Pub Date : 2025-03-10DOI: 10.1016/j.molliq.2025.127357
Jacobo Troncoso
Aqueous solutions of the fully miscible monohydric alcohols, namely, methanol, ethanol, 1-propanol, 2-propanol and tert-butanol are studied using a calorimeter able to work at pressures as high as 450 MPa. Heat capacities of the solutions are determined from the experiments. Apparent heat capacity is calculated from these data. The sharp enhancement of this quantity at low concentrations, typical of amphiphiles such as alcohols, is analyzed against pressure and temperature. Solid-liquid phase equilibria are detected at high pressure for the heaviest alcohols. Remarkably, strong increments in the melting temperature, as compared with those found for atmospheric pressure, are found for solutions at 450 MPa. The results are discussed in terms of the interactions between water and alcohols and the role that hydrophobicity plays in these solutions.
{"title":"Calorimetric analysis of aqueous alcohol solutions up to 450 MPa","authors":"Jacobo Troncoso","doi":"10.1016/j.molliq.2025.127357","DOIUrl":"10.1016/j.molliq.2025.127357","url":null,"abstract":"<div><div>Aqueous solutions of the fully miscible monohydric alcohols, namely, methanol, ethanol, 1-propanol, 2-propanol and <em>tert</em>-butanol are studied using a calorimeter able to work at pressures as high as 450 MPa. Heat capacities of the solutions are determined from the experiments. Apparent heat capacity is calculated from these data. The sharp enhancement of this quantity at low concentrations, typical of amphiphiles such as alcohols, is analyzed against pressure and temperature. Solid-liquid phase equilibria are detected at high pressure for the heaviest alcohols. Remarkably, strong increments in the melting temperature, as compared with those found for atmospheric pressure, are found for solutions at 450 MPa. The results are discussed in terms of the interactions between water and alcohols and the role that hydrophobicity plays in these solutions.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"426 ","pages":"Article 127357"},"PeriodicalIF":5.3,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143628991","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}
The study of self-propelled motion in soft matter systems has garnered significant interest owing to its potential applications in microfluidics, soft robotics, and autonomous system design. Understanding the molecular mechanisms underlying motility is crucial for advancing these applications. This study investigates the self-propelled motion of lauronitrile oil droplets in aqueous surfactant solutions, focusing on the impact of different surfactant molecular structures on droplet dynamics. This study compares surfactants with ester and amide linkages, highlighting their critical role in modulating interfacial tension and driving Marangoni convection, a key factor behind droplet movement. Surfactants with ester linkages exhibit a high affinity for lauronitrile and rapidly adsorb at the oil–water interface, generating strong Marangoni flows and driving fast droplet motion. In contrast, amide-containing surfactants exhibit slower adsorption and weaker interactions with lauronitrile, leading to reduced or absent motion. These findings provide new insights into the molecular mechanisms underlying the self-propelled droplet behavior in non-equilibrium systems and contribute to a deeper understanding of self-organizing phenomena.
{"title":"Molecular insights into the motion of oil droplets in aqueous solutions of ester- and amide-containing cationic surfactants","authors":"Kazuki Ueno , Yuuki Ishiwatari , Ken Sasaki , Tomoya Kojima , Atsuro Takai , Kouichi Asakura , Noriyoshi Arai , Taisuke Banno","doi":"10.1016/j.molliq.2025.127352","DOIUrl":"10.1016/j.molliq.2025.127352","url":null,"abstract":"<div><div>The study of self-propelled motion in soft matter systems has garnered significant interest owing to its potential applications in microfluidics, soft robotics, and autonomous system design. Understanding the molecular mechanisms underlying motility is crucial for advancing these applications. This study investigates the self-propelled motion of lauronitrile oil droplets in aqueous surfactant solutions, focusing on the impact of different surfactant molecular structures on droplet dynamics. This study compares surfactants with ester and amide linkages, highlighting their critical role in modulating interfacial tension and driving Marangoni convection, a key factor behind droplet movement. Surfactants with ester linkages exhibit a high affinity for lauronitrile and rapidly adsorb at the oil–water interface, generating strong Marangoni flows and driving fast droplet motion. In contrast, amide-containing surfactants exhibit slower adsorption and weaker interactions with lauronitrile, leading to reduced or absent motion. These findings provide new insights into the molecular mechanisms underlying the self-propelled droplet behavior in non-equilibrium systems and contribute to a deeper understanding of self-organizing phenomena.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"426 ","pages":"Article 127352"},"PeriodicalIF":5.3,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143628990","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 : 2025-03-10DOI: 10.1016/j.molliq.2025.127316
Nicolás Espitia-Galindo , Glenn Hefter , Edgar F. Vargas
Understanding supramolecular chemistry requires comprehensive knowledge of macrocycle behaviour in solution. This study reports standard molar volumes and compressibilities of the chloride salts of two cationic macrocycles C-methylresorcin[4]arene-tetraminoethylated-hydrochloride (TAE⋅(HCl)4) and their C-ethyl analogue (ETAM⋅(HCl)4) in aqueous and DMSO solutions. These quantities were obtained using density and speed of sound measurements at concentrations (0.005 to 0.08) mol⋅kg−1 and temperatures in the range (278.15 to 308.15) K. NMR techniques were used to study the structures of the macrocycles in solution, while the corresponding compounds were characterised using mass spectrometry, thermogravimetry and differential scanning calorimetry. The partial molar quantities derived from the volumetric and sonometric data are discussed, along with relevant literature information, in terms of solute–solvent interactions. Structural modifications of macrocycles influence the standard molar compressibilities through changes in solvent organization around functional groups, intrinsic compressibility, and water molecules in the resorcinarene cavity. The effect of carbon chain length on the volumes and compressibilities of substituted resorcin[4]arenes is shown to depend on their location in the macrocycle, but not on the solvent. The standard molar volume is shown to be influenced by ionic moieties and intramolecular hydrogen bonds.
{"title":"Volumetric and sonometric properties of ionic aminated resorcin[4]arenes in water and DMSO at 278.15 K to 303.15 K","authors":"Nicolás Espitia-Galindo , Glenn Hefter , Edgar F. Vargas","doi":"10.1016/j.molliq.2025.127316","DOIUrl":"10.1016/j.molliq.2025.127316","url":null,"abstract":"<div><div>Understanding supramolecular chemistry requires comprehensive knowledge of macrocycle behaviour in solution. This study reports standard molar volumes and compressibilities of the chloride salts of two cationic macrocycles C-methylresorcin[4]arene-tetraminoethylated-hydrochloride (TAE⋅(HCl)<sub>4</sub>) and their C-ethyl analogue (ETAM⋅(HCl)<sub>4</sub>) in aqueous and DMSO solutions. These quantities were obtained using density and speed of sound measurements at concentrations (0.005 to 0.08) mol⋅kg<sup>−1</sup> and temperatures in the range (278.15 to 308.15) K. NMR techniques were used to study the structures of the macrocycles in solution, while the corresponding compounds were characterised using mass spectrometry, thermogravimetry and differential scanning calorimetry. The partial molar quantities derived from the volumetric and sonometric data are discussed, along with relevant literature information, in terms of solute–solvent interactions. Structural modifications of macrocycles influence the standard molar compressibilities through changes in solvent organization around functional groups, intrinsic compressibility, and water molecules in the resorcinarene cavity. The effect of carbon chain length on the volumes and compressibilities of substituted resorcin[4]arenes is shown to depend on their location in the macrocycle, but not on the solvent. The standard molar volume is shown to be influenced by ionic moieties and intramolecular hydrogen bonds.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"427 ","pages":"Article 127316"},"PeriodicalIF":5.3,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143637385","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 : 2025-03-10DOI: 10.1016/j.molliq.2025.127350
Kaiping Tian , Guiqiang Fei , Siying Li , Yuanhong Han , Chen Wang , Qingyuan Chen , Wanfen Pu , Muming Wang
The challenges of difficult injection and low recovery in low-permeability reservoirs significantly impact production efficiency. Nanofluid flooding presents a viable approach to improve to enhance recovery in such reservoirs. In this study, an amphiphilic J nano-BaTiO3 particle (JNB-P) with a particle size of 50–90 nm was synthesized. Characterization results indicated that, compared to unmodified Nano BaTiO3 particles, the JNB-P molecules introduced long-chain groups, leading to improved dispersion and a transition of the particle surface from hydrophilic to amphiphilic. Settling experiments identified the optimal dispersive nanofluid (JNB-FS) as a combination of 0.25 % PEG400 and 0.025 % JNB-P, with complete settling time for nanoparticles decreased as temperature or salinity increased. Emulsification experiments demonstrated that, at a water-to-oil volume ratio of 5:5, JNB-FS and crude oil successfully emulsified into an O/W emulsion with an average particle size of 0.791 μm. Interfacial tension experiments revealed that the interfacial tension of oil–water decreased by more than 50 times after adding JNB-FS. Furthermore, with increasing temperature, the degree of emulsification initially increased before decreasing, while emulsion stability, interfacial tension, and expansion modulus gradually decreased. As salinity increased, the degree of emulsification and emulsion stability declined, with interfacial tension first decreasing and then increasing, and the expansion modulus initially rising before falling. Wetting improvement experiments indicated that the core transitioned from lipophilicity to strong hydrophilicity after soaking in JNB-FS for 60 h. Finally, flow experiments demonstrated that compared to first water flooding, the oil recovery increased by 15.82 %. The oil displacement mechanism of JNB-FS primarily involved reducing interfacial tension, enhancing rock wettability, emulsification, and improving the permeability of the injected water via nanoparticles.
{"title":"Preparation of an amphiphilic BaTiO3 nanofluids and its application to oil displacement in low-permeability reservoirs","authors":"Kaiping Tian , Guiqiang Fei , Siying Li , Yuanhong Han , Chen Wang , Qingyuan Chen , Wanfen Pu , Muming Wang","doi":"10.1016/j.molliq.2025.127350","DOIUrl":"10.1016/j.molliq.2025.127350","url":null,"abstract":"<div><div>The challenges of difficult injection and low recovery in low-permeability reservoirs significantly impact production efficiency. Nanofluid flooding presents a viable approach to improve to enhance recovery in such reservoirs. In this study, an amphiphilic J nano-BaTiO<sub>3</sub> particle (JNB-P) with a particle size of 50–90 nm was synthesized. Characterization results indicated that, compared to unmodified Nano BaTiO<sub>3</sub> particles, the JNB-P molecules introduced long-chain groups, leading to improved dispersion and a transition of the particle surface from hydrophilic to amphiphilic. Settling experiments identified the optimal dispersive nanofluid (JNB-FS) as a combination of 0.25 % PEG400 and 0.025 % JNB-P, with complete settling time for nanoparticles decreased as temperature or salinity increased. Emulsification experiments demonstrated that, at a water-to-oil volume ratio of 5:5, JNB-FS and crude oil successfully emulsified into an O/W emulsion with an average particle size of 0.791 μm. Interfacial tension experiments revealed that the interfacial tension of oil–water decreased by more than 50 times after adding JNB-FS. Furthermore, with increasing temperature, the degree of emulsification initially increased before decreasing, while emulsion stability, interfacial tension, and expansion modulus gradually decreased. As salinity increased, the degree of emulsification and emulsion stability declined, with interfacial tension first decreasing and then increasing, and the expansion modulus initially rising before falling. Wetting improvement experiments indicated that the core transitioned from lipophilicity to strong hydrophilicity after soaking in JNB-FS for 60 h. Finally, flow experiments demonstrated that compared to first water flooding, the oil recovery increased by 15.82 %. The oil displacement mechanism of JNB-FS primarily involved reducing interfacial tension, enhancing rock wettability, emulsification, and improving the permeability of the injected water via nanoparticles.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"426 ","pages":"Article 127350"},"PeriodicalIF":5.3,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143610113","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 imperative issue for achieving good photothermal therapy is to strengthen the photothermal effect of the photosensitizer. Therefore, the rolling circle amplification (RCA) chain generated by the rolling circle amplification reaction was used to induce the self-assembly of gold nanorods (AuNRs) after attaching multiple AS1411 aptamers to form one-dimensional arrays of AuNRs. Due to the presence of multivalent aptamers and AuNRs, RCsL1Au can be utilized for fluorescent imaging and photothermal therapy specifically targeting cancer cells. Due to plasma-plasma interactions between AuNRs, the absorption peak of one-dimensional (1D) self-assembled RCsL1Au at a wavelength of 808 nm is increased compared to AuNRs and L1-AuNRs, and the temperature is nearly 10℃ higher. The maximum temperature increase in the RCsL1Au system corresponded to the highest yield achieved at this specific ratio (1:10). Compared to monovalent aptamers, RCsL1Au with multivalent aptamers exhibits an approximately 57-fold enhancement in its cancer cell targeting efficacy. Additionally, the study demonstrated that incorporating doxorubicin (DOX) into RCsL1Au to create RCsL1Au@DOX has a more pronounced impact on synergistic therapy, resulting in a cancer cell killing rate of up to 70 %. This combined therapeutic platform of enhanced photothermal therapy with precise targeting provides new ideas for cancer detection and photothermal therapy.
Novelty Statement
In this study, we designed a multivalent spatially activatable nanoplatform (MA-NV@DOX-Cas13a) based on rolling circle reactions (RCA) for and imaging and treatment of melanoma cells. The nanoplatform not only has good specificity and sensitivity in recognizing target cells but also can inhibit and kill target cancer cells. It has application value in cancer cell detection and treatment.
{"title":"Rolling circle amplification-Induced Self-Assembly of gold nanorods to form One-Dimensional arrays Equipped ‘Multi-Locator’ for fluorescence imaging and enhancement photothermal tumor therapy","authors":"Huan Du, Fang Wang, Ruyan Zhang, Yaxin Jing, Yishuo Chang, Liqian Wang, Ting Zhou, Xiufeng Wang, Guodong Zhang, Zhiqing Zhang","doi":"10.1016/j.molliq.2025.127317","DOIUrl":"10.1016/j.molliq.2025.127317","url":null,"abstract":"<div><div>An imperative issue for achieving good photothermal therapy is to strengthen the photothermal effect of the photosensitizer. Therefore, the rolling circle amplification (RCA) chain generated by the rolling circle amplification reaction was used to induce the self-assembly of gold nanorods (AuNRs) after attaching multiple AS1411 aptamers to form one-dimensional arrays of AuNRs. Due to the presence of multivalent aptamers and AuNRs, RCsL<sub>1</sub>Au can be utilized for fluorescent imaging and photothermal therapy specifically targeting cancer cells. Due to plasma-plasma interactions between AuNRs, the absorption peak of one-dimensional (1D) self-assembled RCsL<sub>1</sub>Au at a wavelength of 808 nm is increased compared to AuNRs and L<sub>1</sub>-AuNRs, and the temperature is nearly 10℃ higher. The maximum temperature increase in the RCsL<sub>1</sub>Au system corresponded to the highest yield achieved at this specific ratio (1:10). Compared to monovalent aptamers, RCsL<sub>1</sub>Au with multivalent aptamers exhibits an approximately 57-fold enhancement in its cancer cell targeting efficacy. Additionally, the study demonstrated that incorporating doxorubicin (DOX) into RCsL<sub>1</sub>Au to create RCsL<sub>1</sub>Au@DOX has a more pronounced impact on synergistic therapy, resulting in a cancer cell killing rate of up to 70 %. This combined therapeutic platform of enhanced photothermal therapy with precise targeting provides new ideas for cancer detection and photothermal therapy.</div></div><div><h3>Novelty Statement</h3><div>In this study, we designed a multivalent spatially activatable nanoplatform (MA-NV@DOX-Cas13a) based on rolling circle reactions (RCA) for and imaging and treatment of melanoma cells. The nanoplatform not only has good specificity and sensitivity in recognizing target cells but also can inhibit and kill target cancer cells. It has application value in cancer cell detection and treatment.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"426 ","pages":"Article 127317"},"PeriodicalIF":5.3,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143609956","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 : 2025-03-10DOI: 10.1016/j.molliq.2025.127328
Elena Buratti , Silvia Franco , Giulia Di Gregorio , Francesca Ripanti , Valentina Nigro , Monica Bertoldo , Roberta Angelini , Paolo Postorino , Barbara Ruzicka
Microgels based on poly(N-isopropylacrylamide) (PNIPAM) and poly(acrylic acid) (PAAc) were synthesized following two different procedures: random copolymerization of the two monomers, where a single network P(NIPAM-co-AAc) microgel is obtained made of the two repeating units, and polymer interpenetration that provides two separate polymer networks within a single microgel structure (PNIPAM-PAAc IPN). We demonstrate that the synthesis procedure has a profound impact on the resulting microgels as shown by investigating swelling, flow and thermal properties as well as the molecular mechanisms driving the microgel behaviour. To this purpose, a systematic study through Dynamic Light Scattering, Rheology, Calorimetry and Raman spectroscopy has been performed at different temperatures, pH values, and concentrations. The direct comparison between P(NIPAM-co-AAc) and IPN microgels at same PAAc content, same temperatures, and pH values shows a reduced or even absent temperature responsiveness of the microgel in the first case and a Volume Phase Transition, with a pH dependent swelling ratio, in the second one. The mutual interference or independence of PNIPAM and PAAc reflects in the different properties of copolymerized or interpenetrated microgels as deeply addressed in this work.
{"title":"Copolymer vs interpenetrated polymer network microgels: The case of poly(N-isopropylacrylamide) and poly(acrylic acid)","authors":"Elena Buratti , Silvia Franco , Giulia Di Gregorio , Francesca Ripanti , Valentina Nigro , Monica Bertoldo , Roberta Angelini , Paolo Postorino , Barbara Ruzicka","doi":"10.1016/j.molliq.2025.127328","DOIUrl":"10.1016/j.molliq.2025.127328","url":null,"abstract":"<div><div>Microgels based on poly(N-isopropylacrylamide) (PNIPAM) and poly(acrylic acid) (PAAc) were synthesized following two different procedures: random copolymerization of the two monomers, where a single network P(NIPAM-<em>co</em>-AAc) microgel is obtained made of the two repeating units, and polymer interpenetration that provides two separate polymer networks within a single microgel structure (PNIPAM-PAAc IPN). We demonstrate that the synthesis procedure has a profound impact on the resulting microgels as shown by investigating swelling, flow and thermal properties as well as the molecular mechanisms driving the microgel behaviour. To this purpose, a systematic study through Dynamic Light Scattering, Rheology, Calorimetry and Raman spectroscopy has been performed at different temperatures, pH values, and concentrations. The direct comparison between P(NIPAM-<em>co</em>-AAc) and IPN microgels at same PAAc content, same temperatures, and pH values shows a reduced or even absent temperature responsiveness of the microgel in the first case and a Volume Phase Transition, with a pH dependent swelling ratio, in the second one. The mutual interference or independence of PNIPAM and PAAc reflects in the different properties of copolymerized or interpenetrated microgels as deeply addressed in this work.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"427 ","pages":"Article 127328"},"PeriodicalIF":5.3,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143637582","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}
Hydroxyapatite (HA), a crucial biomaterial for bone repair and tissue engineering, exhibits properties highly influenced by its crystal morphology. The hydrothermal synthesis of HA usually involves alcohols such as methanol (MeOH), ethanol (EtOH), and isopropanol (iPrOH) to control the reaction environment. Currently, a prediction model that explains the alcohol-induced morphology transformation in HA is still lacking. In this study, we introduce the modified attachment energy (AE) model to predict the HA morphology in alcohol-water solvents. We optimize model parameters by analyzing the crystal structure and intermolecular interactions of HA. Through a detailed study of predicted morphology, surface-solvent interfaces, radial distribution functions, and coordination numbers, we reveal that as the alcohol content increases, the aspect ratio of the crystal morphology decreases. This trend can be attributed to alcohol molecules gradually replacing water molecules in the solvation shell, altering the interaction energy between the crystal face and the solvent. As a result, the relative growth rates of the crystal faces are modified. Notably, iPrOH has a more pronounced effect on reducing the aspect ratio compared to MeOH and EtOH, which benefits from its unique molecular structure and adsorption conformation. This work expands the application of the AE model to complex ionic crystals, enriching the theoretical foundation for the morphology control of HA and providing valuable insights into alcohol-induced morphology transformation.
羟基磷灰石（HA）是骨修复和组织工程的重要生物材料，其特性受晶体形态的影响很大。HA 的水热合成通常使用甲醇 (MeOH)、乙醇 (EtOH) 和异丙醇 (iPrOH) 等醇类来控制反应环境。目前，还缺乏一种预测模型来解释酒精诱导的 HA 形态转变。在本研究中，我们引入了改进的附着能（AE）模型来预测 HA 在水醇溶剂中的形态。我们通过分析 HA 的晶体结构和分子间相互作用来优化模型参数。通过对预测形态、表面-溶剂界面、径向分布函数和配位数的详细研究，我们发现随着酒精含量的增加，晶体形态的长宽比会减小。这一趋势可归因于醇分子逐渐取代了溶壳中的水分子，从而改变了晶面与溶剂之间的相互作用能。因此，晶面的相对生长率发生了变化。值得注意的是，与 MeOH 和 EtOH 相比，iPrOH 在降低长宽比方面的效果更为明显，这得益于其独特的分子结构和吸附构象。这项工作拓展了 AE 模型在复杂离子晶体中的应用，丰富了 HA 形态控制的理论基础，并为酒精诱导的形态转变提供了宝贵的见解。
{"title":"Understanding the morphology transformation of hydrothermally prepared hydroxyapatite via attachment energy model","authors":"Lingling Dong , Jia Fu , Xiaoxue Weng , Antian Xu , Hongxi Peng , Chen Zhuang","doi":"10.1016/j.molliq.2025.127340","DOIUrl":"10.1016/j.molliq.2025.127340","url":null,"abstract":"<div><div>Hydroxyapatite (HA), a crucial biomaterial for bone repair and tissue engineering, exhibits properties highly influenced by its crystal morphology. The hydrothermal synthesis of HA usually involves alcohols such as methanol (MeOH), ethanol (EtOH), and isopropanol (iPrOH) to control the reaction environment. Currently, a prediction model that explains the alcohol-induced morphology transformation in HA is still lacking. In this study, we introduce the modified attachment energy (AE) model to predict the HA morphology in alcohol-water solvents. We optimize model parameters by analyzing the crystal structure and intermolecular interactions of HA. Through a detailed study of predicted morphology, surface-solvent interfaces, radial distribution functions, and coordination numbers, we reveal that as the alcohol content increases, the aspect ratio of the crystal morphology decreases. This trend can be attributed to alcohol molecules gradually replacing water molecules in the solvation shell, altering the interaction energy between the crystal face and the solvent. As a result, the relative growth rates of the crystal faces are modified. Notably, iPrOH has a more pronounced effect on reducing the aspect ratio compared to MeOH and EtOH, which benefits from its unique molecular structure and adsorption conformation. This work expands the application of the AE model to complex ionic crystals, enriching the theoretical foundation for the morphology control of HA and providing valuable insights into alcohol-induced morphology transformation.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"427 ","pages":"Article 127340"},"PeriodicalIF":5.3,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143643891","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 : 2025-03-10DOI: 10.1016/j.molliq.2025.127333
Faezeh Mirshafiee, Mehran Rezaei
The study aimed to investigate the esterification reaction of sunflower oil with methanol using K2O/M-aluminate nanocatalysts (M = Mg, Zn, Cu) and compare its performance with pure K2O nanoparticles. A heterogeneous K2O/M-aluminate nanocatalyst was synthesized through the mechanochemical-impregnation method. The properties of the catalysts were identified using XRD, FESEM, EDX, and the BET methods. The accuracy of each catalyst’s synthesis was verified, followed by analyzing biodiesel success production and conversion measurement using 1H NMR spectroscopy. Benefiting from the higher surface area (17.82 ), pore volume (0.062 ), and good dispersion of K2O nanoparticles over the aluminate-based support, the highest conversion (93 %) and yield (94 %) in biodiesel production were achieved using the K2O/Zn-aluminate catalyst under specific operational conditions. These conditions included a reaction temperature of 70 °C, a reaction time of 3 h, a methanol-to-oil ratio of 1:16, and a catalyst amount of 1 wt%. Furthermore, the catalyst’s potential for reusability was investigated, and the results showed that it could be used at least four times with a little reduction in the yield.
{"title":"Catalytic efficiency and reusability of K2O/M-aluminate (M = Mg, Zn, Cu) nanocatalyst in the esterification of sunflower oil with methanol for biodiesel production","authors":"Faezeh Mirshafiee, Mehran Rezaei","doi":"10.1016/j.molliq.2025.127333","DOIUrl":"10.1016/j.molliq.2025.127333","url":null,"abstract":"<div><div>The study aimed to investigate the esterification reaction of sunflower oil with methanol using K<sub>2</sub>O/M-aluminate nanocatalysts (M = Mg, Zn, Cu) and compare its performance with pure K<sub>2</sub>O nanoparticles. A heterogeneous K<sub>2</sub>O/M-aluminate nanocatalyst was synthesized through the mechanochemical-impregnation method. The properties of the catalysts were identified using XRD, FESEM, EDX, and the BET methods. The accuracy of each catalyst’s synthesis was verified, followed by analyzing biodiesel success production and conversion measurement using <sup>1</sup>H NMR spectroscopy. Benefiting from the higher surface area (17.82 <span><math><mfrac><msup><mrow><mi>m</mi></mrow><mn>2</mn></msup><mi>g</mi></mfrac></math></span>), pore volume (0.062 <span><math><mfrac><mrow><mi>mL</mi></mrow><mi>g</mi></mfrac></math></span>), and good dispersion of K<sub>2</sub>O nanoparticles over the aluminate-based support, the highest conversion (93 %) and yield (94 %) in biodiesel production were achieved using the K<sub>2</sub>O/Zn-aluminate catalyst under specific operational conditions. These conditions included a reaction temperature of 70 °C, a reaction time of 3 h, a methanol-to-oil ratio of 1:16, and a catalyst amount of 1 wt%. Furthermore, the catalyst’s potential for reusability was investigated, and the results showed that it could be used at least four times with a little reduction in the yield.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"426 ","pages":"Article 127333"},"PeriodicalIF":5.3,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143620921","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 : 2025-03-10DOI: 10.1016/j.molliq.2025.127331
Younes Dehmani , Omayma Bouzekri , Taibi Lamhasni , Imane Aadnan , Sadik Abouarnadasse , Eder C. Lima
Volatile organic compounds (VOCs) are critical gaseous air pollutants attracting increasing attention. Isopropanol, recognized as a hazardous pollutant, has been studied for its potential use in removing this contaminant through various methods. Among these approaches, catalytic oxidation stands out as an effective technique that avoids secondary contamination from isopropanol degradation products. This review discusses isopropanol catalytic oxidation, considering the medium, catalysts, and factors influencing the various processes. The benefits of precipitation, oxygen addition, and water usage are notably highlighted. Furthermore, the progress and performance of several families of catalysts, particularly noble and transition metals, are presented individually. Finally, the catalytic oxidation of isopropanol in a mixture with other VOCs is also examined. The primary aim of this review is to investigate the isopropanol catalytic oxidation process using novel composites and evaluate their effectiveness.
{"title":"Catalytic oxidation of isopropanol: A critical review","authors":"Younes Dehmani , Omayma Bouzekri , Taibi Lamhasni , Imane Aadnan , Sadik Abouarnadasse , Eder C. Lima","doi":"10.1016/j.molliq.2025.127331","DOIUrl":"10.1016/j.molliq.2025.127331","url":null,"abstract":"<div><div>Volatile organic compounds (VOCs) are critical gaseous air pollutants attracting increasing attention. Isopropanol, recognized as a hazardous pollutant, has been studied for its potential use in removing this contaminant through various methods. Among these approaches, catalytic oxidation stands out as an effective technique that avoids secondary contamination from isopropanol degradation products. This review discusses isopropanol catalytic oxidation, considering the medium, catalysts, and factors influencing the various processes. The benefits of precipitation, oxygen addition, and water usage are notably highlighted. Furthermore, the progress and performance of several families of catalysts, particularly noble and transition metals, are presented individually. Finally, the catalytic oxidation of isopropanol in a mixture with other VOCs is also examined. The primary aim of this review is to investigate the isopropanol catalytic oxidation process using novel composites and evaluate their effectiveness.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"426 ","pages":"Article 127331"},"PeriodicalIF":5.3,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143620914","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 : 2025-03-09DOI: 10.1016/j.molliq.2025.127341
Qiang Chen , Jian Qin , Yuexia Huang , Xiao Liu , Pingxia Guo , Meirong Cai , Feng Zhou
Two dodecane-substituted saturated and unsaturated imidazolium-based ionic liquids (ILs) with symmetric structure ([IM1212][Doss], [sIM1212][Doss]) were prepared, characterized and evaluated as potential neat lubricants and lubricating additives for PAO2. The results suggested that hydrogenating the imidazolium ring to afford the saturated IL [sIM1212][Doss] not only improved its thermostability (292 vs 253.2°C), but also improved its anti-friction, wear protection properties at high temperature (175°C). Notably, both of them could be dissolved in the synthetic oil polyalphaolefin PAO2, and exhibited good tribological performances as lubricating additives. The lubricating mechanism analysis results indicated that the unique lubricating properties benefited from the tribofilm formed via complex tribological reactions between lubricants and steel surfaces.
{"title":"Dodecane-substituted saturated and unsaturated imidazolium-based ionic liquids: Investigated as potential lubricants and lubricating additives","authors":"Qiang Chen , Jian Qin , Yuexia Huang , Xiao Liu , Pingxia Guo , Meirong Cai , Feng Zhou","doi":"10.1016/j.molliq.2025.127341","DOIUrl":"10.1016/j.molliq.2025.127341","url":null,"abstract":"<div><div>Two dodecane-substituted saturated and unsaturated imidazolium-based ionic liquids (ILs) with symmetric structure ([IM<sub>1212</sub>][Doss], [<em>s</em>IM<sub>1212</sub>][Doss]) were prepared, characterized and evaluated as potential neat lubricants and lubricating additives for PAO2. The results suggested that hydrogenating the imidazolium ring to afford the saturated IL [<em>s</em>IM<sub>1212</sub>][Doss] not only improved its thermostability (292 vs 253.2°C), but also improved its anti-friction, wear protection properties at high temperature (175°C). Notably, both of them could be dissolved in the synthetic oil polyalphaolefin PAO2, and exhibited good tribological performances as lubricating additives. The lubricating mechanism analysis results indicated that the unique lubricating properties benefited from the tribofilm formed via complex tribological reactions between lubricants and steel surfaces.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"426 ","pages":"Article 127341"},"PeriodicalIF":5.3,"publicationDate":"2025-03-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143610423","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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