Pub Date : 2025-04-15DOI: 10.1021/acs.langmuir.4c05100
Jingwen Luo, Mingshuo Cui, Xiaodong Lian, Bin Yuan, Chenhao Song, Yingchao Ma, Yapei Wang
The multicomponent structure and the large area of oil–water interfaces make multiple emulsions promising for use in cosmetic manufacturing, food industries, and agricultural production. However, the high energy input and extensive use of emulsifiers in the process of multiple emulsion preparation severely limit their application. In this work, we propose a simple but highly efficient emulsification strategy to realize one-step multiple emulsions. To this end, the interfacial acid–base neutralization reaction by oleic acid and ammonia is employed as the driving force to construct a spontaneous emulsifying system, thus realizing emulsion formation in a low-energy manner. Moreover, the products generated by the interfacial neutralization reaction can act as emulsifiers to stabilize both the O/W and W/O interfaces and construct multiple emulsions with an O/W/O structure. Compared to conventional methods of multiple emulsion formation, the one-step multiple emulsion method driven by an interfacial neutralization reaction can significantly reduce the energy consumption and the emulsifier dosage during the emulsifying process, thus avoiding the probable environmental problems caused by the residual emulsifiers. This study not only provides a new idea for the preparation of multiple emulsions but also effectively promotes the development of low-surfactant emulsification methods.
{"title":"One-Step Multiple Emulsions Driven by Interfacial Neutralization Reaction","authors":"Jingwen Luo, Mingshuo Cui, Xiaodong Lian, Bin Yuan, Chenhao Song, Yingchao Ma, Yapei Wang","doi":"10.1021/acs.langmuir.4c05100","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c05100","url":null,"abstract":"The multicomponent structure and the large area of oil–water interfaces make multiple emulsions promising for use in cosmetic manufacturing, food industries, and agricultural production. However, the high energy input and extensive use of emulsifiers in the process of multiple emulsion preparation severely limit their application. In this work, we propose a simple but highly efficient emulsification strategy to realize one-step multiple emulsions. To this end, the interfacial acid–base neutralization reaction by oleic acid and ammonia is employed as the driving force to construct a spontaneous emulsifying system, thus realizing emulsion formation in a low-energy manner. Moreover, the products generated by the interfacial neutralization reaction can act as emulsifiers to stabilize both the O/W and W/O interfaces and construct multiple emulsions with an O/W/O structure. Compared to conventional methods of multiple emulsion formation, the one-step multiple emulsion method driven by an interfacial neutralization reaction can significantly reduce the energy consumption and the emulsifier dosage during the emulsifying process, thus avoiding the probable environmental problems caused by the residual emulsifiers. This study not only provides a new idea for the preparation of multiple emulsions but also effectively promotes the development of low-surfactant emulsification methods.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"2 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837194","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 modulation of self-assembled structures of a surface-active ionic liquid (SAIL), 1-butyl-3-methylimidazolium octyl sulfate [C4mim][C8OSO3], upon their interaction with bovine liver catalase (CAT) enzyme is investigated in this study. The intrinsic fluorescence of tryptophan (Trp) was investigated to monitor the conformational changes in CAT with [C4mim][C8OSO3]. Extrinsic fluorescence of the 8-anilino-1-naphthalenesulfonic acid (ANS) probe was further utilized to determine the structural and conformational changes along with the binding location of [C4mim][C8OSO3] in the enzyme. Fourier transform infrared (FTIR) measurements quantify the secondary structure changes, leading to modulation in the fluorescence characteristics. To elucidate modulation of the self-assembled structures, fluorescence lifetime imaging microscopy (FLIM) measurements were utilized. On adding CAT to an aqueous micellar solution of [C4mim][C8OSO3], there was the appearance of highly fluorescent ring-like structures. The internal structure of these was further investigated using transmission electron microscopy (TEM), where the ring sizes were found to be dependent upon the quantity of enzyme taken. These structures completely collapse and accumulate when the CAT concentration reaches near ∼5–7 μM. Further, the activity of the CAT enzyme was assessed in the presence of [C4mim][C8OSO3] depending upon the premicelle and micelle self-assemblies. Molecular dynamics (MD) simulation study was used to further analyze the binding location of the micelle-forming entity, [C8OSO3], and it was found that the [C8OSO3] species tends to remain at the enzyme active site. The results describe the unique transformation in self-assemblies of a SAIL by enzymatic action that has not been studied so far and opens up the interesting applications of SAIL in biomedical applications.
{"title":"Influence of Bovine Liver Catalase on Self-Assembled Structures of a Surface-Active Ionic Liquid","authors":"Sudhanshu Sharma, Dineshbabu Takkella, Jyoti Vishwakarma, Krishna Gavvala","doi":"10.1021/acs.langmuir.4c05028","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c05028","url":null,"abstract":"The modulation of self-assembled structures of a surface-active ionic liquid (SAIL), 1-butyl-3-methylimidazolium octyl sulfate [C<sub>4</sub>mim][C<sub>8</sub>OSO<sub>3</sub>], upon their interaction with bovine liver catalase (CAT) enzyme is investigated in this study. The intrinsic fluorescence of tryptophan (Trp) was investigated to monitor the conformational changes in CAT with [C<sub>4</sub>mim][C<sub>8</sub>OSO<sub>3</sub>]. Extrinsic fluorescence of the 8-anilino-1-naphthalenesulfonic acid (ANS) probe was further utilized to determine the structural and conformational changes along with the binding location of [C<sub>4</sub>mim][C<sub>8</sub>OSO<sub>3</sub>] in the enzyme. Fourier transform infrared (FTIR) measurements quantify the secondary structure changes, leading to modulation in the fluorescence characteristics. To elucidate modulation of the self-assembled structures, fluorescence lifetime imaging microscopy (FLIM) measurements were utilized. On adding CAT to an aqueous micellar solution of [C<sub>4</sub>mim][C<sub>8</sub>OSO<sub>3</sub>], there was the appearance of highly fluorescent ring-like structures. The internal structure of these was further investigated using transmission electron microscopy (TEM), where the ring sizes were found to be dependent upon the quantity of enzyme taken. These structures completely collapse and accumulate when the CAT concentration reaches near ∼5–7 μM. Further, the activity of the CAT enzyme was assessed in the presence of [C<sub>4</sub>mim][C<sub>8</sub>OSO<sub>3</sub>] depending upon the premicelle and micelle self-assemblies. Molecular dynamics (MD) simulation study was used to further analyze the binding location of the micelle-forming entity, [C<sub>8</sub>OSO<sub>3</sub>], and it was found that the [C<sub>8</sub>OSO<sub>3</sub>] species tends to remain at the enzyme active site. The results describe the unique transformation in self-assemblies of a SAIL by enzymatic action that has not been studied so far and opens up the interesting applications of SAIL in biomedical applications.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"183 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832137","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 : 2025-04-15DOI: 10.1021/acs.langmuir.4c04150
Anna Syguda, Marta Wojcieszak, Sylwia Zięba, Adam Mizera, Andrzej Łapiński, Jacek Różański, Alicja Putowska, Agnieszka Marcinkowska, Adam Grzywaczyk, Ewa Kaczorek, Katarzyna Materna
Amidequats have attracted considerable attention in research; however, their surface activity remains largely unknown, and their potential as emulsifiers is still unexplored. In this work, series of novel surface-active amidequats based on ecofriendly caprylic acid were synthesized and their micellization behavior in water was explored systematically. The surface tension, wettability, foamability and stability, and measurements of melting and crystallization temperatures were employed to characterize the compounds. The functionalization of amidequats containing an alkoxymethyl substituent significantly enhances micellization properties compared to the structurally analogous anionic surfactant, sodium caprylate. Moreover, for optimized molecule geometries, electrical dipole moments were determined and correlated with surface activity. Experimental and theoretical studies indicate that amidequats with 12 carbon atoms in the alkyl chain exhibit the highest surface and foam-forming activity, making them promising emulsifiers. Due to this fact, oil-in-water (o/w) or water-in-oil (w/o) emulsions using the mentioned amidequat were prepared, and their rheological analysis, ζ potential, topography analysis, and particle size were studied. A detailed investigation of the surface properties of amidequats was undertaken to assess their potential application in the cleaning agent and cosmetic industries.
{"title":"Surface-Active Amidequats with an Alkoxymethyl Substituent: Synthesis, Analysis, and Preliminary Evaluation as Potential Emulsifiers and Substitutes for Conventional Surfactants","authors":"Anna Syguda, Marta Wojcieszak, Sylwia Zięba, Adam Mizera, Andrzej Łapiński, Jacek Różański, Alicja Putowska, Agnieszka Marcinkowska, Adam Grzywaczyk, Ewa Kaczorek, Katarzyna Materna","doi":"10.1021/acs.langmuir.4c04150","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c04150","url":null,"abstract":"Amidequats have attracted considerable attention in research; however, their surface activity remains largely unknown, and their potential as emulsifiers is still unexplored. In this work, series of novel surface-active amidequats based on ecofriendly caprylic acid were synthesized and their micellization behavior in water was explored systematically. The surface tension, wettability, foamability and stability, and measurements of melting and crystallization temperatures were employed to characterize the compounds. The functionalization of amidequats containing an alkoxymethyl substituent significantly enhances micellization properties compared to the structurally analogous anionic surfactant, sodium caprylate. Moreover, for optimized molecule geometries, electrical dipole moments were determined and correlated with surface activity. Experimental and theoretical studies indicate that amidequats with 12 carbon atoms in the alkyl chain exhibit the highest surface and foam-forming activity, making them promising emulsifiers. Due to this fact, oil-in-water (o/w) or water-in-oil (w/o) emulsions using the mentioned amidequat were prepared, and their rheological analysis, ζ potential, topography analysis, and particle size were studied. A detailed investigation of the surface properties of amidequats was undertaken to assess their potential application in the cleaning agent and cosmetic industries.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"26 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837011","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 : 2025-04-15DOI: 10.1021/acs.langmuir.4c05249
Thanseeha Sherin P A, Akhil Raman T. S, M.M. Juvaid, Anchal Rana, Sambasivam Sangaraju, Sabyasachi Chakrabortty, Abhimanyu Rana, K. C. James Raju, Siddhartha Ghosh
Reduced graphene oxide (rGO) has captivated the scientific community due to its exceptional electrical conductivity, high specific surface area, and excellent mechanical strength. The physical properties of reduced graphene oxide (rGO) are strongly dependent on the presence of different functional groups in its structural framework, along with surface roughness. In this study, laser annealing was employed by a nanosecond Nd:YAG laser to investigate the impact of varying laser energies on the wettability and conductivity of reduced graphene oxide (rGO) samples grown by the pulsed laser deposition (PLD) technique. The rGO films were annealed with different laser fluences, such as 10, 20, 30, 38, 48, 55, and 250 mJ/cm2. Our results reveal a notable transition in wettability, transforming the initially hydrophobic rGO samples into a hydrophilic state. Hydrophilic graphene oxide (GO) or reduced graphene oxide (rGO) surfaces have significant potential for use in biomedical applications due to their unique combination of properties, including biocompatibility, high surface area, and abundant oxygen-containing functional groups. Along with wettability properties, conductivity changes were also observed. The presented findings not only contribute to the understanding of laser-induced modifications in rGO but also highlight the potential applications of controlled laser annealing in tailoring the surface properties of graphene-based materials for diverse technological advancements.
{"title":"Tuning the Hydrophobicity of Laser-Annealed rGO Thin Films Synthesized by Pulsed Laser Deposition","authors":"Thanseeha Sherin P A, Akhil Raman T. S, M.M. Juvaid, Anchal Rana, Sambasivam Sangaraju, Sabyasachi Chakrabortty, Abhimanyu Rana, K. C. James Raju, Siddhartha Ghosh","doi":"10.1021/acs.langmuir.4c05249","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c05249","url":null,"abstract":"Reduced graphene oxide (rGO) has captivated the scientific community due to its exceptional electrical conductivity, high specific surface area, and excellent mechanical strength. The physical properties of reduced graphene oxide (rGO) are strongly dependent on the presence of different functional groups in its structural framework, along with surface roughness. In this study, laser annealing was employed by a nanosecond Nd:YAG laser to investigate the impact of varying laser energies on the wettability and conductivity of reduced graphene oxide (rGO) samples grown by the pulsed laser deposition (PLD) technique. The rGO films were annealed with different laser fluences, such as 10, 20, 30, 38, 48, 55, and 250 mJ/cm<sup>2</sup>. Our results reveal a notable transition in wettability, transforming the initially hydrophobic rGO samples into a hydrophilic state. Hydrophilic graphene oxide (GO) or reduced graphene oxide (rGO) surfaces have significant potential for use in biomedical applications due to their unique combination of properties, including biocompatibility, high surface area, and abundant oxygen-containing functional groups. Along with wettability properties, conductivity changes were also observed. The presented findings not only contribute to the understanding of laser-induced modifications in rGO but also highlight the potential applications of controlled laser annealing in tailoring the surface properties of graphene-based materials for diverse technological advancements.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"2 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837010","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}
In order to overcome the environmental problems associated with ammonia volatilization during the ammonia leaching process, the leaching effects of copper by amino acids with various numbers and substitution positions of amino functional groups were systematically studied. The results showed that lysine had the best leaching efficiency for copper. When the concentration of lysine was 0.2 mol/L, the leaching temperature was 20 °C, the molar ratio of lysine to copper was 3.88, the stirring speed was 250 rpm, the pH was 10, and the leaching time was 14 h, the leaching rate of copper reached 99%. The leaching results of copper containing smelting slag showed that lysine has an excellent effect on selective leaching of copper. The leaching kinetic results indicated that the rate-limiting step of the leaching process is controlled by the interfacial chemical reaction, with an apparent activation energy of 64.8 kJ/mol. Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS) analyses confirmed that COO– and –NH groups in lysine can form complexes with copper ions. Compared to conventional methods, this approach not only achieves environmentally benign disposal of heavy metal pollutants but also provides a novel strategy for the green recovery of valuable metals from secondary resources.
{"title":"Mechanism and Kinetics for Copper Leaching by Complexing with Lysine Bearing Two Amino Groups","authors":"Mengying Li, Qingliang Wang, Weiduo Guo, Shaobo Zhou, Jinlong Fan, Liping Zhao, Zhen He, Zhiwu Lei, Yahui Zhang","doi":"10.1021/acs.langmuir.4c05274","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c05274","url":null,"abstract":"In order to overcome the environmental problems associated with ammonia volatilization during the ammonia leaching process, the leaching effects of copper by amino acids with various numbers and substitution positions of amino functional groups were systematically studied. The results showed that lysine had the best leaching efficiency for copper. When the concentration of lysine was 0.2 mol/L, the leaching temperature was 20 °C, the molar ratio of lysine to copper was 3.88, the stirring speed was 250 rpm, the pH was 10, and the leaching time was 14 h, the leaching rate of copper reached 99%. The leaching results of copper containing smelting slag showed that lysine has an excellent effect on selective leaching of copper. The leaching kinetic results indicated that the rate-limiting step of the leaching process is controlled by the interfacial chemical reaction, with an apparent activation energy of 64.8 kJ/mol. Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS) analyses confirmed that COO<sup>–</sup> and –NH groups in lysine can form complexes with copper ions. Compared to conventional methods, this approach not only achieves environmentally benign disposal of heavy metal pollutants but also provides a novel strategy for the green recovery of valuable metals from secondary resources.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"108 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837012","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 : 2025-04-15DOI: 10.1021/acs.langmuir.5c00695
Ruiling Jin, Qin Xu, Xiaodong Yang
The low pozzolanic activity of recycled stone powder limits its application in cement-based materials. Calcium silicate hydrate (CSH) is one of the hydration products of cement and also has the function of promoting hydration and improving strength. Therefore, the behavior of CSH in enhancing the activity of stone powder has been studied, including the workability and mechanical properties, and the mechanism of activity enhancement has been explained at the microscopic level. The results showed that when the amount of stone powder was 30%, the setting time was shortened by 26.14% to 34.34%, the slump increased by 7.89%, and the compressive strength at 3 and 28 days decreased by 40.94% and 37.99%, respectively. On this basis, when CSH was added at a dosage of 1%, compared with the specimen with a dosage of 30% stone powder, the setting time was shortened by 18.29% ∼ 21.53%, the slump was increased by 2.44%, and the compressive strength at 3 and 28 d was increased by 15.95% and 16.25%, respectively. The pozzolanic activity of stone powder has increased from 62.00% to 71.82%, reaching the pozzolanic activity level of fly ash. The mechanism of CSH enhancing pozzolanic activity was explained at the micro level, which broadened the application channels for the high-dosage application of stone powder.
{"title":"Hydrated Calcium Silicate (C–S–H) Improves the Performance of Stone Powder as Cement Admixtures","authors":"Ruiling Jin, Qin Xu, Xiaodong Yang","doi":"10.1021/acs.langmuir.5c00695","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c00695","url":null,"abstract":"The low pozzolanic activity of recycled stone powder limits its application in cement-based materials. Calcium silicate hydrate (CSH) is one of the hydration products of cement and also has the function of promoting hydration and improving strength. Therefore, the behavior of CSH in enhancing the activity of stone powder has been studied, including the workability and mechanical properties, and the mechanism of activity enhancement has been explained at the microscopic level. The results showed that when the amount of stone powder was 30%, the setting time was shortened by 26.14% to 34.34%, the slump increased by 7.89%, and the compressive strength at 3 and 28 days decreased by 40.94% and 37.99%, respectively. On this basis, when CSH was added at a dosage of 1%, compared with the specimen with a dosage of 30% stone powder, the setting time was shortened by 18.29% ∼ 21.53%, the slump was increased by 2.44%, and the compressive strength at 3 and 28 d was increased by 15.95% and 16.25%, respectively. The pozzolanic activity of stone powder has increased from 62.00% to 71.82%, reaching the pozzolanic activity level of fly ash. The mechanism of CSH enhancing pozzolanic activity was explained at the micro level, which broadened the application channels for the high-dosage application of stone powder.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"50 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837044","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}
Ionic liquids (ILs), which are commonly referred to as ″green solvents”, are excellent sorbents that can absorb carbon dioxide (CO2) reversibly. ILs are highly attractive solvents for CO2 absorption due to their tunable chemical structures, low vapor pressure, and high thermal stability. Here, we have synthesized three different aliphatic acid-functionalized ionic liquids (AAILs), tetraethylammonium oleate ([N2222][OL]), tetraethylammonium caprylate ([N2222][Cap]), and tetraethylammonium acetate ([N2222][OAc]), and employed the aqueous solutions of these AAILs to absorb CO2 via vapor–liquid equilibrium (VLE) experiments. It has been observed that the CO2 uptake value gradually increases as the chain length of the AAILs increases, which follows the order: [N2222][OAc] < [N2222][Cap] < [N2222][OL]. The carbon capture process is analyzed using turbidity, viscosity, and nuclear magnetic resonance (NMR) spectroscopy studies. The NMR spectra of AAILs before and after CO2 absorption reveal that [N2222][OAc] and [N2222][Cap] mainly absorb CO2 via a physical absorption process, and [N2222][OL] absorbs CO2 through a chemical absorption process. Before and after CO2 capture, the turbidity values of [N2222][OAc] and [N2222][Cap] in the aqueous medium are almost unchanged, whereas the [N2222][OL] aqueous solution turns turbid after CO2 capture, which corroborates the NMR data. The AAILs are highly reversible with regard to the absorption and desorption of CO2, and we can reuse them up to several cycles. The transparent micellar solution of [N2222][OL] transforms into a turbid vesicular solution after capturing CO2. From the steady-state and time-resolved fluorescence studies, we have seen that the emission intensity and the fluorescence lifetime of the hydrophobic dyes are enhanced after CO2 capture by [N2222][OL] because of the increase in the hydrophobicity of the vesicular aggregates compared to the micellar system.
{"title":"Effect of Anion Chain Length on the Reversible Absorption of CO2 by Aliphatic Acid-Based Ionic Liquids and Transition from Micellar to Vesicular Aggregates","authors":"Nanigopal Bera, Puspendu Sardar, Sudheer Tripathi, Pratyush Kiran Nandi, Amar Nath Samanta, Nilmoni Sarkar","doi":"10.1021/acs.langmuir.5c00405","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c00405","url":null,"abstract":"Ionic liquids (ILs), which are commonly referred to as ″green solvents”, are excellent sorbents that can absorb carbon dioxide (CO<sub>2</sub>) reversibly. ILs are highly attractive solvents for CO<sub>2</sub> absorption due to their tunable chemical structures, low vapor pressure, and high thermal stability. Here, we have synthesized three different aliphatic acid-functionalized ionic liquids (AAILs), tetraethylammonium oleate ([N<sub>2222</sub>][OL]), tetraethylammonium caprylate ([N<sub>2222</sub>][Cap]), and tetraethylammonium acetate ([N<sub>2222</sub>][OAc]), and employed the aqueous solutions of these AAILs to absorb CO<sub>2</sub> via vapor–liquid equilibrium (VLE) experiments. It has been observed that the CO<sub>2</sub> uptake value gradually increases as the chain length of the AAILs increases, which follows the order: [N<sub>2222</sub>][OAc] < [N<sub>2222</sub>][Cap] < [N<sub>2222</sub>][OL]. The carbon capture process is analyzed using turbidity, viscosity, and nuclear magnetic resonance (NMR) spectroscopy studies. The NMR spectra of AAILs before and after CO<sub>2</sub> absorption reveal that [N<sub>2222</sub>][OAc] and [N<sub>2222</sub>][Cap] mainly absorb CO<sub>2</sub> via a physical absorption process, and [N<sub>2222</sub>][OL] absorbs CO<sub>2</sub> through a chemical absorption process. Before and after CO<sub>2</sub> capture, the turbidity values of [N<sub>2222</sub>][OAc] and [N<sub>2222</sub>][Cap] in the aqueous medium are almost unchanged, whereas the [N<sub>2222</sub>][OL] aqueous solution turns turbid after CO<sub>2</sub> capture, which corroborates the NMR data. The AAILs are highly reversible with regard to the absorption and desorption of CO<sub>2</sub>, and we can reuse them up to several cycles. The transparent micellar solution of [N<sub>2222</sub>][OL] transforms into a turbid vesicular solution after capturing CO<sub>2</sub>. From the steady-state and time-resolved fluorescence studies, we have seen that the emission intensity and the fluorescence lifetime of the hydrophobic dyes are enhanced after CO<sub>2</sub> capture by [N<sub>2222</sub>][OL] because of the increase in the hydrophobicity of the vesicular aggregates compared to the micellar system.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"10 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832377","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 : 2025-04-15DOI: 10.1021/acs.langmuir.5c00420
Tao Yao, Mingyu Zhang, Dongli Guo, Fen Ran
Nanofiltration membranes have the advantages of high flux and good selectivity, making them ideal materials for solving water resource pollution and scarcity; however, the mechanism of interface polymer membrane wrinkling induced by nanofillers is not clear, and the low flux of interface polymer membranes is a pressing issue for researchers. In this work, superhydrophilic l-histidine-modified nanoparticles are successfully synthesized and added to the interface polymerization process, where the nanoparticles also participate in the interface polymerization reaction, inducing interface polymerization. The formation of layered wrinkles on the membrane surface greatly increases the contact area of the membrane surface and enhances the hydrophilicity. The water contact angle on the membrane surface decreases from the original 51.85 to 28.72°. When the modifier-modified dopamine particles are added at a concentration of 0.1 wt %, the water permeance of the nanofiltration membrane reaches 145.57 L m–2 h–1 MPa–1, with a dye rejection rate of over 99% and high permeability to inorganic salt ions, confirming that the membrane can be used for efficient dye/salt separation. Furthermore, the stability of the membrane is improved, greatly enhancing its practical applicability.
{"title":"Nanofiltration Membrane via Organic Nanoparticle-Assisted Interface Polymerization for Efficient Dye/Salt Separation","authors":"Tao Yao, Mingyu Zhang, Dongli Guo, Fen Ran","doi":"10.1021/acs.langmuir.5c00420","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c00420","url":null,"abstract":"Nanofiltration membranes have the advantages of high flux and good selectivity, making them ideal materials for solving water resource pollution and scarcity; however, the mechanism of interface polymer membrane wrinkling induced by nanofillers is not clear, and the low flux of interface polymer membranes is a pressing issue for researchers. In this work, superhydrophilic <span>l</span>-histidine-modified nanoparticles are successfully synthesized and added to the interface polymerization process, where the nanoparticles also participate in the interface polymerization reaction, inducing interface polymerization. The formation of layered wrinkles on the membrane surface greatly increases the contact area of the membrane surface and enhances the hydrophilicity. The water contact angle on the membrane surface decreases from the original 51.85 to 28.72°. When the modifier-modified dopamine particles are added at a concentration of 0.1 wt %, the water permeance of the nanofiltration membrane reaches 145.57 L m<sup>–2</sup> h<sup>–1</sup> MPa<sup>–1</sup>, with a dye rejection rate of over 99% and high permeability to inorganic salt ions, confirming that the membrane can be used for efficient dye/salt separation. Furthermore, the stability of the membrane is improved, greatly enhancing its practical applicability.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"60 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837196","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}
Two-dimensional (2D) materials have attracted significant attention owing to their exceptional electrical and optical properties. The high-quality monolayer 2D materials are usually fabricated by mechanical exfoliation from bulk single crystals using a scotch tape method, limiting the flake size and production yield. Extensive efforts have been made to increase the production yield and size by using an Au-assisted process, such as the modified mechanical exfoliation method. However, the wet-etching processes are inevitable in the scalable Au-assisted mechanical exfoliation method, which causes defect formation and unintentional contamination, leading to a quality decrease in the monolayer 2D material flakes. Here, we developed a Au-assisted all dry transfer method without any wet process for fabricating 2D materials and their van der Waals (vdW) heterostructures. The developed dry transfer technique using patterned Au substrates and h-BN on polymer stamps gives us a large area and designed shape of monolayer 2D materials and their vdW heterostructures with clean interfaces. It will be beneficial for building high-quality vdW heterostructures, allowing us to explore and develop more potential applications in electrical and optical devices based on monolayer 2D materials.
{"title":"All Dry Transfer Processes Utilizing Au Exfoliation for Predetermined Shapes of Transition Metal Dichalcogenide","authors":"Daiki Murase, Keisuke Shinokita, Yusai Wakafuji, Momoko Onodera, Tomoki Machida, Kenji Watanabe, Takashi Taniguchi, Jianfeng Bi, Zhou Zhou, Sihan Zhao, Kazunari Matsuda","doi":"10.1021/acs.langmuir.4c04629","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c04629","url":null,"abstract":"Two-dimensional (2D) materials have attracted significant attention owing to their exceptional electrical and optical properties. The high-quality monolayer 2D materials are usually fabricated by mechanical exfoliation from bulk single crystals using a scotch tape method, limiting the flake size and production yield. Extensive efforts have been made to increase the production yield and size by using an Au-assisted process, such as the modified mechanical exfoliation method. However, the wet-etching processes are inevitable in the scalable Au-assisted mechanical exfoliation method, which causes defect formation and unintentional contamination, leading to a quality decrease in the monolayer 2D material flakes. Here, we developed a Au-assisted all dry transfer method without any wet process for fabricating 2D materials and their van der Waals (vdW) heterostructures. The developed dry transfer technique using patterned Au substrates and <i>h</i>-BN on polymer stamps gives us a large area and designed shape of monolayer 2D materials and their vdW heterostructures with clean interfaces. It will be beneficial for building high-quality vdW heterostructures, allowing us to explore and develop more potential applications in electrical and optical devices based on monolayer 2D materials.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"7 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837009","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 : 2025-04-15DOI: 10.1021/acs.langmuir.4c05130
Riyadi Priyo Darminto, Muhammad Arkan Nuruzzahran, Dzaki Ahmad Syaifullah, Hardika Ilhami, Nadhratun Naiim Mobarak, Hamad AlMohamadi, Fadjar Fathurrahman, Ni Luh Wulan Septiani, Adhitya Gandaryus Saputro
This study presents a comprehensive investigation of the oxygen evolution reaction (OER) activity on nickel phosphate (NiPO) surfaces doped with transition metals (Mn, Fe, Co, and Cu). By combining density functional theory calculations, the computational hydrogen electrode approximation, and microkinetic simulations, we demonstrate that transition metal doping significantly enhances OER performance compared to the pristine NiPO surface. The observed trends in overpotential values align with the oxygen adsorption energies on the doped surfaces, indicating a consistent improvement in catalytic activity. Despite the incorporation of different transition metals, the electronic profiles of surface nickel atoms remain largely unchanged, resulting in similar overpotential values at these sites. This suggests that the enhanced OER activity is primarily driven by the localized electronic states of the embedded transition metal dopants rather than changes in the nickel sites. Among the dopants studied, Fe and Mn exhibit the best OER performance, followed by Co and Cu.
{"title":"Influence of Transition Metal Doping on the Oxygen Evolution Reaction Activity of Nickel Phosphate Surface","authors":"Riyadi Priyo Darminto, Muhammad Arkan Nuruzzahran, Dzaki Ahmad Syaifullah, Hardika Ilhami, Nadhratun Naiim Mobarak, Hamad AlMohamadi, Fadjar Fathurrahman, Ni Luh Wulan Septiani, Adhitya Gandaryus Saputro","doi":"10.1021/acs.langmuir.4c05130","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c05130","url":null,"abstract":"This study presents a comprehensive investigation of the oxygen evolution reaction (OER) activity on nickel phosphate (NiPO) surfaces doped with transition metals (Mn, Fe, Co, and Cu). By combining density functional theory calculations, the computational hydrogen electrode approximation, and microkinetic simulations, we demonstrate that transition metal doping significantly enhances OER performance compared to the pristine NiPO surface. The observed trends in overpotential values align with the oxygen adsorption energies on the doped surfaces, indicating a consistent improvement in catalytic activity. Despite the incorporation of different transition metals, the electronic profiles of surface nickel atoms remain largely unchanged, resulting in similar overpotential values at these sites. This suggests that the enhanced OER activity is primarily driven by the localized electronic states of the embedded transition metal dopants rather than changes in the nickel sites. Among the dopants studied, Fe and Mn exhibit the best OER performance, followed by Co and Cu.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"42 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832376","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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