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}
Pub Date : 2026-02-03DOI: 10.1021/acs.langmuir.5c05586
Song Xu,Kangli Xiao,Lei Fang,Xiangjie Niu,Qiang Yuan,Ju Lin,Xiaojuan Jia
The ultraviolet-induced aging of cement-emulsified asphalt (CA) mortar in slab ballastless tracks progressively degrades its dynamic mechanical properties, compromising both ride comfort and operational safety. In order to investigate the ultraviolet (UV) aging of CA mortar, the changes in asphalt components and the degradation patterns of its dynamic mechanical properties were analyzed. Moreover, the linear rheological solid model with a fractional derivative, which accurately reflects the viscoelastic properties of CA mortar, was established to evaluate its UV aging degree. Results showed that CA mortar with an asphalt/cement (A/C) ratio of 0.9 exhibited greater aging sensitivity than that with a ratio of 0.3, with 33% higher increases in asphaltenes, 47% higher increases in dynamic modulus, and the peak loss factor also exhibited a greater decrease after 48 days of UV exposure. Cement enhances the UV-aging resistance of CA mortar by physically shielding asphalt through hydration products and by strengthening cement–asphalt interfacial adhesion at lower A/C ratios, which helps limit light fractions migration and volatilization. The linear rheological solid model demonstrated great fitting accuracy for the dynamic mechanical properties of CA mortar under UV aging, with the fractional order (α) serving as a reliable metric for quantifying the degree of aging.
{"title":"Assessment of Degradation in Dynamic Mechanical Properties and Aging Degree of Cement Emulsified Asphalt Mortar under Ultraviolet Aging","authors":"Song Xu,Kangli Xiao,Lei Fang,Xiangjie Niu,Qiang Yuan,Ju Lin,Xiaojuan Jia","doi":"10.1021/acs.langmuir.5c05586","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c05586","url":null,"abstract":"The ultraviolet-induced aging of cement-emulsified asphalt (CA) mortar in slab ballastless tracks progressively degrades its dynamic mechanical properties, compromising both ride comfort and operational safety. In order to investigate the ultraviolet (UV) aging of CA mortar, the changes in asphalt components and the degradation patterns of its dynamic mechanical properties were analyzed. Moreover, the linear rheological solid model with a fractional derivative, which accurately reflects the viscoelastic properties of CA mortar, was established to evaluate its UV aging degree. Results showed that CA mortar with an asphalt/cement (A/C) ratio of 0.9 exhibited greater aging sensitivity than that with a ratio of 0.3, with 33% higher increases in asphaltenes, 47% higher increases in dynamic modulus, and the peak loss factor also exhibited a greater decrease after 48 days of UV exposure. Cement enhances the UV-aging resistance of CA mortar by physically shielding asphalt through hydration products and by strengthening cement–asphalt interfacial adhesion at lower A/C ratios, which helps limit light fractions migration and volatilization. The linear rheological solid model demonstrated great fitting accuracy for the dynamic mechanical properties of CA mortar under UV aging, with the fractional order (α) serving as a reliable metric for quantifying the degree of aging.","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":"146111285","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}
Achieving reliable hydrogen sensing at room temperature remains a critical challenge due to the limited carrier transport and unstable surface chemistry of conventional polycrystalline oxides. Here, we demonstrate that precise growth-mode control of epitaxial anatase TiO2 thin films via sputtering atmosphere engineering provides an effective route to overcoming these limitations. By systematically tuning the Ar/O2 ratio, the TiO2 growth mode transitions from a defective island-like mode to a layer-by-layer mode and finally to a stress-induced island. The film deposited at an 8/1 Ar/O2 ratio achieves an ideal combination of perfect crystallinity, an atomically flat surface, and a balanced oxygen vacancy concentration, yielding a clean and well-defined Pd-TiO2 interface upon catalyst deposition. The resulting Pd/TiO2 sensor exhibits exceptional room-temperature hydrogen sensing performance: a strong response of 11.34 to 100 ppm of H2, a low detection limit (5 ppm), excellent selectivity over other battery abuse gases, remarkable humidity resistance, and long-term stability. Comprehensive structural and mechanistic analyses reveal that the superior performance originates from an efficient interface-dominated sensing mechanism, rather than the conventional surface reaction pathway. This work establishes a “structure over stoichiometry” paradigm for developing advanced gas sensors and provides an effective route toward high-reliability, low-power hydrogen safety monitoring.
{"title":"Growth-Mode Engineering of Epitaxial TiO2 Thin Films for Room-Temperature Hydrogen Sensing and Battery Safety","authors":"Yuanyuan Fu,Hanwen Chi,Ni Tu,Jianing Mao,Juncheng Li,Zhizhen Ye,Liping Zhu,Jie Jiang","doi":"10.1021/acs.langmuir.5c06387","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c06387","url":null,"abstract":"Achieving reliable hydrogen sensing at room temperature remains a critical challenge due to the limited carrier transport and unstable surface chemistry of conventional polycrystalline oxides. Here, we demonstrate that precise growth-mode control of epitaxial anatase TiO2 thin films via sputtering atmosphere engineering provides an effective route to overcoming these limitations. By systematically tuning the Ar/O2 ratio, the TiO2 growth mode transitions from a defective island-like mode to a layer-by-layer mode and finally to a stress-induced island. The film deposited at an 8/1 Ar/O2 ratio achieves an ideal combination of perfect crystallinity, an atomically flat surface, and a balanced oxygen vacancy concentration, yielding a clean and well-defined Pd-TiO2 interface upon catalyst deposition. The resulting Pd/TiO2 sensor exhibits exceptional room-temperature hydrogen sensing performance: a strong response of 11.34 to 100 ppm of H2, a low detection limit (5 ppm), excellent selectivity over other battery abuse gases, remarkable humidity resistance, and long-term stability. Comprehensive structural and mechanistic analyses reveal that the superior performance originates from an efficient interface-dominated sensing mechanism, rather than the conventional surface reaction pathway. This work establishes a “structure over stoichiometry” paradigm for developing advanced gas sensors and provides an effective route toward high-reliability, low-power hydrogen safety monitoring.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"58 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111099","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.5c05952
Chong Li,Jie Chen,Jian Zheng,Baojiang Liu,Chunyan Hu
Photothermal materials possess efficient light absorption and light-to-energy conversion capabilities, and have been widely applied in research on seawater desalination and sewage treatment. However, traditional solar desalination faces challenges such as poor salt resistance, low photothermal conversion efficiency, and the inability to effectively remove wastewater discharged from seawater. In this study, we designed a self-floating solar evaporator with a vertically arranged and porous structure. By employing a simple “impregnation-crosslinking-reduction” method, we induced cross-linking in balsa wood/MXene/MnO2 (MMW). Among them, MXene exhibits exceptionally Superior efficiency in photothermal energy conversion and is widely applied as a photothermal material in the field of seawater desalination. Meanwhile, MnO2 nanoflowers, rich in oxygen vacancies, can effectively activate peroxydisulfate (PDS), demonstrating efficient catalytic performance. Within the evaporator, they spontaneously establish a wet, porous internal structure and specialized water pathways. Under such conditions, The system demonstrates a maximum evaporation capacity of 1.90 kg m–2 h–1, along with an evaporation efficiency of 113.4%. Moreover, the evaporator demonstrates high degradation rates(94.09% for 50 mg L–1 methylene blue and 95.31% for 100 mg L–1 Rhodamine 6G). In addition, this evaporator enables salt to be expelled from its interior to the surface via convection,which can acquire freshwater efficiently and sustainably. Furthermore, we used the purified water collected from evaporation to irrigate mung beans, which were able to germinate and grow normally. This work provides a direction for the application of evaporators and offers an alternative approach to addressing water scarcity and enhancing water utilization.
光热材料具有高效的光吸收和光能转换能力，在海水淡化和污水处理研究中得到了广泛的应用。然而，传统的太阳能脱盐面临着耐盐性差、光热转换效率低、无法有效去除海水排放废水等挑战。在本研究中，我们设计了一种垂直排列多孔结构的自漂浮式太阳能蒸发器。通过简单的“浸渍-交联-还原”方法，我们诱导了轻木/MXene/MnO2 （MMW）的交联。其中，MXene在光热能量转换方面表现出异常优异的效率，作为光热材料广泛应用于海水淡化领域。同时，MnO2纳米花富含氧空位，能有效活化过硫酸氢盐（PDS），表现出高效的催化性能。在蒸发器内部，它们自发地建立了一个潮湿的、多孔的内部结构和专门的水通道。在此条件下，系统的最大蒸发量为1.90 kg m-2 h-1，蒸发效率为113.4%。此外，蒸发器具有较高的降解率（对50 mg L-1亚甲基蓝的降解率为94.09%，对100 mg L-1罗丹明的降解率为95.31%）。此外，蒸发器使盐通过对流从其内部排出到表面，可以有效和可持续地获取淡水。此外，我们使用蒸发收集的纯化水来灌溉绿豆，绿豆能够正常发芽和生长。本研究为蒸发器的应用提供了方向，为解决水资源短缺和提高水资源利用率提供了另一种途径。
{"title":"A Self-Floating Balsa Wood Solar Evaporator: Simultaneously Achieving Seawater Desalination and Catalytic Degradation","authors":"Chong Li,Jie Chen,Jian Zheng,Baojiang Liu,Chunyan Hu","doi":"10.1021/acs.langmuir.5c05952","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c05952","url":null,"abstract":"Photothermal materials possess efficient light absorption and light-to-energy conversion capabilities, and have been widely applied in research on seawater desalination and sewage treatment. However, traditional solar desalination faces challenges such as poor salt resistance, low photothermal conversion efficiency, and the inability to effectively remove wastewater discharged from seawater. In this study, we designed a self-floating solar evaporator with a vertically arranged and porous structure. By employing a simple “impregnation-crosslinking-reduction” method, we induced cross-linking in balsa wood/MXene/MnO2 (MMW). Among them, MXene exhibits exceptionally Superior efficiency in photothermal energy conversion and is widely applied as a photothermal material in the field of seawater desalination. Meanwhile, MnO2 nanoflowers, rich in oxygen vacancies, can effectively activate peroxydisulfate (PDS), demonstrating efficient catalytic performance. Within the evaporator, they spontaneously establish a wet, porous internal structure and specialized water pathways. Under such conditions, The system demonstrates a maximum evaporation capacity of 1.90 kg m–2 h–1, along with an evaporation efficiency of 113.4%. Moreover, the evaporator demonstrates high degradation rates(94.09% for 50 mg L–1 methylene blue and 95.31% for 100 mg L–1 Rhodamine 6G). In addition, this evaporator enables salt to be expelled from its interior to the surface via convection,which can acquire freshwater efficiently and sustainably. Furthermore, we used the purified water collected from evaporation to irrigate mung beans, which were able to germinate and grow normally. This work provides a direction for the application of evaporators and offers an alternative approach to addressing water scarcity and enhancing water utilization.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"88 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111103","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}
Layered double hydroxides (LDH), characterized by a unique layered structure with exchangeable interlayer anions, are an important class of inorganic functional materials. Their tunable composition and structure make them promising candidates as lubrication additives. However, LDH are limited in their long-term dispersibility and stability, and their compatibility with industrial lubrication mixtures has yet to be fully investigated, so their application in lubrication remains a major difficulty. This study involved the intercalation modification of LDH by alkyl alcohol amine phosphate ionic liquids (PIL) to ensure their stable distribution in water. The results showed that the use of ionic liquid intercalated double hydroxide (PIL-LDH) as an aqueous lubricant additive could significantly reduce friction and wear resistance and even reduce peak wear by 99.7%. PIL-LDH achieves self-lubrication and self-healing through interlayer slip and PIL release combined with chemisorbed and physically deposited layers.
{"title":"Ionic Liquid Functionalized Layered Double Hydroxides Achieve Near-Zero Wear on Steel–Steel Contacts","authors":"Zhengkun Yao,Ru Liu,Zekun Kang,Huanchen Liu,Qingyu Li,Xia Zhang","doi":"10.1021/acs.langmuir.5c05736","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c05736","url":null,"abstract":"Layered double hydroxides (LDH), characterized by a unique layered structure with exchangeable interlayer anions, are an important class of inorganic functional materials. Their tunable composition and structure make them promising candidates as lubrication additives. However, LDH are limited in their long-term dispersibility and stability, and their compatibility with industrial lubrication mixtures has yet to be fully investigated, so their application in lubrication remains a major difficulty. This study involved the intercalation modification of LDH by alkyl alcohol amine phosphate ionic liquids (PIL) to ensure their stable distribution in water. The results showed that the use of ionic liquid intercalated double hydroxide (PIL-LDH) as an aqueous lubricant additive could significantly reduce friction and wear resistance and even reduce peak wear by 99.7%. PIL-LDH achieves self-lubrication and self-healing through interlayer slip and PIL release combined with chemisorbed and physically deposited layers.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"58 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146097831","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：