Pub Date : 2026-03-05DOI: 10.1021/acsomega.5c13167
Rafaelle de Sertorio dos Santos, Ariane Krause Padilha Lorenzett, Gabriela Casa Grande de Matos, Patrícia de Souza Bonfim-Mendonça, Vanderlei Aparecido de Lima, Rubiana Mara Mainardes
Silibinin (SLB) is a poorly water-soluble flavonolignan with relevant therapeutic potential but limited oral bioavailability. In this study, SLB-loaded zein−chitosan nanoparticles (SLB-ZNP) were developed by nanoprecipitation and optimized using a full 24 factorial design to investigate the effects of zein concentration, chitosan concentration, incubation time, and organic-to-water ratio on particle size, polydispersity index (PDI), zeta potential, and encapsulation efficiency. The factorial approach enabled systematic evaluation of the most influential variables and their interactions, with zein and chitosan concentrations exerting major effects on particle size and surface charge, while the organic-to-water ratio significantly affected particle size distribution. The optimized formulation produced nanoparticles with a mean diameter of approximately 145 nm, low PDI (∼0.19), high positive zeta potential (∼+40 mV), and high encapsulation efficiency (∼90%). Transmission electron microscopy revealed spherical and homogeneous nanoparticles, with enhanced structural organization upon SLB incorporation. In vitro cytotoxicity assays in HeLa and SiHa cervical cancer cell lines showed that nanoencapsulation modulates carrier-associated cytotoxicity in a cell line- and concentration-dependent manner. Overall, this study demonstrates the utility of factorial design as a formulation-centered strategy for engineering zein−chitosan nanoparticles with well-defined physicochemical and in vitro properties.
{"title":"Factorial Design−Driven Optimization of Zein−Chitosan Nanoparticles for Oral Delivery of Silibinin","authors":"Rafaelle de Sertorio dos Santos, Ariane Krause Padilha Lorenzett, Gabriela Casa Grande de Matos, Patrícia de Souza Bonfim-Mendonça, Vanderlei Aparecido de Lima, Rubiana Mara Mainardes","doi":"10.1021/acsomega.5c13167","DOIUrl":"https://doi.org/10.1021/acsomega.5c13167","url":null,"abstract":"Silibinin (SLB) is a poorly water-soluble flavonolignan with relevant therapeutic potential but limited oral bioavailability. In this study, SLB-loaded zein−chitosan nanoparticles (SLB-ZNP) were developed by nanoprecipitation and optimized using a full 2<sup>4</sup> factorial design to investigate the effects of zein concentration, chitosan concentration, incubation time, and organic-to-water ratio on particle size, polydispersity index (PDI), zeta potential, and encapsulation efficiency. The factorial approach enabled systematic evaluation of the most influential variables and their interactions, with zein and chitosan concentrations exerting major effects on particle size and surface charge, while the organic-to-water ratio significantly affected particle size distribution. The optimized formulation produced nanoparticles with a mean diameter of approximately 145 nm, low PDI (∼0.19), high positive zeta potential (∼+40 mV), and high encapsulation efficiency (∼90%). Transmission electron microscopy revealed spherical and homogeneous nanoparticles, with enhanced structural organization upon SLB incorporation. In vitro cytotoxicity assays in HeLa and SiHa cervical cancer cell lines showed that nanoencapsulation modulates carrier-associated cytotoxicity in a cell line- and concentration-dependent manner. Overall, this study demonstrates the utility of factorial design as a formulation-centered strategy for engineering zein−chitosan nanoparticles with well-defined physicochemical and in vitro properties.","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"199 1","pages":""},"PeriodicalIF":4.1,"publicationDate":"2026-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147371232","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-05DOI: 10.1021/acsomega.5c10009
Minglei Wang, Pinqiang Cao
Despite the common occurrence of hydrate particle agglomerations in engineering applications and naturally occurring environments, there is still a gap in exploring the agglomeration mechanism of gas hydrate particles in aqueous solutions due to the experimental challenges and limitations. Herein, particle agglomerations of methane hydrates are investigated by using dissipative particle dynamics. Our results show that the agglomeration behaviors of methane hydrate particles are related to particle sizes, the particle size ratios, and the shapes of hydrate particles. Before hydrate particle agglomerations, the distance between any two hydrate particles in these hydrate particle systems exhibits an oscillation manner, and their fluctuation amplitude strongly depends on the particle sizes. Furthermore, the hydrate particle motions in those agglomeration processes are consistent with previous studies at the microscopic scale. This work not only extends the research scale of hydrate particle agglomerations but also provides a new computational method framework for gas hydrate communities in the world.
{"title":"Agglomerations of Methane Hydrate Particles in Aqueous Solutions: Insight from Dissipative Particle Dynamics Simulations","authors":"Minglei Wang, Pinqiang Cao","doi":"10.1021/acsomega.5c10009","DOIUrl":"https://doi.org/10.1021/acsomega.5c10009","url":null,"abstract":"Despite the common occurrence of hydrate particle agglomerations in engineering applications and naturally occurring environments, there is still a gap in exploring the agglomeration mechanism of gas hydrate particles in aqueous solutions due to the experimental challenges and limitations. Herein, particle agglomerations of methane hydrates are investigated by using dissipative particle dynamics. Our results show that the agglomeration behaviors of methane hydrate particles are related to particle sizes, the particle size ratios, and the shapes of hydrate particles. Before hydrate particle agglomerations, the distance between any two hydrate particles in these hydrate particle systems exhibits an oscillation manner, and their fluctuation amplitude strongly depends on the particle sizes. Furthermore, the hydrate particle motions in those agglomeration processes are consistent with previous studies at the microscopic scale. This work not only extends the research scale of hydrate particle agglomerations but also provides a new computational method framework for gas hydrate communities in the world.","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"29 1","pages":""},"PeriodicalIF":4.1,"publicationDate":"2026-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147371275","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-05DOI: 10.1021/acsomega.5c12466
João Gabriel da Cruz e Silva, Fernando de Sá Ribeiro, Luís Maurício T. R. Lima
Insulin is known to form subvisible particles and amyloid material, which can lead to iatrogenic amyloidosis and reduced potency necessary for glycemic control. In the intensive care unit, insulin is commonly diluted in saline (1-unit/mL) for intravenous infusion. While reports of insulin aggregation in such dilutions exist, it remains unclear whether these conditions favor the formation of amyloid or subvisible particles. Here, we report standardized assays for detecting amorphous and amyloid insulin aggregation and applied them to investigate these particles in insulin infusion setups. Amorphous insulin was produced by heating insulin (100 U/mL) in plastic tubes, while amyloid insulin formed within 3 days by incubating in saline or sodium phosphate buffer, pH 7.0. Electron microscopy confirmed the amyloid nature of these aggregates, and dynamic light scattering detected subvisible particles as low as 0.05 U/mL. Insulin incubated at 1-unit/mL in saline showed no detectable amyloid material or subvisible particles up to 48 h at room temperature. These results suggest that insulin diluted to 1-unit/mL in saline does not form detectable amyloid or subvisible particles under the tested conditions and that these analytical approaches may be helpful for other biopharmaceuticals.
{"title":"Physicochemical Stability of Insulin and Analogues in Saline Infusion: Screening for Amyloid and Amorphous High-Molecular-Weight Material","authors":"João Gabriel da Cruz e Silva, Fernando de Sá Ribeiro, Luís Maurício T. R. Lima","doi":"10.1021/acsomega.5c12466","DOIUrl":"https://doi.org/10.1021/acsomega.5c12466","url":null,"abstract":"Insulin is known to form subvisible particles and amyloid material, which can lead to iatrogenic amyloidosis and reduced potency necessary for glycemic control. In the intensive care unit, insulin is commonly diluted in saline (1-unit/mL) for intravenous infusion. While reports of insulin aggregation in such dilutions exist, it remains unclear whether these conditions favor the formation of amyloid or subvisible particles. Here, we report standardized assays for detecting amorphous and amyloid insulin aggregation and applied them to investigate these particles in insulin infusion setups. Amorphous insulin was produced by heating insulin (100 U/mL) in plastic tubes, while amyloid insulin formed within 3 days by incubating in saline or sodium phosphate buffer, pH 7.0. Electron microscopy confirmed the amyloid nature of these aggregates, and dynamic light scattering detected subvisible particles as low as 0.05 U/mL. Insulin incubated at 1-unit/mL in saline showed no detectable amyloid material or subvisible particles up to 48 h at room temperature. These results suggest that insulin diluted to 1-unit/mL in saline does not form detectable amyloid or subvisible particles under the tested conditions and that these analytical approaches may be helpful for other biopharmaceuticals.","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"36 1","pages":""},"PeriodicalIF":4.1,"publicationDate":"2026-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147371194","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Paclitaxel (Taxol) is a widely used anticancer drug, but its limited natural availability necessitates alternative production strategies. In this study, Aspergillus flavus isolated from wastewater was identified as a source of paclitaxel, which was confirmed by chromatographic and spectroscopic analyses. To improve solubility and delivery, paclitaxel was incorporated into a three-dimensional bioprinted hydrogel composed of sodium alginate and hyaluronic acid. A 2:1 sodium alginate-to-hyaluronic acid ratio provided the most suitable formulation, as it balanced viscosity, stability, and printability. The resulting scaffolds exhibited uniform porosity and elastic recovery, supporting controlled drug release. Paclitaxel-loaded hydrogels showed significant cytotoxicity against breast cancer cells (IC50 = 11.63 μg/mL) and inhibited cell migration. These findings demonstrate a sustainable microbial route for paclitaxel production and highlight the potential of bioprinted hydrogels for targeted, controlled anticancer therapy.
{"title":"Development of an Anticancer Fungal Paclitaxel-Loaded Hydrogel System via 3D Bioprinting: A Next-Generation Biomedical Platform","authors":"Swathe Sriee Angalaparameshwari Elayarasan, Vijayalakshmi Shankar","doi":"10.1021/acsomega.5c07662","DOIUrl":"https://doi.org/10.1021/acsomega.5c07662","url":null,"abstract":"Paclitaxel (Taxol) is a widely used anticancer drug, but its limited natural availability necessitates alternative production strategies. In this study, <i>Aspergillus flavus</i> isolated from wastewater was identified as a source of paclitaxel, which was confirmed by chromatographic and spectroscopic analyses. To improve solubility and delivery, paclitaxel was incorporated into a three-dimensional bioprinted hydrogel composed of sodium alginate and hyaluronic acid. A 2:1 sodium alginate-to-hyaluronic acid ratio provided the most suitable formulation, as it balanced viscosity, stability, and printability. The resulting scaffolds exhibited uniform porosity and elastic recovery, supporting controlled drug release. Paclitaxel-loaded hydrogels showed significant cytotoxicity against breast cancer cells (IC<sub>50</sub> = 11.63 μg/mL) and inhibited cell migration. These findings demonstrate a sustainable microbial route for paclitaxel production and highlight the potential of bioprinted hydrogels for targeted, controlled anticancer therapy.","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"6 1","pages":""},"PeriodicalIF":4.1,"publicationDate":"2026-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147371199","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-05DOI: 10.1021/acsomega.5c10598
Ivana Karabogdan, Francisco Yanqui-Rivera, Deepak Sayeeram, Ahmed Sadik, Aubry K. Miller, Saskia Trump, Ute F. Röhrig, Christiane A. Opitz
The aryl hydrocarbon receptor (AHR) is a ligand-activated transcription factor involved in metabolism, cell motility, development, and immune responses. Its dysregulation is linked to various diseases, including cancer, in which it can enhance tumor progression and suppress immune responses. High-resolution cryo-electron microscopy (cryo-EM) structures of the human cytosolic AHR complex have recently been solved and have provided insights into its agonist-binding mechanisms. However, our understanding of AHR antagonist binding remains limited. Our computational study, using the structure of the indirubin-bound human cytosolic AHR complex together with state-of-the-art docking algorithms and molecular dynamics simulations, suggests that AHR antagonists may bind either to the ligand-binding pocket or to alternative, as yet unexplored, sites outside of the ligand-binding pocket. These findings suggest novel molecular mechanisms of AHR inhibition and provide the foundation for experimental evaluation to advance our understanding of the therapeutic potential of current AHR inhibitors and to support future drug development efforts.
{"title":"Exploration of Agonist and Antagonist Binding Sites within the Cytosolic AHR Complex Using Molecular Modeling","authors":"Ivana Karabogdan, Francisco Yanqui-Rivera, Deepak Sayeeram, Ahmed Sadik, Aubry K. Miller, Saskia Trump, Ute F. Röhrig, Christiane A. Opitz","doi":"10.1021/acsomega.5c10598","DOIUrl":"https://doi.org/10.1021/acsomega.5c10598","url":null,"abstract":"The aryl hydrocarbon receptor (AHR) is a ligand-activated transcription factor involved in metabolism, cell motility, development, and immune responses. Its dysregulation is linked to various diseases, including cancer, in which it can enhance tumor progression and suppress immune responses. High-resolution cryo-electron microscopy (cryo-EM) structures of the human cytosolic AHR complex have recently been solved and have provided insights into its agonist-binding mechanisms. However, our understanding of AHR antagonist binding remains limited. Our computational study, using the structure of the indirubin-bound human cytosolic AHR complex together with state-of-the-art docking algorithms and molecular dynamics simulations, suggests that AHR antagonists may bind either to the ligand-binding pocket or to alternative, as yet unexplored, sites outside of the ligand-binding pocket. These findings suggest novel molecular mechanisms of AHR inhibition and provide the foundation for experimental evaluation to advance our understanding of the therapeutic potential of current AHR inhibitors and to support future drug development efforts.","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"9 1","pages":""},"PeriodicalIF":4.1,"publicationDate":"2026-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147371221","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-05DOI: 10.1021/acsomega.6c00218
Chi Ho Lee, Jay Liu, Joseph Sang-Il Kwon
Per- and polyfluoroalkyl substances (PFAS) are persistent pollutants with highly stable carbon–fluorine bonds, which makes catalytic degradation difficult. Among various catalytic strategies, electrochemical reduction has emerged as a practical alternative because it promotes C–F cleavage and H/F exchange. Transition metals (TMs) are particularly attractive for this process, since their conductivity and d-orbitals facilitate electron transfer into the C–F bond. Yet many theoretical studies overlook essential electrochemical factors; these include the hydrogen evolution reaction, surface oxidation, fluorine poisoning, and physisorption exclusion, and neglecting them limits realistic assessment of TM catalysts for PFAS degradation. Consequently, no theoretical framework exists to systematically screen catalysts under such rigorous constraints. To bridge this gap, we developed a theoretical screening protocol and applied it to 27 TMs, evaluating 81 surface facets. Specifically, this approach evaluates the viability of each metal surface for the electrochemical C–F cleavage in perfluorobutanoic acid (PFBA), chosen as a representative short-chain PFAS. Our screening incorporates all four essential electrochemical criteria, enabling the identification of 14 promising TM surface facets that satisfy the demanding requirements for PFBA degradation. An interesting trend emerging from this screening is that the difficulty of C–F cleavage is closely tied to how effectively electron density accumulates on the reacting carbon site. As defluorination progresses, later cleavage steps show sharply reduced charge transfer and correspondingly higher reaction free energies. This relationship suggests that a simple electronic descriptor can anticipate when C–F cleavage becomes energetically demanding.
{"title":"Theoretical Guidelines for Electrochemical C–F Bond Cleavage in Perfluorobutanoic Acid Using Transition Metal Catalysts","authors":"Chi Ho Lee, Jay Liu, Joseph Sang-Il Kwon","doi":"10.1021/acsomega.6c00218","DOIUrl":"https://doi.org/10.1021/acsomega.6c00218","url":null,"abstract":"Per- and polyfluoroalkyl substances (PFAS) are persistent pollutants with highly stable carbon–fluorine bonds, which makes catalytic degradation difficult. Among various catalytic strategies, electrochemical reduction has emerged as a practical alternative because it promotes C–F cleavage and H/F exchange. Transition metals (TMs) are particularly attractive for this process, since their conductivity and d-orbitals facilitate electron transfer into the C–F bond. Yet many theoretical studies overlook essential electrochemical factors; these include the hydrogen evolution reaction, surface oxidation, fluorine poisoning, and physisorption exclusion, and neglecting them limits realistic assessment of TM catalysts for PFAS degradation. Consequently, no theoretical framework exists to systematically screen catalysts under such rigorous constraints. To bridge this gap, we developed a theoretical screening protocol and applied it to 27 TMs, evaluating 81 surface facets. Specifically, this approach evaluates the viability of each metal surface for the electrochemical C–F cleavage in perfluorobutanoic acid (PFBA), chosen as a representative short-chain PFAS. Our screening incorporates all four essential electrochemical criteria, enabling the identification of 14 promising TM surface facets that satisfy the demanding requirements for PFBA degradation. An interesting trend emerging from this screening is that the difficulty of C–F cleavage is closely tied to how effectively electron density accumulates on the reacting carbon site. As defluorination progresses, later cleavage steps show sharply reduced charge transfer and correspondingly higher reaction free energies. This relationship suggests that a simple electronic descriptor can anticipate when C–F cleavage becomes energetically demanding.","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"193 1","pages":""},"PeriodicalIF":4.1,"publicationDate":"2026-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147371142","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-05DOI: 10.1021/acsomega.5c09595
Ting Tao, Qilin Liu, Yahui Xu
During multistage fracturing, cyclic loading can easily lead to cement sheath failure and annular pressure leakage. To clarify the evolution of stress states and their impact on annular sealing integrity, this study applies shakedown theory. The cement sheath is treated as an ideal elastoplastic material, and the Mohr–Coulomb criterion is used to derive an analytical solution for the shakedown limit load. The effects of in situ stress, wellbore geometry, material parameters, and fracturing operations on the cement sheath are systematically analyzed. Results show that the shakedown limit load of the cement sheath is influenced by in situ stress, wellbore geometry, and cement properties. The limit load increases with higher in situ stress but decreases as the diameter ratio increases. Both the cohesion and internal friction angle of the cement significantly enhance its load-bearing capacity. In Well L119, the bottom-hole pressure during fracturing exceeded the elastic limit. When the inner wall pressure reached 123.10 MPa, the cement sheath yielded plastically. The plastic zone nonlinearly propagated from the inner wall to a radius of 242.5 mm. Therefore, cement sheaths in deeper sections exhibit better structural stability, while the sealing integrity of shallow sections should be carefully monitored during multistage fracturing. Optimizing the well design with a diameter ratio of 0.64 and using cement with a higher cohesion and internal friction angle can effectively improve the resistance of the cement to damage and its load-bearing limit. This study offers a quantitative basis for optimizing fracturing parameters and provides practical guidance for wellbore integrity management.
{"title":"Research on the Damage Evolution Mechanism of the Cement Sheath under Hydraulic Fracturing Cyclic Loading Conditions","authors":"Ting Tao, Qilin Liu, Yahui Xu","doi":"10.1021/acsomega.5c09595","DOIUrl":"https://doi.org/10.1021/acsomega.5c09595","url":null,"abstract":"During multistage fracturing, cyclic loading can easily lead to cement sheath failure and annular pressure leakage. To clarify the evolution of stress states and their impact on annular sealing integrity, this study applies shakedown theory. The cement sheath is treated as an ideal elastoplastic material, and the Mohr–Coulomb criterion is used to derive an analytical solution for the shakedown limit load. The effects of in situ stress, wellbore geometry, material parameters, and fracturing operations on the cement sheath are systematically analyzed. Results show that the shakedown limit load of the cement sheath is influenced by in situ stress, wellbore geometry, and cement properties. The limit load increases with higher in situ stress but decreases as the diameter ratio increases. Both the cohesion and internal friction angle of the cement significantly enhance its load-bearing capacity. In Well L119, the bottom-hole pressure during fracturing exceeded the elastic limit. When the inner wall pressure reached 123.10 MPa, the cement sheath yielded plastically. The plastic zone nonlinearly propagated from the inner wall to a radius of 242.5 mm. Therefore, cement sheaths in deeper sections exhibit better structural stability, while the sealing integrity of shallow sections should be carefully monitored during multistage fracturing. Optimizing the well design with a diameter ratio of 0.64 and using cement with a higher cohesion and internal friction angle can effectively improve the resistance of the cement to damage and its load-bearing limit. This study offers a quantitative basis for optimizing fracturing parameters and provides practical guidance for wellbore integrity management.","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"4 1","pages":""},"PeriodicalIF":4.1,"publicationDate":"2026-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147371198","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-05DOI: 10.1021/acsomega.5c08905
Lucas A. Portela, Aline R. Passos
Hierarchically porous silica was prepared via a sol–gel route accompanied by phase separation, using low-molecular-weight poly(ethylene oxide) (PEO) as a phase separation inducer. The interplay between gelation and spinodal decomposition was investigated in situ through the combined use of ultra-small-angle X-ray scattering (USAXS) and X-ray photon correlation spectroscopy (XPCS), enabling simultaneous characterization of structural and dynamic evolution. The silica-rich domains are initially formed by ramified cluster aggregates, which progressively grow and reorganize into more compact structures as gelation proceeds. Arrest of the transient phase-separated state occurs when the gel network structure becomes established, dominated by superdiffusive dynamics, and constrains further growth of the separated domains. Increasing PEO content induces earlier gelation and earlier arrest of the phase-separated transient state, leading to thinner silica skeletons and smaller macropores in the final material. The results establish how the initial composition modulates the sol–gel transition and the arrest of separated domains, which control the pore size. The insights obtained in this work contribute to a deeper understanding of how gelation and phase separation govern the development of hierarchical porosity in silica materials, which is critical for designing materials with tailored structural and functional properties.
{"title":"In Situ Coherent X-Ray Scattering Investigation of Macropore Formation in Porous Silica","authors":"Lucas A. Portela, Aline R. Passos","doi":"10.1021/acsomega.5c08905","DOIUrl":"https://doi.org/10.1021/acsomega.5c08905","url":null,"abstract":"Hierarchically porous silica was prepared via a sol–gel route accompanied by phase separation, using low-molecular-weight poly(ethylene oxide) (PEO) as a phase separation inducer. The interplay between gelation and spinodal decomposition was investigated in situ through the combined use of ultra-small-angle X-ray scattering (USAXS) and X-ray photon correlation spectroscopy (XPCS), enabling simultaneous characterization of structural and dynamic evolution. The silica-rich domains are initially formed by ramified cluster aggregates, which progressively grow and reorganize into more compact structures as gelation proceeds. Arrest of the transient phase-separated state occurs when the gel network structure becomes established, dominated by superdiffusive dynamics, and constrains further growth of the separated domains. Increasing PEO content induces earlier gelation and earlier arrest of the phase-separated transient state, leading to thinner silica skeletons and smaller macropores in the final material. The results establish how the initial composition modulates the sol–gel transition and the arrest of separated domains, which control the pore size. The insights obtained in this work contribute to a deeper understanding of how gelation and phase separation govern the development of hierarchical porosity in silica materials, which is critical for designing materials with tailored structural and functional properties.","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"53 1","pages":""},"PeriodicalIF":4.1,"publicationDate":"2026-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147371224","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hydroxyl radical (•OH)-based decontamination approach is considered an efficient and eco-friendly technology, which can be a competitive solution to odor pollution. Geosmin (GSM) is an odor metabolite produced by the cyanobacterium Anabaena sp., which can seriously compromise the drinking water source quality. The independently developed •OH equipment based on strong ionization discharge produced •OH solution with high concentration, which was identified using electron spin resonance spectroscopy. Complete inactivation on Anabaena sp. and efficient degradation on GSM (to 4.26 ng/L, which is below the odor threshold of 10 ng/L) by •OH occurred concurrently within 12 s at a total reactive oxidant (TRO) concentration of 1.1 mg/L. The scanning electron microscopy results revealed that Anabaena sp. cells kept their physical integrity during •OH inactivation. The intracellular GSM barely released from the cells. The results of gas chromatograph/mass spectrometer analyses showed that the chromatogram converged to the baseline with a TRO concentration of 3 mg/L in 12 s, demonstrating that GSM was mineralized. •OH can open the ring structures to finally form CO2, H2O, and inorganic ions. While O3 and ClO2 failed to mineralize GSM when the reaction times are 10 and 60 min. Hence, •OH can inactivate Anabaena sp. without cell integrity loss and mineralize GSM simultaneously, the results of which support that the •OH technology may serve as the next-generation drinking water treatment to control algal odor problems.
{"title":"Hydroxyl Radical-Mediated System for Effective Geosmin Mineralization and Anabaena sp. Inactivation for the Decontamination of Drinking Water","authors":"Yubo Zhang, Ying Jie, Yixuan Yu, Chenzheng Wei, Jinming Liu, Yanming Liu, Mindong Bai","doi":"10.1021/acsomega.5c08792","DOIUrl":"https://doi.org/10.1021/acsomega.5c08792","url":null,"abstract":"Hydroxyl radical (<sup>•</sup>OH)-based decontamination approach is considered an efficient and eco-friendly technology, which can be a competitive solution to odor pollution. Geosmin (GSM) is an odor metabolite produced by the cyanobacterium <i>Anabaena</i> sp., which can seriously compromise the drinking water source quality. The independently developed <sup>•</sup>OH equipment based on strong ionization discharge produced <sup>•</sup>OH solution with high concentration, which was identified using electron spin resonance spectroscopy. Complete inactivation on <i>Anabaena</i> sp. and efficient degradation on GSM (to 4.26 ng/L, which is below the odor threshold of 10 ng/L) by <sup>•</sup>OH occurred concurrently within 12 s at a total reactive oxidant (TRO) concentration of 1.1 mg/L. The scanning electron microscopy results revealed that <i>Anabaena</i> sp. cells kept their physical integrity during <sup>•</sup>OH inactivation. The intracellular GSM barely released from the cells. The results of gas chromatograph/mass spectrometer analyses showed that the chromatogram converged to the baseline with a TRO concentration of 3 mg/L in 12 s, demonstrating that GSM was mineralized. <sup>•</sup>OH can open the ring structures to finally form CO<sub>2</sub>, H<sub>2</sub>O, and inorganic ions. While O<sub>3</sub> and ClO<sub>2</sub> failed to mineralize GSM when the reaction times are 10 and 60 min. Hence, <sup>•</sup>OH can inactivate <i>Anabaena</i> sp. without cell integrity loss and mineralize GSM simultaneously, the results of which support that the <sup>•</sup>OH technology may serve as the next-generation drinking water treatment to control algal odor problems.","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"53 1","pages":""},"PeriodicalIF":4.1,"publicationDate":"2026-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147371193","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-05DOI: 10.1021/acsomega.5c11138
Shengqian Wu, Xiaocheng Wang, Yun Ma, Lin Ma
This work reports the use of red mud (RM) (a widely available industrial byproduct) as the primary raw material for synthesizing cost-effective MIL-53(Fe) (denoted as RM-MIL-53(Fe)), which was subsequently applied for the high-efficiency removal of methylene blue (MB) from aqueous environments. The optimum preparation conditions of RM-MIL-53(Fe) were determined by analyzing the crystal structure and adsorption performance, as follows: pH 1.85, mass ratio of RM to terephthalic acid disodium salt (Na2BDC) 1:0.5, stirring speed 450 rpm, and temperature 80 °C. Characterization results verified the successful construction of a metal–organic framework possessing the typical MIL-53(Fe) topology, which exhibited a notably high specific surface area of 176.5 mg·g–1. Fitting the equilibrium adsorption data to the Langmuir model yielded a high correlation coefficient, indicating that MB uptake occurred via monolayer coverage on a uniform surface. The calculated saturation capacity reached 167.8 mg·g–1. Thermodynamic parameters demonstrated that the MB adsorption process on RM-MIL-53(Fe) was thermodynamically spontaneous, where chemisorption acted as the dominant mechanism, and electrostatic interaction served as the auxiliary pathway. Kinetic data fitting results exhibited a superior correlation with the pseudo-second-order kinetic model, further confirming the predominance of chemisorption in the adsorption process. Furthermore, intraparticle diffusion and liquid film diffusion were identified as the colimiting steps governing the adsorption rate. The adsorption efficacy of RM-MIL-53(Fe) was strongly dependent on the sorbent dosage, solution pH, and coexisting ionic species. Mechanistic analysis revealed that MB retention on RM-MIL-53(Fe) proceeded via a combination of hydrogen bonds, π–π stacking interactions, electrostatic forces, and intrapore filling.
本文报道了利用红泥（一种广泛使用的工业副产物）作为主要原料合成具有成本效益的MIL-53(Fe)（表示为RM-MIL-53(Fe)），随后将其用于水环境中亚甲基蓝（MB）的高效去除。通过晶体结构和吸附性能分析，确定了RM- mil -53（Fe）的最佳制备条件：pH为1.85，RM与对苯二甲酸二钠盐（Na2BDC）的质量比为1:0.5，搅拌速度为450 rpm，温度为80℃。表征结果证实成功构建了具有典型MIL-53（Fe）拓扑结构的金属有机骨架，其比表面积高达176.5 mg·g-1。将平衡吸附数据拟合到Langmuir模型中得到了很高的相关系数，表明MB的吸收是通过均匀表面上的单层覆盖发生的。计算饱和容量达到167.8 mg·g-1。热力学参数表明，MB在RM-MIL-53（Fe）上的吸附过程为热力学自发过程，化学吸附为主要吸附机理，静电相互作用为辅助吸附途径。动力学数据拟合结果与拟二级动力学模型具有较好的相关性，进一步证实了化学吸附在吸附过程中占主导地位。此外，颗粒内扩散和液膜扩散是控制吸附速率的限制步骤。RM-MIL-53（Fe）的吸附效果与吸附剂用量、溶液pH和共存离子种类密切相关。机制分析表明，MB在RM-MIL-53（Fe）上的保留是通过氢键、π -π堆叠相互作用、静电力和孔内填充的组合进行的。
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