ACS Applied Materials & Interfaces最新文献

{"title":"Current Direction Regulates Ion Transport Across Layer-by-Layer One-Side-Coated Ion-Exchange Membranes in Electrodialysis","authors":"Alaaeldin A. E. Elozeiri, Jouke E. Dykstra, Rob G. H. Lammertink, Huub H. M. Rijnaarts","doi":"10.1021/acsami.5c00155","DOIUrl":"https://doi.org/10.1021/acsami.5c00155","url":null,"abstract":"Polyelectrolyte multilayer (PEM) modified membranes can attain selective ion separations in electrodialysis with several potential applications, such as sustainable brine management. To understand the ion transport across PEM-coated membranes, we coated six different commercial cation-exchange membranes (CEMs) with PEM via the layer-by-layer technique. Coating one side of the membrane with a PEM leads to an asymmetric current–voltage response in case of solutions containing Mg²⁺ and Ca²⁺ ions. When the coating faces the counterion transport direction (FT), the coated membrane reaches a limiting current density which does not occur if the applied current is reversed. We investigated these phenomena via several electrochemical techniques. After coating, the total membrane resistance increases significantly at solutions of Mg²⁺ or Ca²⁺ (relative to the bare membrane resistance). Furthermore, the transport characteristics of the PEM coating are highly influenced by the base membrane resistance and fixed-charge density. Regarding the counterion type, the resistance of the coated membrane increases in the same order as the bare membrane: K⁺ < Na⁺< Ca²⁺ < Mg²⁺. The higher the bare membrane resistance is, the higher the PEM resistance is. The co-ion valency (i.e., monovalent Cl^– or divalent SO₄^2–) had limited to insignificant effects on the current–voltage response of the coated membranes. Therefore, dielectric exclusion is insignificant for these coated membranes at the tested concentrations, i.e., 0.25 M SO₄^2–. Lastly, we employed an ion transport model to explain the observed effect of the current direction on the current–voltage response and analyze the effective properties of the PEM coating.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"70 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-03-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143736480","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Modular Platform for Efficient Assembly of Multifunctional Antibodies Using Orthogonal Protein–Protein Interactions","authors":"Baizhen Gao, Rushant Sabnis, Siddhi Kotnis, Sofia Feliciano, Kyge Poling, Tracy Mei, Min Feng, Jugal Kishore Das, Jianxun Song, Qing Sun","doi":"10.1021/acsami.4c21958","DOIUrl":"https://doi.org/10.1021/acsami.4c21958","url":null,"abstract":"Multifunctional antibodies, capable of simultaneously engaging multiple targets, are a unique class of antibodies that have sparked growing interest. Current approaches for making multifunctional antibodies, including chemical conjugation or genetic modifications, suffer from low product yield, complex structure design, and complicated manufacturing processes. In this study, we report a modular post-translational platform with highly specific protein–protein interactions for multifunctional antibody assembly and an elastin-like polypeptide (ELP) for easy purification. We generated and purified multifunctional antibodies with over 90% assembled scaffold and overall product purity. Additionally, we assembled antibodies with diverse applications, including detecting cancer, inhibiting cancer cell growth, and directing T cells to cancer cells for enhanced therapeutic efficacy. This platform offers high assembly efficiency, easy purification, and modularity for the redesign of antibody functions.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"102 4 Pt 1 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-03-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143736680","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Hierarchical Cellular Engineering toward Exceptional Mechanical and Thermal Insulating Aerogels","authors":"Yang Ding, Xin Song, Fangjun Shao, Xiaolong Li, Guohuan Gu, Zhongzhe Wei, Jianguo Wang","doi":"10.1021/acsami.5c02175","DOIUrl":"https://doi.org/10.1021/acsami.5c02175","url":null,"abstract":"Aerogels are considered highly promising materials for superior thermal insulation across building, electric vehicle, and textile area. Nevertheless, the inherent deficiency in mechanical compressibility and stability of sole ceramic aerogels poses significant challenges to their further application. The hybrid aerogels with an oriented cellular structure and parallel walls connected by bridges in the orthogonal direction are presented through a physical process. The fibrous frames composed of bacterial cellulose are constructed and enhanced by montmorillonite nanosheets and silica sols through the self-assembly process to achieve high compressibility (>99% strain) and mechanical robustness (1.015 MPa), retaining 97.8% height retention under a considerable compressive strain of 50% for 500 cycles. Moreover, the aerogels demonstrate a remarkable set of properties, such as being superlight (8.85 mg·cm^–3 and 99.39% porosity), excellent thermal insulating performance (λ = 0.0131 W·m^–1·K^–1), wide working temperature range (−196 to 200 °C), self-extinguishing, and self-cleaning/hydrophobic performance (126.4° WCA). The successful synthesis of hybrid aerogels provides more opportunities to design high compressive and mechanical robust aerogels for thermal management.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"11 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-03-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143736484","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Dual-Regulated Biomimetic Nanocomposites For Promoted Tumor Photodynamic Immunotherapy","authors":"Li Liao, Yufei Liu, Xianhai Li, Zewei Jiang, Zhijie Jiang, Jing Yao","doi":"10.1021/acsami.5c00763","DOIUrl":"https://doi.org/10.1021/acsami.5c00763","url":null,"abstract":"Effective tumor immunotherapy is hindered by an immunosuppressive tumor microenvironment (TME), especially in triple-negative breast cancer. Though phototherapy could induce immunogenic cell death (ICD) to increase antitumor immunity, the simultaneous upregulation of indoleamine 2,3-dioxygenase (IDO) induces the negative immunomodulatory effect termed as the “immune-metabolism” loop to compromise immunotherapeutic efficacy. Herein, we developed IMMGP consisting of biomimetic IND-Mn@PM (IDP) and ICG-MnO₂@PM (IMP), which combines the phototherapy-induced ICD and metabolic reprogramming to solve the dilemma. During the light-on phase, IMP effectively kills cancer cells with potent photodynamic ROS generation with the assistance of MnO₂-produced oxygen and induces ICD to reverse the immunosuppressive TME. In the light-off phase, Mn²⁺ (from IDP and MnO₂-based redox reaction) elicits a Fenton-like reaction to relay ROS generation, which is further orchestrated with continuous exhaustion of intratumoral GSH by the conversion of Mn³⁺ to Mn²⁺, and promotes dendritic cell maturation. Moreover, the released indoximod (IND) downregulated IDO to inhibit kynurenine metabolism, which reinvigorates T cell-mediated antitumor immunity. Collectively, IMMGP amplifies the immune response by breaking the “immune-metabolism” loop and sustaining the “immunologically hot” state after phototherapy, thus leading to nearly complete tumor inhibition (94.25%). Thus, IMMGP-mediated dual-phase photodynamic immunotherapy offers a novel approach in cancer nanomedicine.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"216 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-03-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143736482","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Nonmonotonic Enhancement of Friction Regulation via Strain-Induced Moiré Patterns on MoS2 Substrate Surface","authors":"Yun Dong, Chunjie Zhang, Rong Deng, Yi Tao, Yuxin Zhang","doi":"10.1021/acsami.5c01833","DOIUrl":"https://doi.org/10.1021/acsami.5c01833","url":null,"abstract":"Traditionally, strain-induced moiré patterns at the friction interface can produce superlubrication. Here, we construct moiré patterns on the surface of a two-layer MoS₂ substrate through applying biaxial strain to the bottom layer of the substrate and investigate the effect of moiré patterns on friction energy dissipation. Results indicate friction enhances nonmonotonically with an increase of strain. Notably, two types of frictional dissipation channels have been discovered, corresponding to washboard and moiré-washboard frequencies. Based on this discovery, we determine that the nonmonotonic increase in friction is the result of coupling enhancement of the two dissipative channels and nonmonotonic change in moiré surface roughness. Moreover, friction gradually evolves into a monotonic increase with strain as the adhesion factor between substrate layers enhances. This is because strong interlayer interaction leads to an extremely low moiré barrier, which in turn makes moiré-surface roughness vary minimally, and thus the coupling of two dissipative channels plays a dominant role in friction. Our observations provide strategies for actively controlling friction in 2D material systems.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"31 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-03-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143736483","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Effects of Thermal Oxidation and Proton Irradiation on Optically Detected Magnetic Resonance Sensitivity in Sub-100 nm Nanodiamonds","authors":"Pietro Aprà, Gabriele Zanelli, Elena Losero, Nour-Hanne Amine, Greta Andrini, Mario Barozzi, Ettore Bernardi, Adam Britel, Roberto Canteri, Ivo Pietro Degiovanni, Lorenzo Mino, Ekaterina Moreva, Paolo Olivero, Elisa Redolfi, Claudia Stella, Sofia Sturari, Paolo Traina, Veronica Varzi, Marco Genovese, Federico Picollo","doi":"10.1021/acsami.4c08780","DOIUrl":"https://doi.org/10.1021/acsami.4c08780","url":null,"abstract":"In recent decades, nanodiamonds (NDs) have emerged as innovative nanotools for weak magnetic fields and small temperature variation sensing, especially in biological systems. At the basis of the use of NDs as quantum sensors are nitrogen-vacancy center lattice defects, whose electronic structures are influenced by the surrounding environment and can be probed by the optically detected magnetic resonance technique. Ideally, limiting the NDs’ size as much as possible is important to ensure higher biocompatibility and provide higher spatial resolution. However, size reduction typically worsens the NDs’ sensing properties. This study endeavors to obtain sub-100 nm NDs suitable to be used as quantum sensors. Thermal processing and surface oxidations were performed to purify NDs and control their surface chemistry and size. Ion irradiation techniques were also employed to increase the concentration of the nitrogen-vacancy centers. The impact of these processes was explored in terms of surface chemistry (diffuse reflectance infrared Fourier transform spectroscopy), structural and optical properties (Raman and photoluminescence spectroscopy), dimension variation (atomic force microscopy measurements), and optically detected magnetic resonance temperature sensitivity. Our results demonstrate how surface optimization and defect density enhancement can reduce the detrimental impact of size reduction, opening to the possibility of minimally invasive high-performance sensing of physical quantities in biological environments with nanoscale spatial resolution.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"87 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-03-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143736478","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Machine Learning-Driven Quantum Sequencing of Natural and Chemically Modified DNA","authors":"Dipti Maurya, Sneha Mittal, Milan Kumar Jena, Biswarup Pathak","doi":"10.1021/acsami.4c22809","DOIUrl":"https://doi.org/10.1021/acsami.4c22809","url":null,"abstract":"Simultaneous identification of natural and chemically modified DNA nucleotides at molecular resolution remains a pivotal challenge in genomic science. Despite significant advances in current sequencing technologies, the ability to identify subtle changes in natural and chemically modified nucleotides is hindered by structural and configurational complexity. Given the critical role of nucleobase modifications in data storage and personalized medicine, we propose a computational approach using a graphene nanopore coupled with machine learning (ML) to simultaneously recognize both natural and chemically modified nucleotides, exploring a wide range of modifications in the nucleobase, sugar, and phosphate moieties while investigating quantum transport mechanisms to uncover distinct molecular signatures and detailed electronic and orbital insights of the nucleotides. Integrating with the best-fitted model, the graphene nanopore achieves a good classification accuracy of up to 96% for each natural, chemically modified, purine, and pyrimidine nucleotide. Our approach offers a rapid and precise solution for real-time DNA sequencing by decoding natural and chemically modified nucleotides on a single platform.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"4 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734296","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Cascade Nanozyme-Loaded Sprayable Hydrogels for Fibroblast Rejuvenation and Diabetic Wound Regeneration","authors":"Xinyi Zhang, Yuan Yang, Jianyu Su, Hua Zhong, Liming Fang","doi":"10.1021/acsami.5c02168","DOIUrl":"https://doi.org/10.1021/acsami.5c02168","url":null,"abstract":"Multifunctional composite wound dressings hold significant promise for diabetic wound healing. However, the detrimental role of the advanced glycation end-products (AGEs)-reactive oxygen species (ROS) cycle in impeding wound repair remains underexplored. To disrupt this pathological cycle, zeolitic imidazolate framework-8 (ZIF-8) encapsulated cerium dioxide (CeO₂) and adsorbed glucose oxidase (GOx) nanozyme particles ((ZIF-8@CeO₂)@GOx, zcg) were loaded into a methacrylic anhydride-modified gelatin (GelMA) hydrogel to form a sprayable dressing, zcg/GelMA (zcgG). Physicochemical characterization revealed that GOx catalyzes glucose oxidation, triggering ZIF-8 acid-mediated decomposition to release zinc ions and CeO₂ nanoparticles, thereby enabling a cascade of glucose depletion, antioxidant, and antiglycation functions. In vitro antimicrobial and cytotoxicity experiments optimized the zcg concentration in GelMA. Under oxidative and hyperglycemic culture conditions, we validated the zcg mechanism of blocking the AGEs-ROS cycle, restoring fibroblast mitochondrial membrane potential, and subsequently suppressing cellular senescence. In a bacterial-infected diabetic rat skin wound model, the zcgG group demonstrated substantially reduced inflammatory levels, a 68% decrease in AGEs, and a 1.9-fold increase in collagen deposition compared to blank controls. Within 2 weeks, the zcgG group achieved complete wound closure, while the control group retained 28% of the initial wound area. This work provides preliminary evidence for the feasibility of using cascade nanozymes to break the AGEs-ROS cycle and promote wound healing.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"9 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734298","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Efficient One-Step Purification of Methanol-to-Olefin Products Using a Porphyrinyl MOF to Achieve Record C2H4 and C3H6 Productivity","authors":"Jianfei Xiao, Zhenliang Zhu, Min Zhang, Yaoqi Huang, Tian Cheng Zhang, Shaojun Yuan","doi":"10.1021/acsami.4c21500","DOIUrl":"https://doi.org/10.1021/acsami.4c21500","url":null,"abstract":"The separation of methanol-to-olefin (MTO) products to obtain high-purity ethylene (C₂H₄) and propylene (C₃H₆) is a challenging yet critical task, as these compounds are essential industrial raw materials for polymer synthesis. However, developing adsorbents with high selectivity and productivity for C₂H₄/C₃H₆ remains a significant challenge and an urgent necessity. In this study, a porphyrinyl metal–organic framework (MOF), Al-TCPP, was developed for the simultaneous recovery of C₃H₆ and C₂H₄ through a one-step adsorption–desorption process. Benefiting from its well-developed microporous structure and abundant N- and O-accessible sites, Al-TCPP demonstrated exceptional adsorption capacities and selectivity for C₃H₆ and ethane (C₂H₆) over C₂H₄ under ambient conditions. The adsorption capacities (in cm³·g^–1) reached 162.4 for C₃H₆ and 118.5 for C₂H₆ at 298 K and 100 kPa. The ideal adsorbed solution theory (IAST) selectivity values for C₃H₆/C₂H₄ and C₂H₆/C₂H₄ were 10.1 and 1.8, respectively. Thermodynamic studies and theoretical calculations revealed stronger interactions between C₂H₆ and C₃H₆ molecules with the Al-TCPP framework than with C₂H₄. Systematic breakthrough experiments demonstrated outstanding separation performance for binary C₂H₆/C₂H₄ and C₃H₆/C₂H₄ mixtures, as well as ternary C₃H₆/C₂H₆/C₂H₄ mixtures, achieving record productivities of 150.2 and 86.5 L·kg^–1 for polymer-grade C₂H₄ (≥99.9%) and C₃H₆ (≥99.5%), respectively. Notably, the separation performance remained stable under variable flow rates, temperatures, humidities, and multiple adsorption–desorption cycles. Overall, this study highlighted Al-TCPP as a highly competitive adsorbent for addressing the challenges in MTO product separation. Moreover, it offered valuable insights into the design of MOFs with heteroatom-rich accessible sites for efficient separation of low-carbon hydrocarbons.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"23 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734295","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Influence of Nickel-Content and Cycling Rate on the Phase Behavior of Layered Nickel-Rich Cathode Materials for Lithium-Ion Batteries","authors":"Shuanghong Wang, Guangsu Tan, Wenda Li, Shaoyu Yang, Yang Lu, Yi-Fan Huang, Weiwei Wang, Yuzhu Wang, Chao Xu","doi":"10.1021/acsami.4c21038","DOIUrl":"https://doi.org/10.1021/acsami.4c21038","url":null,"abstract":"Nickel-rich layered cathode materials, such as LiNi_<i>x</i>Mn_<i>y</i>Co_1-x-yO₂ (NMC), are essential for high-energy-density lithium-ion batteries used in electric vehicles due to their higher specific capacities as compared to their lower nickel-content analogs. However, these materials suffer from structural instability, which becomes increasingly severe as the nickel content rises. Despite their significant importance, the intrinsic structural change mechanisms of nickel-rich cathodes, especially at practical cycling rates, remain unclear. This study investigates the influence of nickel content and cycling rate on the phase behavior and electrochemical performance of three representative nickel-rich cathode materials: LiNi_0.83Mn_0.05Co_0.12O₂ (Ni-83), LiNi_0.90Mn_0.05Co_0.05O₂ (Ni-90), and LiNiO₂ (Ni-100). Using synchrotron <i>operando</i> X-ray diffraction alongside electrochemical analysis, we have elucidated distinct structural transformation mechanisms: a solid-solution process for Ni-83, a quasi-two-phase mechanism for Ni-90, and classic H1-M–H2-H3 phase transitions at slow rates for Ni-100. Our findings highlight significant rate-dependent behaviors which affect these materials’ electrochemical performance and stability under practical conditions. Notably, high cycling rates impede the H2–H3 transition in Ni-100 due to substantial lattice contraction, emphasizing the need for optimizing nickel content to enhance the stability and performance of high-nickel cathodes for next-generation lithium-ion batteries.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"53 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734291","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}