Ping Lu,Mengyuan Shan,Caihong Peng,Wenxuan Ji,Ting Yang,Zhimou Yang,Zhuhong Zhang,Yan Wang
Corneal injury remains a significant clinical challenge due to the limited regenerative capacity of the cornea and the difficulties associated with maintaining drug retention at the injury site. This study presents a novel spatiotemporal repair strategy for corneal wounds, utilizing an alkaline phosphatase (ALP)-triggered, lesion-responsive peptide hydrogel that incorporates TB500, a biologically active peptide with the amino acid sequence LKKTETQ, which has not been previously explored for corneal disease treatment. The hydrogel is designed through enzyme-instructed self-assembly (EISA) of a phosphorylated peptide precursor, Nap-YpYY-TB500, which undergoes site-specific dephosphorylation by elevated ALP levels at the wound site, triggering nanofiber formation and gelation in situ. Among three candidate sequences, Nap-YpYY-TB500 exhibited optimal gelation kinetics, nanostructure, and therapeutic efficacy. In vitro, the hydrogel promoted human corneal epithelial cell (HCEC) migration, proliferation, and tight junction recovery, while also enhancing myofibroblastic differentiation and cytoskeletal reorganization of human corneal stromal fibroblasts (HCSFs). In an alkali burn model, the hydrogel significantly accelerated epithelial regeneration, reduced inflammation, and improved corneal barrier function. Our work represents the first ocular application of TB500 and underscores the potential of enzyme-responsive, self-assembling peptide hydrogel as a localized and sustained delivery system for corneal repair.
{"title":"Alkaline Phosphatase-Triggered Spatiotemporal Repair of Corneal Injury with TB500 Peptide Hydrogel.","authors":"Ping Lu,Mengyuan Shan,Caihong Peng,Wenxuan Ji,Ting Yang,Zhimou Yang,Zhuhong Zhang,Yan Wang","doi":"10.1021/acsami.5c14652","DOIUrl":"https://doi.org/10.1021/acsami.5c14652","url":null,"abstract":"Corneal injury remains a significant clinical challenge due to the limited regenerative capacity of the cornea and the difficulties associated with maintaining drug retention at the injury site. This study presents a novel spatiotemporal repair strategy for corneal wounds, utilizing an alkaline phosphatase (ALP)-triggered, lesion-responsive peptide hydrogel that incorporates TB500, a biologically active peptide with the amino acid sequence LKKTETQ, which has not been previously explored for corneal disease treatment. The hydrogel is designed through enzyme-instructed self-assembly (EISA) of a phosphorylated peptide precursor, Nap-YpYY-TB500, which undergoes site-specific dephosphorylation by elevated ALP levels at the wound site, triggering nanofiber formation and gelation in situ. Among three candidate sequences, Nap-YpYY-TB500 exhibited optimal gelation kinetics, nanostructure, and therapeutic efficacy. In vitro, the hydrogel promoted human corneal epithelial cell (HCEC) migration, proliferation, and tight junction recovery, while also enhancing myofibroblastic differentiation and cytoskeletal reorganization of human corneal stromal fibroblasts (HCSFs). In an alkali burn model, the hydrogel significantly accelerated epithelial regeneration, reduced inflammation, and improved corneal barrier function. Our work represents the first ocular application of TB500 and underscores the potential of enzyme-responsive, self-assembling peptide hydrogel as a localized and sustained delivery system for corneal repair.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"47 8 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145696915","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}
Twisted trilayer graphene (TTG) provides a tunable moiré platform to study correlated phases emerging from flat-band physics. Here, we investigate the interplay between superconductivity and spontaneous orbital magnetism (OM) in alternating TTG devices with intermediate twist angles (1.38–1.44°). Using electrostatically defined Josephson junctions, we demonstrate that OM, stabilized near the charge neutrality point (CNP), competes with gate-induced superconductivity. The OM phase is characterized by sharp jumps in Hall resistance, current-induced bistability, and a Curie–Bloch temperature dependence, indicating broken time-reversal symmetry. Additionally, nonreciprocal Josephson transport─manifested as asymmetric Fraunhofer patterns and a superconducting diode effect─provides independent evidence of an orbital magnetic state confined to the weak link. The observed critical temperature hierarchy, where superconductivity dominates over OM at higher carrier densities and displacement fields, reveals a tunable competition between two broken-symmetry ground states. Our findings establish alternating TTG Josephson devices as a minimal and versatile platform to probe the coexistence of magnetism and superconductivity in engineered moiré systems.
{"title":"Gate-Tunable Orbital Magnetism and Competing Superconductivity in Twisted Trilayer Graphene Josephson Junctions","authors":"Vishal Bhardwaj, Lekshmi Rajagopal, Lorenzo Arici, Matan Bocarsly, Alexey Ilin, Gal Shavit, Kenji Watanabe, Takashi Taniguchi, Yuval Oreg, Tobias Holder, Yuval Ronen","doi":"10.1021/acsami.5c15822","DOIUrl":"https://doi.org/10.1021/acsami.5c15822","url":null,"abstract":"Twisted trilayer graphene (TTG) provides a tunable moiré platform to study correlated phases emerging from flat-band physics. Here, we investigate the interplay between superconductivity and spontaneous orbital magnetism (OM) in alternating TTG devices with intermediate twist angles (1.38–1.44°). Using electrostatically defined Josephson junctions, we demonstrate that OM, stabilized near the charge neutrality point (CNP), competes with gate-induced superconductivity. The OM phase is characterized by sharp jumps in Hall resistance, current-induced bistability, and a Curie–Bloch temperature dependence, indicating broken time-reversal symmetry. Additionally, nonreciprocal Josephson transport─manifested as asymmetric Fraunhofer patterns and a superconducting diode effect─provides independent evidence of an orbital magnetic state confined to the weak link. The observed critical temperature hierarchy, where superconductivity dominates over OM at higher carrier densities and displacement fields, reveals a tunable competition between two broken-symmetry ground states. Our findings establish alternating TTG Josephson devices as a minimal and versatile platform to probe the coexistence of magnetism and superconductivity in engineered moiré systems.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"8 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145703911","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}
Yongxing Guo, Baorui Li, Li Xiong, Shuang Zhang, Lin Zhang, Kun Xiao, Xiaoli Li, Rui Min, Zhuo Wang
Embedding computational capabilities directly into the physical structure of soft materials is a central goal for developing next-generation smart sensors and human–machine interfaces. However, achieving deterministic information processing within a compliant material remains a significant design and fabrication challenge. We introduce a “computational metamaterial” that physically performs information encoding through a deterministic process termed “mechanical compilation”. This structured elastomer, embedded with a sparse optical sensing network, is engineered to deterministically map complex high-dimensional spatial pressure patterns, benchmarked using 26 distinct Braille characters, into unique low-dimensional optical signals with 100% classification accuracy. The physically encoded information is of such high quality that a synergistic physics-informed machine learning (PIML) decoder maintains over 96% accuracy with an 80% reduction in training data, demonstrating a profound enhancement in data efficiency. This work pioneers a structure-driven design paradigm for computational metamaterials, shifting the computational burden from software to the material itself and paving a new path toward highly efficient, low-complexity sensing systems.
{"title":"In-Material Computation: A Computational Metamaterial for Data-Efficient Tactile Interfaces","authors":"Yongxing Guo, Baorui Li, Li Xiong, Shuang Zhang, Lin Zhang, Kun Xiao, Xiaoli Li, Rui Min, Zhuo Wang","doi":"10.1021/acsami.5c19143","DOIUrl":"https://doi.org/10.1021/acsami.5c19143","url":null,"abstract":"Embedding computational capabilities directly into the physical structure of soft materials is a central goal for developing next-generation smart sensors and human–machine interfaces. However, achieving deterministic information processing within a compliant material remains a significant design and fabrication challenge. We introduce a “computational metamaterial” that physically performs information encoding through a deterministic process termed “mechanical compilation”. This structured elastomer, embedded with a sparse optical sensing network, is engineered to deterministically map complex high-dimensional spatial pressure patterns, benchmarked using 26 distinct Braille characters, into unique low-dimensional optical signals with 100% classification accuracy. The physically encoded information is of such high quality that a synergistic physics-informed machine learning (PIML) decoder maintains over 96% accuracy with an 80% reduction in training data, demonstrating a profound enhancement in data efficiency. This work pioneers a structure-driven design paradigm for computational metamaterials, shifting the computational burden from software to the material itself and paving a new path toward highly efficient, low-complexity sensing systems.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"30 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145703950","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}
Seongheon Kim, Taehoon Kim, Jieun Lee, Soo Hyun Cho, Tae Eon Kim, Yun Seog Lee
In this study, we applied the vacuum-assisted solution process (VASP), a scalable method for large-area perovskite film formation, to wide-bandgap (WBG) perovskites. The effects of various key process parameters on film morphology and quality were systematically investigated, and their impact on device performance was also analyzed. By monitoring the time-dependent chamber pressure, we revealed that faster vacuum depressurization enhances dimethylformamide evaporation, yielding larger grains and more uniform perovskite films, consistent with the LaMer nucleation model. These findings were further validated by theoretical calculations. Optimization of vacuum retention time showed that prolonged delays (>45 s) increased nucleation density, reduced N-methyl-2-pyrrolidone content in the intermediate phase, and induced wrinkled textures associated with iodide-rich domains, thereby degrading film uniformity and optical quality. These textures indicate the occurrence of halide segregation in WBG perovskites, which we experimentally confirmed this behavior. Molarity variation experiments demonstrated that increasing precursor concentration thickened the films, but excessive thickness at 1.5 M promoted wrinkling, phase segregation, and performance loss despite higher absorbance. Device characterization confirmed that optimal performance was achieved at a 15 s vacuum retention time (60 mTorr) and 1.4 M precursor concentration with high open-circuit voltage and photocurrent. These results provide quantitative evidence for the critical role of solvent evaporation kinetics and morphological control in VASP, offering practical guidelines for the scalable production of high-quality WBG perovskite layers for tandem solar cell applications.
在这项研究中，我们将真空辅助溶液工艺（VASP），一种大面积钙钛矿薄膜形成的可扩展方法，应用于宽带隙（WBG）钙钛矿。系统研究了各关键工艺参数对薄膜形貌和质量的影响，并分析了其对器件性能的影响。通过监测随时间变化的腔室压力，我们发现更快的真空减压增强了二甲基甲酰胺的蒸发，产生更大的颗粒和更均匀的钙钛矿膜，与LaMer成核模型一致。理论计算进一步验证了这些发现。真空保留时间的优化表明，延长的延迟时间（45 s）增加了成核密度，降低了中间相n -甲基-2-吡咯烷酮的含量，并诱导了与富碘畴相关的褶皱织构，从而降低了薄膜的均匀性和光学质量。这些织构表明WBG钙钛矿中存在卤化物偏析，我们通过实验证实了这种行为。摩尔浓度变化实验表明，增加前驱体浓度会使薄膜增厚，但在1.5 M时厚度过大会导致薄膜起皱、相偏析和性能损失，尽管吸光度较高。器件表征证实，在高开路电压和高光电流条件下，真空保持时间为15 s (60 mTorr)，前驱体浓度为1.4 M时，器件性能最佳。这些结果为溶剂蒸发动力学和形态控制在VASP中的关键作用提供了定量证据，为串联太阳能电池应用的高质量WBG钙钛矿层的规模化生产提供了实用指南。
{"title":"Vacuum-Controlled Solvent Evaporation for Morphological Engineering of Wide-Bandgap Perovskite Films","authors":"Seongheon Kim, Taehoon Kim, Jieun Lee, Soo Hyun Cho, Tae Eon Kim, Yun Seog Lee","doi":"10.1021/acsami.5c21734","DOIUrl":"https://doi.org/10.1021/acsami.5c21734","url":null,"abstract":"In this study, we applied the vacuum-assisted solution process (VASP), a scalable method for large-area perovskite film formation, to wide-bandgap (WBG) perovskites. The effects of various key process parameters on film morphology and quality were systematically investigated, and their impact on device performance was also analyzed. By monitoring the time-dependent chamber pressure, we revealed that faster vacuum depressurization enhances dimethylformamide evaporation, yielding larger grains and more uniform perovskite films, consistent with the LaMer nucleation model. These findings were further validated by theoretical calculations. Optimization of vacuum retention time showed that prolonged delays (>45 s) increased nucleation density, reduced <i>N</i>-methyl-2-pyrrolidone content in the intermediate phase, and induced wrinkled textures associated with iodide-rich domains, thereby degrading film uniformity and optical quality. These textures indicate the occurrence of halide segregation in WBG perovskites, which we experimentally confirmed this behavior. Molarity variation experiments demonstrated that increasing precursor concentration thickened the films, but excessive thickness at 1.5 M promoted wrinkling, phase segregation, and performance loss despite higher absorbance. Device characterization confirmed that optimal performance was achieved at a 15 s vacuum retention time (60 mTorr) and 1.4 M precursor concentration with high open-circuit voltage and photocurrent. These results provide quantitative evidence for the critical role of solvent evaporation kinetics and morphological control in VASP, offering practical guidelines for the scalable production of high-quality WBG perovskite layers for tandem solar cell applications.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"3 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145703956","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}
Harrison Szeto,Runqing Yang,Erick Lawrence,Jiya Singh,Raphaële J Clément,Bolin Liao,Yangying Zhu
Commercial Li-ion batteries have been optimized to operate in temperate environments. While moderately high or low temperatures are known to reduce battery performance and safety, the effect of passive exposure to more extreme low temperatures remains largely unexplored. In this work, the effect of thermally cycling a Li-ion battery at a controlled rate between room temperature and cryogenic levels (83 K) was characterized using in situ transient grating spectroscopy. Our results show that the acoustic pulses generated by transient grating spectroscopy travel within the porous composite graphite electrode and their time-of-flight is sensitive to changes in state of charge as well as temperature. At room temperature, an increase in time-of-flight was observed when the state of charge of the composite graphite electrode was increased which is attributed to the volume expansion of the electrode. During controlled-rate cooling, a decrease in time-of-flight was observed for cells at different states of charge that is primarily ascribed to an increase in the effective Young's modulus of the porous composite graphite electrode. This claim was validated with variable-temperature, synchrotron X-ray diffraction on ex situ graphite electrode samples at different states of charge where minimal thermal volume contraction (<1%) of the graphite active material at different degrees of lithiation was observed during cooling to cryogenic temperatures. Upon subsequent controlled-rate warming, time-of-flight values for cells at different states of charge returned to their original values, which suggests that passive exposure to extreme low temperatures induces reversible thermomechanical changes.
{"title":"In Situ Photoacoustic Monitoring of Thermomechanical Changes in Graphite Anodes during Cryogenic Thermal Cycling.","authors":"Harrison Szeto,Runqing Yang,Erick Lawrence,Jiya Singh,Raphaële J Clément,Bolin Liao,Yangying Zhu","doi":"10.1021/acsami.5c17563","DOIUrl":"https://doi.org/10.1021/acsami.5c17563","url":null,"abstract":"Commercial Li-ion batteries have been optimized to operate in temperate environments. While moderately high or low temperatures are known to reduce battery performance and safety, the effect of passive exposure to more extreme low temperatures remains largely unexplored. In this work, the effect of thermally cycling a Li-ion battery at a controlled rate between room temperature and cryogenic levels (83 K) was characterized using in situ transient grating spectroscopy. Our results show that the acoustic pulses generated by transient grating spectroscopy travel within the porous composite graphite electrode and their time-of-flight is sensitive to changes in state of charge as well as temperature. At room temperature, an increase in time-of-flight was observed when the state of charge of the composite graphite electrode was increased which is attributed to the volume expansion of the electrode. During controlled-rate cooling, a decrease in time-of-flight was observed for cells at different states of charge that is primarily ascribed to an increase in the effective Young's modulus of the porous composite graphite electrode. This claim was validated with variable-temperature, synchrotron X-ray diffraction on ex situ graphite electrode samples at different states of charge where minimal thermal volume contraction (<1%) of the graphite active material at different degrees of lithiation was observed during cooling to cryogenic temperatures. Upon subsequent controlled-rate warming, time-of-flight values for cells at different states of charge returned to their original values, which suggests that passive exposure to extreme low temperatures induces reversible thermomechanical changes.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"30 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145696918","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}
Olatunji Ajiteru,Ok Joo Lee,Jinsoo Kim,Ji Seung Lee,Hanna Lee,Kyu Young Choi,Insun Hong,Hyung-Joo Kwon,Soon Hee Kim,Chan Hum Park
Developing a lung-on-a-chip (LOC) platform that is both physiologically and pathologically relevant is crucial due to the mortality and recurrent pandemics of zoonotically transmitted pathogens. This study reports the fabrication of an LOC with an intrinsic air-liquid interface (ALI) via a digital light processing (DLP) 3D bioprinter. The platform architecture supports the localization of different cells, such as human lung epithelial cells (HLEC), human fibroblasts, and human endothelial cells, to mimic their in vivo counterparts. While the air layer of the LOC undergoes cyclic air-breathing via a custom-built lung bioreactor device, the epithelial cells in the LOC express relevant physiological proteins such as aquaporin 5, E-cadherin, and prosurfactant C. Furthermore, the platform incorporates a dynamic perfusion system in the liquid layer of the LOC, which improves the viability of the cells in the inner core of the 3D model and enhances the expression of V-Cadherin and VEGF-A. We mimicked the infection of the airborne SARS-CoV-2 virus to replicate the disease characteristics of the lungs during SARS-CoV-2 infection by the expression of CoV-NP and OAS1 as an innate response to the viral infection. Incorporating the endothelial layer, ALI, 3D hydrogel, air-induced 3D stretching, and airborne viral infection enhances the physiological relevance of the platform, making it an attractive option for respiratory preclinical testing.
{"title":"Advancement of a Physiologically Relevant 3D Lung Model through One-Stage DLP Bioprinting for the Study of Lung Diseases.","authors":"Olatunji Ajiteru,Ok Joo Lee,Jinsoo Kim,Ji Seung Lee,Hanna Lee,Kyu Young Choi,Insun Hong,Hyung-Joo Kwon,Soon Hee Kim,Chan Hum Park","doi":"10.1021/acsami.5c16281","DOIUrl":"https://doi.org/10.1021/acsami.5c16281","url":null,"abstract":"Developing a lung-on-a-chip (LOC) platform that is both physiologically and pathologically relevant is crucial due to the mortality and recurrent pandemics of zoonotically transmitted pathogens. This study reports the fabrication of an LOC with an intrinsic air-liquid interface (ALI) via a digital light processing (DLP) 3D bioprinter. The platform architecture supports the localization of different cells, such as human lung epithelial cells (HLEC), human fibroblasts, and human endothelial cells, to mimic their in vivo counterparts. While the air layer of the LOC undergoes cyclic air-breathing via a custom-built lung bioreactor device, the epithelial cells in the LOC express relevant physiological proteins such as aquaporin 5, E-cadherin, and prosurfactant C. Furthermore, the platform incorporates a dynamic perfusion system in the liquid layer of the LOC, which improves the viability of the cells in the inner core of the 3D model and enhances the expression of V-Cadherin and VEGF-A. We mimicked the infection of the airborne SARS-CoV-2 virus to replicate the disease characteristics of the lungs during SARS-CoV-2 infection by the expression of CoV-NP and OAS1 as an innate response to the viral infection. Incorporating the endothelial layer, ALI, 3D hydrogel, air-induced 3D stretching, and airborne viral infection enhances the physiological relevance of the platform, making it an attractive option for respiratory preclinical testing.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"38 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145696921","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}
Qian Yu,Charles D Brewster,Rajan Jagpal,Arthur Graf,Xiayi Hu,Timothy J Mays,Mi Tian
Metal-organic frameworks (MOFs) are promising materials for hydrogen storage due to their high specific surface area and structural tunability. In this study, we provide the first demonstration of enhanced hydrogen storage performance in a CuBTC (also known as HKUST-1) MOF by incorporating nickel and magnesium through a combination of in situ and postmodification solvent-free mechanochemical ball milling. A comprehensive combination of structural and adsorption-desorption characterization is employed to examine and understand the impact of Ni2+ and Mg2+ divalent metal ions through in situ and postmodification methods. In general, the post-Ni-modification method achieved higher hydrogen storage capacities than in situ-Ni-modification routes. The post-Ni-modified CuBTC with 30 min milling time exhibited the highest hydrogen storage capacity of 4.2 wt % at 20 bar and 77 K, which is 31% higher than the pristine CuBTC. The substitution of Cu2+ by Ni2+ during the postmodification process increased the active metal sites and Cu+ content, thus contributing to enhanced hydrogen storage capacity. Our findings indicate that modification via a solvent-free mechanochemical route is an effective novel strategy for improving the hydrogen storage performance of MOF materials.
{"title":"Mechanochemical Dual-Metal Modification of CuBTC Metal-Organic Frameworks for Enhanced Hydrogen Storage.","authors":"Qian Yu,Charles D Brewster,Rajan Jagpal,Arthur Graf,Xiayi Hu,Timothy J Mays,Mi Tian","doi":"10.1021/acsami.5c18519","DOIUrl":"https://doi.org/10.1021/acsami.5c18519","url":null,"abstract":"Metal-organic frameworks (MOFs) are promising materials for hydrogen storage due to their high specific surface area and structural tunability. In this study, we provide the first demonstration of enhanced hydrogen storage performance in a CuBTC (also known as HKUST-1) MOF by incorporating nickel and magnesium through a combination of in situ and postmodification solvent-free mechanochemical ball milling. A comprehensive combination of structural and adsorption-desorption characterization is employed to examine and understand the impact of Ni2+ and Mg2+ divalent metal ions through in situ and postmodification methods. In general, the post-Ni-modification method achieved higher hydrogen storage capacities than in situ-Ni-modification routes. The post-Ni-modified CuBTC with 30 min milling time exhibited the highest hydrogen storage capacity of 4.2 wt % at 20 bar and 77 K, which is 31% higher than the pristine CuBTC. The substitution of Cu2+ by Ni2+ during the postmodification process increased the active metal sites and Cu+ content, thus contributing to enhanced hydrogen storage capacity. Our findings indicate that modification via a solvent-free mechanochemical route is an effective novel strategy for improving the hydrogen storage performance of MOF materials.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"4 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145696922","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}
Osteosarcoma resection creates critical-sized bone defects plagued by residual tumor cells and compromised regeneration due to chemo-radiotherapy toxicity. While 3D-printed scaffolds offer anatomical precision, multifunctional implants enabling concurrent tumor ablation and vascularized bone repair remain an unmet need. Here, we engineered a tritherapeutic platform by functionalizing mesoporous bioactive glass (MBG) with polydopamine (PDA) for photothermal tumor eradication under NIR irradiation (808 nm), followed by Mg2+ chelation (MBG@PM) to confer pro-angiogenic activity. The resulting MBG@PM nanoparticles were incorporated into chitosan (CS) bioinks for cryogenic 3D printing, fabricating patient-specific MBG@PM-CS scaffolds. These constructs demonstrated exceptional photothermal capacity and tumor elimination in vitro/vivo. Sustained release of Mg2+/Ca2+/Si4+ ions from MBG@PM synergistically stimulated angiogenesis and osteogenesis. In rat critical-sized femoral defects, MBG@PM-CS scaffolds accelerated coupled vascularization and bone regeneration, achieving enhanced defect healing at 8 weeks via microcomputed tomography (Micro-CT) and histological analysis. This platform introduces a tripartite strategy enabling concurrent tumor ablation, osteo-angiogenic coupling, and structural bone restoration, providing a promising approach for the treatment of osteosarcoma.
{"title":"Dual-Functional Interface Engineering of Mesoporous Bioactive Glass via Polydopamine Chelation for 3D-Printed Scaffolds with Synergistic Photothermal Therapy and Enhanced Osteogenesis.","authors":"Shengbiao Ma, Xuechen Ding, Wen Tian, Xiaoxiao Liang, Peng Zhang, Weitao Yao","doi":"10.1021/acsami.5c19186","DOIUrl":"https://doi.org/10.1021/acsami.5c19186","url":null,"abstract":"<p><p>Osteosarcoma resection creates critical-sized bone defects plagued by residual tumor cells and compromised regeneration due to chemo-radiotherapy toxicity. While 3D-printed scaffolds offer anatomical precision, multifunctional implants enabling concurrent tumor ablation and vascularized bone repair remain an unmet need. Here, we engineered a tritherapeutic platform by functionalizing mesoporous bioactive glass (MBG) with polydopamine (PDA) for photothermal tumor eradication under NIR irradiation (808 nm), followed by Mg<sup>2+</sup> chelation (MBG@PM) to confer pro-angiogenic activity. The resulting MBG@PM nanoparticles were incorporated into chitosan (CS) bioinks for cryogenic 3D printing, fabricating patient-specific MBG@PM-CS scaffolds. These constructs demonstrated exceptional photothermal capacity and tumor elimination in vitro/vivo. Sustained release of Mg<sup>2+</sup>/Ca<sup>2+</sup>/Si<sup>4+</sup> ions from MBG@PM synergistically stimulated angiogenesis and osteogenesis. In rat critical-sized femoral defects, MBG@PM-CS scaffolds accelerated coupled vascularization and bone regeneration, achieving enhanced defect healing at 8 weeks via microcomputed tomography (Micro-CT) and histological analysis. This platform introduces a tripartite strategy enabling concurrent tumor ablation, osteo-angiogenic coupling, and structural bone restoration, providing a promising approach for the treatment of osteosarcoma.</p>","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":" ","pages":""},"PeriodicalIF":8.2,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145706748","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}
Printing technology is a leading strategy for creating customized 3D matrices for tissue engineering. Our study developed an injectable nanocomposite hydrogel (bHAGel) for high-fidelity 3D extrusion printing composed of gelatin (Gel) and magnesium-doped biomimetic hydroxyapatite (bHA) particles that mimics a bone extracellular matrix. bHA particles, synthesized through a bioinspired mineralization process, acted as multifunctional additives, modulating rheology for printability, ensuring homogeneous phase distribution, enabling excellent model fidelity, and providing osteoinductive cues. The optimized hydrogel formulation enables the fabrication of porous scaffolds with interconnected macro- and microporosity via extrusion-based printing and freeze-drying. This key feature promoted cell infiltration and nutrient diffusion during tissue engineering procedures. Biological validation involves tailoring 3D scaffolds to fit a perfusion bioreactor chamber supporting seamless handling, seeding, and long-term culturing without scaffold removal or repositioning. Dynamic in vitro experiments with donor-derived human bone marrow stromal cells assessed the constructs' stability, ability to maintain geometry and perfusability, cytocompatibility and osteoconductivity, as well as robust osteogenic differentiation over 28 days. A more complex dynamic coculture model further demonstrated that the scaffold supports osteoclastogenesis under physiological, osteoblast-mediated conditions. Altogether, bHAGel scaffolds provided a customizable, bioactive platform suitable for engineering bone-mimetic organoids under dynamic conditions. Their modularity and biological relevance could be exploited in bone regeneration, disease modeling, and drug testing.
{"title":"Injectable Nanocomposite Biomaterial for 3D Printing of Personalized Matrices and Their Use in Bioreactors for Bioengineering Advanced Cell Culture Models.","authors":"Elisabetta Campodoni,Andrea Mazzoleni,Margherita Montanari,Gaia Vicinelli,Valentina Possetti,Antonio Inforzato,Ivan Martin,Manuele G Muraro,Monica Sandri","doi":"10.1021/acsami.5c18437","DOIUrl":"https://doi.org/10.1021/acsami.5c18437","url":null,"abstract":"Printing technology is a leading strategy for creating customized 3D matrices for tissue engineering. Our study developed an injectable nanocomposite hydrogel (bHAGel) for high-fidelity 3D extrusion printing composed of gelatin (Gel) and magnesium-doped biomimetic hydroxyapatite (bHA) particles that mimics a bone extracellular matrix. bHA particles, synthesized through a bioinspired mineralization process, acted as multifunctional additives, modulating rheology for printability, ensuring homogeneous phase distribution, enabling excellent model fidelity, and providing osteoinductive cues. The optimized hydrogel formulation enables the fabrication of porous scaffolds with interconnected macro- and microporosity via extrusion-based printing and freeze-drying. This key feature promoted cell infiltration and nutrient diffusion during tissue engineering procedures. Biological validation involves tailoring 3D scaffolds to fit a perfusion bioreactor chamber supporting seamless handling, seeding, and long-term culturing without scaffold removal or repositioning. Dynamic in vitro experiments with donor-derived human bone marrow stromal cells assessed the constructs' stability, ability to maintain geometry and perfusability, cytocompatibility and osteoconductivity, as well as robust osteogenic differentiation over 28 days. A more complex dynamic coculture model further demonstrated that the scaffold supports osteoclastogenesis under physiological, osteoblast-mediated conditions. Altogether, bHAGel scaffolds provided a customizable, bioactive platform suitable for engineering bone-mimetic organoids under dynamic conditions. Their modularity and biological relevance could be exploited in bone regeneration, disease modeling, and drug testing.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"135 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145696666","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}
The existence of O2 in flue gas, which can induce oxidative degradation and cause adsorption capacity losses, has been an obstacle for solid amine adsorbents in practical applications. Herein, a simple and scalable synthesis of PEI-impregnated silica modified with low-dose inhibitors is reported. Compared to previous studies, the novelty of this work lied in its simplicity and its ability to maintain high adsorption capacity (over 170 mg/g) when achieving excellent antioxidation and antiurea effects. The strategy can slow down the oxidation kinetics as well as relieve oxidative degradation of the adsorbents under conditions of high oxidation temperature, high O2 concentration, and long oxidation time. The cyclic stability can be increased by 43.8%, and the O2 resistance can be improved by 66.8%. Using a multitechnique approach, we have unraveled the effects of the separate and coexisting presence of CO2 and O2 in long-term applications and provided important guidance for the selection of certain inhibitors (NaH2PO4, Na3PO4, or HCOONa) based on actual application situations. This study demonstrated that the adsorbent modified with NaH2PO4 can avoid the weakening of antiurea effects when CO2 and O2 coexist, while Na3PO4 can still exhibit the overall effect of high cyclic stability even with the weakened antiurea effects; thus, NaH2PO4 and Na3PO4 have the potential for long-term carbon capture from O2-containing flue gas.
{"title":"Antioxidation Strategy of Modification with Low-Dose Inhibitors to Solid Amine Adsorbents for Long-Term Cyclic Carbon Capture from O2-Containing Flue Gas","authors":"Li Lin, Kailun Chen, Jinglin Li, Endian Hu, Jingwen Chang, Jianguo Jiang","doi":"10.1021/acsami.5c17529","DOIUrl":"https://doi.org/10.1021/acsami.5c17529","url":null,"abstract":"The existence of O<sub>2</sub> in flue gas, which can induce oxidative degradation and cause adsorption capacity losses, has been an obstacle for solid amine adsorbents in practical applications. Herein, a simple and scalable synthesis of PEI-impregnated silica modified with low-dose inhibitors is reported. Compared to previous studies, the novelty of this work lied in its simplicity and its ability to maintain high adsorption capacity (over 170 mg/g) when achieving excellent antioxidation and antiurea effects. The strategy can slow down the oxidation kinetics as well as relieve oxidative degradation of the adsorbents under conditions of high oxidation temperature, high O<sub>2</sub> concentration, and long oxidation time. The cyclic stability can be increased by 43.8%, and the O<sub>2</sub> resistance can be improved by 66.8%. Using a multitechnique approach, we have unraveled the effects of the separate and coexisting presence of CO<sub>2</sub> and O<sub>2</sub> in long-term applications and provided important guidance for the selection of certain inhibitors (NaH<sub>2</sub>PO<sub>4</sub>, Na<sub>3</sub>PO<sub>4</sub>, or HCOONa) based on actual application situations. This study demonstrated that the adsorbent modified with NaH<sub>2</sub>PO<sub>4</sub> can avoid the weakening of antiurea effects when CO<sub>2</sub> and O<sub>2</sub> coexist, while Na<sub>3</sub>PO<sub>4</sub> can still exhibit the overall effect of high cyclic stability even with the weakened antiurea effects; thus, NaH<sub>2</sub>PO<sub>4</sub> and Na<sub>3</sub>PO<sub>4</sub> have the potential for long-term carbon capture from O<sub>2</sub>-containing flue gas.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"29 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145703947","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}
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