Pub Date : 2026-02-04DOI: 10.1021/acs.langmuir.5c06296
Yuru Yang,Xiaoxia Li,Qian Xiao,Shuang Zhou,Qingmiao Pu,Bingyu Luo,Xiaodong Su
To prevent the proliferation of the OTC resistance genes in wastewater and their spread in the environment, advanced treatment of the OTC-containing wastewater has become necessary. In this study, an adsorbent material consisting of CDs/o-MWCNTs was synthesized using a combination of DBD technology and a hydrothermal method. The material was characterized by TEM, SEM, FT-IR, XRD, XPS, BET, TGA, and surface ζ-potential analysis. The effects of the adsorbent dosage, adsorption temperature, solution pH, adsorption time, and ionic interference on the adsorption of the OTC by CDs/o-MWCNTs were investigated. The results showed that the material contains 73.42% C, 6.39% O, and 5.78% N, with abundant active sites, a specific surface area of 148.48 m2/g, and a maximum adsorption capacity of 12.619 mg/g. The adsorption process followed the pseudo-second-order kinetic model and the Freundlich isotherm model. A series of analyses indicated that the adsorption and removal of OTC from water by CDs/o-MWCNTs occur through the synergistic effects of hydrogen bonding, π–π interactions, and van der Waals forces. After 10 adsorption–desorption cycles, the adsorption efficiency of CDs/o-MWCNTs remained above 91%. Moreover, for aquaculture wastewater with the OTC concentration below 0.1 mg/L, the material achieved a removal efficiency close to 100%. It also exhibited good salt tolerance and is suitable for the advanced treatment of OTC in high-salinity (1.0 mol/L NaCl) wastewater.
{"title":"Hydrothermal Synthesis of Carbon Dot-Modified Multiwalled Carbon Nanotube Composites for Advanced Treatment of Oxytetracycline in Water","authors":"Yuru Yang,Xiaoxia Li,Qian Xiao,Shuang Zhou,Qingmiao Pu,Bingyu Luo,Xiaodong Su","doi":"10.1021/acs.langmuir.5c06296","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c06296","url":null,"abstract":"To prevent the proliferation of the OTC resistance genes in wastewater and their spread in the environment, advanced treatment of the OTC-containing wastewater has become necessary. In this study, an adsorbent material consisting of CDs/o-MWCNTs was synthesized using a combination of DBD technology and a hydrothermal method. The material was characterized by TEM, SEM, FT-IR, XRD, XPS, BET, TGA, and surface ζ-potential analysis. The effects of the adsorbent dosage, adsorption temperature, solution pH, adsorption time, and ionic interference on the adsorption of the OTC by CDs/o-MWCNTs were investigated. The results showed that the material contains 73.42% C, 6.39% O, and 5.78% N, with abundant active sites, a specific surface area of 148.48 m2/g, and a maximum adsorption capacity of 12.619 mg/g. The adsorption process followed the pseudo-second-order kinetic model and the Freundlich isotherm model. A series of analyses indicated that the adsorption and removal of OTC from water by CDs/o-MWCNTs occur through the synergistic effects of hydrogen bonding, π–π interactions, and van der Waals forces. After 10 adsorption–desorption cycles, the adsorption efficiency of CDs/o-MWCNTs remained above 91%. Moreover, for aquaculture wastewater with the OTC concentration below 0.1 mg/L, the material achieved a removal efficiency close to 100%. It also exhibited good salt tolerance and is suitable for the advanced treatment of OTC in high-salinity (1.0 mol/L NaCl) wastewater.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"8 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111067","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 : 2026-02-04DOI: 10.1021/acs.langmuir.5c05439
Biplab Mondal,Tanushree Mondal,Anushree Sinha,Ian W. Hamley,Susmita Roy,Arindam Banerjee
A hydrogel formed by a short peptide is presented that exhibits remarkable stimuli-responsiveness and plasticity, undergoing a morphological transformation from nanofibers to nanospheres in the presence of monovalent (Li+, Na+, K+) or trivalent (Al3+, Fe3+) metal ions under physiological conditions. The nanofibrillar structure of the hydrogel was examined using transmission electron microscopy (TEM), atomic force microscopy (AFM), small-angle X-ray scattering (SAXS), and X-ray diffraction (XRD) studies and atomistic molecular dynamics simulations, in complement, to explain the nanostructural transitions at the microscopic level. Interestingly, exposure to divalent metal ions (Mg2+, Ca2+, Co2+, Ni2+) induces a unique shrinking (syneresis) behavior, accompanied by a morphological shift to nanoribbons. Both simulations and SAXS analysis confirm that these ions cause a contraction in the packing of gelator peptides, significantly reducing the interpeptide distance. This ion-specific adaptability confers tunable physicochemical properties and morphological plasticity. Hydrogels incorporating mono- or trivalent ions exhibit enhanced thermal stability and mechanical strength relative to ion-free counterparts, underscoring the reinforcing role of metal coordination. Strikingly, shrunken gels formed in the presence of divalent ions display even greater stiffness than freshly prepared gels in the absence of any metal ions, suggesting that syneresis acts as a postassembly strengthening mechanism. These findings highlight a versatile, stimuli-responsive soft material in which ion-peptide interactions orchestrate nanoscale morphology, mesoscale network architecture, and macroscopic mechanical performance-opening avenues for adaptive hydrogel systems in targeted biomedical, sensing, and controlled-release applications.
{"title":"Ion-Induced Morphological Plasticity in a Self-Assembling Peptide Hydrogel","authors":"Biplab Mondal,Tanushree Mondal,Anushree Sinha,Ian W. Hamley,Susmita Roy,Arindam Banerjee","doi":"10.1021/acs.langmuir.5c05439","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c05439","url":null,"abstract":"A hydrogel formed by a short peptide is presented that exhibits remarkable stimuli-responsiveness and plasticity, undergoing a morphological transformation from nanofibers to nanospheres in the presence of monovalent (Li+, Na+, K+) or trivalent (Al3+, Fe3+) metal ions under physiological conditions. The nanofibrillar structure of the hydrogel was examined using transmission electron microscopy (TEM), atomic force microscopy (AFM), small-angle X-ray scattering (SAXS), and X-ray diffraction (XRD) studies and atomistic molecular dynamics simulations, in complement, to explain the nanostructural transitions at the microscopic level. Interestingly, exposure to divalent metal ions (Mg2+, Ca2+, Co2+, Ni2+) induces a unique shrinking (syneresis) behavior, accompanied by a morphological shift to nanoribbons. Both simulations and SAXS analysis confirm that these ions cause a contraction in the packing of gelator peptides, significantly reducing the interpeptide distance. This ion-specific adaptability confers tunable physicochemical properties and morphological plasticity. Hydrogels incorporating mono- or trivalent ions exhibit enhanced thermal stability and mechanical strength relative to ion-free counterparts, underscoring the reinforcing role of metal coordination. Strikingly, shrunken gels formed in the presence of divalent ions display even greater stiffness than freshly prepared gels in the absence of any metal ions, suggesting that syneresis acts as a postassembly strengthening mechanism. These findings highlight a versatile, stimuli-responsive soft material in which ion-peptide interactions orchestrate nanoscale morphology, mesoscale network architecture, and macroscopic mechanical performance-opening avenues for adaptive hydrogel systems in targeted biomedical, sensing, and controlled-release applications.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"106 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111091","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}
g-C3N4-based photocatalysts have attracted considerable research attention for their applicability in green H2O2 production. However, the photocatalytic activity of these catalysts is limited by their low light-absorption efficiency and high carrier recombination rate. This study developed a highly crystalline carbon nitride (CDCN-X) through thermal polymerization using eutectic salt, which promoted the incorporation of cyano groups, created electron-transport “bridges”, and guided directional material growth into a nanorod morphology. Enhanced crystallinity effectively minimized internal defects within the material, thus notably suppressing the recombination of photogenerated electron–hole pairs. Cyano groups and Na+/K+ ions were introduced to modulate the electronic band structure of CDCN-X and establish an internal built-in electric field, thus achieving a broader light absorption range and efficient transport channels for photogenerated charge carriers. Additionally, the cyano groups served as active sites, enhancing the adsorption capacity for O2 and promoting the reaction progress. As a result of these modifications, CDCN-550 enabled rapid two-step single electron oxygen reduction, thereby promoting rapid H2O2 generation. Furthermore, a CDCN-550-catalyzed H2O2 yield of 36.69 mmol g–1 h–1 was achieved, representing a 17.39-fold increase compared to conventional carbon nitride (DCN). Overall, the proposed approach is viable for the rational design and modification of carbon nitride materials to achieve excellent photocatalytic performance.
{"title":"Na+/K+-Intercalation Crystalline Carbon Nitride with High Charge Transfer Efficiency For Synergistically Enhanced Photocatalytic H2O2 Production","authors":"Zibin Shang,Zelin Wang,Chenglong Yang,Keyao Liu,Yuyao Liu,Changsheng An,Weijun Li,Ruiting Li,Zhongfu Li,Shumin Zhang,Chao Cai,Jianmei Li","doi":"10.1021/acs.langmuir.5c06128","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c06128","url":null,"abstract":"g-C3N4-based photocatalysts have attracted considerable research attention for their applicability in green H2O2 production. However, the photocatalytic activity of these catalysts is limited by their low light-absorption efficiency and high carrier recombination rate. This study developed a highly crystalline carbon nitride (CDCN-X) through thermal polymerization using eutectic salt, which promoted the incorporation of cyano groups, created electron-transport “bridges”, and guided directional material growth into a nanorod morphology. Enhanced crystallinity effectively minimized internal defects within the material, thus notably suppressing the recombination of photogenerated electron–hole pairs. Cyano groups and Na+/K+ ions were introduced to modulate the electronic band structure of CDCN-X and establish an internal built-in electric field, thus achieving a broader light absorption range and efficient transport channels for photogenerated charge carriers. Additionally, the cyano groups served as active sites, enhancing the adsorption capacity for O2 and promoting the reaction progress. As a result of these modifications, CDCN-550 enabled rapid two-step single electron oxygen reduction, thereby promoting rapid H2O2 generation. Furthermore, a CDCN-550-catalyzed H2O2 yield of 36.69 mmol g–1 h–1 was achieved, representing a 17.39-fold increase compared to conventional carbon nitride (DCN). Overall, the proposed approach is viable for the rational design and modification of carbon nitride materials to achieve excellent photocatalytic performance.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"295 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111068","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 : 2026-02-04DOI: 10.1021/acs.langmuir.5c05129
Sruthi T. ,V. Shivani,S. Sriram,Vincent Mathew
Synergistic integration of atomic-scale doping and Moiré superlattices opens up new possibilities for manipulating the electrical characteristics of two-dimensional (2D) materials. Here, we report the first thorough first-principles investigation of site-specific chemical doping-based quantum capacitance (CQ) modulation in Moiré-patterned bilayer MoS2 (mBL-MoS2). Periodic potential fluctuations caused by a 21.79° interlayer twist change the density of states close to the Fermi level. By performing transition-metal-site substitution (Mo → Nb) and chalcogen-site substitution (S → Se), further improvements are achieved. Nb doping, which induces a semiconductor-to-metal transition, greatly enhances electronic delocalization and quantum capacitance, whereas Se doping has a comparatively smaller impact owing to its isoelectronic nature with S. The structural and electronic tunability of these systems is confirmed by a comprehensive analysis that includes electronic structure, differential and integral CQ calculations, electron localization function (ELF) mapping, Bader charge analysis, phonon stability, and work function evaluation. The superior charge storage capacity of Nb-doped mBL-MoS2 in the low-bias domain is demonstrated by benchmarking against other 2D materials. These results show how Moiré engineering and chemical doping can work together to create a new design framework for CQ-dominated supercapacitor electrodes.
{"title":"Engineering Bilayer MoS2 with Moiré–Dopant Synergy for Advanced Supercapacitor Electrodes","authors":"Sruthi T. ,V. Shivani,S. Sriram,Vincent Mathew","doi":"10.1021/acs.langmuir.5c05129","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c05129","url":null,"abstract":"Synergistic integration of atomic-scale doping and Moiré superlattices opens up new possibilities for manipulating the electrical characteristics of two-dimensional (2D) materials. Here, we report the first thorough first-principles investigation of site-specific chemical doping-based quantum capacitance (CQ) modulation in Moiré-patterned bilayer MoS2 (mBL-MoS2). Periodic potential fluctuations caused by a 21.79° interlayer twist change the density of states close to the Fermi level. By performing transition-metal-site substitution (Mo → Nb) and chalcogen-site substitution (S → Se), further improvements are achieved. Nb doping, which induces a semiconductor-to-metal transition, greatly enhances electronic delocalization and quantum capacitance, whereas Se doping has a comparatively smaller impact owing to its isoelectronic nature with S. The structural and electronic tunability of these systems is confirmed by a comprehensive analysis that includes electronic structure, differential and integral CQ calculations, electron localization function (ELF) mapping, Bader charge analysis, phonon stability, and work function evaluation. The superior charge storage capacity of Nb-doped mBL-MoS2 in the low-bias domain is demonstrated by benchmarking against other 2D materials. These results show how Moiré engineering and chemical doping can work together to create a new design framework for CQ-dominated supercapacitor electrodes.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"1 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111089","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 : 2026-02-03DOI: 10.1021/acs.langmuir.5c05167
Scott McGuigan, Erika Ortega Ortiz, Sungho Jeon, Carrie L Donley, Eric A Stach, Paul A Maggard
Controlling the morphological parameters of extended covalent organic frameworks remains challenging and represents an important yet often elusive metric of consideration. Typically, carbon nitride materials possess local ordering but remain largely amorphous in terms of their long-range order and orientation. This study probes the synthesis of a crystalline carbon nitride, poly(triazine imide) lithium bromide which possesses an atomically-precise extended structure, and demonstrates its exfoliation into a two-dimensional hexagonal sheet-like morphology. Furthermore, a previously unreported carbon nitride material, poly(triazine imide) copper bromide, or PTI-CuBr, was developed through an additional flux-assisted cation-exchange process and is shown to retain its internal Cu cations during solvothermal exfoliation. Characterization by dynamic light scattering and high-angle annular dark-field scanning electron microscopy reveals the morphological changes and captures the high aspect ratio of the thin carbon nitride sheets with <10 nm thickness while maintaining hundreds of nm in width. Additional characterization by energy-dispersive spectroscopy and X-ray photoelectron spectroscopy confirms that the Cu:Br:N molar ratio was maintained within the extended layers throughout the exfoliation process. This top-down synthesis approach differs from typical methods that isolate thin sheets for subsequent metal-cation coordination and illustrates the importance of maintaining oxygen-free conditions to minimize copper clustering. Thus, this new approach is demonstrated to provide a consistent and more homogeneous occupancy of the PTI pore spaces throughout the carbon nitride framework.
{"title":"Exfoliation of Cu-Containing Poly(triazine imide): From Three-Dimensional to Two-Dimensional Particle Morphology.","authors":"Scott McGuigan, Erika Ortega Ortiz, Sungho Jeon, Carrie L Donley, Eric A Stach, Paul A Maggard","doi":"10.1021/acs.langmuir.5c05167","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c05167","url":null,"abstract":"<p><p>Controlling the morphological parameters of extended covalent organic frameworks remains challenging and represents an important yet often elusive metric of consideration. Typically, carbon nitride materials possess local ordering but remain largely amorphous in terms of their long-range order and orientation. This study probes the synthesis of a crystalline carbon nitride, poly(triazine imide) lithium bromide which possesses an atomically-precise extended structure, and demonstrates its exfoliation into a two-dimensional hexagonal sheet-like morphology. Furthermore, a previously unreported carbon nitride material, poly(triazine imide) copper bromide, or PTI-CuBr, was developed through an additional flux-assisted cation-exchange process and is shown to retain its internal Cu cations during solvothermal exfoliation. Characterization by dynamic light scattering and high-angle annular dark-field scanning electron microscopy reveals the morphological changes and captures the high aspect ratio of the thin carbon nitride sheets with <10 nm thickness while maintaining hundreds of nm in width. Additional characterization by energy-dispersive spectroscopy and X-ray photoelectron spectroscopy confirms that the Cu:Br:N molar ratio was maintained within the extended layers throughout the exfoliation process. This top-down synthesis approach differs from typical methods that isolate thin sheets for subsequent metal-cation coordination and illustrates the importance of maintaining oxygen-free conditions to minimize copper clustering. Thus, this new approach is demonstrated to provide a consistent and more homogeneous occupancy of the PTI pore spaces throughout the carbon nitride framework.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":" ","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146103063","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}
ZnO-based photocatalysts severely limit solar energy utilization efficiency due to their exclusive CO2absorption of ultraviolet light. In this study, Ni-ZnO/Zn0.25Cd0.75S Z-scheme heterojunctions were constructed to enhance photocatalytic performance. Results demonstrate that Ni2+ doping not only broadens the light absorption range of ZnO but also introduces oxygen vacancies that effectively suppress carrier recombination. Meanwhile, heterojunction construction facilitates the uneven adherence of Zn0.25Cd0.75S particles to rod-shaped ZnO. A Z-type charge transfer mechanism has been constructed under the influence of the built-in potential at the interface. This mechanism maintains strong redox capacity and achieves efficient carrier separation, improving the hydrogen evolution activity of the composite photocatalyst. The hydrogen production rate reaches 16.5 mmol·g–1·h–1, which is 56 and 9.9 times that of Ni-ZnO and Zn0.25Cd0.75S, respectively.
{"title":"Unveiling Charge Transfer in a Ni-Doped ZnO/Zn0.25Cd0.75S Z-Scheme Heterojunction for Enhanced Photocatalytic H2 Evolution","authors":"Zihuan Zhang,Yanli Zhuang,Limin Dong,Yancheng Hao,Jikun Pan,Haobin Wang,Wanru Zhang,Zhishun Zhang,Dan Li,Jian Li,Honghui Liu","doi":"10.1021/acs.langmuir.5c06214","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c06214","url":null,"abstract":"ZnO-based photocatalysts severely limit solar energy utilization efficiency due to their exclusive CO2absorption of ultraviolet light. In this study, Ni-ZnO/Zn0.25Cd0.75S Z-scheme heterojunctions were constructed to enhance photocatalytic performance. Results demonstrate that Ni2+ doping not only broadens the light absorption range of ZnO but also introduces oxygen vacancies that effectively suppress carrier recombination. Meanwhile, heterojunction construction facilitates the uneven adherence of Zn0.25Cd0.75S particles to rod-shaped ZnO. A Z-type charge transfer mechanism has been constructed under the influence of the built-in potential at the interface. This mechanism maintains strong redox capacity and achieves efficient carrier separation, improving the hydrogen evolution activity of the composite photocatalyst. The hydrogen production rate reaches 16.5 mmol·g–1·h–1, which is 56 and 9.9 times that of Ni-ZnO and Zn0.25Cd0.75S, respectively.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"106 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111101","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 : 2026-02-03DOI: 10.1021/acs.langmuir.5c05353
Giuliana Valentini,Álvaro Javier Patiño-Agudelo,Paulo Ricardo de Abreu Furtado Garcia,Watson Loh
In this study, we investigated the micellization of bioinspired anionic glycolipids with distinct headgroups (xylose, rhamnose, and galactose) using surface tension, small-angle X-ray scattering (SAXS), and isothermal titration calorimetry (ITC) measurements across a range of temperatures. Surface and interfacial analyses revealed that their critical micelle concentration (CMC) is strongly influenced by the hydrophilicity of their sugar headgroups. SAXS data demonstrated that the aggregates are ellipsoidal micelles, with size and distortion influenced by their headgroup structure. Thermodynamic analyses indicate that micellization is driven by a delicate balance between enthalpic and entropic contributions, both being significantly affected by the sugar ring architecture, particularly the nature of the substituent at the C5 position. These findings show that the chemical features of the headgroup strongly influence the aggregate structure and micellization energetics of ionic glycolipids, providing relevant molecular-level insights for the rational design of new bioinspired amphiphiles.
{"title":"Influence of Sugar Headgroup on the Self-Assembly of Bioinspired Anionic Glycolipids","authors":"Giuliana Valentini,Álvaro Javier Patiño-Agudelo,Paulo Ricardo de Abreu Furtado Garcia,Watson Loh","doi":"10.1021/acs.langmuir.5c05353","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c05353","url":null,"abstract":"In this study, we investigated the micellization of bioinspired anionic glycolipids with distinct headgroups (xylose, rhamnose, and galactose) using surface tension, small-angle X-ray scattering (SAXS), and isothermal titration calorimetry (ITC) measurements across a range of temperatures. Surface and interfacial analyses revealed that their critical micelle concentration (CMC) is strongly influenced by the hydrophilicity of their sugar headgroups. SAXS data demonstrated that the aggregates are ellipsoidal micelles, with size and distortion influenced by their headgroup structure. Thermodynamic analyses indicate that micellization is driven by a delicate balance between enthalpic and entropic contributions, both being significantly affected by the sugar ring architecture, particularly the nature of the substituent at the C5 position. These findings show that the chemical features of the headgroup strongly influence the aggregate structure and micellization energetics of ionic glycolipids, providing relevant molecular-level insights for the rational design of new bioinspired amphiphiles.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"108 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111124","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 : 2026-02-03DOI: 10.1021/acs.langmuir.5c05198
Yue Yuan,Zhefei Yang,Scott T. Retterer,Ilia N. Ivanov,Liam Collins,Tzu-Yen Huang,John Lasseter,Lynnicia Massenburg,Alexis N. Williams,Hanyu Wang
Reducing protein adhesion is a critical strategy in fouling-resistant material innovation, with broad applications spanning biomedical and healthcare devices, biosensors, industrial and environmental systems, and other important technological domains. In this study, we elucidated protein adhesion behavior on polystyrene-based thin films by neutron reflectometry (NR) and quartz crystal microbalance with dissipation (QCM-D), using both lysozyme and bovine serum albumin (BSA) as model proteins. To this end, semifluorinated polystyrene thin films with gradient wettability and surface energy were fabricated through dry processing using plasma oxidation and gas-phase deposition. Although it is believed that a fully fluorinated alkyl chain offers extremely low surface energy, thus rejecting foulants, and has been used in many fouling-resistant surface designs, enhanced protein–surface interactions were observed consistently in NR and QCM-D results, due to the combined effects of surface morphology and chemistry. On the contrary, depositing shorter fluorinated silane onto a hydrophilic PS surface contributed to a more homogeneous nanoscale fluorine coating, resulting in less initial protein adsorption and improved surface recovery. Comparative analysis of proteins with different sizes on the nanopatterned semifluorinated surface revealed the influence of molecular characteristics on surface interactions. Lysozyme, being smaller and more compact, showed faster adsorption kinetics and higher surface coverage but largely reversible binding, whereas BSA, with its larger and more flexible structure, formed broader and more stable interfacial layers. This study fills the gap in understanding protein adhesion within the range of hydrophobicity (water contact angle ∼90°), as current strategies often associate with extreme hydrophilic and superhydrophobic surfaces due to hydration or low-surface-energy rejection mechanisms, respectively. It also provides in-depth insights into current combinatorial fouling-resistant surface design.
{"title":"Protein Adhesion on Semi-Fluorinated Polystyrene Surfaces in Static and Dynamic Measurements","authors":"Yue Yuan,Zhefei Yang,Scott T. Retterer,Ilia N. Ivanov,Liam Collins,Tzu-Yen Huang,John Lasseter,Lynnicia Massenburg,Alexis N. Williams,Hanyu Wang","doi":"10.1021/acs.langmuir.5c05198","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c05198","url":null,"abstract":"Reducing protein adhesion is a critical strategy in fouling-resistant material innovation, with broad applications spanning biomedical and healthcare devices, biosensors, industrial and environmental systems, and other important technological domains. In this study, we elucidated protein adhesion behavior on polystyrene-based thin films by neutron reflectometry (NR) and quartz crystal microbalance with dissipation (QCM-D), using both lysozyme and bovine serum albumin (BSA) as model proteins. To this end, semifluorinated polystyrene thin films with gradient wettability and surface energy were fabricated through dry processing using plasma oxidation and gas-phase deposition. Although it is believed that a fully fluorinated alkyl chain offers extremely low surface energy, thus rejecting foulants, and has been used in many fouling-resistant surface designs, enhanced protein–surface interactions were observed consistently in NR and QCM-D results, due to the combined effects of surface morphology and chemistry. On the contrary, depositing shorter fluorinated silane onto a hydrophilic PS surface contributed to a more homogeneous nanoscale fluorine coating, resulting in less initial protein adsorption and improved surface recovery. Comparative analysis of proteins with different sizes on the nanopatterned semifluorinated surface revealed the influence of molecular characteristics on surface interactions. Lysozyme, being smaller and more compact, showed faster adsorption kinetics and higher surface coverage but largely reversible binding, whereas BSA, with its larger and more flexible structure, formed broader and more stable interfacial layers. This study fills the gap in understanding protein adhesion within the range of hydrophobicity (water contact angle ∼90°), as current strategies often associate with extreme hydrophilic and superhydrophobic surfaces due to hydration or low-surface-energy rejection mechanisms, respectively. It also provides in-depth insights into current combinatorial fouling-resistant surface design.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"7 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111125","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 : 2026-02-03DOI: 10.1021/acs.langmuir.5c05889
Zhenxing Liu,Xingxu Liu,Zhaoyi Zong,Guangyong Liu
Butyl Rubber (IIR) and Brominated Butyl Rubber (BIIR) are potential candidates for the sealing solutions in the lithium-ion battery area. In this work, the electrolyte resistance of IIR- and BIIR-based membranes under various thermo-oxidative conditions is characterized by the evolution of macromolecular structures, mechanical properties, and fluid transport performance. The changes in mechanical properties of the BIIR are more evident than those of IIR after aging under various conditions. FTIR analysis reveals that −Br groups induce aberrant cross-linking and oxidation of BIIR, generating carbonyl groups at 1710 cm–1. Transport kinetics indicates that BIIR exhibits a higher diffusion coefficient and permeability coefficient, while IIR maintains a lower uptake ratio and dimensional stability within the range of 45–80 °C. The electrolyte swelling experiment shows that the residual electrolyte crystal powder on the surface of IIR and BIIR samples increases with the temperature. The permeation activation energies (EP) accounting for the electrolyte resistance are fitted by the Arrhenius equation for IIR and BIIR samples, being in the range of 177.4–208.8 kJ mol–1 and 170.8–203.0 kJ mol–1, respectively. Theoretical support can be obtained from this work for the selection of sealing membrane materials and prediction of service life in the lithium-ion battery area under enhanced thermal-oxidative conditions.
{"title":"Coupled Evolution of Network Structure and Electrolyte Permeation in Butyl-Rubber Sealing Membranes under Thermal-Oxidative Stress","authors":"Zhenxing Liu,Xingxu Liu,Zhaoyi Zong,Guangyong Liu","doi":"10.1021/acs.langmuir.5c05889","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c05889","url":null,"abstract":"Butyl Rubber (IIR) and Brominated Butyl Rubber (BIIR) are potential candidates for the sealing solutions in the lithium-ion battery area. In this work, the electrolyte resistance of IIR- and BIIR-based membranes under various thermo-oxidative conditions is characterized by the evolution of macromolecular structures, mechanical properties, and fluid transport performance. The changes in mechanical properties of the BIIR are more evident than those of IIR after aging under various conditions. FTIR analysis reveals that −Br groups induce aberrant cross-linking and oxidation of BIIR, generating carbonyl groups at 1710 cm–1. Transport kinetics indicates that BIIR exhibits a higher diffusion coefficient and permeability coefficient, while IIR maintains a lower uptake ratio and dimensional stability within the range of 45–80 °C. The electrolyte swelling experiment shows that the residual electrolyte crystal powder on the surface of IIR and BIIR samples increases with the temperature. The permeation activation energies (EP) accounting for the electrolyte resistance are fitted by the Arrhenius equation for IIR and BIIR samples, being in the range of 177.4–208.8 kJ mol–1 and 170.8–203.0 kJ mol–1, respectively. Theoretical support can be obtained from this work for the selection of sealing membrane materials and prediction of service life in the lithium-ion battery area under enhanced thermal-oxidative conditions.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"23 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111102","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 the field of photocatalytic water splitting for hydrogen (H2) production, heterojunction engineering is regarded as one of the effective strategies to enhance the separation efficiency of photogenerated charge carriers and the redox capability. In this work, a simple electrostatic self-assembly method was employed to intimately couple CuWO4 nanoparticles with CdS nanorods, thereby constructing a CdS/CuWO4 heterojunction for photocatalytic H2 evolution from water. In situ XPS and surface photovoltage measurements confirm the presence of a strong built-in electric field (IEF) and an S-scheme charge transfer pathway at the CdS/CuWO4 heterojunction interface. Meanwhile, the IEF strength in the CdS/CuWO4 heterojunction is 2.16 and 5.23 times that of CdS and CuWO4, respectively. Furthermore, DFT calculations reveal that the H* adsorption energy on the CdS/CuWO4 heterojunction is −0.19 eV, compared with −0.57 eV on CdS, indicating that constructing an S-scheme heterojunction can optimally tune the reaction kinetics of photocatalytic H2 evolution and thereby enhance the H2 production activity. Using lactic acid as a sacrificial agent, the optimized CdS/CuWO4 S-scheme heterojunction exhibits a higher H2 evolution rate of 54.53 mmol·g–1·h–1, which is approximately 3.86 times that of CdS nanorods (14.1 mmol·g–1·h–1). Continuous photocatalytic H2 evolution tests demonstrate that the CdS/CuWO4 heterojunction maintains excellent photostability after 12 h of uninterrupted illumination. This study provides insights into the design and development of efficient S-scheme heterojunctions to further improve the activity and stability of photocatalytic H2 production.
{"title":"S-Scheme CdS/CuWO4 Heterojunction Optimizes Reaction Kinetics for Enhanced Photocatalytic H2 Evolution","authors":"Shuang Ma,Wenke Wang,Zhenze Hu,Shukui shi,Peiying Yang,Yanmin Hou,Heng Zhang,Changdong Chen,Zifan wang,Haopeng Jiang","doi":"10.1021/acs.langmuir.5c06431","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c06431","url":null,"abstract":"In the field of photocatalytic water splitting for hydrogen (H2) production, heterojunction engineering is regarded as one of the effective strategies to enhance the separation efficiency of photogenerated charge carriers and the redox capability. In this work, a simple electrostatic self-assembly method was employed to intimately couple CuWO4 nanoparticles with CdS nanorods, thereby constructing a CdS/CuWO4 heterojunction for photocatalytic H2 evolution from water. In situ XPS and surface photovoltage measurements confirm the presence of a strong built-in electric field (IEF) and an S-scheme charge transfer pathway at the CdS/CuWO4 heterojunction interface. Meanwhile, the IEF strength in the CdS/CuWO4 heterojunction is 2.16 and 5.23 times that of CdS and CuWO4, respectively. Furthermore, DFT calculations reveal that the H* adsorption energy on the CdS/CuWO4 heterojunction is −0.19 eV, compared with −0.57 eV on CdS, indicating that constructing an S-scheme heterojunction can optimally tune the reaction kinetics of photocatalytic H2 evolution and thereby enhance the H2 production activity. Using lactic acid as a sacrificial agent, the optimized CdS/CuWO4 S-scheme heterojunction exhibits a higher H2 evolution rate of 54.53 mmol·g–1·h–1, which is approximately 3.86 times that of CdS nanorods (14.1 mmol·g–1·h–1). Continuous photocatalytic H2 evolution tests demonstrate that the CdS/CuWO4 heterojunction maintains excellent photostability after 12 h of uninterrupted illumination. This study provides insights into the design and development of efficient S-scheme heterojunctions to further improve the activity and stability of photocatalytic H2 production.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"176 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111281","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：