Surface-enhanced Raman scattering (SERS) is a powerful tool for ultrasensitive molecular detection, yet its performance is critically dependent on the control of light–matter interactions. Here, we demonstrate that self-assembled gold nanoparticle films, composed of anisotropic gold nanotriangles (AuNTs) or isotropic gold nanospheres (AuNSs), exhibit shape-dependent SERS enhancement in a tailorable manner when coupled with a Fabry–Pérot (FP) cavity structure. The nanoparticle films were transferred onto semi-opened FP cavities consisting of a TiO2 dielectric layer on a gold film. Systematic tuning of the TiO2 thickness revealed modal ultrastrong coupling between the cavity and localized surface plasmon modes, yielding a peak splitting energy of ∼650 meV, as confirmed by reflection spectroscopy and finite-difference time-domain (FDTD) simulations. This modal ultrastrong coupling altered the extinction characteristics of the gold nanoparticle films, thereby significantly modulating the local electromagnetic fields and SERS signals. Shape-dependent SERS behaviors highlight the dominant influence of extinction-governed near-field intensity and hotspot distribution with additional contributions from surface chemistry factors associated with molecular accessibility. Under analyte-rich conditions, AuNT films exhibited strong SERS signals that were relatively insensitive to variations in the underlying TiO2 thickness, owing to the broad hybrid band arising from multiple modal coupling. In contrast, AuNS films displayed a greater SERS enhancement but were more susceptible to shifts in the position of the sharp hybrid peaks. In analyte-limited conditions─where SERS is especially valuable due to the need for high sensitivity─AuNT films provided superior SERS signal quality, benefiting from their shape anisotropy, which promotes stronger hotspots and more efficient access to them. These insights contribute to the rational design of practical SERS platforms and highlight the potential of integrating self-assembled plasmonic films with FP cavities in advanced photonic and chemical sensing applications.
表面增强拉曼散射（SERS）是超灵敏分子检测的有力工具，但其性能严重依赖于光-物质相互作用的控制。在这里，我们证明了自组装的金纳米颗粒薄膜，由各向异性金纳米三角形（阿姨）或各向同性金纳米球（阿姨）组成，当与fabry - p (FP)腔结构耦合时，以一种可定制的方式表现出形状依赖的SERS增强。纳米颗粒薄膜被转移到由金膜上的TiO2介电层组成的半开放的FP腔中。通过反射光谱和时域有限差分（FDTD）模拟证实，系统调整TiO2厚度揭示了腔和局部表面等离子体模式之间的模态超强耦合，产生了约650 meV的峰值分裂能量。这种模态超强耦合改变了金纳米颗粒薄膜的消光特性，从而显著地调制了局部电磁场和SERS信号。形状依赖的SERS行为突出了灭绝控制的近场强度和热点分布的主要影响，以及与分子可及性相关的表面化学因素的额外贡献。在富含分析物的条件下，阿姨膜表现出强烈的SERS信号，对底层TiO2厚度的变化相对不敏感，这是因为多模态耦合产生了宽的杂化带。相比之下，AuNS薄膜显示出更大的SERS增强，但更容易受到尖锐杂化峰位置变化的影响。在受分析物限制的条件下──由于需要高灵敏度，SERS特别有价值──姑妈薄膜提供了卓越的SERS信号质量，受益于它们的形状各向异性，这促进了更强的热点和更有效的访问。这些见解有助于实际SERS平台的合理设计，并突出了将自组装等离子体膜与FP腔集成在先进光子和化学传感应用中的潜力。
{"title":"Shape-Dependent Surface-Enhanced Raman Scattering under Modal Ultrastrong Coupling between Self-Assembled Gold Nanoparticles and Fabry–Pérot Cavities","authors":"Zhiyu He, Xu Shi, Keiji Sasaki, Hiroaki Misawa, Kuniharu Ijiro, Hideyuki Mitomo","doi":"10.1021/acsami.5c19317","DOIUrl":"https://doi.org/10.1021/acsami.5c19317","url":null,"abstract":"Surface-enhanced Raman scattering (SERS) is a powerful tool for ultrasensitive molecular detection, yet its performance is critically dependent on the control of light–matter interactions. Here, we demonstrate that self-assembled gold nanoparticle films, composed of anisotropic gold nanotriangles (AuNTs) or isotropic gold nanospheres (AuNSs), exhibit shape-dependent SERS enhancement in a tailorable manner when coupled with a Fabry–Pérot (FP) cavity structure. The nanoparticle films were transferred onto semi-opened FP cavities consisting of a TiO<sub>2</sub> dielectric layer on a gold film. Systematic tuning of the TiO<sub>2</sub> thickness revealed modal ultrastrong coupling between the cavity and localized surface plasmon modes, yielding a peak splitting energy of ∼650 meV, as confirmed by reflection spectroscopy and finite-difference time-domain (FDTD) simulations. This modal ultrastrong coupling altered the extinction characteristics of the gold nanoparticle films, thereby significantly modulating the local electromagnetic fields and SERS signals. Shape-dependent SERS behaviors highlight the dominant influence of extinction-governed near-field intensity and hotspot distribution with additional contributions from surface chemistry factors associated with molecular accessibility. Under analyte-rich conditions, AuNT films exhibited strong SERS signals that were relatively insensitive to variations in the underlying TiO<sub>2</sub> thickness, owing to the broad hybrid band arising from multiple modal coupling. In contrast, AuNS films displayed a greater SERS enhancement but were more susceptible to shifts in the position of the sharp hybrid peaks. In analyte-limited conditions─where SERS is especially valuable due to the need for high sensitivity─AuNT films provided superior SERS signal quality, benefiting from their shape anisotropy, which promotes stronger hotspots and more efficient access to them. These insights contribute to the rational design of practical SERS platforms and highlight the potential of integrating self-assembled plasmonic films with FP cavities in advanced photonic and chemical sensing applications.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"15 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145729230","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}
Aaron Hennessy, Abinaya Sankaran, Adrian Hannon, Marco Cornago, Tadhg Kennedy, Hugh Geaney, Kevin M. Ryan
Kerf waste is a byproduct of the semiconductor industry and is a cost-effective source of high-purity Si, which is highly sought after for Li-ion battery anodes. However, recycled kerf waste contains particles with various sizes and morphologies that induce additional stresses during battery cycling and lack the chemo-mechanical advantages of nanostructured Si. In this study, a lithium polyacrylate/polyacrylamide (LiPAA/PAM) binder system that is specifically tuned for kerf Si active materials is developed and contrasted with the performance of PAM and CMC binders. The combined binder system benefits from covalent and hydrogen bonding, ionic cross-linking, and electrostatic interactions provided by carboxylate and amide groups. The recycled PAM binder alone delivered a ∼3× enhanced capacity retention compared to the CMC binder, which was further boosted by a factor of 2 with the addition of lithium polyacrylate (LiPAA), resulting in a specific capacity of 1528 mAh g–1 after extended cycling. The study shows that recycled LiPAA/PAM binder can unlock the use of silicon kerf waste as a cost-effective anode material, with improved electrochemical performance and reduced environmental footprint.
切屑废料是半导体工业的副产品，是高纯度硅的成本效益来源，是锂离子电池阳极的高度追捧。然而，回收的切屑废料含有各种尺寸和形态的颗粒，在电池循环过程中会产生额外的应力，并且缺乏纳米结构Si的化学机械优势。在本研究中，开发了一种专门用于kerf Si活性材料的聚丙烯酸锂/聚丙烯酰胺（LiPAA/PAM）粘结剂体系，并与PAM和CMC粘结剂的性能进行了对比。该结合剂体系得益于共价键和氢键、离子交联以及羧酸基和酰胺基提供的静电相互作用。与CMC粘结剂相比，再生PAM粘结剂单独提供了约3倍的容量保留，在添加聚丙烯酸锂（LiPAA）后，进一步提高了2倍，经过长时间循环后，比容量达到1528 mAh g-1。研究表明，回收的LiPAA/PAM粘结剂可以解锁利用硅屑作为一种具有成本效益的阳极材料，提高了电化学性能，减少了环境足迹。
{"title":"Unlocking Stable Cycling in Silicon Kerf Waste Anodes with Recycled Polyacrylamide-Based Binders for Lithium-Ion Battery Applications","authors":"Aaron Hennessy, Abinaya Sankaran, Adrian Hannon, Marco Cornago, Tadhg Kennedy, Hugh Geaney, Kevin M. Ryan","doi":"10.1021/acsami.5c19882","DOIUrl":"https://doi.org/10.1021/acsami.5c19882","url":null,"abstract":"Kerf waste is a byproduct of the semiconductor industry and is a cost-effective source of high-purity Si, which is highly sought after for Li-ion battery anodes. However, recycled kerf waste contains particles with various sizes and morphologies that induce additional stresses during battery cycling and lack the chemo-mechanical advantages of nanostructured Si. In this study, a lithium polyacrylate/polyacrylamide (LiPAA/PAM) binder system that is specifically tuned for kerf Si active materials is developed and contrasted with the performance of PAM and CMC binders. The combined binder system benefits from covalent and hydrogen bonding, ionic cross-linking, and electrostatic interactions provided by carboxylate and amide groups. The recycled PAM binder alone delivered a ∼3× enhanced capacity retention compared to the CMC binder, which was further boosted by a factor of 2 with the addition of lithium polyacrylate (LiPAA), resulting in a specific capacity of 1528 mAh g<sup>–1</sup> after extended cycling. The study shows that recycled LiPAA/PAM binder can unlock the use of silicon kerf waste as a cost-effective anode material, with improved electrochemical performance and reduced environmental footprint.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"18 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145718213","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}
Siyu Liu, Di Jiang, Nan Lu, Leibo Li, Zhenni Zhang, Guida Kang, Shiyu Wang, Guibin Wang
The development of aqueous zinc-ion batteries (AZIBs) has attracted attention owing to their excellent safety and electrochemical performances; however, the practical application is still limited by the poor temperature tolerance of water. Therefore, hydrogel electrolytes with superb conductivity and mechanical properties over a wide temperature range are highly desirable to assemble an all-climate AZIB. Herein, a hydrogel electrolyte with excellent comprehensive performance was successfully fabricated by constructing double-network (DN) hydrogels and introducing a certain concentration of salt solution. Surprisingly, the electrolyte exhibited an impressive ionic conductivity (23 mS cm–1 at −30 °C) and tensile strength (107 KPa at −60 °C) due to the interactions of internal networks. The prepared Zn-MnO2 battery showed excellent rate performance and specific capacity (251.9 mAh g–1 at room temperature) within a wide operating temperature range (−30 to 60 °C). Remarkably, the battery could work normally even under 85% compressive strain or 135° bending. It is believed that the flexible Zn-MnO2 battery with a wide operating temperature based on the DN hydrogel electrolyte holds enormous potential as a reliable power source for flexible wearable electronic devices.
水性锌离子电池（azib）因其优异的安全性和电化学性能而备受关注；然而，实际应用仍然受到水的耐温性差的限制。因此，在宽温度范围内具有优异导电性和机械性能的水凝胶电解质非常适合用于组装全气候AZIB。本文通过构建双网络（DN）水凝胶并引入一定浓度的盐溶液，成功制备了一种综合性能优异的水凝胶电解质。令人惊讶的是，由于内部网络的相互作用，电解质表现出令人印象深刻的离子电导率（- 30°C时为23 mS cm-1）和抗拉强度（- 60°C时为107 KPa）。在−30 ~ 60℃的工作温度范围内，所制备的锌- mno2电池具有优异的倍率性能和室温比容量（251.9 mAh g-1）。值得注意的是，即使在85%的压缩应变或135°弯曲下，电池也可以正常工作。研究认为，基于DN水凝胶电解质的宽工作温度柔性Zn-MnO2电池作为柔性可穿戴电子设备的可靠电源具有巨大的潜力。
{"title":"A Double-Network Hydrogel Electrolyte for a Flexible Zn-MnO2 Battery with a Wide Operating Temperature Range","authors":"Siyu Liu, Di Jiang, Nan Lu, Leibo Li, Zhenni Zhang, Guida Kang, Shiyu Wang, Guibin Wang","doi":"10.1021/acsami.5c18814","DOIUrl":"https://doi.org/10.1021/acsami.5c18814","url":null,"abstract":"The development of aqueous zinc-ion batteries (AZIBs) has attracted attention owing to their excellent safety and electrochemical performances; however, the practical application is still limited by the poor temperature tolerance of water. Therefore, hydrogel electrolytes with superb conductivity and mechanical properties over a wide temperature range are highly desirable to assemble an all-climate AZIB. Herein, a hydrogel electrolyte with excellent comprehensive performance was successfully fabricated by constructing double-network (DN) hydrogels and introducing a certain concentration of salt solution. Surprisingly, the electrolyte exhibited an impressive ionic conductivity (23 mS cm<sup>–1</sup> at −30 °C) and tensile strength (107 KPa at −60 °C) due to the interactions of internal networks. The prepared Zn-MnO<sub>2</sub> battery showed excellent rate performance and specific capacity (251.9 mAh g<sup>–1</sup> at room temperature) within a wide operating temperature range (−30 to 60 °C). Remarkably, the battery could work normally even under 85% compressive strain or 135° bending. It is believed that the flexible Zn-MnO<sub>2</sub> battery with a wide operating temperature based on the DN hydrogel electrolyte holds enormous potential as a reliable power source for flexible wearable electronic devices.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"45 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145729231","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}
Maciej Cieplak, Dominik Korol, Piyush Sindhu Sharma
Molecularly imprinted polymers (MIPs) are often referred to as “plastic antibodies” and promoted as alternatives to antibodies in selective recognition. However, MIPs can also catalyze chemical reactions and, thus, mimic the operation of enzymes. The advantages of MIPs include stability, robustness, and a lower synthesis cost compared with their biological counterparts. Moreover, MIPs can be targeted for those reactions for which the corresponding enzymes are not available. The application of MIPs in the catalysis field requires careful design of molecular cavities. Simple approaches to molecular imprinting are not sufficiently precise. Therefore, alternative, advanced approaches, including covalent imprinting, metal-coordinating monomers, and postimprinting modification, have been employed in the past five years. They resulted in sufficient selectivity and catalytic efficiency of molecular cavities. In this review, various methodologies for designing molecular cavities in MIPs to enhance selectivity and performance in catalysis are discussed and critically reviewed.
{"title":"Molecularly Imprinted Polymer-Based Catalysts: An Emerging New Trend in the Selective Catalysis Field?","authors":"Maciej Cieplak, Dominik Korol, Piyush Sindhu Sharma","doi":"10.1021/acsami.5c14646","DOIUrl":"https://doi.org/10.1021/acsami.5c14646","url":null,"abstract":"Molecularly imprinted polymers (MIPs) are often referred to as “plastic antibodies” and promoted as alternatives to antibodies in selective recognition. However, MIPs can also catalyze chemical reactions and, thus, mimic the operation of enzymes. The advantages of MIPs include stability, robustness, and a lower synthesis cost compared with their biological counterparts. Moreover, MIPs can be targeted for those reactions for which the corresponding enzymes are not available. The application of MIPs in the catalysis field requires careful design of molecular cavities. Simple approaches to molecular imprinting are not sufficiently precise. Therefore, alternative, advanced approaches, including covalent imprinting, metal-coordinating monomers, and postimprinting modification, have been employed in the past five years. They resulted in sufficient selectivity and catalytic efficiency of molecular cavities. In this review, various methodologies for designing molecular cavities in MIPs to enhance selectivity and performance in catalysis are discussed and critically reviewed.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"9 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145718164","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}
Yiyu Wang, Chunqing Niu, Yushan Li, Hangqi Shu, Jian Shi, Ick Soo Kim, Xin Zheng, Xinyu Wang, Kai Zhao
Recently, injectable hydrogels with synergistic antioxidant and antimicrobial properties have emerged as promising candidates for diabetic wound treatment. However, the outstanding flowability of injectable hydrogels often compromises their mechanical properties, and few systems provide the multiple synergistic cues needed for rapid healing. Here, we designed an injectable dual-cross-linked hydrogel (SCO@M) that integrated MXene nanosheets (NNs) to furnish simultaneous photothermal antibacterial activity and intrinsic immunomodulation. At first, a dynamic network was formed in situ through reversible Schiff-base and hydrogen bonds among oxidized hyaluronic acid, carboxymethyl chitosan, and methacrylated silk fibroin (SF-MA), endowing the precursor with shear-thinning behavior and easy injectability. Brief UV exposure then photo-cross-linked residual SF-MA to form a covalent secondary network, markedly reinforcing mechanical strength without sacrificing injectability. Importantly, the incorporation of MXene NNs not only enhanced the mechanical properties but also imparted robust photothermal antibacterial activity under near-infrared irradiation alongside excellent reactive oxygen species (ROS) scavenging capacity. Both in vitro and in vivo results demonstrated that SCO@M normalized the inflammatory response by modulating the M1/M2 macrophage balance via IL-17/MAPK/TNF-α pathways, enhanced angiogenesis and cell migration, and accelerated wound closure in diabetic rats, representing a promising strategy for chronic wound healing.
{"title":"Mechanically Reinforced In Situ Injectable Hydrogels Integrating MXene Nanosheet-Driven Photothermal Antibacterial and Immunomodulatory Capacities for Enhanced Diabetic Wound Healing","authors":"Yiyu Wang, Chunqing Niu, Yushan Li, Hangqi Shu, Jian Shi, Ick Soo Kim, Xin Zheng, Xinyu Wang, Kai Zhao","doi":"10.1021/acsami.5c16938","DOIUrl":"https://doi.org/10.1021/acsami.5c16938","url":null,"abstract":"Recently, injectable hydrogels with synergistic antioxidant and antimicrobial properties have emerged as promising candidates for diabetic wound treatment. However, the outstanding flowability of injectable hydrogels often compromises their mechanical properties, and few systems provide the multiple synergistic cues needed for rapid healing. Here, we designed an injectable dual-cross-linked hydrogel (SCO@M) that integrated MXene nanosheets (NNs) to furnish simultaneous photothermal antibacterial activity and intrinsic immunomodulation. At first, a dynamic network was formed in situ through reversible Schiff-base and hydrogen bonds among oxidized hyaluronic acid, carboxymethyl chitosan, and methacrylated silk fibroin (SF-MA), endowing the precursor with shear-thinning behavior and easy injectability. Brief UV exposure then photo-cross-linked residual SF-MA to form a covalent secondary network, markedly reinforcing mechanical strength without sacrificing injectability. Importantly, the incorporation of MXene NNs not only enhanced the mechanical properties but also imparted robust photothermal antibacterial activity under near-infrared irradiation alongside excellent reactive oxygen species (ROS) scavenging capacity. Both in vitro and in vivo results demonstrated that SCO@M normalized the inflammatory response by modulating the M1/M2 macrophage balance via IL-17/MAPK/TNF-α pathways, enhanced angiogenesis and cell migration, and accelerated wound closure in diabetic rats, representing a promising strategy for chronic wound healing.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"170 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145718211","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}
Norfloxacin (NOR), a recalcitrant antibiotic, poses significant threats to aquatic ecosystems and human health. Employing a facile one-pot hydrothermal approach, this work pioneers a novel three-dimensional carboxymethyl cellulose (CMC)/MIL-125(Ti)-NH2 composite for ultraefficient NOR removal. The CMC scaffold effectively prevented nanoparticle aggregation and structural collapse of MIL-125(Ti)-NH2, significantly enhancing the active site accessibility. The optimized composite (CMC/MIL-125(Ti)-NH2-300) demonstrated exceptional adsorption capacities of 1251.8 mg/g (55 °C), substantially exceeding those of its individual components (CMC: 39.5 mg/g; MIL-125(Ti)-NH2: 174.9 mg/g). The material achieved >90% NOR removal at concentrations ≤100 mg/L, exhibited rapid adsorption kinetics (best fitted by Elovich model, R2 = 0.996), maintained robust performance across pH 3–10, and showed excellent cyclic stability of 92.4% adsorption capacity retention after 5 regeneration cycles. Combined density functional theory (DFT)/Multiwfn analyses deciphered synergistic adsorption mechanisms governed by electrostatic forces, π–π stacking, multihydrogen bonding, and van der Waals forces. This study delivers a high-performance and sustainable adsorbent for the remediation of antibiotic-contaminated wastewater.
{"title":"High-Capacity Norfloxacin Capture by CMC/MIL-125(Ti)-NH2: One-Pot Synthesis, Performance, and Synergistic Mechanisms","authors":"Tian Peng, Fengting Chen, Jinglong Yang, Mingzhu Xia, Fengyun Wang, Sidi Zhu, Fenghe Wang","doi":"10.1021/acsami.5c17816","DOIUrl":"https://doi.org/10.1021/acsami.5c17816","url":null,"abstract":"Norfloxacin (NOR), a recalcitrant antibiotic, poses significant threats to aquatic ecosystems and human health. Employing a facile one-pot hydrothermal approach, this work pioneers a novel three-dimensional carboxymethyl cellulose (CMC)/MIL-125(Ti)-NH<sub>2</sub> composite for ultraefficient NOR removal. The CMC scaffold effectively prevented nanoparticle aggregation and structural collapse of MIL-125(Ti)-NH<sub>2</sub>, significantly enhancing the active site accessibility. The optimized composite (CMC/MIL-125(Ti)-NH<sub>2</sub>-300) demonstrated exceptional adsorption capacities of 1251.8 mg/g (55 °C), substantially exceeding those of its individual components (CMC: 39.5 mg/g; MIL-125(Ti)-NH<sub>2</sub>: 174.9 mg/g). The material achieved >90% NOR removal at concentrations ≤100 mg/L, exhibited rapid adsorption kinetics (best fitted by Elovich model, <i>R</i><sup>2</sup> = 0.996), maintained robust performance across pH 3–10, and showed excellent cyclic stability of 92.4% adsorption capacity retention after 5 regeneration cycles. Combined density functional theory (DFT)/Multiwfn analyses deciphered synergistic adsorption mechanisms governed by electrostatic forces, π–π stacking, multihydrogen bonding, and van der Waals forces. This study delivers a high-performance and sustainable adsorbent for the remediation of antibiotic-contaminated wastewater.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"33 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145729237","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}
Fan He, Eleanor Gillette, Xingxing Wang, Aila Huxford, Chuanxiao Xiao, Yong Yan, Matthew C. Beard, Jing Gu
The discovery of chirality-induced spin selectivity (CISS) revolutionized our understanding of the capabilities of chiral molecules, revealing that chiral molecules can function as spin filters, aligning the spin orientation of electrons when they transmit through them. Recently, CISS has been exploited to direct energy conversion, especially the oxygen evolution reaction (OER). However, despite the remarkable progress that has been achieved, the effect of CISS in influencing the intermediate species formation and changing the rate-determining step (RDS) is still vague. To understand those key reaction mechanism steps, electrocatalysts with distinct magnetic characteristics, ferromagnetic CoFe2O4 and paramagnetic Co3O4, were synthesized. The results show that spin-polarized charge carriers retain their spin alignment when coupled with ferromagnetic CoFe2O4, akin to the behavior observed under a magnetic field. The Tafel analysis and kinetic isotope studies (kinetic isotope effect) suggest that in the absence of chiral molecules, the initial electron transfer step, the formation of O* species, governs the rate-determining step (RDS). However, introducing chiral molecules shifts the RDS to a combination of the first and second electron transfers, leading to the formation of OOH*. This conclusion was further supported by in situ infrared spectroscopy, which shows that l-methionine-modified CoFe2O4 (l-CoFe2O4) promotes the formation of OOH*, a key intermediate for O2 generation. This study highlights the critical role of CISS in affecting the OER mechanism and intermediate species formation.
{"title":"Spin-Polarized Oxygen Evolution Reaction Enabled by Chiral Molecules Coupled with Ferromagnetic Electrocatalysts","authors":"Fan He, Eleanor Gillette, Xingxing Wang, Aila Huxford, Chuanxiao Xiao, Yong Yan, Matthew C. Beard, Jing Gu","doi":"10.1021/acsami.5c18273","DOIUrl":"https://doi.org/10.1021/acsami.5c18273","url":null,"abstract":"The discovery of chirality-induced spin selectivity (CISS) revolutionized our understanding of the capabilities of chiral molecules, revealing that chiral molecules can function as spin filters, aligning the spin orientation of electrons when they transmit through them. Recently, CISS has been exploited to direct energy conversion, especially the oxygen evolution reaction (OER). However, despite the remarkable progress that has been achieved, the effect of CISS in influencing the intermediate species formation and changing the rate-determining step (RDS) is still vague. To understand those key reaction mechanism steps, electrocatalysts with distinct magnetic characteristics, ferromagnetic CoFe<sub>2</sub>O<sub>4</sub> and paramagnetic Co<sub>3</sub>O<sub>4</sub>, were synthesized. The results show that spin-polarized charge carriers retain their spin alignment when coupled with ferromagnetic CoFe<sub>2</sub>O<sub>4</sub>, akin to the behavior observed under a magnetic field. The Tafel analysis and kinetic isotope studies (kinetic isotope effect) suggest that in the absence of chiral molecules, the initial electron transfer step, the formation of O* species, governs the rate-determining step (RDS). However, introducing chiral molecules shifts the RDS to a combination of the first and second electron transfers, leading to the formation of OOH*. This conclusion was further supported by in situ infrared spectroscopy, which shows that <span>l</span>-methionine-modified CoFe<sub>2</sub>O<sub>4</sub> (<span>l</span>-CoFe<sub>2</sub>O<sub>4</sub>) promotes the formation of OOH*, a key intermediate for O<sub>2</sub> generation. This study highlights the critical role of CISS in affecting the OER mechanism and intermediate species formation.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"6 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145729239","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}
Cátia Correia, Daniela Cruz-Moreira, Fábio S. Gonçalves, Vanessa F. Cardoso, Maria C. Paiva, Rui L. Reis, Iva Pashkuleva, Daniela Peixoto, Natália M. Alves
Spinal cord injury (SCI) is a condition that interrupts neural electrical conduction, resulting in significant motor and sensory dysfunction. Current treatments remain inadequate for fully restoring neuronal activity, highlighting the urgent need for advanced neurodegenerative materials to reconnect disrupted nerve pathways and recover neural connectivity and function. Herein, conductive and adhesive hydrogel composites based on hyaluronic acid (HA) filled with exfoliated graphite nanoplatelets (EG) or pyrrolidine-functionalized EG (f-EG) are developed. Adhesive catechol-conjugated HA (HA-Cat) is obtained by a reaction of HA-aldehyde with dopamine and subsequent reduction. Then, hydrogel composites (HA-C) are produced using sodium periodate as an oxidative agent. The incorporation of 50% f-EG substantially increased the electrical conductivity of HA-C, supporting efficient electrical signal transmission, which is essential for nerve repair. The hydrogels exhibited mechanical properties suitable for neural tissue regeneration along with adhesive and self-healing capabilities that promote integration at the injury site. Moreover, undifferentiated SH-SY5Y cells cultured on HA-C reinforced with EG or f-EG showed enhanced cell attachment and viability after electrical stimulation. The results demonstrate that the developed hydrogel composites are promising biomaterials for SCI repair by filling the injury site, bridging the damaged neural pathway, and mimicking the bioelectrical properties of the spinal cord’s bioelectrical properties.
{"title":"Multifunctional Hyaluronic Acid/Graphite Nanoplatelet Hydrogels as Tools for Spinal Cord Regeneration","authors":"Cátia Correia, Daniela Cruz-Moreira, Fábio S. Gonçalves, Vanessa F. Cardoso, Maria C. Paiva, Rui L. Reis, Iva Pashkuleva, Daniela Peixoto, Natália M. Alves","doi":"10.1021/acsami.5c20777","DOIUrl":"https://doi.org/10.1021/acsami.5c20777","url":null,"abstract":"Spinal cord injury (SCI) is a condition that interrupts neural electrical conduction, resulting in significant motor and sensory dysfunction. Current treatments remain inadequate for fully restoring neuronal activity, highlighting the urgent need for advanced neurodegenerative materials to reconnect disrupted nerve pathways and recover neural connectivity and function. Herein, conductive and adhesive hydrogel composites based on hyaluronic acid (HA) filled with exfoliated graphite nanoplatelets (EG) or pyrrolidine-functionalized EG (f-EG) are developed. Adhesive catechol-conjugated HA (HA-Cat) is obtained by a reaction of HA-aldehyde with dopamine and subsequent reduction. Then, hydrogel composites (HA-C) are produced using sodium periodate as an oxidative agent. The incorporation of 50% f-EG substantially increased the electrical conductivity of HA-C, supporting efficient electrical signal transmission, which is essential for nerve repair. The hydrogels exhibited mechanical properties suitable for neural tissue regeneration along with adhesive and self-healing capabilities that promote integration at the injury site. Moreover, undifferentiated SH-SY5Y cells cultured on HA-C reinforced with EG or f-EG showed enhanced cell attachment and viability after electrical stimulation. The results demonstrate that the developed hydrogel composites are promising biomaterials for SCI repair by filling the injury site, bridging the damaged neural pathway, and mimicking the bioelectrical properties of the spinal cord’s bioelectrical properties.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"38 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145718220","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}
Mónica Onrubia-Márquez, Francisco Navas, Esther M. Sánchez-Carnerero, Antonio Martín, Anselma Liturri, Morena Miciaccia, Raúl Sanz, Antonio Scilimati, Rafael A. García-Muñoz, Maria Grazia Perrone, Victoria Morales
Neurodegenerative diseases (NDs) are progressive and fatal disorders that primarily affect the elderly and remain incurable. Characterized by irreversible neuronal loss, they leave patients increasingly dependent on caregivers. Despite diverse clinical presentations, NDs share common pathological features, such as protein aggregation, metal accumulation, oxidative stress, and chronic neuroinflammation. Despite numerous efforts, most therapeutic candidates fail due to poor efficacy, toxicity concerns, or limited blood–brain barrier (BBB) permeability, thereby highlighting the need for enhanced formulations. Nanomedicine offers a promising strategy to improve the therapeutic performance of existing compounds. This study presents a nanoformulation of the metal chelator deferoxamine (DFO) based on the drug-structure-directing agent (DSDA) concept, in which a hydrophobic chain is covalently linked to the DFO molecule to impart amphiphilic properties and acts as a template for the synthesis of a mesoporous silica nanoparticle (MSN). This approach allows for the one-pot fabrication of DFO-loaded MSNs (DFO@MSNs) with controlled sizes of below 20 nm without the need for surfactant removal. Compared to MCM-41-based systems, DFO@MSNs exhibited a higher drug loading capacity (10 mg of DFO/100 mg of MSNs) and a significantly more sustained release profile, minimizing premature leakage, with less than 20% of the cargo released over 24 h. Safety of DFO@MSN was assessed using BV-2 microglial and human neuroblastoma SH-SY5Y cell lines, and in vitro assays confirmed its enhanced iron-chelating capacity and effective inhibition of aluminum-induced amyloid aggregation. Furthermore, permeability studies using a Caco-2 in vitro BBB model revealed that a smaller particle size greatly enhances transport across the barrier. These results support DFO@MSNs as a promising multifunctional nanoplatform for targeted chelation therapy and neuroprotection in ND treatment.
{"title":"Size-Controlled Mesoporous Silica Nanoparticles via Template Nanoarchitectonics from a Deferoxamine Derivative for Enhanced Blood–Brain Barrier Permeability and Neuroprotective Chelation Therapy","authors":"Mónica Onrubia-Márquez, Francisco Navas, Esther M. Sánchez-Carnerero, Antonio Martín, Anselma Liturri, Morena Miciaccia, Raúl Sanz, Antonio Scilimati, Rafael A. García-Muñoz, Maria Grazia Perrone, Victoria Morales","doi":"10.1021/acsami.5c18528","DOIUrl":"https://doi.org/10.1021/acsami.5c18528","url":null,"abstract":"Neurodegenerative diseases (NDs) are progressive and fatal disorders that primarily affect the elderly and remain incurable. Characterized by irreversible neuronal loss, they leave patients increasingly dependent on caregivers. Despite diverse clinical presentations, NDs share common pathological features, such as protein aggregation, metal accumulation, oxidative stress, and chronic neuroinflammation. Despite numerous efforts, most therapeutic candidates fail due to poor efficacy, toxicity concerns, or limited blood–brain barrier (BBB) permeability, thereby highlighting the need for enhanced formulations. Nanomedicine offers a promising strategy to improve the therapeutic performance of existing compounds. This study presents a nanoformulation of the metal chelator deferoxamine (DFO) based on the drug-structure-directing agent (DSDA) concept, in which a hydrophobic chain is covalently linked to the DFO molecule to impart amphiphilic properties and acts as a template for the synthesis of a mesoporous silica nanoparticle (MSN). This approach allows for the one-pot fabrication of DFO-loaded MSNs (DFO@MSNs) with controlled sizes of below 20 nm without the need for surfactant removal. Compared to MCM-41-based systems, DFO@MSNs exhibited a higher drug loading capacity (10 mg of DFO/100 mg of MSNs) and a significantly more sustained release profile, minimizing premature leakage, with less than 20% of the cargo released over 24 h. Safety of DFO@MSN was assessed using BV-2 microglial and human neuroblastoma SH-SY5Y cell lines, and <i>in vitro</i> assays confirmed its enhanced iron-chelating capacity and effective inhibition of aluminum-induced amyloid aggregation. Furthermore, permeability studies using a Caco-2 <i>in vitro</i> BBB model revealed that a smaller particle size greatly enhances transport across the barrier. These results support DFO@MSNs as a promising multifunctional nanoplatform for targeted chelation therapy and neuroprotection in ND treatment.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"38 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145718166","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}
Gan Zhou, Matthew J. Yee, Jun Tae Huh, Ingrid Safina, Woo Sung Chang, Alia Koch, Mildred C. Embree
Osteoarthritis (OA) is a degenerative joint disease that causes chronic pain, disability, and cartilage loss, yet there are no approved disease-modifying OA therapies. Decellularized extracellular matrix (dECM) hydrogels preserve the biochemical complexity of native tissue and offer a promising platform for cartilage repair, yet their development and application for OA treatments remain poorly understood. We previously identified the perichondrium-like fibrocartilage lining the temporomandibular joint (TMJ) condyle as a niche harboring fibrocartilage stem/progenitor cells that support cartilage homeostasis. Based on this discovery, we developed a decellularized perichondrium-derived hydrogel (d-PC hydrogel) from native TMJ tissue, characterized its rheological and biological properties, and assessed its regenerative capacity. Decellularized hydrogels were prepared from New Zealand white rabbit TMJ perichondrium (d-PC) and condylar cartilage (d-CC), evaluated via rheological testing, and tested for chondrogenic potential by seeding primary human perichondrial or chondrocyte cells onto hydrogels followed by implantation into nude mice. Unlike the d-CC hydrogel, the d-PC hydrogel demonstrated superior gel-like properties and induced fibrocartilage stem/progenitor cells to form cartilage in vivo. In a post-traumatic rabbit TMJ-OA model, monthly intra-articular injections of d-PC hydrogel significantly improved TMJ cartilage tissue architecture and reduced MMP13 expression compared to d-CC hydrogel- and PBS-treated groups. These findings identify the TMJ perichondrium as a source of the dECM hydrogel capable of supporting chondrogenesis and TMJ cartilage repair. In future studies, we will explore its utility as an organoid system or delivery platform for cell- and drug-based disease-modifying OA therapies.
{"title":"Hydrogels Derived from Native Decellularized Perichondrium for Chondrocyte Differentiation and Temporomandibular Joint Repair","authors":"Gan Zhou, Matthew J. Yee, Jun Tae Huh, Ingrid Safina, Woo Sung Chang, Alia Koch, Mildred C. Embree","doi":"10.1021/acsami.5c18997","DOIUrl":"https://doi.org/10.1021/acsami.5c18997","url":null,"abstract":"Osteoarthritis (OA) is a degenerative joint disease that causes chronic pain, disability, and cartilage loss, yet there are no approved disease-modifying OA therapies. Decellularized extracellular matrix (dECM) hydrogels preserve the biochemical complexity of native tissue and offer a promising platform for cartilage repair, yet their development and application for OA treatments remain poorly understood. We previously identified the perichondrium-like fibrocartilage lining the temporomandibular joint (TMJ) condyle as a niche harboring fibrocartilage stem/progenitor cells that support cartilage homeostasis. Based on this discovery, we developed a decellularized perichondrium-derived hydrogel (d-PC hydrogel) from native TMJ tissue, characterized its rheological and biological properties, and assessed its regenerative capacity. Decellularized hydrogels were prepared from New Zealand white rabbit TMJ perichondrium (d-PC) and condylar cartilage (d-CC), evaluated via rheological testing, and tested for chondrogenic potential by seeding primary human perichondrial or chondrocyte cells onto hydrogels followed by implantation into nude mice. Unlike the d-CC hydrogel, the d-PC hydrogel demonstrated superior gel-like properties and induced fibrocartilage stem/progenitor cells to form cartilage <i>in vivo</i>. In a post-traumatic rabbit TMJ-OA model, monthly intra-articular injections of d-PC hydrogel significantly improved TMJ cartilage tissue architecture and reduced MMP13 expression compared to d-CC hydrogel- and PBS-treated groups. These findings identify the TMJ perichondrium as a source of the dECM hydrogel capable of supporting chondrogenesis and TMJ cartilage repair. In future studies, we will explore its utility as an organoid system or delivery platform for cell- and drug-based disease-modifying OA therapies.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"2 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145718215","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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