Pub Date : 2026-01-29DOI: 10.1021/acs.langmuir.5c05905
Masoud Outokesh,Mahdi Saeedipour,Mark W Hlawitschka
Bubble and particle interactions are fundamental in numerous industrial applications, particularly in the chemical and petrochemical industries, where three-phase reactors and slurry bubble columns are widely employed. Characterizing these interactions is inherently complicated as the mobility of the settling particle is coupled with the deformable nature of the rising bubble. This study attempts to unravel this complex system by developing a small-scale experimental approach to investigate and classify the different collision regimes. By utilizing a robust in-house image processing technique, we extracted the three-dimensional (3D) path of the particle during the interaction. A hydrodynamic force analysis method is applied to investigate the force balance exerted on the particle and the impulse variation during the interaction. Four distinguished regimes, called shuttling, bouncing, penetration, and flotation, are identified by the outcomes of the collision, based on hydrodynamic force balance. This approach can capture the transition between the different regimes at even higher particle concentrations or under different systematic parameters. These results provide fundamental insights into the bubble-particle interactions, offering a basis for developing scaled-up numerical models for the real-sized three-phase bubble columns.
{"title":"Experimental Characterization of the Hydrodynamic Interactions between a Freely Rising Bubble and a Settling Particle.","authors":"Masoud Outokesh,Mahdi Saeedipour,Mark W Hlawitschka","doi":"10.1021/acs.langmuir.5c05905","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c05905","url":null,"abstract":"Bubble and particle interactions are fundamental in numerous industrial applications, particularly in the chemical and petrochemical industries, where three-phase reactors and slurry bubble columns are widely employed. Characterizing these interactions is inherently complicated as the mobility of the settling particle is coupled with the deformable nature of the rising bubble. This study attempts to unravel this complex system by developing a small-scale experimental approach to investigate and classify the different collision regimes. By utilizing a robust in-house image processing technique, we extracted the three-dimensional (3D) path of the particle during the interaction. A hydrodynamic force analysis method is applied to investigate the force balance exerted on the particle and the impulse variation during the interaction. Four distinguished regimes, called shuttling, bouncing, penetration, and flotation, are identified by the outcomes of the collision, based on hydrodynamic force balance. This approach can capture the transition between the different regimes at even higher particle concentrations or under different systematic parameters. These results provide fundamental insights into the bubble-particle interactions, offering a basis for developing scaled-up numerical models for the real-sized three-phase bubble columns.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"74 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146073035","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 : 2026-01-29DOI: 10.1021/acs.langmuir.5c05507
Mengjuan Yang, Yulong Zhao, Ting Li, Xuhui Zhang, Bihua Xia, Jing Huang, Guanglong Li, Shibo Wang, Weifu Dong, Yang Wang
Organic room-temperature phosphorescence (RTP) materials have significant application potential in anticounterfeiting and biological imaging due to their large Stokes shifts and long phosphorescence lifetimes. Conventional RTP materials, which typically contain aromatic structures, often involve complex preparation processes and exhibit limited biocompatibility. In this work, a series of nontraditional intrinsic cluster-emitting polymeric materials with RTP properties were developed by utilizing strong ionic bonds and spatial confinement effects. Specifically, RTP-emitting derivatives of poly(maleic anhydride-alt-vinyl acetate) (PMV) were obtained via alkaline hydrolysis. The introduction of montmorillonite (MMT) enabled the construction of a nacre-mimetic structure through electrostatic interactions and ionic cross-linking between the layered inorganic framework of MMT and ionic sites on polymer chains, combined with the spatial confinement effect of MMT. By optimizing the reaction conditions, the resulting materials show improved photophysical properties, with a maximum phosphorescence lifetime of 30.5 ms and a maximum quantum yield of 16.09%. This study provides an alternative strategy for developing high-performance nontraditional luminescent polymers that do not require aromatic structures or heavy atoms.
{"title":"Room-Temperature Phosphorescent Polymer Composite Materials with Nacre-Mimetic Structures.","authors":"Mengjuan Yang, Yulong Zhao, Ting Li, Xuhui Zhang, Bihua Xia, Jing Huang, Guanglong Li, Shibo Wang, Weifu Dong, Yang Wang","doi":"10.1021/acs.langmuir.5c05507","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c05507","url":null,"abstract":"<p><p>Organic room-temperature phosphorescence (RTP) materials have significant application potential in anticounterfeiting and biological imaging due to their large Stokes shifts and long phosphorescence lifetimes. Conventional RTP materials, which typically contain aromatic structures, often involve complex preparation processes and exhibit limited biocompatibility. In this work, a series of nontraditional intrinsic cluster-emitting polymeric materials with RTP properties were developed by utilizing strong ionic bonds and spatial confinement effects. Specifically, RTP-emitting derivatives of poly(maleic anhydride-<i>alt</i>-vinyl acetate) (PMV) were obtained via alkaline hydrolysis. The introduction of montmorillonite (MMT) enabled the construction of a nacre-mimetic structure through electrostatic interactions and ionic cross-linking between the layered inorganic framework of MMT and ionic sites on polymer chains, combined with the spatial confinement effect of MMT. By optimizing the reaction conditions, the resulting materials show improved photophysical properties, with a maximum phosphorescence lifetime of 30.5 ms and a maximum quantum yield of 16.09%. This study provides an alternative strategy for developing high-performance nontraditional luminescent polymers that do not require aromatic structures or heavy atoms.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":" ","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146083495","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 : 2026-01-28DOI: 10.1021/acs.langmuir.5c05701
Raju S Kangutkar,Priyanka Walko,Girish Praveen Nayaka,Sandeep Nigam,Chiranjib Majumder,Jayappa Manjanna
Water splitting for hydrogen production and reducing water pollution using solar light are part of the Sustainable Development Goals, which require highly active photocatalytic materials. The heterostructures have demonstrated remarkable photocatalytic advantages in visible light. Herein, we report microwave-assisted green synthesis of CuO/Cu2O nanoparticles using Tridax plant leaf extract. The synthesized nanoparticles were characterized by using PXRD, UV-DRS, Raman spectroscopy, XPS, PL, TRPL, FE-SEM, HR-TEM, BET, and photocurrent. The photocatalytic water splitting performance of CuO/Cu2O and CuO was measured under visible light (λ ≥ 420 nm) irradiation using methanol as a sacrificial reagent in DI water and natural seawater. The H2 evolution rates in DI water for CuO/Cu2O and CuO are 2043.21 and 970.09 μmol g-1 h-1 with apparent quantum efficiency (AQE) values of 5.60 and 2.66 %, respectively. In natural seawater, the H2 evolution rates are 2599.29 and 1370.54 μmol g-1 h-1 with AQE values of 7.12 and 3.75 %, respectively. The rate of H2 evolution slightly increased in natural seawater. Also, the degradation of the methylene blue dye was examined here, and the efficiency of CuO/Cu2O was determined to be 97 % under natural sunlight. Electrocatalytic H2 evolution was also studied here by using linear sweep voltammetry. Tafel slope values for CuO/Cu2O and CuO are 153 and 250 mV dec-1, respectively. The lowest Tafel value of CuO/Cu2O indicates a faster rate of reaction, thereby producing easier charge separation and lowering the electron-hole recombination due to the presence of surface defects, smaller particle size, enhanced crystallinity, and the synergistic effect between Cu2O and CuO.
{"title":"Enhanced Photocatalytic Hydrogen Evolution in Deionized/Natural Seawater and Removal of Organic Pollutants Using the Heterostructure of CuO/Cu2O Nanoparticles under Visible Light.","authors":"Raju S Kangutkar,Priyanka Walko,Girish Praveen Nayaka,Sandeep Nigam,Chiranjib Majumder,Jayappa Manjanna","doi":"10.1021/acs.langmuir.5c05701","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c05701","url":null,"abstract":"Water splitting for hydrogen production and reducing water pollution using solar light are part of the Sustainable Development Goals, which require highly active photocatalytic materials. The heterostructures have demonstrated remarkable photocatalytic advantages in visible light. Herein, we report microwave-assisted green synthesis of CuO/Cu2O nanoparticles using Tridax plant leaf extract. The synthesized nanoparticles were characterized by using PXRD, UV-DRS, Raman spectroscopy, XPS, PL, TRPL, FE-SEM, HR-TEM, BET, and photocurrent. The photocatalytic water splitting performance of CuO/Cu2O and CuO was measured under visible light (λ ≥ 420 nm) irradiation using methanol as a sacrificial reagent in DI water and natural seawater. The H2 evolution rates in DI water for CuO/Cu2O and CuO are 2043.21 and 970.09 μmol g-1 h-1 with apparent quantum efficiency (AQE) values of 5.60 and 2.66 %, respectively. In natural seawater, the H2 evolution rates are 2599.29 and 1370.54 μmol g-1 h-1 with AQE values of 7.12 and 3.75 %, respectively. The rate of H2 evolution slightly increased in natural seawater. Also, the degradation of the methylene blue dye was examined here, and the efficiency of CuO/Cu2O was determined to be 97 % under natural sunlight. Electrocatalytic H2 evolution was also studied here by using linear sweep voltammetry. Tafel slope values for CuO/Cu2O and CuO are 153 and 250 mV dec-1, respectively. The lowest Tafel value of CuO/Cu2O indicates a faster rate of reaction, thereby producing easier charge separation and lowering the electron-hole recombination due to the presence of surface defects, smaller particle size, enhanced crystallinity, and the synergistic effect between Cu2O and CuO.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"73 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070085","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 resource recovery and high-value utilization of coal gasification slag (CGS) are vital to promoting green and sustainable advancement in the coal chemical industry. However, synthesizing advanced functional materials with stable performance and high economic value from CGS remains a significant challenge. This research presents an approach to utilize coal gasification fine slag (CGFS) as an economical silicon source for the continuous production of SiO2 nanofluids in a spiral microreactor. The excellent mixing efficiency in the developed 3D-printed spiral microreactor is verified through numerical simulation and fluorescence visualization experiments. Following activation and desilication treatment of CGFS, the microreactor enables the continuous production of SiO2 nanofluids, which exhibit homogeneous particle dimensions and outstanding colloidal stability. The flow boiling heat transfer performance of the fabricated nanofluids in high-power chip cooling applications is systematically evaluated. The results reveal that the 0.01 wt % SiO2 nanofluids exhibit the best heat transfer enhancement, achieving a maximum increase of 49.52% in critical heat flux (CHF) and a 34.00% improvement in maximum heat transfer coefficient (HTC) compared to deionized water as the basic fluid. Through bubble visualization combined with deposition surface characteristic analysis, it is found that nanofluids effectively reduce the bubble size and shorten the bubble lifetime by increasing surface nucleation sites, improving wall wettability, and delaying bubble coalescence, thereby enhancing the boiling heat transfer process. This study not only establishes a novel pathway for the high-value utilization of CGFS but also offers theoretical insights and a technical foundation for developing cost-effective, high-performance cooling fluids.
{"title":"Microfluidic-Based Sustainable Synthesis of SiO2 Nanofluids from Coal Gasification Fine Slag for Advanced Thermal Management.","authors":"Zihan Ding,Junsheng Hou,Baiqi Tian,Li Ma,Dongyu Li,Xiong Zhao,Zhenzhen Chen,Chunlei Gao,Jinjia Wei,Nanjing Hao","doi":"10.1021/acs.langmuir.5c06120","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c06120","url":null,"abstract":"The resource recovery and high-value utilization of coal gasification slag (CGS) are vital to promoting green and sustainable advancement in the coal chemical industry. However, synthesizing advanced functional materials with stable performance and high economic value from CGS remains a significant challenge. This research presents an approach to utilize coal gasification fine slag (CGFS) as an economical silicon source for the continuous production of SiO2 nanofluids in a spiral microreactor. The excellent mixing efficiency in the developed 3D-printed spiral microreactor is verified through numerical simulation and fluorescence visualization experiments. Following activation and desilication treatment of CGFS, the microreactor enables the continuous production of SiO2 nanofluids, which exhibit homogeneous particle dimensions and outstanding colloidal stability. The flow boiling heat transfer performance of the fabricated nanofluids in high-power chip cooling applications is systematically evaluated. The results reveal that the 0.01 wt % SiO2 nanofluids exhibit the best heat transfer enhancement, achieving a maximum increase of 49.52% in critical heat flux (CHF) and a 34.00% improvement in maximum heat transfer coefficient (HTC) compared to deionized water as the basic fluid. Through bubble visualization combined with deposition surface characteristic analysis, it is found that nanofluids effectively reduce the bubble size and shorten the bubble lifetime by increasing surface nucleation sites, improving wall wettability, and delaying bubble coalescence, thereby enhancing the boiling heat transfer process. This study not only establishes a novel pathway for the high-value utilization of CGFS but also offers theoretical insights and a technical foundation for developing cost-effective, high-performance cooling fluids.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"103 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070024","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 : 2026-01-28DOI: 10.1021/acs.langmuir.5c05009
Anderson Arboleda-Lamus,Christian Forero,Enrique Mejia-Ospino
Molecular dynamics simulations were employed to investigate the transfer and detachment energies of graphene oxide (GO) and pristine graphene sheets at liquid-liquid and solid-liquid interfaces. Using the umbrella sampling technique, the potential of mean force profiles were calculated to assess how the degree of oxidation of the GO sheets, the chemistry of the surface of a sandstone rock, and the nature of reservoir fluids influence these processes. Water and toluene were selected as the aqueous and crude oil models of the reservoir fluids, respectively, while the (001) crystallographic plane of the α-quartz at Q3 and Q4 saturations was used to mimic the sandstone surface. The results revealed that the Q3 surface, rich in silanol groups, is hydrophilic while the Q4 surface, composed of siloxane, exhibits hydrophobic behavior. GO sheets display interfacial activity that increases with the degree of oxidation, promoting solubility in the aqueous model and reducing the affinity for the crude oil model. Conversely, pristine graphene is non-interfacially active and preferentially resides in the toluene. On the other hand, the detachment of the sheets from the rock surface is strongly dependent on its surface chemistry, the degree of oxidation of the sheet, and the characteristics of the reservoir fluid. The detachment of GO and pristine graphene is energetically most favorable from the Q3-aqueous model interface (free energy of less than 12.8 kcal/mol), followed by the Q4-crude oil model interface (free energy of less than 53.8 kcal/mol). The highest detachment energies occur from the Q3-crude oil model and Q4-aqueous model interfaces (free energy of less than 90.7 kcal/mol), with inverse trends in sheet behavior, highlighting the complex interplay of interfacial interactions.
{"title":"Molecular Dynamics Study of the Interactions of Graphene Oxide and Sandstone Surfaces.","authors":"Anderson Arboleda-Lamus,Christian Forero,Enrique Mejia-Ospino","doi":"10.1021/acs.langmuir.5c05009","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c05009","url":null,"abstract":"Molecular dynamics simulations were employed to investigate the transfer and detachment energies of graphene oxide (GO) and pristine graphene sheets at liquid-liquid and solid-liquid interfaces. Using the umbrella sampling technique, the potential of mean force profiles were calculated to assess how the degree of oxidation of the GO sheets, the chemistry of the surface of a sandstone rock, and the nature of reservoir fluids influence these processes. Water and toluene were selected as the aqueous and crude oil models of the reservoir fluids, respectively, while the (001) crystallographic plane of the α-quartz at Q3 and Q4 saturations was used to mimic the sandstone surface. The results revealed that the Q3 surface, rich in silanol groups, is hydrophilic while the Q4 surface, composed of siloxane, exhibits hydrophobic behavior. GO sheets display interfacial activity that increases with the degree of oxidation, promoting solubility in the aqueous model and reducing the affinity for the crude oil model. Conversely, pristine graphene is non-interfacially active and preferentially resides in the toluene. On the other hand, the detachment of the sheets from the rock surface is strongly dependent on its surface chemistry, the degree of oxidation of the sheet, and the characteristics of the reservoir fluid. The detachment of GO and pristine graphene is energetically most favorable from the Q3-aqueous model interface (free energy of less than 12.8 kcal/mol), followed by the Q4-crude oil model interface (free energy of less than 53.8 kcal/mol). The highest detachment energies occur from the Q3-crude oil model and Q4-aqueous model interfaces (free energy of less than 90.7 kcal/mol), with inverse trends in sheet behavior, highlighting the complex interplay of interfacial interactions.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"5 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070025","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 : 2026-01-28DOI: 10.1021/acs.langmuir.5c03566
Paul Jaouen,Line Cantin,Élodie Boisselier
S100 proteins are a family of calcium-binding proteins involved in a wide range of physiological and pathological processes. While substantial structural and functional information exists for S100 homodimers, the heterodimerization of S100 proteins remains poorly studied, and its biological significance is largely unknown. In particular, the influence of heterodimerization on membrane-binding properties and their modulation by calcium has yet to be fully elucidated. In this study, the calcium-dependent and independent membrane-binding behavior of S100A1, S100B, S100P, and their heterodimers (S100A1-S100B and S100A1-S100P) was investigating using a Langmuir monolayer model combined with surface tensiometry to probe protein-lipid interactions under controlled environments. The proteins were overexpressed in Escherichia coli and purified via affinity and hydrophobic interaction chromatographies. Binding parameters of the purified proteins and their heterodimers were evaluated in the presence and absence of calcium ions. Surface pressure analyses revealed distinct binding profiles, modulated by calcium. S100B exhibited enhanced membrane interaction upon calcium binding, while S100A1 and its heterodimers displayed reduced membrane association in the calcium-bound state. Interestingly, S100P showed calcium-independent behavior, whereas the S100A1-S100P heterodimer demonstrated unique lipid-binding properties, suggesting that heterodimerization significantly influences membrane interaction. These findings provide valuable insights into the interplay between calcium signaling, dimerization, and phospholipid interactions in the S100 protein family. They also highlight the structural and functional diversity within the S100 family and emphasize the potential role of heterodimerization in modulating protein-membrane interactions.
{"title":"Calcium-Dependent Membrane Interactions of S100A1, S100B, and S100P Homodimers and Their Heterodimeric Complexes.","authors":"Paul Jaouen,Line Cantin,Élodie Boisselier","doi":"10.1021/acs.langmuir.5c03566","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c03566","url":null,"abstract":"S100 proteins are a family of calcium-binding proteins involved in a wide range of physiological and pathological processes. While substantial structural and functional information exists for S100 homodimers, the heterodimerization of S100 proteins remains poorly studied, and its biological significance is largely unknown. In particular, the influence of heterodimerization on membrane-binding properties and their modulation by calcium has yet to be fully elucidated. In this study, the calcium-dependent and independent membrane-binding behavior of S100A1, S100B, S100P, and their heterodimers (S100A1-S100B and S100A1-S100P) was investigating using a Langmuir monolayer model combined with surface tensiometry to probe protein-lipid interactions under controlled environments. The proteins were overexpressed in Escherichia coli and purified via affinity and hydrophobic interaction chromatographies. Binding parameters of the purified proteins and their heterodimers were evaluated in the presence and absence of calcium ions. Surface pressure analyses revealed distinct binding profiles, modulated by calcium. S100B exhibited enhanced membrane interaction upon calcium binding, while S100A1 and its heterodimers displayed reduced membrane association in the calcium-bound state. Interestingly, S100P showed calcium-independent behavior, whereas the S100A1-S100P heterodimer demonstrated unique lipid-binding properties, suggesting that heterodimerization significantly influences membrane interaction. These findings provide valuable insights into the interplay between calcium signaling, dimerization, and phospholipid interactions in the S100 protein family. They also highlight the structural and functional diversity within the S100 family and emphasize the potential role of heterodimerization in modulating protein-membrane interactions.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"296 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146069817","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 : 2026-01-28DOI: 10.1021/acs.langmuir.5c04094
Tobias Komsthöft, Michele do Nascimento Tomaz, Pedro R. M. Veloso, Ana R. S. Ribeiro, Lucca Trachsel, Jutta Horejs-Höck, Mark W. Tibbitt, Samuele Tosatti, Emanuele Papini, Stefan Zürcher, Fabrizio Mancin
Inorganic nanoparticles (NP), particularly gold nanoparticles, hold great promise for biomedical applications. However, one of the major challenges in the implementation of therapeutic applications based on inorganic nanoparticles is the individuation of appropriate coatings, which are indeed responsible for stability, escape from the immune system, and further functionalization. In this paper, we explore the properties of the multi-azide-containing and highly nonfouling polymer PAcrAm-g-(PMCA, NH2, ND), based on poly(oxazoline) derivatives grafted to a poly(acrylamide), as a coating for gold nanoparticles that can grant stability and easiness of derivatization and can prevent nonspecific protein adhesion on gold nanoparticles (Au-NP). We found that the addition of the polymer to citrate-stabilized gold nanoparticles led to the formation of NP suspensions with excellent colloidal stability, as confirmed by dynamic light scattering (DLS), ζ potential, thermogravimetric analysis (TGA), and transmission electron microscopy (TEM) investigations. In addition, the AuNP coating strongly decreases the protein adsorption corona and does not activate dendritic cells (DCs), showing low immunogenicity and potentially decreasing the NP clearance by the mononuclear phagocyte system.
{"title":"Conjugable, Antifouling, and Non-immunogenic Coatings for Gold Nanoparticles by Multivalent Grafting of Azide-Bearing Polyoxazoline Brushes","authors":"Tobias Komsthöft, Michele do Nascimento Tomaz, Pedro R. M. Veloso, Ana R. S. Ribeiro, Lucca Trachsel, Jutta Horejs-Höck, Mark W. Tibbitt, Samuele Tosatti, Emanuele Papini, Stefan Zürcher, Fabrizio Mancin","doi":"10.1021/acs.langmuir.5c04094","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c04094","url":null,"abstract":"Inorganic nanoparticles (NP), particularly gold nanoparticles, hold great promise for biomedical applications. However, one of the major challenges in the implementation of therapeutic applications based on inorganic nanoparticles is the individuation of appropriate coatings, which are indeed responsible for stability, escape from the immune system, and further functionalization. In this paper, we explore the properties of the multi-azide-containing and highly nonfouling polymer PAcrAm-<i>g</i>-(PMCA, NH2, ND), based on poly(oxazoline) derivatives grafted to a poly(acrylamide), as a coating for gold nanoparticles that can grant stability and easiness of derivatization and can prevent nonspecific protein adhesion on gold nanoparticles (Au-NP). We found that the addition of the polymer to citrate-stabilized gold nanoparticles led to the formation of NP suspensions with excellent colloidal stability, as confirmed by dynamic light scattering (DLS), ζ potential, thermogravimetric analysis (TGA), and transmission electron microscopy (TEM) investigations. In addition, the AuNP coating strongly decreases the protein adsorption corona and does not activate dendritic cells (DCs), showing low immunogenicity and potentially decreasing the NP clearance by the mononuclear phagocyte system.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"73 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146056999","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 dynamic covalent complexation between phenylboronic acid (PBA)-functionalized polymers and diol-containing surfactants presents a powerful strategy for fabricating smart interfacial materials. This work presents a comprehensive investigation into a pH-responsive system composed of Alg-PBA and the diol-bearing surfactant alkyl polyglycoside (APG). The pH-governed formation of boronate ester (B–O) bonds between Alg-PBA and APG dictates their interaction regimes, leading to distinct behaviors in bulk solution, at the oil–water interface, and in macroscopic emulsions. At pH 3, weak hydrogen bonding dominates, while above the pKa of PBA (pH 9 and 10), strong dynamic covalent complexes form. At intermediate pH (pH 6), the interaction is in a dynamic transitional state. These molecular-level interactions directly govern tunable interfacial activity and adsorption kinetics. Crucially, a pH-dependent “bridging effect” is identified: at low APG concentrations, Alg-PBA chains connect oil droplets into a three-dimensional network, yielding gel-like emulsions stabilized by hydrogen bonds (pH 3) or robust B–O bonds (pH 6, 9 and 10). At high APG concentrations, hydrophobic interactions disrupt this network, fluidizing the emulsion. By decoupling the interplay between pH-tunable binding, polymer conformation, and surfactant concentration, this study establishes the Alg-PBA/APG complex as a versatile, stimuli-responsive emulsifier platform. This provides a design principle for creating emulsions with on-demand rheological properties and stability for applications in drug delivery, food, and cosmetics.
{"title":"Dynamic Covalent Bonding and Bridging: pH-Governed Complexation of Phenylboronic Acid-Modified Alginate with Alkyl Polyglycoside for Smart Emulsification","authors":"Junhao Huang, Zixuan Ma, Bohan Xie, Yiheng Lin, Youming Lei, Caifeng Wang, Junyu He","doi":"10.1021/acs.langmuir.5c05992","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c05992","url":null,"abstract":"The dynamic covalent complexation between phenylboronic acid (PBA)-functionalized polymers and diol-containing surfactants presents a powerful strategy for fabricating smart interfacial materials. This work presents a comprehensive investigation into a pH-responsive system composed of Alg-PBA and the diol-bearing surfactant alkyl polyglycoside (APG). The pH-governed formation of boronate ester (B–O) bonds between Alg-PBA and APG dictates their interaction regimes, leading to distinct behaviors in bulk solution, at the oil–water interface, and in macroscopic emulsions. At pH 3, weak hydrogen bonding dominates, while above the p<i>K</i><sub>a</sub> of PBA (pH 9 and 10), strong dynamic covalent complexes form. At intermediate pH (pH 6), the interaction is in a dynamic transitional state. These molecular-level interactions directly govern tunable interfacial activity and adsorption kinetics. Crucially, a pH-dependent “bridging effect” is identified: at low APG concentrations, Alg-PBA chains connect oil droplets into a three-dimensional network, yielding gel-like emulsions stabilized by hydrogen bonds (pH 3) or robust B–O bonds (pH 6, 9 and 10). At high APG concentrations, hydrophobic interactions disrupt this network, fluidizing the emulsion. By decoupling the interplay between pH-tunable binding, polymer conformation, and surfactant concentration, this study establishes the Alg-PBA/APG complex as a versatile, stimuli-responsive emulsifier platform. This provides a design principle for creating emulsions with on-demand rheological properties and stability for applications in drug delivery, food, and cosmetics.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"38 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146057002","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 : 2026-01-28DOI: 10.1021/acs.langmuir.5c04744
Ying Han,Junying Zhang,Wenjing Hao,Chengcheng Jiang,Akiko Nakabayashi,Dehua Ma,Xinyuan Xia,Dejie Li
Electron paramagnetic resonance (EPR) is a technique for studying the microscopic structures by detecting the transitions of the spin magnetic moments of unpaired electrons. Since its discovery by E. K. Zavoisky in 1944, EPR has evolved from a tool for analyzing atomic structures in physics into a core characterization method in the fields of chemistry, biology, and materials science. In surface chemistry, due to its high sensitivity to the local environment, EPR has become a unique technique for elucidating surface-active sites, free radical intermediates, and defect structures. However, for many chemists, EPR testing and analysis, which are based on mathematical and physical principles, is not an easy field to engage in due to its high level of specialization. Some introductory textbooks provide excellent and comprehensive explanations of the basic knowledge, and recent work reports have also demonstrated the continuously developing magnetic resonance spectroscopy methods. Nevertheless, they are not intended to provide a brief and clear overview through a wide range of examples. To bridge the knowledge gap between EPR spectroscopists and chemists unfamiliar with EPR, this work reviews the progress in the application of EPR in surface chemistry, discussing its principles, applications, innovative cases and future challenges. It is hoped that nonprofessionals would gain certain knowledge and technical accumulation from this work, thereby promoting the development of surface chemistry.
电子顺磁共振（EPR）是一种通过探测未成对电子自旋磁矩的跃迁来研究微观结构的技术。自1944年E. K. Zavoisky发现EPR以来，它已经从物理学中分析原子结构的工具发展成为化学、生物学和材料科学领域的核心表征方法。在表面化学中，由于其对局部环境的高度敏感性，EPR已成为一种独特的技术，用于阐明表面活性位点，自由基中间体和缺陷结构。然而，对于许多化学家来说，基于数学和物理原理的EPR测试和分析，由于其高度专业化，并不是一个容易从事的领域。一些入门教材对基础知识提供了出色而全面的解释，最近的工作报告也展示了磁共振波谱方法的不断发展。然而，它们并不打算通过广泛的示例提供一个简短而清晰的概述。为了弥合EPR光谱学家和不熟悉EPR的化学家之间的知识差距，本文综述了EPR在表面化学中的应用进展，讨论了EPR的原理、应用、创新案例和未来挑战。希望非专业人员能从这项工作中获得一定的知识和技术积累，从而促进表面化学的发展。
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Pub Date : 2026-01-28DOI: 10.1021/acs.langmuir.5c05805
Fathimath Sanooba N. K, Subbiah Alwarappan
Electrode fouling is a daunting challenge during the electrochemical detection of uric acid (UA), particularly in complex biological environments. Herein, silanized reduced graphene oxide was explored as an antifouling platform to modify glassy carbon electrode (GCE) for the electrochemical detection of UA. Silanization imparts less polarity to the rGO surface upon introducing bulky siloxane groups that effectively minimizes non-specific adsorption of biomolecules. In order to evaluate the impact of different silane molecules on the antifouling performance, three different silanes, namely, triethoxymethylsilane (TEMS), dodecyltrimethoxysilane (DTMS), and trimethoxyphenylsilane (TMPS), were employed individually for rGO functionalization. Of these modified electrodes, rGO-TEMS/GCE and rGO-TMPS/GCE showed superior electrochemical responses toward UA, with rGO-TMPS/GCE exhibiting enhanced resistance to both electrochemical fouling and biofouling. rGO-TMPS/GCE maintained a stable current response after 1 h of incubation in a solution containing effective foulants such as bovine serum albumin (BSA) and cytochrome c (Cyt c). As a result, rGO-TMPS/GCE was further employed for the detection of UA by differential pulse voltammetry (DPV). The modified electrode exhibited a limit of detection of 0.76 μM ± 0.14 (N = 3), with a sensitivity of 1.04 μA μM–1 cm–2. These results emphasize the usefulness of rGO-TMPS/GCE as an effective antifouling electrode material for the stable and sensitive detection of UA.
{"title":"Silanized Reduced Graphene Oxide as an Effective Modified Electrode to Minimize Fouling during Uric Acid Detection","authors":"Fathimath Sanooba N. K, Subbiah Alwarappan","doi":"10.1021/acs.langmuir.5c05805","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c05805","url":null,"abstract":"Electrode fouling is a daunting challenge during the electrochemical detection of uric acid (UA), particularly in complex biological environments. Herein, silanized reduced graphene oxide was explored as an antifouling platform to modify glassy carbon electrode (GCE) for the electrochemical detection of UA. Silanization imparts less polarity to the rGO surface upon introducing bulky siloxane groups that effectively minimizes non-specific adsorption of biomolecules. In order to evaluate the impact of different silane molecules on the antifouling performance, three different silanes, namely, triethoxymethylsilane (TEMS), dodecyltrimethoxysilane (DTMS), and trimethoxyphenylsilane (TMPS), were employed individually for rGO functionalization. Of these modified electrodes, rGO-TEMS/GCE and rGO-TMPS/GCE showed superior electrochemical responses toward UA, with rGO-TMPS/GCE exhibiting enhanced resistance to both electrochemical fouling and biofouling. rGO-TMPS/GCE maintained a stable current response after 1 h of incubation in a solution containing effective foulants such as bovine serum albumin (BSA) and cytochrome c (Cyt c). As a result, rGO-TMPS/GCE was further employed for the detection of UA by differential pulse voltammetry (DPV). The modified electrode exhibited a limit of detection of 0.76 μM ± 0.14 (<i>N</i> = 3), with a sensitivity of 1.04 μA μM<sup>–1</sup> cm<sup>–2</sup>. These results emphasize the usefulness of rGO-TMPS/GCE as an effective antifouling electrode material for the stable and sensitive detection of UA.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"14 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146057001","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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