ACS Applied Materials & Interfaces最新文献

{"title":"Orientational Disorder and Molecular Correlations in Hybrid Organic–Inorganic Perovskites: From Fundamental Insights to Technological Applications","authors":"Carlos Escorihuela-Sayalero, Ares Sanuy, Luis Carlos Pardo, Claudio Cazorla","doi":"10.1021/acsami.4c12762","DOIUrl":"https://doi.org/10.1021/acsami.4c12762","url":null,"abstract":"Hybrid organic–inorganic perovskites (HOIP) have emerged in recent years as highly promising semiconducting materials for a wide range of optoelectronic and energy applications. Nevertheless, the rotational dynamics of the organic components and many-molecule interdependencies, which may strongly impact the functional properties of HOIP, are not yet fully understood. In this study, we quantitatively analyze the orientational disorder and molecular correlations in archetypal perovskite CH₃NH₃PbI₃ (MAPI) by performing comprehensive molecular dynamics simulations and entropy calculations. We found that, in addition to the usual vibrational and orientational contributions, rigid molecular rotations around the C–N axis and correlations between neighboring molecules noticeably contribute to the entropy increment associated with the temperature-induced order–disorder phase transition, Δ<i>S</i>_<i>t</i>. Molecular conformational changes are equally infrequent in the low-<i>T</i> ordered and high-<i>T</i> disordered phases and have a null effect on Δ<i>S</i>_<i>t</i>. Conversely, the couplings between the angular and vibrational degrees of freedom are substantially reinforced in the high-<i>T</i> disordered phase and significantly counteract the phase-transition entropy increase resulting from other factors. Furthermore, the tendency for neighboring molecules to be orientationally ordered is markedly local, consequently inhibiting the formation of extensive polar nanodomains at both low and high temperatures. This theoretical investigation not only advances the fundamental knowledge of HOIP but also establishes physically insightful connections with contemporary technological applications like photovoltaics, solid-state cooling, and energy storage.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"108 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2024-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142879980","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":"Cluster Engineering in Water Catalytic Reactions: Synthesis, Structure–Activity Relationship and Mechanism","authors":"Zhijie Kong, Xue Zhao, Wu-Chu Li, Jia-Yun Wang, Si Li, Zhijuan Liu, Xi-Yan Dong, Rui Wang, Ren-Wu Huang, Shuang-Quan Zang","doi":"10.1021/acsami.4c16063","DOIUrl":"https://doi.org/10.1021/acsami.4c16063","url":null,"abstract":"Four fundamental reactions are essential to harnessing energy from water sustainably: oxidation reduction reaction (ORR), oxygen reduction reaction (OER), hydrogen oxidation reaction (HOR), and hydrogen evolution reaction (HER). This review summarizes the research advancements in the electrocatalytic reaction of metal nanoclusters for water splitting. It covers various types of nanoclusters, particularly those at the size level, that enhance these catalytic reactions. The synthesis of cluster-based catalysts and the elucidation of the structure–activity relationships and reaction mechanisms are discussed. Emphasis is placed on utilizing atomically precise cluster materials and the interplay between the carrier and cluster in water catalysis, especially for applying catalytic engineering principles (such as synergy, coordination, heterointerface, and lattice strain engineering) to understand structure–activity relationships and catalytic mechanisms for cluster-based catalysts. Finally, the field of cluster water catalysis is summarized and prospected. We believe that developing cluster-based catalysts with high activity, excellent stability, and high selectivity will significantly promote the development of renewable energy conversion reactions.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"41 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2024-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142879981","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":"Tuning the Crowding Effect of Water and Imidazole in Covalent Organic Frameworks for Proton Conduction","authors":"Kun Zhang, Lei Wu, Yanting Zhang, Hong Zhang, Dongshuang Wu","doi":"10.1021/acsami.4c15871","DOIUrl":"https://doi.org/10.1021/acsami.4c15871","url":null,"abstract":"The proton conduction of imidazole under confined conditions has attracted widespread attention from researchers. Under anhydrous conditions, the proton transfer behavior is primarily governed by the molecular dynamics of imidazole. However, within a water-mediated system, the crowding effect of water and imidazole in a confined space may outweigh the intrinsic properties of imidazole itself. In this study, we have meticulously adjusted the structural fragments within the covalent organic frameworks (COFs), fine-tuning the saturation level of imidazole loading and adjusting the crowding degree of imidazole and water molecules. As a result, the two COF composites exhibit distinctly different proton conduction mechanisms from 32 to 100% relative humidity (RH), of which one possesses proton conduction progressively shifting from the Grotthuss mechanism to the vehicle mechanism, while the other has proton conduction undergoing a transition from the vehicle mechanism at 32% RH through the Grotthuss mechanism at 75% RH and finally back to the vehicle mechanism at 100% RH. These results highlight the critical role of the crowding effect of water and imidazole within confined spaces in proton conduction.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"64 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142879983","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":"Intrinsically Healable and Photoresponsive Electrospun Fabrics: Integrating PVDF-HFP, TPU, and Azobenzene Ionic Liquids","authors":"Chun-Chi Chang, Lin-Ruei Lee, Sheng Zheng, Tse-Yu Lo, Chia-Wei Chang, Chia-Ti Wu, Tsung-Hung Tsai, Huan-Ru Chen, Yi-Fan Chen, Ming-Hsuan Chang, Jiun-Tai Chen","doi":"10.1021/acsami.4c17199","DOIUrl":"https://doi.org/10.1021/acsami.4c17199","url":null,"abstract":"In recent years, the integration of multifunctional properties into electrospun fabrics has garnered significant attention for applications in wearable devices and smart textiles. A major challenge lies in achieving a balance among intermolecular interactions, structural stability, and responsiveness to external stimuli. In this study, we address this challenge by developing intrinsically healable and photoresponsive electrospun fabrics composed of poly(vinylidene fluoride-<i>co</i>-hexafluoropropylene) (PVDF-HFP), thermoplastic polyurethane (TPU), and an azobenzene-based ionic liquid ([AzoC₆MIM][TFSI]). The interactions between PVDF-HFP and [AzoC₆MIM][TFSI] enable intrinsic self-healing and light-induced responsiveness, while the incorporation of TPU prevents fiber fusion during electrospinning, maintaining structural integrity and porosity. Our results demonstrate that these fabrics can recover up to 97% of their original mechanical properties after self-healing and exhibit reversible changes in electrical conductivity under UV and visible lights. This versatile approach paves the way for the incorporation of high concentrations of functional ionic liquids into electrospun fabrics, enabling the development of multifunctional textiles with potential applications in self-healing wearable devices and advanced sensors.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"1 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142879986","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":"A Redox-Enzyme Integrated Microbial Fuel Cell Design Using the Surface Display System in Shewanella oneidensis MR-1","authors":"Seungwoo Baek, Hyeryeong Lee, Yoo Seok Lee, In Seop Chang, In-Geol Choi","doi":"10.1021/acsami.4c16868","DOIUrl":"https://doi.org/10.1021/acsami.4c16868","url":null,"abstract":"A biofuel cell is an electrochemical device using exoelectrogen or biocatalysts to transfer electrons from redox reactions to the electrodes. While wild-type microbes and natural enzymes are often employed as exoelectrogen and biocatalysts, genetically engineered or modified organisms have been developed to enhance exoelectrogen activity. Here, we demonstrated a redox-enzyme integrated microbial fuel cell (REI-MFC) design based on an exoelectrogen-enhancing strategy that reinforces the electrogenic activity of <i>Shewanella oneidensis</i> MR1 by displaying an extra redox enzyme on the cell surface. We constructed the cell-surface display system for <i>Shewanella oneidensis</i> MR-1 by porting the autotransporter of <i>Escherichia coli</i> into the MR-1 strain. The functionality of the display system was validated by examining the various enzymes displayed on the cell surface of <i>S. oneidensis</i> MR-1. The implementation of the REI-MFC design was accomplished by an engineered MR-1 strain displaying a redox enzyme originating from swine NADH-cytochrome b5 reductase 3 (B5R3). At the polarization test of enhanced exoelectrogen in an operating MFC environment, the current generation (Δ<i>I</i>_a, peak: 10.4 ± 1.9 μA) of the MR-1 displaying B5R3 was 4.7-fold higher than that of wild-type MR-1 (2.2 ± 0.3 μA). The maximum charge transfer resistance (<i>R</i>_ct) under the optimized electrochemical test conditions was 70% lower than the wild-type MR-1. The cell surface display system for <i>S. oneidensis</i> MR-1 exploited in this study facilitated the exoelectrogen activity in the REI-MFC design.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"14 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142879988","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":"High-Voltage Fe-Based Tunnel-Type Na0.66[Mn0.33Fe0.33Ti0.3Sn0.04]O2 Cathode for Aqueous Rechargeable Sodium-Ion Battery","authors":"Fei Dong, Bin Yang, Xueqian Zhang, Ziqiang Yang, Sen Wang, Zhiguo Hou, Pu Chen","doi":"10.1021/acsami.4c18772","DOIUrl":"https://doi.org/10.1021/acsami.4c18772","url":null,"abstract":"Tunnel-type-structure Na_0.44MnO₂ has been extensively researched for cathode material in aqueous rechargeable sodium-ion battery owing to its high specific capacity (120 mA h g^–1), large channels facilitating Na extraction/insertion, chemical and electrochemical stability in aqueous electrolytes, and low cost. However, the low average working potential (0.1 V versus standard hydrogen electrode, SHE) and no more than half of its available theoretical capacity within full batteries limit the practical application. Herein, we develop an Fe-based tunnel-type Na_0.66[Mn_0.33Fe_0.33Ti_0.3Sn_0.04]O₂ cathode, delivering a high reversible specific capacity (95 mA h g^–1) under a high working voltage (0.75 V versus SHE). A full battery, assembled with a NaTi₂(PO₄)₃@C anode, exhibits a high energy density of 80 W h kg^–1 (total mass of cathode and anode active materials) and a long cycle life with 84% capacity retention after 1000 cycles at 1 C.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"53 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142879989","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":"Detachable Cyclic Poly(ethylene glycol)-Embedded Choline Phosphate Liposome Used for Long-Acting and Accurate Cancer Chemo-Immunotherapy with High Security","authors":"Shengran Li, Chenyang Zou, Jingyan An, Meiying Lv, Xifei Yu","doi":"10.1021/acsami.4c20191","DOIUrl":"https://doi.org/10.1021/acsami.4c20191","url":null,"abstract":"Liposomes have attracted attention in biomedicine and pharmacy for their benefits including reduced toxicity, extended pharmacokinetics, and biocompatibility. However, their limitations include susceptibility to blood clearance, rapid disintegration, and lack of functionality, restricting their further applications. To address these challenges, inspired by the unique topological features of cyclic polymers and the specific binding property of the choline phosphate (CP) lipid, dipole–dipole interactions between CP molecules are utilized to create a detachable cyclic PEG-embedded CP liposome (d-cycPEG-lipo). In comparison to linear PEG-embedded liposomes (d-linPEG-lipo) and PEGylated liposomes (linPEG-lipo), d-cycPEG-lipo demonstrates enhanced resistance to proteins and macrophages in the bloodstream due to its higher compactness and smoother interface. The packing behavior and lubrication property of cyclic PEG also result in reduced accumulation in organs, leading to an extended pharmacokinetic half-life of 13.6 h. At the tumor site, the PEG embedded in d-cycPEG-lipo detached and facilitated a 3.3-fold higher cell uptake than linPEG-lipo. Notably, d-cycPEG-lipo induces lower inflammation and triggers a stronger immune response than d-linPEG-lipo. In the treatment of breast cancer, d-cycPEG-lipo exhibits a significantly high efficacy of 98.5%. Hence, the reversible combination of cyclic PEG with CP liposomes holds tremendous promise for enhancing drug and antibody delivery in clinical tumor therapy.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"288 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142879992","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":"Design of Extruded Nanostructured Composites via Decoupling of the Cellulose Nanofibril/Poly(butylene adipate-co-terephthalate) Interface","authors":"Angelica Avella, Maria Rosella Telaretti Leggieri, Alexandros Efraim Alexakis, Eva Malmström, Giada Lo Re","doi":"10.1021/acsami.4c17899","DOIUrl":"https://doi.org/10.1021/acsami.4c17899","url":null,"abstract":"The full exploitation of the outstanding mechanical properties of cellulose nanofibrils (CNFs) as potential reinforcements in nanocomposite materials is limited by the poor interactions at the CNF–polymer matrix interface. Within this work, tailor-made copolymers were designed to mediate the interface between CNFs and biodegradable poly(butylene adipate-<i>co</i>-terephthalate) (PBAT), and their effect on extruded nanocomposite performance was tested. For this purpose, two well-defined amphiphilic anchor–tail diblock copolymer structures were compared, with a fixed anchor block length and a large difference in the hydrophobic tail block length. The aim was to evaluate the impact of the copolymers’ chain length on the nanocomposite interface. The presence of amphiphilic diblock copolymers significantly improved the mechanical properties compared to those of PBAT nanocomposites containing unmodified CNFs. In particular, the copolymer with a longer tail was more effective for CNF–PBAT dispersion interactions, leading to a 65% increase of Young’s modulus of neat PBAT, while retaining high deformability (670%). The results provide insights into the effectiveness of a waterborne third component at the CNF–matrix interface and its structure–property relationship.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"48 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142879991","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":"Biomimetic Anisotropic-Functionalized Platelet-Membrane-Coated Polymeric Particles for Targeted Drug Delivery to Human Breast Cancer Cells","authors":"Hongzhe Yu, Elana Ben-Akiva, Randall A. Meyer, Jordan J. Green","doi":"10.1021/acsami.4c15471","DOIUrl":"https://doi.org/10.1021/acsami.4c15471","url":null,"abstract":"Biomimetic particles that can replicate aspects of natural biological cell function are useful for advanced biological engineering applications. Engineering such particles requires mimicking the chemical complexity of the surface of biological cells, and this can be achieved by coating synthetic particles with naturally derived cell membranes. Past research has demonstrated the feasibility of utilizing cell membrane coatings from a variety of cell types to achieve extended blood circulation half-life. A particle’s shape can also be designed to mimic a biological cell or virus, and this physical attribute can cause particular transport and biodistribution properties. However, the potential synergy between engineering a biomimetic particle’s core shape in combination with functionalizing its surface with cell membranes to achieve targeted drug delivery has not been well-investigated. Here, anisotropic poly(lactic-<i>co</i>-glycolic acid) (PLGA) particles are coated with platelet membranes to engineer particles with enhanced stealth properties that are biomimetic in size, shape, and surface composition to natural platelets. The natural ability of platelets to target tumor cells was harnessed to develop a particulate system for targeted dual delivery of a small molecule and protein to cancer cells. The particles had targeted binding to metastatic human breast cancer cells, leading to enhanced killing of these cells in a mouse model through codelivery of TRAIL and doxorubicin. This system can be used for cancer cell killing and could potentially be utilized in preventing breast cancer metastasis. By engineering both the physical and chemical properties of the particles, biomimicry and therapeutic promise can be best achieved.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"60 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874068","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":"Aminopeptidase-Responsive NIR Photosensitizer for Precision Targeting and Eradication of Pseudomonas aeruginosa Biofilms","authors":"Yang Liu, Kaixuan Liu, Ling lei, Qinghua Wang, Xiang Wang, Xiangchuan Meng, Qian Liu, Jiacheng Du, Leilei Zhang, Marc Nazaré, Hai-Yu Hu","doi":"10.1021/acsami.4c16028","DOIUrl":"https://doi.org/10.1021/acsami.4c16028","url":null,"abstract":"The emergence of resistance in <i>Pseudomonas aeruginosa</i> represents a significant global health challenge, particularly due to the hurdle of effectively penetrating biofilms with antimicrobials. Moreover, the rise of antibiotic-resistant pathogens has driven the urgent need for developing innovative therapeutic approaches to overcome antibiotic resistance. Antibacterial phototherapy strategies have shown great potential for combating pathogens due to their broad-spectrum antimicrobial activity, spatiotemporal controllability, and relatively low rate of resistance emergence. However, due to the lack of bacterial specificity and penetration, photosensitizers cause considerable damage to mammalian cells and normal tissues and are less effective against bacterial biofilms. Herein, we developed a novel dual-targeting antibacterial strategy to construct a near-infrared photosensitizer, Cy-NEO-Leu. Cy-NEO-Leu showed great bacterial targeting affinity, penetrating and accumulating in biofilms. At the site of infection, it was specifically activated by <i>P. aeruginosa</i> aminopeptidase (PaAP), producing Cy-NEO-NH₂, which demonstrated outstanding photothermal (PTT) and photodynamic (PDT) properties, with a photothermal conversion efficiency of up to 70.34%. Both <i>in vitro</i> and <i>in vivo</i> results demonstrated that Cy-NEO-Leu significantly reduced the biofilm biomass and bacterial viability in <i>P. aeruginosa</i> biofilms. Moreover, phototherapy with Cy-NEO-Leu further activated the immune system, enhancing therapeutic efficacy and promoting wound healing. RNA-seq analysis revealed that the antibacterial mechanism of Cy-NEO-Leu-mediated phototherapy involves disruption of the transcriptional and translational processes of <i>P. aeruginosa</i> under laser irradiation. Overall, our results present a promising therapeutic approach against <i>P. aeruginosa</i> biofilms and inspire the development of next-generation antimicrobials.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"22 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874139","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}