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}
To address the limitations of conventional fluorescent probes, including aggregation-caused quenching (ACQ) and poor water solubility, an intelligent nanoprobe (LPNPs@SA) with tumor microenvironment responsiveness and aggregation-induced emission (AIE) properties was developed. This nanoprobe enables sequential, reversible, and highly sensitive detection of Cu2+ and S2–. The AIE-active fluorophore salicylaldehyde azine (SA) was designed and synthesized, exhibiting intense emission in aggregated states but poor stability under non-neutral pH conditions. To overcome this limitation, SA was encapsulated into lipid-polymer hybrid nanoparticles (LPNPs) via self-assembly using an amphiphilic copolymer (C16-SS-PEG/DMMA), polycaprolactone (PCL), and phosphatidylcholine (PC). The resulting LPNPs@SA nanoprobe possessed favorable storage stability, broad pH tolerance, effective surface charge conversion, and good hemocompatibility, with a hemolysis rate below 5%. In terms of sensing performance, the nanoprobe showed selective fluorescence quenching (“turn-off” mode) toward Cu2+. Stern–Volmer analysis revealed a quenching constant (Ksv) of 2.9 × 105 L/mol. Further fluorescence titration and Job’s plot analyses confirmed a 1:1 binding stoichiometry between the nanoprobe and Cu2+, with an association constant (Ka) of 2.2 × 104 L/mol. The detection limit (LOD) for Cu2+ was determined to be 1.2 μmol/L, demonstrating high sensitivity. Remarkably, upon introducing S2– into the copper-loaded nanoprobe system, substantial fluorescence recovery was observed, yielding a distinct “turn-on” signal for S2– detection. In summary, this work presents a biocompatible nanoprobe with excellent optical properties that functions as an effective reversible fluorescence-switching platform. It offers a promising analytical tool for dynamically monitoring Cu2+ and S2– in biological environments, facilitating studies of related pathological processes and potential diagnostic applications.
{"title":"Sequential Turn-on/off Aggregation-Induced Emission Nanoprobe Based on Salicylaldehyde Azine for Detection of Copper(II) and Sulfide Ions","authors":"Shixi Li,Jiamin Feng,Xixi Liu,Xuhua Liang,Min Cheng,Xue Liu,Furong Huang,Ruya Feng,Rong Zheng","doi":"10.1021/acs.langmuir.5c05751","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c05751","url":null,"abstract":"To address the limitations of conventional fluorescent probes, including aggregation-caused quenching (ACQ) and poor water solubility, an intelligent nanoprobe (LPNPs@SA) with tumor microenvironment responsiveness and aggregation-induced emission (AIE) properties was developed. This nanoprobe enables sequential, reversible, and highly sensitive detection of Cu2+ and S2–. The AIE-active fluorophore salicylaldehyde azine (SA) was designed and synthesized, exhibiting intense emission in aggregated states but poor stability under non-neutral pH conditions. To overcome this limitation, SA was encapsulated into lipid-polymer hybrid nanoparticles (LPNPs) via self-assembly using an amphiphilic copolymer (C16-SS-PEG/DMMA), polycaprolactone (PCL), and phosphatidylcholine (PC). The resulting LPNPs@SA nanoprobe possessed favorable storage stability, broad pH tolerance, effective surface charge conversion, and good hemocompatibility, with a hemolysis rate below 5%. In terms of sensing performance, the nanoprobe showed selective fluorescence quenching (“turn-off” mode) toward Cu2+. Stern–Volmer analysis revealed a quenching constant (Ksv) of 2.9 × 105 L/mol. Further fluorescence titration and Job’s plot analyses confirmed a 1:1 binding stoichiometry between the nanoprobe and Cu2+, with an association constant (Ka) of 2.2 × 104 L/mol. The detection limit (LOD) for Cu2+ was determined to be 1.2 μmol/L, demonstrating high sensitivity. Remarkably, upon introducing S2– into the copper-loaded nanoprobe system, substantial fluorescence recovery was observed, yielding a distinct “turn-on” signal for S2– detection. In summary, this work presents a biocompatible nanoprobe with excellent optical properties that functions as an effective reversible fluorescence-switching platform. It offers a promising analytical tool for dynamically monitoring Cu2+ and S2– in biological environments, facilitating studies of related pathological processes and potential diagnostic applications.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"1 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111122","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 conventional synthesis of superparamagnetic Fe3O4 superparamagnetic nanoparticles (Fe3O4SNPs) for biomedical applications often suffers from poor aqueous dispersibility, complex multistep processes, and potential toxicity from organic solvents or surfactants. Achieving precise control over both particle size and magnetic field-driven aggregation state in a biocompatible manner remains a significant challenge. A facile one-pot hydrothermal synthesis strategy was developed using a polysaccharide-iron complex as the precursor to prepare nano-Fe3O4 with excellent water dispersibility. With this method, we achieved precise regulation of Fe3O4 particle size (3.2–12.5 nm) and magnetic field-driven aggregation behavior by optimizing reaction conditions (such as sugar content, NaOH concentration, and reaction time), making them suitable for different biomedical scenarios such as the separation of active ingredients, in vivo targeted delivery, or MRI contrast agent. The solution of synthesized Fe3O4SNPs remained stable at room temperature for up to six months without any precipitation and did not exhibit significant toxicity at different particle sizes. In vitro MRI performance evaluation revealed that Fe3O4SNPs with a particle size of 8.1 nm exhibited a high transverse relaxation rate (r2 = 189.8 mM–1 s–1) and a prominent r2/r1 ratio of 172.5, demonstrating potential as a T2 contrast agent; nanoparticles with a particle size of 4.0 nm displayed an r1 value approximately 1.6 times that of Gd-DTPA contrast agents, showing application potential as T1 contrast agents. This green synthesis method only uses water and polysaccharide iron complexes, thus providing a technical reference for the production of medical magnetic nanomaterials.
{"title":"A Preparation for High Aqueous Dispersion Fe3O4 with Controllable Particle Size and Adjustable Aggregation State in a Magnetic Field","authors":"Yun Zhang,Wei Wei,Yiwen Guo,Jinyu Chai,Lu Liu,Jinhua Zhu","doi":"10.1021/acs.langmuir.5c05472","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c05472","url":null,"abstract":"The conventional synthesis of superparamagnetic Fe3O4 superparamagnetic nanoparticles (Fe3O4SNPs) for biomedical applications often suffers from poor aqueous dispersibility, complex multistep processes, and potential toxicity from organic solvents or surfactants. Achieving precise control over both particle size and magnetic field-driven aggregation state in a biocompatible manner remains a significant challenge. A facile one-pot hydrothermal synthesis strategy was developed using a polysaccharide-iron complex as the precursor to prepare nano-Fe3O4 with excellent water dispersibility. With this method, we achieved precise regulation of Fe3O4 particle size (3.2–12.5 nm) and magnetic field-driven aggregation behavior by optimizing reaction conditions (such as sugar content, NaOH concentration, and reaction time), making them suitable for different biomedical scenarios such as the separation of active ingredients, in vivo targeted delivery, or MRI contrast agent. The solution of synthesized Fe3O4SNPs remained stable at room temperature for up to six months without any precipitation and did not exhibit significant toxicity at different particle sizes. In vitro MRI performance evaluation revealed that Fe3O4SNPs with a particle size of 8.1 nm exhibited a high transverse relaxation rate (r2 = 189.8 mM–1 s–1) and a prominent r2/r1 ratio of 172.5, demonstrating potential as a T2 contrast agent; nanoparticles with a particle size of 4.0 nm displayed an r1 value approximately 1.6 times that of Gd-DTPA contrast agents, showing application potential as T1 contrast agents. This green synthesis method only uses water and polysaccharide iron complexes, thus providing a technical reference for the production of medical magnetic nanomaterials.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"18 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111234","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}
Saccharose (SA) was used as a passivation agent to post-treat an oxidic NiMo/Al2O3 hydrotreating catalyst to inhibit the ambient oxidation of the sulfurized catalyst. The effect of SA usage and passivation temperature on oxidation resistance and dibenzothiophene (DBT) hydrodesulfurization (HDS) activity was investigated. Porous carbonaceous deposits with pore sizes of 3–4 nm formed after passivation could effectively prevent ambient air from entering but allow sulfurizing agents and reactants to access metals under high pressure and temperature. SA passivation significantly improved the oxidation resistance of the sulfurized catalyst. Higher SA usage reduced the oxidation resistance, but higher passivation temperatures enhanced it. For the catalyst passivated at 450 °C with a SA/Ni molar ratio of 1.5 (LHT-1.5–450), the oxidation degrees of Mo and Ni sulfides determined by TG were decreased by 50.3% and 53.6%, respectively, after air exposure for 7 days. Additionally, carbonaceous deposits could act as support-like carbon to prevent metals from aggregation and weaken the metal-alumina interaction, resulting in similar activity between the sulfurized catalysts with and without passivation. The passivated catalysts show a considerable reduction in activity loss after exposure to air. LHT-1.5–450 exhibits the lowest activity loss with a 2.7% reduction in DBT removal over each Mo atom, much less than that of the unpassivated catalyst (12.9%). By combining the oxidation resistance of carbonaceous deposits with their promotional effects on activity, the sulfurized catalyst can preserve its activity after exposure to air.
{"title":"Effects of Saccharose Passivation on Oxidation Resistance and Hydrodesulfurization Activity of Sulfurized NiMo/Al2O3 Catalyst","authors":"Bangqi Zhao,Minghao Wen,Yang Li,Xinyue Liu,Hao Wang,Yan Wu","doi":"10.1021/acs.langmuir.5c06472","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c06472","url":null,"abstract":"Saccharose (SA) was used as a passivation agent to post-treat an oxidic NiMo/Al2O3 hydrotreating catalyst to inhibit the ambient oxidation of the sulfurized catalyst. The effect of SA usage and passivation temperature on oxidation resistance and dibenzothiophene (DBT) hydrodesulfurization (HDS) activity was investigated. Porous carbonaceous deposits with pore sizes of 3–4 nm formed after passivation could effectively prevent ambient air from entering but allow sulfurizing agents and reactants to access metals under high pressure and temperature. SA passivation significantly improved the oxidation resistance of the sulfurized catalyst. Higher SA usage reduced the oxidation resistance, but higher passivation temperatures enhanced it. For the catalyst passivated at 450 °C with a SA/Ni molar ratio of 1.5 (LHT-1.5–450), the oxidation degrees of Mo and Ni sulfides determined by TG were decreased by 50.3% and 53.6%, respectively, after air exposure for 7 days. Additionally, carbonaceous deposits could act as support-like carbon to prevent metals from aggregation and weaken the metal-alumina interaction, resulting in similar activity between the sulfurized catalysts with and without passivation. The passivated catalysts show a considerable reduction in activity loss after exposure to air. LHT-1.5–450 exhibits the lowest activity loss with a 2.7% reduction in DBT removal over each Mo atom, much less than that of the unpassivated catalyst (12.9%). By combining the oxidation resistance of carbonaceous deposits with their promotional effects on activity, the sulfurized catalyst can preserve its activity after exposure to air.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"57 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111098","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 development of sensitive, accurate, and multimodal approaches for the detection of viral gene fragments and the diagnosis of infections is essential for effective pandemic management across various contexts. This study introduces a CRISPR switch integrated with strand displacement amplification (SDA) for the binary channel detection of SARS-CoV-2 gene fragments and the diagnosis of SARS-CoV-2 infections. In the conventional channel, a specific single gene fragment can directly facilitate the formation of a three-way junction, thereby initiating the SDA process and resulting in the production of a substantial amount of single-stranded DNA. In the logical channel, two gene fragments can first induce the release of a substitute, which subsequently leads to the formation of the three-way junction and the ensuing SDA process. The single-stranded SDA product acts as the target sequence that activates the CRISPR switch, which performs reporter cleavage functions, thereby generating enhanced and detectable fluorescence signals. This method achieves sensitive and selective detection of SARS-CoV-2 gene fragments, with limits of detection (LODs) of 1.0 aM for the ORF1ab gene and 0.9 aM for the N gene in the conventional channel and 3.7 aM for simultaneous detection of both ORF1ab and N in the logical channel. Furthermore, accurate detection of these gene fragments in real samples obtained from patients exhibiting upper respiratory symptoms was successfully conducted, along with the corresponding diagnosis of SARS-CoV-2 infections. Consequently, this method represents a novel binary channel approach for viral gene detection and holds significant promise for clinical diagnosis and potential future epidemic control.
{"title":"A CRISPR Switch Integrated with Strand Displacement Amplification for Binary Channel Detection of SARS-CoV-2 Gene Fragments and Infectious Diagnosis","authors":"Wei Li,Manman Duan,Shang Sun,Jiayue Li,Meng Wang,Haiyan Zhao","doi":"10.1021/acs.langmuir.5c06262","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c06262","url":null,"abstract":"The development of sensitive, accurate, and multimodal approaches for the detection of viral gene fragments and the diagnosis of infections is essential for effective pandemic management across various contexts. This study introduces a CRISPR switch integrated with strand displacement amplification (SDA) for the binary channel detection of SARS-CoV-2 gene fragments and the diagnosis of SARS-CoV-2 infections. In the conventional channel, a specific single gene fragment can directly facilitate the formation of a three-way junction, thereby initiating the SDA process and resulting in the production of a substantial amount of single-stranded DNA. In the logical channel, two gene fragments can first induce the release of a substitute, which subsequently leads to the formation of the three-way junction and the ensuing SDA process. The single-stranded SDA product acts as the target sequence that activates the CRISPR switch, which performs reporter cleavage functions, thereby generating enhanced and detectable fluorescence signals. This method achieves sensitive and selective detection of SARS-CoV-2 gene fragments, with limits of detection (LODs) of 1.0 aM for the ORF1ab gene and 0.9 aM for the N gene in the conventional channel and 3.7 aM for simultaneous detection of both ORF1ab and N in the logical channel. Furthermore, accurate detection of these gene fragments in real samples obtained from patients exhibiting upper respiratory symptoms was successfully conducted, along with the corresponding diagnosis of SARS-CoV-2 infections. Consequently, this method represents a novel binary channel approach for viral gene detection and holds significant promise for clinical diagnosis and potential future epidemic control.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"84 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111100","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.5c05638
Shuying Han,Jinli Xiong,Dehui Li,Biwei Qiu,Hua Zou
Multihollow polymer–silica nanocomposite particles combine the advantages of multihollow architectures with those of organic-inorganic nanocomposite particles, yet their synthesis remains challenging and rarely reported. In this work, a convenient route has been developed to synthesize multihollow nanocomposite particles from submicrometer-sized polystyrene-silica (PS-SiO2) nanocomposite particles via swelling in a THF/water mixture and subsequent drying. The influence of key swelling parameters, including the THF concentration, the stirring rate, the swelling time, and the surfactant concentration on the formation of the multihollow nanocomposite particles, is investigated. Optimal conditions (70 vol % THF, 300–500 rpm, 6 h swelling, 10 mg mL–1 SDS) afforded nearly 100% multihollow particles with a mean diameter of ∼1.43 μm, significantly larger than the original particles (∼341 nm), while the silica shell remained intact on the surface. The formation mechanism is proposed to involve THF-induced swelling and plasticization of the PS core, phase separation of water/THF domains within the swollen polymer, and fixation of the hollow structure upon solvent removal. This approach represents a new paradigm in the synthesis of multihollow polymer colloids without requiring specially functionalized polymer precursors.
{"title":"Synthesis of Multihollow Polystyrene-Silica Nanocomposite Particles by Solvent Swelling","authors":"Shuying Han,Jinli Xiong,Dehui Li,Biwei Qiu,Hua Zou","doi":"10.1021/acs.langmuir.5c05638","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c05638","url":null,"abstract":"Multihollow polymer–silica nanocomposite particles combine the advantages of multihollow architectures with those of organic-inorganic nanocomposite particles, yet their synthesis remains challenging and rarely reported. In this work, a convenient route has been developed to synthesize multihollow nanocomposite particles from submicrometer-sized polystyrene-silica (PS-SiO2) nanocomposite particles via swelling in a THF/water mixture and subsequent drying. The influence of key swelling parameters, including the THF concentration, the stirring rate, the swelling time, and the surfactant concentration on the formation of the multihollow nanocomposite particles, is investigated. Optimal conditions (70 vol % THF, 300–500 rpm, 6 h swelling, 10 mg mL–1 SDS) afforded nearly 100% multihollow particles with a mean diameter of ∼1.43 μm, significantly larger than the original particles (∼341 nm), while the silica shell remained intact on the surface. The formation mechanism is proposed to involve THF-induced swelling and plasticization of the PS core, phase separation of water/THF domains within the swollen polymer, and fixation of the hollow structure upon solvent removal. This approach represents a new paradigm in the synthesis of multihollow polymer colloids without requiring specially functionalized polymer precursors.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"22 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111123","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}
Zr-based bulk metallic glasses (Zr-BMGs), Zr58.4Cu28.7Al11.3Nb1.6 (ZR01) and Zr51.8Cu18.2Ni14.8Al10.7Ti4.5 (ZR02), show excellent mechanical properties and contain alloying elements with potential antibacterial activity, such as Cu. In this study, we investigated the surface oxide films and antibacterial activities of ZR01 and ZR02. These samples showed amorphous structures and comparable surface roughness values. Surface analysis revealed that thermodynamically stable metal oxides were detected from the sample surfaces, while Cu was detected in the metallic state. In particular, ZR01 had a higher surface content of Cu than ZR02, suggesting more pronounced Cu segregation, which is consistent with the difference in alloy composition. The in vitro evaluation against methicillin-resistant Staphylococcus aureus (MRSA) showed that ZR01 exhibited antibacterial activity, whereas ZR02 did not, despite a higher level of Cu ion release. Our results support the antibacterial activity of ZR01 caused by the direct contact between metallic Cu in the surface oxide film and bacteria, rather than from the Cu ion release. Furthermore, our results provide the importance of the segregation of Cu on the ZR01 surface for exhibiting its antibacterial activity. These findings suggest that the bulk composition of Zr-BMGs determines the composition of the surface oxide film, which, in turn, affects the surface properties, particularly the antibacterial activity.
{"title":"Surface Oxide Film and Antibacterial Activity of Zirconium-Based Bulk Metallic Glasses","authors":"Zhibin Wang,Masaya Shimabukuro,W. M. Ruvini Lasanthika Kumari Wijekoon,Taiyo Yukawa,Hidemi Kato,Masakazu Kawashita","doi":"10.1021/acs.langmuir.5c05795","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c05795","url":null,"abstract":"Zr-based bulk metallic glasses (Zr-BMGs), Zr58.4Cu28.7Al11.3Nb1.6 (ZR01) and Zr51.8Cu18.2Ni14.8Al10.7Ti4.5 (ZR02), show excellent mechanical properties and contain alloying elements with potential antibacterial activity, such as Cu. In this study, we investigated the surface oxide films and antibacterial activities of ZR01 and ZR02. These samples showed amorphous structures and comparable surface roughness values. Surface analysis revealed that thermodynamically stable metal oxides were detected from the sample surfaces, while Cu was detected in the metallic state. In particular, ZR01 had a higher surface content of Cu than ZR02, suggesting more pronounced Cu segregation, which is consistent with the difference in alloy composition. The in vitro evaluation against methicillin-resistant Staphylococcus aureus (MRSA) showed that ZR01 exhibited antibacterial activity, whereas ZR02 did not, despite a higher level of Cu ion release. Our results support the antibacterial activity of ZR01 caused by the direct contact between metallic Cu in the surface oxide film and bacteria, rather than from the Cu ion release. Furthermore, our results provide the importance of the segregation of Cu on the ZR01 surface for exhibiting its antibacterial activity. These findings suggest that the bulk composition of Zr-BMGs determines the composition of the surface oxide film, which, in turn, affects the surface properties, particularly the antibacterial activity.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"41 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111121","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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