Blanca Escriche-Navarro, Eva Garrido, Sandra Clara-Trujillo, Anna Labernadie, Félix Sancenon, Alba García-Fernández, Ramón Martínez-Máñez
Senescent cells are involved in age-related disorders in different organs and are therapeutic targets for fibrotic and chronic pathologies. Immune-modulating agents, able to enhance senescent cell detection and elimination by endogenous immune cells, have emerged as pharmacological strategies. We report herein a nanoparticle for immune cell-mediated senolytic therapy designed to recruit immune cells in response to specific enzymatic matrix metalloproteinase-3 (MMP-3) activity in the senescence-associated secretory phenotype. For this, mesoporous silica nanoparticles (MSNs) are coated with a peptide substrate of the metalloproteinase MMP-3, and the peptide is decorated with chemokine CXCL12 that enhances immune cell recruitment (NPs@CXCL12). Controlled release studies confirmed the progressive and specific release of CXCL12 in the presence of MMP-3. The ability of immune cell recruitment in response to a senescent microenvironment (senescent WI-38 fibroblasts) is confirmed by Transwell migration assays with green fluorescent Jurkat T-cells, showing NPs@CXCL12 has an enhanced chemotaxis effect toward senescent cells compared to free CXCL12 (2-fold). Moreover, the cytotoxic capacity of human primary natural killer (NK) cells over senescent WI-38 is also confirmed, and their migration trajectories in response to NPs@CXCL12 or free CXCL12 are monitored by using a microfluidic device. Results confirm the ability of NPs@CXCL12 to generate a chemotactic gradient able to attract NK cells. When compared with free CXCL12, the NPs@CXCL12 system showed a reduction of up to 15.56% in the population of NK cells migrating toward free CXCL12 under competitive conditions. This study demonstrates the potential of designing nanoparticles to recruit immune cells under specific responses to eliminate senescent cells. Results confirm that NPs@CXCL12 can effectively establish a chemotactic gradient to attract NK cells.
{"title":"Nanodevice-Mediated Immune Cell Recruitment: Targeting Senescent Cells via MMP-3-Responsive CXCL12-Coated Nanoparticles","authors":"Blanca Escriche-Navarro, Eva Garrido, Sandra Clara-Trujillo, Anna Labernadie, Félix Sancenon, Alba García-Fernández, Ramón Martínez-Máñez","doi":"10.1021/acsami.4c17748","DOIUrl":"https://doi.org/10.1021/acsami.4c17748","url":null,"abstract":"Senescent cells are involved in age-related disorders in different organs and are therapeutic targets for fibrotic and chronic pathologies. Immune-modulating agents, able to enhance senescent cell detection and elimination by endogenous immune cells, have emerged as pharmacological strategies. We report herein a nanoparticle for immune cell-mediated senolytic therapy designed to recruit immune cells in response to specific enzymatic matrix metalloproteinase-3 (MMP-3) activity in the senescence-associated secretory phenotype. For this, mesoporous silica nanoparticles (MSNs) are coated with a peptide substrate of the metalloproteinase MMP-3, and the peptide is decorated with chemokine CXCL12 that enhances immune cell recruitment (NPs@CXCL12). Controlled release studies confirmed the progressive and specific release of CXCL12 in the presence of MMP-3. The ability of immune cell recruitment in response to a senescent microenvironment (senescent WI-38 fibroblasts) is confirmed by Transwell migration assays with green fluorescent Jurkat T-cells, showing NPs@CXCL12 has an enhanced chemotaxis effect toward senescent cells compared to free CXCL12 (2-fold). Moreover, the cytotoxic capacity of human primary natural killer (NK) cells over senescent WI-38 is also confirmed, and their migration trajectories in response to NPs@CXCL12 or free CXCL12 are monitored by using a microfluidic device. Results confirm the ability of NPs@CXCL12 to generate a chemotactic gradient able to attract NK cells. When compared with free CXCL12, the NPs@CXCL12 system showed a reduction of up to 15.56% in the population of NK cells migrating toward free CXCL12 under competitive conditions. This study demonstrates the potential of designing nanoparticles to recruit immune cells under specific responses to eliminate senescent cells. Results confirm that NPs@CXCL12 can effectively establish a chemotactic gradient to attract NK cells.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"1 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990838","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 unique optical properties of perovskite quantum dots (PQDs), particularly the tunable photoluminescence (PL) across the visible spectrum, make them a promising tool for chlorinated detection. However, the correlation between the fluorescence emission shift behavior and the interface of phase transformation in PQDs has not been thoroughly explored. In this study, we synthesized CsPbBr3 PQDs via the hot-injection method and demonstrated their ability to detect chlorinated volatile compounds such as HCl and NaOCl through a halide exchange process between the PQDs’ solid thin film and the chlorinated vapor phase. This exchange process, which occurs alongside chloride (Cl) and bromine (Br) ion exchange and halide atom rearrangement, leads to sequential structural changes: the initial CsPbBr3 cubic Pm3̅m phase transitions to the CsPb2BrxCl5–x tetragonal I4/mcm phase, which subsequently transforms into the CsPbBrxCl3–x orthorhombic Pnma phase. The detailed exploration of this proposed mechanism during chlorinated vapor detection with CsPbBr3 PQDs thin films, supported by X-ray diffraction (XRD) analysis and PL spectrum over time, revealed high sensitivity to HCl vapor. The limit of detection (LOD) for HCl vapor was determined to be 0.02 ppm in visual recognition and 0.005 ppm via PL spectra. Additionally, the LOD for NaOCl was established at 0.50 ppm, facilitated by the photolysis reaction accelerating the conversion of NaOCl to HCl vapor under UV light irradiation. These insights have enriched our understanding of the mechanisms involved and broadened the potential use of CsPbBr3 PQDs as PL detection probes for chloride ions.
{"title":"A Study of Halide Ion Exchange-Induced Phase Transition in CsPbBr3 Perovskite Quantum Dots for Detecting Chlorinated Volatile Compounds","authors":"Chia-Chien Kuo, Duc-Binh Nguyen, Yi-Hsin Chien","doi":"10.1021/acsami.4c14868","DOIUrl":"https://doi.org/10.1021/acsami.4c14868","url":null,"abstract":"The unique optical properties of perovskite quantum dots (PQDs), particularly the tunable photoluminescence (PL) across the visible spectrum, make them a promising tool for chlorinated detection. However, the correlation between the fluorescence emission shift behavior and the interface of phase transformation in PQDs has not been thoroughly explored. In this study, we synthesized CsPbBr<sub>3</sub> PQDs via the hot-injection method and demonstrated their ability to detect chlorinated volatile compounds such as HCl and NaOCl through a halide exchange process between the PQDs’ solid thin film and the chlorinated vapor phase. This exchange process, which occurs alongside chloride (Cl) and bromine (Br) ion exchange and halide atom rearrangement, leads to sequential structural changes: the initial CsPbBr<sub>3</sub> cubic Pm3̅m phase transitions to the CsPb<sub>2</sub>Br<sub><i>x</i></sub>Cl<sub>5–<i>x</i></sub> tetragonal <i>I</i>4/<i>mcm</i> phase, which subsequently transforms into the CsPbBr<sub><i>x</i></sub>Cl<sub>3–<i>x</i></sub> orthorhombic <i>Pnma</i> phase. The detailed exploration of this proposed mechanism during chlorinated vapor detection with CsPbBr<sub>3</sub> PQDs thin films, supported by X-ray diffraction (XRD) analysis and PL spectrum over time, revealed high sensitivity to HCl vapor. The limit of detection (LOD) for HCl vapor was determined to be 0.02 ppm in visual recognition and 0.005 ppm via PL spectra. Additionally, the LOD for NaOCl was established at 0.50 ppm, facilitated by the photolysis reaction accelerating the conversion of NaOCl to HCl vapor under UV light irradiation. These insights have enriched our understanding of the mechanisms involved and broadened the potential use of CsPbBr<sub>3</sub> PQDs as PL detection probes for chloride ions.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"7 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990836","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}
Gagan Rastogi, Abhinab Mohapatra, Rajamanickam Ganesan, P. S. Anil Kumar
The quest for anisotropic superconductors has been a long-standing pursuit due to their potential applications in quantum computing. In this regard, experimentally, d-wave and anisotropic s-wave superconducting order parameters are predominantly observed, while p-wave superconductors remain largely elusive. Achieving p-wave superconductivity in topological phases is highly desirable, as it is considered suitable for creating topologically protected qubits. To achieve topological superconductivity in the dual topological insulator BiSe, we place an s-wave superconductor NbSe2 in its close proximity employing the van der Waals epitaxy technique. Low-temperature differential conductance measurements performed at the heterojunction exhibit a dual-dip feature with a V-shaped inner dip, a characteristic of p-wave superconductivity. This observation is corroborated by the multiband 2D Blonder–Tinkham–Klapwijk (BTK) fitting, where the inner and outer gaps exhibit p-wave and s-wave character, respectively. Furthermore, the BTK analysis reveals that the two superconducting gaps experience distinct effective critical fields and transition temperatures.
{"title":"Emergent p-Wave Superconductivity in a Dual Topological Insulator BiSe via Superconducting Proximity Effect","authors":"Gagan Rastogi, Abhinab Mohapatra, Rajamanickam Ganesan, P. S. Anil Kumar","doi":"10.1021/acsami.4c15770","DOIUrl":"https://doi.org/10.1021/acsami.4c15770","url":null,"abstract":"The quest for anisotropic superconductors has been a long-standing pursuit due to their potential applications in quantum computing. In this regard, experimentally, d-wave and anisotropic s-wave superconducting order parameters are predominantly observed, while p-wave superconductors remain largely elusive. Achieving p-wave superconductivity in topological phases is highly desirable, as it is considered suitable for creating topologically protected qubits. To achieve topological superconductivity in the dual topological insulator BiSe, we place an s-wave superconductor NbSe<sub>2</sub> in its close proximity employing the van der Waals epitaxy technique. Low-temperature differential conductance measurements performed at the heterojunction exhibit a dual-dip feature with a V-shaped inner dip, a characteristic of p-wave superconductivity. This observation is corroborated by the multiband 2D Blonder–Tinkham–Klapwijk (BTK) fitting, where the inner and outer gaps exhibit p-wave and s-wave character, respectively. Furthermore, the BTK analysis reveals that the two superconducting gaps experience distinct effective critical fields and transition temperatures.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"138 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990837","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}
Zhongshuai Gao, Shuya Zhang, Yanyi Duan, Heng Chang, Mei Cui, Renliang Huang, Rongxin Su
Marine biofouling and corrosion have become the main problems affecting the development of the marine industry. Silicone-based coatings have been widely used for antifouling and anticorrosion due to their low surface energy. However, the poor adhesion and low mechanical stability of these materials limit their application in complex marine environments. In this work, we presented a marine antifouling and anticorrosion coating named POSS-DMA@PDMS-TCM through photoinitiated thiol–ene click reaction combined with (mercaptopropyl) methylsiloxane dimethylsiloxane (PDMS-SH), dopamine methacrylamide (DMA), sulfhydryl-functionalized organosiloxanes (POSS-(SH)8), and N-(2,4,6-trichlorophenyl) maleimide (TCM). The POSS-DMA@PDMS-TCM coating exhibited strong stability and bonding ability both in air (2.17 MPa) and underwater (2.11 MPa) when the DMA content was 3 wt %. The high antibacterial (98.1% for Staphylococcus aureus and 99.5% for Escherichia coli) and antidiatom (94.5%) properties of the POSS-DMA@PDMS-TCM coatings have also been confirmed. Moreover, the POSS-DMA@PDMS-TCM coatings show excellent antifouling abilities in 120-day marine field tests, reducing fouling by 65.5% in comparison to the blank group. The coating also displayed superior anticorrosion performance with Ecorr values of −0.055 V, Icorr values of 7.67 × 10–6 , and Rp values of 3.10 × 105 Ω for Cu, which benefited from excellent chelating effect and liquid repellency. This study provides a novel strategy for the development of high-quality marine antifouling and anticorrosion coatings.
{"title":"Photoinitiated Thiol–Ene Click Reaction for Preparation of Highly Adhesive and Mechanically Stable Silicone Coatings for Marine Antifouling and Anticorrosion","authors":"Zhongshuai Gao, Shuya Zhang, Yanyi Duan, Heng Chang, Mei Cui, Renliang Huang, Rongxin Su","doi":"10.1021/acsami.4c18569","DOIUrl":"https://doi.org/10.1021/acsami.4c18569","url":null,"abstract":"Marine biofouling and corrosion have become the main problems affecting the development of the marine industry. Silicone-based coatings have been widely used for antifouling and anticorrosion due to their low surface energy. However, the poor adhesion and low mechanical stability of these materials limit their application in complex marine environments. In this work, we presented a marine antifouling and anticorrosion coating named POSS-DMA@PDMS-TCM through photoinitiated thiol–ene click reaction combined with (mercaptopropyl) methylsiloxane dimethylsiloxane (PDMS-SH), dopamine methacrylamide (DMA), sulfhydryl-functionalized organosiloxanes (POSS-(SH)<sub>8</sub>), and <i>N</i>-(2,4,6-trichlorophenyl) maleimide (TCM). The POSS-DMA@PDMS-TCM coating exhibited strong stability and bonding ability both in air (2.17 MPa) and underwater (2.11 MPa) when the DMA content was 3 wt %. The high antibacterial (98.1% for <i>Staphylococcus aureus</i> and 99.5% for <i>Escherichia coli</i>) and antidiatom (94.5%) properties of the POSS-DMA@PDMS-TCM coatings have also been confirmed. Moreover, the POSS-DMA@PDMS-TCM coatings show excellent antifouling abilities in 120-day marine field tests, reducing fouling by 65.5% in comparison to the blank group. The coating also displayed superior anticorrosion performance with <i>E</i><sub>corr</sub> values of −0.055 V, <i>I</i><sub>corr</sub> values of 7.67 × 10<sup>–6</sup> , and <i>R</i><sub>p</sub> values of 3.10 × 10<sup>5</sup> Ω for Cu, which benefited from excellent chelating effect and liquid repellency. This study provides a novel strategy for the development of high-quality marine antifouling and anticorrosion coatings.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"102 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990840","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}
Xiaoyu Meng, Tao Shen, Wenbo Zhang, Ran Luo, Jiangjie Zhou, Ruotong Liao, Ruibo Zhao, Cong Cao
Lanthanide-doped upconversion luminescent nanoparticles (UCNPs) have garnered extensive attention due to their notable anti-Stokes shifts and superior photostability. Notably, Ho3+-based UCNPs present a complex energy level configuration, which poses challenges in augmenting their luminescence efficiency. Herein, a rational design strategy was used to enhance the upconversion luminescence intensity of Ho3+ ions by improving the photon absorption ability and energy utilization efficiency. Efficient absorption and transfer of excitation light energy were achieved through carefully selected host materials, precisely controlled sensitizers, and the design of external energy antennas using organic dyes, enhancing upconversion luminescence. Due to the attenuation effect of hydroxyl vibration on upconversion luminescence, the nanomaterials exhibit multicolor luminescent characteristics in different solution environments. Significantly, the composites exhibit intense upconversion of red light in aqueous solution, showing great application potential in biomedicine and colorimetry.
{"title":"Energy Aggregation for Illuminating Upconversion Multicolor Emission Based on Ho3+ Ions","authors":"Xiaoyu Meng, Tao Shen, Wenbo Zhang, Ran Luo, Jiangjie Zhou, Ruotong Liao, Ruibo Zhao, Cong Cao","doi":"10.1021/acsami.4c18871","DOIUrl":"https://doi.org/10.1021/acsami.4c18871","url":null,"abstract":"Lanthanide-doped upconversion luminescent nanoparticles (UCNPs) have garnered extensive attention due to their notable anti-Stokes shifts and superior photostability. Notably, Ho<sup>3+</sup>-based UCNPs present a complex energy level configuration, which poses challenges in augmenting their luminescence efficiency. Herein, a rational design strategy was used to enhance the upconversion luminescence intensity of Ho<sup>3+</sup> ions by improving the photon absorption ability and energy utilization efficiency. Efficient absorption and transfer of excitation light energy were achieved through carefully selected host materials, precisely controlled sensitizers, and the design of external energy antennas using organic dyes, enhancing upconversion luminescence. Due to the attenuation effect of hydroxyl vibration on upconversion luminescence, the nanomaterials exhibit multicolor luminescent characteristics in different solution environments. Significantly, the composites exhibit intense upconversion of red light in aqueous solution, showing great application potential in biomedicine and colorimetry.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"5 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990842","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}
Adam Fish, James Forster, III, Vaishali Malik, Ashish Kulkarni
The innate immune system is tightly regulated by a complex network of chemical signals triggered by pathogens, cellular damage, and environmental stimuli. While it is well-established that changes in the extracellular environment can significantly influence the immune response to pathogens and damage-associated molecules, there remains a limited understanding of how changes in environmental stimuli specifically impact the activation of the NLRP3 inflammasome, a key component of innate immunity. Here, we demonstrated how shear stress can act as Signal 2 in the NLRP3 inflammasome activation pathway by treating LPS-primed immortalized bone marrow-derived macrophages (iBMDMs) with several physiologically relevant magnitudes of shear stress to induce inflammasome activation. We demonstrated that magnitudes of shear stress within 1.0 to 50 dyn/cm2 were able to induce ASC speck formation, while 50 dyn/cm2 was sufficient to induce significant calcium signaling, gasdermin-D cleavage, caspase-1 activity, and IL-1β secretion, all hallmarks of inflammasome activation. Utilizing NLRP3 and caspase-1 knockout iBMDMs, we demonstrated that the NLRP3 inflammasome was primarily activated as a result of shear stress exposure. Quantitative polymerase chain reaction (qPCR), ELISA, and a small molecule inhibitor study aided us in demonstrating that expression of Piezo1, NLRP3, gasdermin-D, IL-1β, and CCL2 secretion were all upregulated in iBMDMs treated with shear stress. This study provides a foundation for further understanding the interconnected pathogenesis of chronic inflammatory diseases and the ability of shear stress to play a role in their progression.
{"title":"Shear-Stress Initiates Signal Two of NLRP3 Inflammasome Activation in LPS-Primed Macrophages through Piezo1","authors":"Adam Fish, James Forster, III, Vaishali Malik, Ashish Kulkarni","doi":"10.1021/acsami.4c18845","DOIUrl":"https://doi.org/10.1021/acsami.4c18845","url":null,"abstract":"The innate immune system is tightly regulated by a complex network of chemical signals triggered by pathogens, cellular damage, and environmental stimuli. While it is well-established that changes in the extracellular environment can significantly influence the immune response to pathogens and damage-associated molecules, there remains a limited understanding of how changes in environmental stimuli specifically impact the activation of the NLRP3 inflammasome, a key component of innate immunity. Here, we demonstrated how shear stress can act as Signal 2 in the NLRP3 inflammasome activation pathway by treating LPS-primed immortalized bone marrow-derived macrophages (iBMDMs) with several physiologically relevant magnitudes of shear stress to induce inflammasome activation. We demonstrated that magnitudes of shear stress within 1.0 to 50 dyn/cm<sup>2</sup> were able to induce ASC speck formation, while 50 dyn/cm<sup>2</sup> was sufficient to induce significant calcium signaling, gasdermin-D cleavage, caspase-1 activity, and IL-1β secretion, all hallmarks of inflammasome activation. Utilizing NLRP3 and caspase-1 knockout iBMDMs, we demonstrated that the NLRP3 inflammasome was primarily activated as a result of shear stress exposure. Quantitative polymerase chain reaction (qPCR), ELISA, and a small molecule inhibitor study aided us in demonstrating that expression of Piezo1, NLRP3, gasdermin-D, IL-1β, and CCL2 secretion were all upregulated in iBMDMs treated with shear stress. This study provides a foundation for further understanding the interconnected pathogenesis of chronic inflammatory diseases and the ability of shear stress to play a role in their progression.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"9 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990841","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}
M. Motiur Mazumder, Hazel Gerber, Paul A. Kohl, Shelley D. Minteer
Nonaqueous redox flow batteries (NARFBs) have been plagued by the lack of appropriate separators to prevent crossover. In this article, the synthesis and characterization of poly(norbornene) (PNB) anion-exchange membranes (AEMs) were studied. PNB is a copolymer of butyl norbornene (BuNB) and bromobutyl norbornene (BrBuNB) with varying amounts of tetramethyl hexadiamine cross-linker. The performance of the AEMs was investigated in nonaqueous redox flow batteries under ideal conditions. Performance evaluation encompassed several key factors, including durability in a nonaqueous solvent, charge-carrying ions permeability, electric cell resistance, crossover of redox-active molecules, and mechanical properties. The BuNB-based AEMs outperformed the commercial Fumasep membrane in battery cycling tests, showcasing their superior performance characteristics. Long-term performance tests showed that the top performing PNB membrane exhibited an impressive 83% total capacity retention over 1000 charge/discharge cycles. The low loss was primarily due to minimal crossover. In contrast, the FAPQ-375 commercial membrane experienced significantly lower capacity retention, measuring only 28%, due to high crossover.
{"title":"Development and Evaluation of Butyl Norbornene Based Cross-Linked Anion Exchange Membranes for Enhanced Nonaqueous Redox Flow Battery Efficiency","authors":"M. Motiur Mazumder, Hazel Gerber, Paul A. Kohl, Shelley D. Minteer","doi":"10.1021/acsami.4c18366","DOIUrl":"https://doi.org/10.1021/acsami.4c18366","url":null,"abstract":"Nonaqueous redox flow batteries (NARFBs) have been plagued by the lack of appropriate separators to prevent crossover. In this article, the synthesis and characterization of poly(norbornene) (PNB) anion-exchange membranes (AEMs) were studied. PNB is a copolymer of butyl norbornene (BuNB) and bromobutyl norbornene (BrBuNB) with varying amounts of tetramethyl hexadiamine cross-linker. The performance of the AEMs was investigated in nonaqueous redox flow batteries under ideal conditions. Performance evaluation encompassed several key factors, including durability in a nonaqueous solvent, charge-carrying ions permeability, electric cell resistance, crossover of redox-active molecules, and mechanical properties. The BuNB-based AEMs outperformed the commercial Fumasep membrane in battery cycling tests, showcasing their superior performance characteristics. Long-term performance tests showed that the top performing PNB membrane exhibited an impressive 83% total capacity retention over 1000 charge/discharge cycles. The low loss was primarily due to minimal crossover. In contrast, the FAPQ-375 commercial membrane experienced significantly lower capacity retention, measuring only 28%, due to high crossover.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"100 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990391","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}
Nan Jiang, Yirong Cao, Hang Cong, Qingmei Ge, Wenfeng Zhao, Bo You
Various sustainable energy conversion techniques like water electrolyzers, fuel cells, and metal-air battery devices are promising to alleviate the issues in fossil fuel consumption. However, their broad employment has been mainly inhibited by the lack of advanced electrocatalysts to accelerate the sluggish kinetics of the three involved half-reactions including oxygen evolution reaction (OER), oxygen reduction reaction (ORR), and hydrogen evolution reaction (HER). Recent advances have witnessed the cucurbit[n]uril (CB[n])-directed strategy as a prominent tool to develop high performance electrocatalysts with either OER, ORR, or HER activities. In this review, the recent progress on CB[n]-derived electrocatalysts ranging from molecular complexes to heterogeneous nanostructures and single-atoms for the three half-reactions are reviewed, and future opportunities are discussed. A concise introduction to the fundamentals of CB[n]s regarding their synthesis, structure, and chemistry is given first. Subsequently, the systematic summary of CB[n]-derived electrocatalysts and their performance for the OER/ORR/HER are discussed in detail, with a specific emphasis on correlating their structure and activities by combining diverse physiochemical characterizations, electrochemical experiments, and theory simulations. Finally, a brief conclusion and perspective for future opportunities regarding CB[n]-derived electrocatalysts for many other electrocatalytic applications are proposed.
{"title":"Cucurbit[n]uril-Derived Electrocatalysts for Oxygen Evolution, Oxygen Reduction, and Hydrogen Evolution Reactions","authors":"Nan Jiang, Yirong Cao, Hang Cong, Qingmei Ge, Wenfeng Zhao, Bo You","doi":"10.1021/acsami.4c17510","DOIUrl":"https://doi.org/10.1021/acsami.4c17510","url":null,"abstract":"Various sustainable energy conversion techniques like water electrolyzers, fuel cells, and metal-air battery devices are promising to alleviate the issues in fossil fuel consumption. However, their broad employment has been mainly inhibited by the lack of advanced electrocatalysts to accelerate the sluggish kinetics of the three involved half-reactions including oxygen evolution reaction (OER), oxygen reduction reaction (ORR), and hydrogen evolution reaction (HER). Recent advances have witnessed the cucurbit[<i>n</i>]uril (CB[<i>n</i>])-directed strategy as a prominent tool to develop high performance electrocatalysts with either OER, ORR, or HER activities. In this review, the recent progress on CB[<i>n</i>]-derived electrocatalysts ranging from molecular complexes to heterogeneous nanostructures and single-atoms for the three half-reactions are reviewed, and future opportunities are discussed. A concise introduction to the fundamentals of CB[<i>n</i>]s regarding their synthesis, structure, and chemistry is given first. Subsequently, the systematic summary of CB[<i>n</i>]-derived electrocatalysts and their performance for the OER/ORR/HER are discussed in detail, with a specific emphasis on correlating their structure and activities by combining diverse physiochemical characterizations, electrochemical experiments, and theory simulations. Finally, a brief conclusion and perspective for future opportunities regarding CB[<i>n</i>]-derived electrocatalysts for many other electrocatalytic applications are proposed.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"9 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990987","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}
Xinyue Ma, Jie Shao, Baoguang Mao, Fenghui Ye, Zichun Wang, Junjie Mao, Aibing Chen, Dan Wang, Lipeng Zhang, Hui Dong, Husitu Lin, Ning Li, Chuangang Hu
The comprehensive understanding of the effect of the chemical environment surrounding active sites on the pathway for the electrochemical carbon dioxide reduction reaction (eCO2RR) is essential for the development of advanced catalysts for large-scale applications. Based on a series of model catalysts engineered by the coordination of copper ions with various isomers of phenylenediamine [i.e., o-phenylenediamine (oPD), m-phenylenediamine (mPD), and p-phenylenediamine (pPD)] featuring two amino groups in ortho-, meta-, and para-positions, the steric effects could significantly govern the selectivity of the “Cu–N” sites for eCO2RR. It was found the steric distance between adjacent copper and nitrogen active sites in Cu-oPD enhanced the C–C coupling of the *COOH intermediate, thereby resulting in increased selectivity for C2H4 production. In contrast, the weak van der Waals interactions arising from steric electrostatic effects surrounding the *CHO intermediate on Cu-pPD facilitated subsequent hydrogenation, leading to the preferential synthesis of CH4. However, Cu-mPD exhibited diminished eCO2RR activity due to a higher free energy associated with the rate-determining step, which primarily led to the formation of H2. This study underscores the significant role of a steric effect-driven selectivity switch for eCO2RR.
{"title":"“Cu–Nx” Site-Driven Selectivity Switch for Electrocatalytic CO2 Reduction","authors":"Xinyue Ma, Jie Shao, Baoguang Mao, Fenghui Ye, Zichun Wang, Junjie Mao, Aibing Chen, Dan Wang, Lipeng Zhang, Hui Dong, Husitu Lin, Ning Li, Chuangang Hu","doi":"10.1021/acsami.4c18450","DOIUrl":"https://doi.org/10.1021/acsami.4c18450","url":null,"abstract":"The comprehensive understanding of the effect of the chemical environment surrounding active sites on the pathway for the electrochemical carbon dioxide reduction reaction (eCO<sub>2</sub>RR) is essential for the development of advanced catalysts for large-scale applications. Based on a series of model catalysts engineered by the coordination of copper ions with various isomers of phenylenediamine [i.e., <i>o</i>-phenylenediamine (<i>o</i>PD), <i>m</i>-phenylenediamine (<i>m</i>PD), and <i>p</i>-phenylenediamine (<i>p</i>PD)] featuring two amino groups in <i>ortho</i>-, <i>meta</i>-, and <i>para</i>-positions, the steric effects could significantly govern the selectivity of the “Cu–N” sites for eCO<sub>2</sub>RR. It was found the steric distance between adjacent copper and nitrogen active sites in Cu-<i>o</i>PD enhanced the C–C coupling of the *COOH intermediate, thereby resulting in increased selectivity for C<sub>2</sub>H<sub>4</sub> production. In contrast, the weak van der Waals interactions arising from steric electrostatic effects surrounding the *CHO intermediate on Cu-<i>p</i>PD facilitated subsequent hydrogenation, leading to the preferential synthesis of CH<sub>4</sub>. However, Cu-<i>m</i>PD exhibited diminished eCO<sub>2</sub>RR activity due to a higher free energy associated with the rate-determining step, which primarily led to the formation of H<sub>2</sub>. This study underscores the significant role of a steric effect-driven selectivity switch for eCO<sub>2</sub>RR.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"30 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990990","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}
Long-term inflammation and persistent bacterial infection are primary contributors to unhealed chronic wounds. The use of conventional antibiotics often leads to bacteria drug resistance, diminishing wound healing effectiveness. Nanozymes have become a promising alternative to antimicrobial materials due to their low cost, easy synthesis, and good stability. Herein, we develop a novel sprayable hydrogel based on carboxymethyl chitosan (CMCS) and oxidized hyaluronic acid (OHA), incorporating Au nanoparticle-carbon nitride (AuNPs-C3N4) nanozyme, glucose, and Mn2+ for bacteria-infected wound healing. The hydrogel forms rapidly in situ upon spraying and gradually degrades on the wound area, releasing the AuNPs-C3N4 nanozyme, which exhibits robust glucose oxidase-like (GOx-like) activity, initiating a comprehensive catalytic cascade through a Mn2+-mediated Fenton-like reaction that generates hydroxyl radicals (•OH) to eliminate Staphylococcus aureus (S. aureus) and Methicillin-resistant S. aureus (MRSA). Computational results indicate that interactions between AuNPs and g-C3N4 maximize their synergistic effects in a heterojunction, improving O2 adsorption and facilitating electron-O2 interactions to optimize catalytic activity. Further experiments demonstrate that the hydrogel can rapidly cover wounds in situ, while CMCS promotes collagen production and fibroblast proliferation, offering a viable strategy for the healing of bacteria-infected wounds.
{"title":"Sprayable Hydrogel for pH-Responsive Nanozyme-Derived Bacteria-Infected Wound Healing","authors":"Furong Chao, Chengliang Cao, Yin Xu, Yunjie Gu, Xinyu Qu, Qian Wang, Lu−Lu Qu, Yuxin Guo, Xiaochen Dong","doi":"10.1021/acsami.4c18100","DOIUrl":"https://doi.org/10.1021/acsami.4c18100","url":null,"abstract":"Long-term inflammation and persistent bacterial infection are primary contributors to unhealed chronic wounds. The use of conventional antibiotics often leads to bacteria drug resistance, diminishing wound healing effectiveness. Nanozymes have become a promising alternative to antimicrobial materials due to their low cost, easy synthesis, and good stability. Herein, we develop a novel sprayable hydrogel based on carboxymethyl chitosan (CMCS) and oxidized hyaluronic acid (OHA), incorporating Au nanoparticle-carbon nitride (AuNPs-C<sub>3</sub>N<sub>4</sub>) nanozyme, glucose, and Mn<sup>2+</sup> for bacteria-infected wound healing. The hydrogel forms rapidly in situ upon spraying and gradually degrades on the wound area, releasing the AuNPs-C<sub>3</sub>N<sub>4</sub> nanozyme, which exhibits robust glucose oxidase-like (GOx-like) activity, initiating a comprehensive catalytic cascade through a Mn<sup>2+</sup>-mediated Fenton-like reaction that generates hydroxyl radicals (<sup>•</sup>OH) to eliminate <i>Staphylococcus aureus</i> (<i>S. aureus</i>) and Methicillin-resistant <i>S. aureus</i> (MRSA). Computational results indicate that interactions between AuNPs and g-C<sub>3</sub>N<sub>4</sub> maximize their synergistic effects in a heterojunction, improving O<sub>2</sub> adsorption and facilitating electron-O<sub>2</sub> interactions to optimize catalytic activity. Further experiments demonstrate that the hydrogel can rapidly cover wounds in situ, while CMCS promotes collagen production and fibroblast proliferation, offering a viable strategy for the healing of bacteria-infected wounds.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"1 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990350","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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