after 72 h of incubation. Moreover, alterations in <em>p53</em>, <em>MDM2</em>, and <em>MDM4</em> gene expressions were determined using quantitative reverse-transcriptase polymerase chain reaction (qRT-PCR) directly related to the cell-death apoptotic pathway. The expression level of <em>p53</em> increased 2.1 times upon the co-administration of TAM with Fe<sub>3</sub>O<sub>4</sub>@SiO<sub>2</sub>@Cu NPs nanoparticles compared with untreated MCF-7 cancer cells as the control group (P < 0.001); conversely, expression of <em>MDM2</em> and <em>MDM4</em> genes were 2.6 and 2.9 times lower compared to control cancerous cells (P < 0.001). On the other hand, fluorescence microscopy analysis showed that co-administration of TAM (15 µg/mL) with Fe<sub>3</sub>O<sub>4</sub>@SiO<sub>2</sub>@Cu NPs (125 µg/mL) caused cell nuclei to break up. This was accompanied by changes in the cell shape, which proved that the nanoparticle-drug combination was highly cytostatic. Therefore, TAM co-administrated with Fe<sub>3</sub>O<sub>4</sub>@SiO<sub>2</sub>@Cu NPs could be a promising and possible way to deliver TAM in breast cancer chemotherapy and enhanced its therapeutic effect.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"429 ","pages":"Article 127570"},"PeriodicalIF":5.3,"publicationDate":"2025-04-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143869422","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 : 2025-04-19DOI: 10.1016/j.molliq.2025.127626
Usma Manzoor, Ishfaq Ahmad Ahanger, Tanveer Ali Dar
Compelling evidence of co-existence of oxidative stress and altered osmolyte levels, particularly the amino acid derivatives, emphasizes the importance of accumulation of these stress protectant molecules. In this context, the present study investigated the impact of three key amino acid derivative osmolytes – taurine, N-acetylcysteine (NAC), and N-acetylaspartate (NAA) – on the catalytic activity, structural integrity, stability and aggregation propensity of catalase, an important antioxidant enzyme. Results obtained in kientic studies revealed a concentration-dependent decrease in the catalytic activity of catalase in the presence of these osmolytes, with NAC exhibiting the most significant reduction in kinetic parameters. Structural studies revealed that all the three osmolytes induced alterations in the tertiary and secondary structure of catalase with increased β-sheet and β-turn content leading to enhanced aggregation propensity, transmission electron microscopy results confirmed the presence of catalase aggregates in the osmolyte-treated samples of catalase. Collectively, our results suggest that taurine, NAC, and NAA reduced catalase activity with distorted structure while promoting aggregation, providing new insights into the modulatory effects of amino acid derivative osmolytes on the structure-function integrity and stability of antioxdiant enyzme, catalase. The observed results might have implications for understanding the role of metabolite osmolyte in the mechanistics of oxidative stress-related diseases and other protein aggregation disorders.
{"title":"Impact of amino acid derivative osmolytes on structure-function integrity and aggregation propensity of catalase: Implications for inefficient antioxidant defense in protein aggregation disorders","authors":"Usma Manzoor, Ishfaq Ahmad Ahanger, Tanveer Ali Dar","doi":"10.1016/j.molliq.2025.127626","DOIUrl":"10.1016/j.molliq.2025.127626","url":null,"abstract":"<div><div>Compelling evidence of co-existence of oxidative stress and altered osmolyte levels, particularly the amino acid derivatives, emphasizes the importance of accumulation of these stress protectant molecules. In this context, the present study investigated the impact of three key amino acid derivative osmolytes – taurine, N-acetylcysteine (NAC), and N-acetylaspartate (NAA) – on the catalytic activity, structural integrity, stability and aggregation propensity of catalase, an important antioxidant enzyme. Results obtained in kientic studies revealed a concentration-dependent decrease in the catalytic activity of catalase in the presence of these osmolytes, with NAC exhibiting the most significant reduction in kinetic parameters. Structural studies revealed that all the three osmolytes induced alterations in the tertiary and secondary structure of catalase with increased β-sheet and β-turn content leading to enhanced aggregation propensity, transmission electron microscopy results confirmed the presence of catalase aggregates in the osmolyte-treated samples of catalase. Collectively, our results suggest that taurine, NAC, and NAA reduced catalase activity with distorted structure while promoting aggregation, providing new insights into the modulatory effects of amino acid derivative osmolytes on the structure-function integrity and stability of antioxdiant enyzme, catalase. The observed results might have implications for understanding the role of metabolite osmolyte in the mechanistics of oxidative stress-related diseases and other protein aggregation disorders.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"429 ","pages":"Article 127626"},"PeriodicalIF":5.3,"publicationDate":"2025-04-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143864866","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}
This review aims to study the overall impact of Deep Eutectic Solvents (DES) and Natural Deep Eutectic Solvents (NADES) on protein structure and function, exploring their effects on solubility, conformational stability, emulsifying properties, spinnability, and thermal stability based on the recently published articles. This structured approach clearly outlines significant findings regarding the impact of DESs and NADES on proteins structure and function with emphasis on their mechanisms. DESs and NADES can significantly influence protein structure through solvent–solute interactions that may stabilize or destabilize proteins depending on their components. Many proteins show enhanced solubility in DESs and NADES due to favorable interactions with the solvent’s hydrogen-bonding network. The effect of DES and NADES on thermal stability varies; while they may not inherently increase stability, they can provide protective environments against denaturation under certain conditions. Enzymes can maintain active in DES and NADES, although optimal conditions vary for each enzyme-substrate pair. There is a promising trend in the use of DES on an industrial scale, and a lot of research is being done for protein purification and separation of DES, as well as reducing extraction time with the help of new techniques to overcome its high viscosity and interfacial mass transfer resistance.
{"title":"Extraction, purification, and functionality of proteins using deep eutectic solvents: a review","authors":"Ali Khanalipour , Mahnaz Tabibiazar , Behzad Masoumi , Solmaz Tabibi Azar , Aylin Allahyari , Maryam Borji","doi":"10.1016/j.molliq.2025.127623","DOIUrl":"10.1016/j.molliq.2025.127623","url":null,"abstract":"<div><div>This review aims to study the overall impact of Deep Eutectic Solvents (DES) and Natural Deep Eutectic Solvents (NADES) on protein structure and function, exploring their effects on solubility, conformational stability, emulsifying properties, spinnability, and thermal stability based on the recently published articles. This structured approach clearly outlines significant findings regarding the impact of DESs and NADES on proteins structure and function with emphasis on their mechanisms. DESs and NADES can significantly influence protein structure through solvent–solute interactions that may stabilize or destabilize proteins depending on their components. Many proteins show enhanced solubility in DESs and NADES due to favorable interactions with the solvent’s hydrogen-bonding network. The effect of DES and NADES on thermal stability varies; while they may not inherently increase stability, they can provide protective environments against denaturation under certain conditions. Enzymes can maintain active in DES and NADES, although optimal conditions vary for each enzyme-substrate pair. There is a promising trend in the use of DES on an industrial scale, and a lot of research is being done for protein purification and separation of DES, as well as reducing extraction time with the help of new techniques to overcome its high viscosity and interfacial mass transfer resistance.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"429 ","pages":"Article 127623"},"PeriodicalIF":5.3,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143852300","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 : 2025-04-18DOI: 10.1016/j.molliq.2025.127588
Aleksei Pochivalov, Iurii Lodianov, Evgenia Safonova, Andrey Bulatov
In this work, a phenomenon of a supramolecular solvent formation from an isotropic solution of ammonium di(2-ethylhexyl)phosphate under electrolyte-induced coacervation by salting-out effect was discovered for the first time. Ammonia was employed as a weak base to obtain the amphiphile in situ from di(2-ethylhexyl)phosphoric acid. The extraction and preconcentration ability of the supramolecular solvent towards amphoteric analytes (fluoroquinolones) was studied in detail. The maximum enrichment factors (19 and 42 for ofloxacin and moxifloxacin, respectively) were obtained in the presence of sodium chloride as a coacervation agent. The proposed extraction mechanism consists mainly of hydrophobic and electrostatic interactions between the analytes and the aggregates. In contrast to the previously reported supramolecular solvent based on di(2-ethylhexyl)phosphoric acid (molecular form), the novel one ensured efficient extraction of amphoteric analytes. The physicochemical properties (water content, pH, density, viscosity) of the supramolecular solvent phase were established. Moreover, microscopic images of coacervates were obtained, and the phase diagram of the ternary system ammonium di(2-ethylhexyl)phosphate-sodium chloride-water was acquired. The novel liquid-phase microextraction approach was successfully applied to the determination of ofloxacin and moxifloxacin in human urine samples by liquid chromatography with fluorescence detection. The limits of detection were established at 3 and 6 μg L−1 for moxifloxacin and ofloxacin, respectively.
{"title":"Ammonium di(2-ethylhexyl)phosphate-based supramolecular solvent formation: Liquid-phase microextraction of fluoroquinolones from human urine followed by liquid chromatography determination","authors":"Aleksei Pochivalov, Iurii Lodianov, Evgenia Safonova, Andrey Bulatov","doi":"10.1016/j.molliq.2025.127588","DOIUrl":"10.1016/j.molliq.2025.127588","url":null,"abstract":"<div><div>In this work, a phenomenon of a supramolecular solvent formation from an isotropic solution of ammonium di(2-ethylhexyl)phosphate under electrolyte-induced coacervation by salting-out effect was discovered for the first time. Ammonia was employed as a weak base to obtain the amphiphile <em>in situ</em> from di(2-ethylhexyl)phosphoric acid. The extraction and preconcentration ability of the supramolecular solvent towards amphoteric analytes (fluoroquinolones) was studied in detail. The maximum enrichment factors (19 and 42 for ofloxacin and moxifloxacin, respectively) were obtained in the presence of sodium chloride as a coacervation agent. The proposed extraction mechanism consists mainly of hydrophobic and electrostatic interactions between the analytes and the aggregates. In contrast to the previously reported supramolecular solvent based on di(2-ethylhexyl)phosphoric acid (molecular form), the novel one ensured efficient extraction of amphoteric analytes. The physicochemical properties (water content, pH, density, viscosity) of the supramolecular solvent phase were established. Moreover, microscopic images of coacervates were obtained, and the phase diagram of the ternary system ammonium di(2-ethylhexyl)phosphate-sodium chloride-water was acquired. The novel liquid-phase microextraction approach was successfully applied to the determination of ofloxacin and moxifloxacin in human urine samples by liquid chromatography with fluorescence detection. The limits of detection were established at 3 and 6 μg L<sup>−1</sup> for moxifloxacin and ofloxacin, respectively.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"429 ","pages":"Article 127588"},"PeriodicalIF":5.3,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143859425","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 : 2025-04-18DOI: 10.1016/j.molliq.2025.127609
Hossein Haghani , Hua Er , Pet Pakchotanon , Hamid Mosaddeghi , Vitaly V. Chaban , Teerawat Sema
The phenomenon of global warming is linked to excessive industry-associated greenhouse gas emissions. Innovative sorbents are expected to foster green technologies, in which no adverse environmental influences are included. We herein report classical molecular dynamics (MD) simulations to evaluate the absorption of carbon dioxide (CO2) and hydrogen sulfide (H2S) by the newly developed deep eutectic solvents (DESs). The novel DESs represent binary mixtures of menthol (MEN) and diamines (hexyl-ethylene-diamine, HEX, and nonyl-ethylene-diamine, NON,). The simulations revealed that both DESs exhibit a higher affinity to CO2 rather than to H2S due to larger partial atomic electrostatic charges on the oxygen atoms. The increase in pressure resulted in a linear boost in the gas capacities of HEX/MEN and NON/MEN. In turn, no synergistic effect was detected while investigating CO2/H2S simultaneous absorption. The performance of HEX/MEN as an absorbent is somewhat higher as compared to that of NON/MEN in the case of H2S and within the computation uncertainty in the case of CO2. The revealed potential of HEX/MEN and NON/MEN to capture CO2 and H2S suggests that novel interesting gas scavengers were identified and comprehensively characterized.
{"title":"Carbon dioxide and hydrogen sulfide capture by menthol-based deep eutectic solvents: Effects of sorbent structure, composition, gas pressure, and gas polarity","authors":"Hossein Haghani , Hua Er , Pet Pakchotanon , Hamid Mosaddeghi , Vitaly V. Chaban , Teerawat Sema","doi":"10.1016/j.molliq.2025.127609","DOIUrl":"10.1016/j.molliq.2025.127609","url":null,"abstract":"<div><div>The phenomenon of global warming is linked to excessive industry-associated greenhouse gas emissions. Innovative sorbents are expected to foster green technologies, in which no adverse environmental influences are included. We herein report classical molecular dynamics (MD) simulations to evaluate the absorption of carbon dioxide (CO<sub>2</sub>) and hydrogen sulfide (H<sub>2</sub>S) by the newly developed deep eutectic solvents (DESs). The novel DESs represent binary mixtures of menthol (MEN) and diamines (hexyl-ethylene-diamine, HEX, and nonyl-ethylene-diamine, NON,). The simulations revealed that both DESs exhibit a higher affinity to CO<sub>2</sub> rather than to H<sub>2</sub>S due to larger partial atomic electrostatic charges on the oxygen atoms. The increase in pressure resulted in a linear boost in the gas capacities of HEX/MEN and NON/MEN. In turn, no synergistic effect was detected while investigating CO<sub>2</sub>/H<sub>2</sub>S simultaneous absorption. The performance of HEX/MEN as an absorbent is somewhat higher as compared to that of NON/MEN in the case of H<sub>2</sub>S and within the computation uncertainty in the case of CO<sub>2</sub>. The revealed potential of HEX/MEN and NON/MEN to capture CO<sub>2</sub> and H<sub>2</sub>S suggests that novel interesting gas scavengers were identified and comprehensively characterized.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"429 ","pages":"Article 127609"},"PeriodicalIF":5.3,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143859427","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}
This work presents the equilibrium solubility, thermodynamic properties, and molecular simulation of thiourea in twelve organic solvents. The results demonstrate that the solubility of thiourea in pure solvents fits well with the modified Apelblat equation, λh equation, Van’t Hoff equation, and the NRTL model, with <5% average relative deviation (ARD) for all the four thermodynamic models. The thermodynamic properties of thiourea found in the selected solvents are analyzed by the NRTL model, indicating that the mixing process of thiourea in organic solvents is spontaneous. To determine the effect of solvent effects on solubility, the physicochemical properties of the twelve organic solvents are examined. To observe the solubility behavior at atomic level, the molecular simulations were investigated via density functional theory (DFT).
{"title":"Solid–liquid solubility behavior of thiourea in twelve organic solvents; solubility experiments, data correlation, solvent analysis, and molecular simulations","authors":"Natthapol Traiwongsa , Natthawan Srinam , Vanee Mohdee , Ura Pancharoen , Wikorn Punyain , Kasidit Nootong","doi":"10.1016/j.molliq.2025.127622","DOIUrl":"10.1016/j.molliq.2025.127622","url":null,"abstract":"<div><div>This work presents the equilibrium solubility, thermodynamic properties, and molecular simulation of thiourea in twelve organic solvents. The results demonstrate that the solubility of thiourea in pure solvents fits well with the modified Apelblat equation, λh equation, Van’t Hoff equation, and the NRTL model, with <5% average relative deviation (ARD) for all the four thermodynamic models. The thermodynamic properties of thiourea found in the selected solvents are analyzed by the NRTL model, indicating that the mixing process of thiourea in organic solvents is spontaneous. To determine the effect of solvent effects on solubility, the physicochemical properties of the twelve organic solvents are examined. To observe the solubility behavior at atomic level, the molecular simulations were investigated via density functional theory (DFT).</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"429 ","pages":"Article 127622"},"PeriodicalIF":5.3,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143852176","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 : 2025-04-18DOI: 10.1016/j.molliq.2025.127610
Qiong He , Hongkun Zhao
Pentoxifylline is a non-selective inhibitor of methylxanthine phosphodiesterase. Thermodynamic behavior along with the solubility of this drug plays a pivotal role in the solvent selection for liquid phase formulation, extraction and purification of pentoxifylline. The aim of the research is to study the solubility and thermodynamic aspects of pentoxifylline in numerous single solvents as well as inspect the solute–solvent interactions using the molecular dynamic simulation and DFT calculations. At atmospheric pressure and temperatures ranging from 278.15 to 318.15 K, this work determined the mole-fraction solubilities of pentoxifylline in ten different alcohols (2-pentanol, methanol, 1-propanol, ethanol, 1-hexanol, 2-butanol, 1-butanol, 1-pentanol, 1-heptanol, 2-propanol), three different esters (n-butyl acetate, n-propyl acetate, ethyl acetate), dimethyl sulfoxide, cyclohexane, and water. Solubility findings demonstrated that higher temperature improved solubility. It dissolved best in n-butyl acetate and worst in cyclohexane. In diverse neat solvents at a temperature of 298.15 K, the solubility data ranked as n-butyl acetate (28.41 × 10−3) > ethyl acetate (21.55 × 10−3) > 1-pentanol (18.95 × 10−3) > n-propyl acetate (16.69 × 10−3) > 1-hexanol (15.11 × 10−3) > DMSO (13.66 × 10−3) > 1-heptanol (13.18 × 10−3) > methanol (11.66 × 10−3) > 1-butanol (10.18 × 10−3) > 2-butanol (9.102 × 10−3) > 1-propanol (8.724 × 10−3) > water (7.422 × 10−3) > 2-propanol (6.057 × 10−3) > ethanol (5.591 × 10−3) > 2-pentanol (4.700 × 10−3) > cyclohexane (0.09895 × 10−3). The solubility in solvent of water was most sensitive to temperature. From T = 278.15 to T = 318.15 K, it rose 76 times, from 0.7420 × 10−3 to 56.32 × 10−3. Next, the data on pentoxifylline solubility in sixteen different solvents were correlated using the following models: NRTL, Wilson, Buchowski-Ksiazaczak λh, and Apelblat. All four models’ fitting results are satisfactory, with the Apelblat equation coming out on superior. 100RAD and 104RMSD values were all less than 7.73 and 1.76, respectively, with the exception of water. Molecular dynamic simulation and intermolecular interactions of pentoxifylline in various solvents were also performed. Finally, the thermodynamic apparent parameters were explored, and the findings showed that the pentoxifylline dissolution in the solvents under study is endothermic, with a stronger entropic driving force than an enthalpy driving force.
{"title":"Pentoxifylline in sixteen pure solvents: Solubility, DFT calculation, and molecular dynamic simulation","authors":"Qiong He , Hongkun Zhao","doi":"10.1016/j.molliq.2025.127610","DOIUrl":"10.1016/j.molliq.2025.127610","url":null,"abstract":"<div><div>Pentoxifylline is a non-selective inhibitor of methylxanthine phosphodiesterase. Thermodynamic behavior along with the solubility of this drug plays a pivotal role in the solvent selection for liquid phase formulation, extraction and purification of pentoxifylline. The aim of the research is to study the solubility and thermodynamic aspects of pentoxifylline in numerous single solvents as well as inspect the solute–solvent interactions using the molecular dynamic simulation and DFT calculations. At atmospheric pressure and temperatures ranging from 278.15 to 318.15 K, this work determined the mole-fraction solubilities of pentoxifylline in ten different alcohols (2-pentanol, methanol, 1-propanol, ethanol, 1-hexanol, 2-butanol, 1-butanol, 1-pentanol, 1-heptanol, 2-propanol), three different esters (<em>n</em>-butyl acetate, <em>n</em>-propyl acetate, ethyl acetate), dimethyl sulfoxide, cyclohexane, and water. Solubility findings demonstrated that higher temperature improved solubility. It dissolved best in <em>n</em>-butyl acetate and worst in cyclohexane. In diverse neat solvents at a temperature of 298.15 K, the solubility data ranked as <em>n</em>-butyl acetate (28.41 × 10<sup>−3</sup>) > ethyl acetate (21.55 × 10<sup>−3</sup>) > 1-pentanol (18.95 × 10<sup>−3</sup>) > <em>n</em>-propyl acetate (16.69 × 10<sup>−3</sup>) > 1-hexanol (15.11 × 10<sup>−3</sup>) > DMSO (13.66 × 10<sup>−3</sup>) > 1-heptanol (13.18 × 10<sup>−3</sup>) > methanol (11.66 × 10<sup>−3</sup>) > 1-butanol (10.18 × 10<sup>−3</sup>) > 2-butanol (9.102 × 10<sup>−3</sup>) > 1-propanol (8.724 × 10<sup>−3</sup>) > water (7.422 × 10<sup>−3</sup>) > 2-propanol (6.057 × 10<sup>−3</sup>) > ethanol (5.591 × 10<sup>−3</sup>) > 2-pentanol (4.700 × 10<sup>−3</sup>) > cyclohexane (0.09895 × 10<sup>−3</sup>). The solubility in solvent of water was most sensitive to temperature. From <em>T</em> = 278.15 to <em>T</em> = 318.15 K, it rose 76 times, from 0.7420 × 10<sup>−3</sup> to 56.32 × 10<sup>−3</sup>. Next, the data on pentoxifylline solubility in sixteen different solvents were correlated using the following models: NRTL, Wilson, Buchowski-Ksiazaczak <em>λh</em>, and Apelblat. All four models’ fitting results are satisfactory, with the Apelblat equation coming out on superior. 100<em>RAD</em> and 10<sup>4</sup><em>RMSD</em> values were all less than 7.73 and 1.76, respectively, with the exception of water. Molecular dynamic simulation and intermolecular interactions of pentoxifylline in various solvents were also performed. Finally, the thermodynamic apparent parameters were explored, and the findings showed that the pentoxifylline dissolution in the solvents under study is endothermic, with a stronger entropic driving force than an enthalpy driving force.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"429 ","pages":"Article 127610"},"PeriodicalIF":5.3,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143856039","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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