Sean L. Murray, Sahand Serajian, Syed Ibrahim Gnani Peer Mohamed, Shiseido Robinson, Rajavel Krishnamoorthy, Suprem R. Das, Mona Bavarian, Siamak Nejati, Ufuk Kilic, Mathias Schubert, Mohammad Ghashami
MXenes have rapidly ascended as a prominent class of two-dimensional (2D) materials, renowned for their distinctive optical and electrical properties. Despite extensive exploration of MXenes’ optical properties, existing studies predominantly focus on the near-infrared (NIR) to the ultraviolet spectral range, leaving the mid-infrared (mid-IR) range relatively uncharted. In this study, we conducted a comprehensive characterization of the intrinsic optical properties of Ti3C2Tx MXene across an ultrabroadband spectral range, spanning from mid-IR (28 meV) to vacuum ultraviolet (VUV, 6.4 eV). For this purpose, Ti3C2Tx MXene films of varying thicknesses were coated on quartz substrates, resulting in two distinct categories: thin film samples with thicknesses below 50 nm and bulk-like samples with thicknesses exceeding 500 nm. Using spectroscopic ellipsometry, we analyzed the optical properties of films of various thicknesses and extracted detailed information on their dielectric functions. Our findings reveal resonances in the mid-IR to VUV range. Employing the Lorentz–Drude model to examine these resonances has uncovered the optical resistivity of MXene films and led to the identification of multiple plasmonic modes active in the visible to NIR range, as well as broad band-to-band transition-like resonances in the mid-IR range. This ultrabroadband optical versatility of Ti3C2Tx MXene is anticipated to bring about a wide range of thermal and optical applications.
{"title":"Ultrabroadband Optical Properties of 2D Titanium Carbide MXene","authors":"Sean L. Murray, Sahand Serajian, Syed Ibrahim Gnani Peer Mohamed, Shiseido Robinson, Rajavel Krishnamoorthy, Suprem R. Das, Mona Bavarian, Siamak Nejati, Ufuk Kilic, Mathias Schubert, Mohammad Ghashami","doi":"10.1021/acsami.4c12079","DOIUrl":"https://doi.org/10.1021/acsami.4c12079","url":null,"abstract":"MXenes have rapidly ascended as a prominent class of two-dimensional (2D) materials, renowned for their distinctive optical and electrical properties. Despite extensive exploration of MXenes’ optical properties, existing studies predominantly focus on the near-infrared (NIR) to the ultraviolet spectral range, leaving the mid-infrared (mid-IR) range relatively uncharted. In this study, we conducted a comprehensive characterization of the intrinsic optical properties of Ti<sub>3</sub>C<sub>2</sub>T<i><sub>x</sub></i> MXene across an ultrabroadband spectral range, spanning from mid-IR (28 meV) to vacuum ultraviolet (VUV, 6.4 eV). For this purpose, Ti<sub>3</sub>C<sub>2</sub>T<i><sub>x</sub></i> MXene films of varying thicknesses were coated on quartz substrates, resulting in two distinct categories: thin film samples with thicknesses below 50 nm and bulk-like samples with thicknesses exceeding 500 nm. Using spectroscopic ellipsometry, we analyzed the optical properties of films of various thicknesses and extracted detailed information on their dielectric functions. Our findings reveal resonances in the mid-IR to VUV range. Employing the Lorentz–Drude model to examine these resonances has uncovered the optical resistivity of MXene films and led to the identification of multiple plasmonic modes active in the visible to NIR range, as well as broad band-to-band transition-like resonances in the mid-IR range. This ultrabroadband optical versatility of Ti<sub>3</sub>C<sub>2</sub>T<i><sub>x</sub></i> MXene is anticipated to bring about a wide range of thermal and optical applications.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":null,"pages":null},"PeriodicalIF":9.5,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486771","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}
Functionalization of hybrid organic molecules as layers on ZnO nanoflowers (NFs) gives an excellent combination of sensing toward visible light and vapors of various volatile organic compounds (VOCs). In this work, hybrid organic molecules functionalized ZnO NFs were utilized for the photoinduced detection of benzylamine at room temperature. The ZnO NFs were synthesized via a facile solution route and functionalized with four different porphyrin-conjugated molecules namely (i) pyrene-porphyrin (PP), (ii) pyrene- porphyrinato zinc (ZnPP), (iii) triphenylamine- porphyrin (TP) and (iv) triphenylamine- porphyrinato zinc (ZnTP). The diameter of the flower-like structure was found to be ∼3.2 μm with the thickness of petals being ∼24.1 nm. The gas adsorption performance of the functionalized ZnO NFs on light activation at room temperature was studied by using a scanning Kelvin probe (SKP) system. The improved adsorption properties of the samples can be attributed to the heterojunctions and light activation. In particular, an enhanced response of ZnTP functionalized ZnO (ZnTPZ) toward benzylamine was observed. Further, static gas sensing experiments using ZnTPZ under various concentrations (1, 3, 5, 10, 15, and 25 ppm) of benzylamine vapors both in dark and visible light conditions have exhibited a linear increase in the response. The selectively enhanced response of ZnTPZ compared to that of pristine ZnO was thus confirmed at 1 ppm of benzylamine. The sensitivity and limit of detection of the ZnTPZ sensor were calculated to be 0.0292 ppm–1 and 197 ppb, respectively. The coordination metal (Zn) has helped in effective charge transfer between benzylamine and ZnTPZ by providing additional active sites for interactions. Also, density functional theory calculations demonstrated the role of the hybrid organic molecules on the sensor surface in improving gas adsorption. Further, fresh cabbage was utilized for real sample analysis with the proposed sensor under visible light illumination conditions, and a linear response was obtained for low ppm evaluation at room temperature. Overall, the obtained results suggest the development of novel ZnTPZ-based light-activated gas sensors for low ppm benzylamine detection at room temperature. These kinds of sensors can be used to track the freshness of vegetables as they are transported from farms to commercial outlets.
{"title":"Porphyrinoid-Functionalized ZnO Nanoflowers for Visible Light-Enhanced and Selective Benzylamine Detection at Room Temperature","authors":"Sheethal Sasi, Prasanth Palanisamy, Rence Painappallil Reji, Venkatramaiah Nutalapati, Surya Velappa Jayaraman, Yoshiyuki Kawazoe, Yuvaraj Sivalingam","doi":"10.1021/acsami.4c08117","DOIUrl":"https://doi.org/10.1021/acsami.4c08117","url":null,"abstract":"Functionalization of hybrid organic molecules as layers on ZnO nanoflowers (NFs) gives an excellent combination of sensing toward visible light and vapors of various volatile organic compounds (VOCs). In this work, hybrid organic molecules functionalized ZnO NFs were utilized for the photoinduced detection of benzylamine at room temperature. The ZnO NFs were synthesized via a facile solution route and functionalized with four different porphyrin-conjugated molecules namely (i) pyrene-porphyrin (PP), (ii) pyrene- porphyrinato zinc (ZnPP), (iii) triphenylamine- porphyrin (TP) and (iv) triphenylamine- porphyrinato zinc (ZnTP). The diameter of the flower-like structure was found to be ∼3.2 μm with the thickness of petals being ∼24.1 nm. The gas adsorption performance of the functionalized ZnO NFs on light activation at room temperature was studied by using a scanning Kelvin probe (SKP) system. The improved adsorption properties of the samples can be attributed to the heterojunctions and light activation. In particular, an enhanced response of ZnTP functionalized ZnO (ZnTPZ) toward benzylamine was observed. Further, static gas sensing experiments using ZnTPZ under various concentrations (1, 3, 5, 10, 15, and 25 ppm) of benzylamine vapors both in dark and visible light conditions have exhibited a linear increase in the response. The selectively enhanced response of ZnTPZ compared to that of pristine ZnO was thus confirmed at 1 ppm of benzylamine. The sensitivity and limit of detection of the ZnTPZ sensor were calculated to be 0.0292 ppm<sup>–1</sup> and 197 ppb, respectively. The coordination metal (Zn) has helped in effective charge transfer between benzylamine and ZnTPZ by providing additional active sites for interactions. Also, density functional theory calculations demonstrated the role of the hybrid organic molecules on the sensor surface in improving gas adsorption. Further, fresh cabbage was utilized for real sample analysis with the proposed sensor under visible light illumination conditions, and a linear response was obtained for low ppm evaluation at room temperature. Overall, the obtained results suggest the development of novel ZnTPZ-based light-activated gas sensors for low ppm benzylamine detection at room temperature. These kinds of sensors can be used to track the freshness of vegetables as they are transported from farms to commercial outlets.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":null,"pages":null},"PeriodicalIF":9.5,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486769","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}
Wei Ping, Xiaoxin Zhang, Hao Zeng, Taomin Zhu, Ni Zhang, Qi Yan
Non-small-cell lung cancer (NSCLC) is the most prevalent type of lung cancer, and there is an urgent need for developing novel therapies. Sonodynamic therapy exhibits exceptional tissue penetration and minimal harm to healthy tissue, making it extremely promising for cancer treatment. The efficacy of SDT is limited by the intricate immunological microenvironment and the resistance to tumor treatment. This study developed targeted nanoparticles that use ultrasound to concentrate on treating NSCLC. The hybrid targeted nanoparticles utilize gold nanoparticles as their fundamental component, with the outside modified with engineered macrophage exosomes and the aptamer S11e to specifically target NSCLC. Ultrasound could effectively eliminate tumors in NSCLC cells by destroying lysosomes via targeted nanoparticles. Simultaneously, fragmented tumor antigens could effectively activate dendritic cell cells to recruit T cells. This method has significant efficacy in suppressing the development of NSCLC and exhibits potential for therapeutic application.
非小细胞肺癌（NSCLC）是最常见的肺癌类型，因此迫切需要开发新型疗法。声动力疗法具有极强的组织穿透力，对健康组织的伤害极小，因此在癌症治疗中极具前景。但错综复杂的免疫微环境和肿瘤治疗的抗药性限制了 SDT 的疗效。本研究开发了利用超声波集中治疗 NSCLC 的靶向纳米粒子。这种混合型靶向纳米粒子以金纳米粒子为基本成分，外部用工程化巨噬细胞外泌体和适配体S11e修饰，可特异性地靶向NSCLC。通过靶向纳米粒子破坏溶酶体，超声波可有效消除 NSCLC 细胞中的肿瘤。同时，破碎的肿瘤抗原可有效激活树突状细胞，从而招募 T 细胞。这种方法对抑制非小细胞肺癌的发展有明显疗效，具有治疗应用潜力。
{"title":"Ultrasound-Driven Nanomachine for Enhanced Sonodynamic Therapy of Non-Small-Cell Lung Cancer","authors":"Wei Ping, Xiaoxin Zhang, Hao Zeng, Taomin Zhu, Ni Zhang, Qi Yan","doi":"10.1021/acsami.4c11546","DOIUrl":"https://doi.org/10.1021/acsami.4c11546","url":null,"abstract":"Non-small-cell lung cancer (NSCLC) is the most prevalent type of lung cancer, and there is an urgent need for developing novel therapies. Sonodynamic therapy exhibits exceptional tissue penetration and minimal harm to healthy tissue, making it extremely promising for cancer treatment. The efficacy of SDT is limited by the intricate immunological microenvironment and the resistance to tumor treatment. This study developed targeted nanoparticles that use ultrasound to concentrate on treating NSCLC. The hybrid targeted nanoparticles utilize gold nanoparticles as their fundamental component, with the outside modified with engineered macrophage exosomes and the aptamer S11e to specifically target NSCLC. Ultrasound could effectively eliminate tumors in NSCLC cells by destroying lysosomes via targeted nanoparticles. Simultaneously, fragmented tumor antigens could effectively activate dendritic cell cells to recruit T cells. This method has significant efficacy in suppressing the development of NSCLC and exhibits potential for therapeutic application.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":null,"pages":null},"PeriodicalIF":9.5,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486687","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}
Stepan Kutsiy, Dmytro Volyniuk, Smruti Ranjan Sahoo, Magdalena Ceborska, Agnieszka Wisniewska, Pavlo Stakhira, Juozas Vidas Grazulevicius, Glib V. Baryshnikov, Mykhaylo A. Potopnyk
Two donor–acceptor dyes with an ortho-phenylene-linked carbazole electron donor and a benzothiazole-fused boron heterocyclic acceptor were designed, synthesized, and spectroscopically investigated. Due to the steric effects of boron heterocyclic units, the dyes demonstrate different conformations in the crystalline state. The presence of numerous hydrogen-bonding intermolecular interactions and the very weak π–π stacking in the molecular packing results in intense solid-state emission with photoluminescence quantum yields of 40 and 18% for crystals and 50 and 42% for host-based light-emitting layers. The compounds show aggregation-induced emission and thermally activated delayed fluorescence (TADF). The received ionization potential and electron affinity values suggested good charge-injecting ability and bipolar charge-transporting properties of the developed dyes. Transport of holes and electrons was detected in layers of one dye by the time-of-flight measurements. The benzothiazole-based boron difluoride complexes showed high electron mobility of 1.5 × 10–4 and 0.7 × 10–4 cm2 V–1 s–1 at an electric field of 1.35 × 106 V cm–1. Therefore, these dyes were successfully applied as emitters in organic light-emitting diodes with external quantum efficiencies of 15 and 13%, respectively. Our study marks a critical advancement in the area of solid-state emissive boron difluoride dyes, which can be applied as TADF emitters into organic light-emitting diodes. The obtained results reveal that the orientation of the acceptor unit in the ortho-phenylene-linked donor–acceptor dyes makes a significant impact on the TADF activity.
{"title":"Sterically Tuned Ortho-Phenylene-Linked Donor–Acceptor Benzothiazole-Based Boron Difluoride Complexes as Thermally-Activated Delayed Fluorescence Emitters for Organic Light-Emitting Diodes","authors":"Stepan Kutsiy, Dmytro Volyniuk, Smruti Ranjan Sahoo, Magdalena Ceborska, Agnieszka Wisniewska, Pavlo Stakhira, Juozas Vidas Grazulevicius, Glib V. Baryshnikov, Mykhaylo A. Potopnyk","doi":"10.1021/acsami.4c12662","DOIUrl":"https://doi.org/10.1021/acsami.4c12662","url":null,"abstract":"Two donor–acceptor dyes with an <i>ortho</i>-phenylene-linked carbazole electron donor and a benzothiazole-fused boron heterocyclic acceptor were designed, synthesized, and spectroscopically investigated. Due to the steric effects of boron heterocyclic units, the dyes demonstrate different conformations in the crystalline state. The presence of numerous hydrogen-bonding intermolecular interactions and the very weak π–π stacking in the molecular packing results in intense solid-state emission with photoluminescence quantum yields of 40 and 18% for crystals and 50 and 42% for host-based light-emitting layers. The compounds show aggregation-induced emission and thermally activated delayed fluorescence (TADF). The received ionization potential and electron affinity values suggested good charge-injecting ability and bipolar charge-transporting properties of the developed dyes. Transport of holes and electrons was detected in layers of one dye by the time-of-flight measurements. The benzothiazole-based boron difluoride complexes showed high electron mobility of 1.5 × 10<sup>–4</sup> and 0.7 × 10<sup>–4</sup> cm<sup>2</sup> V<sup>–1</sup> s<sup>–1</sup> at an electric field of 1.35 × 10<sup>6</sup> V cm<sup>–1</sup>. Therefore, these dyes were successfully applied as emitters in organic light-emitting diodes with external quantum efficiencies of 15 and 13%, respectively. Our study marks a critical advancement in the area of solid-state emissive boron difluoride dyes, which can be applied as TADF emitters into organic light-emitting diodes. The obtained results reveal that the orientation of the acceptor unit in the <i>ortho</i>-phenylene-linked donor–acceptor dyes makes a significant impact on the TADF activity.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":null,"pages":null},"PeriodicalIF":9.5,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486691","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 oxidation and lattice distortion of spinel oxides used for magnesium-ion battery (MIB) cathodes lead to poor stability and cycling performance. Herein, the highly inverted spinel oxide Mg(Al, Fe, Mn, REE)2O4 of i = 0.62 with incorporated rare-earth elements (REE) and decent specific surface area was prepared by utilizing leachate of the pelagic rare-earth-rich clays via a foamed sol–gel/calcination method. Measurements of specific capacity, cycling performance, and multiplicity performance showed that the foamed spinel exhibited distinguished electrochemical performance of MIB. At the current density of 100 mA h–1, the initial discharge and charge specific capacity were 125.7 mAh g–1 and 139.7 mAh g–1, and the reversible discharge and charge specific capacities were maintained as 96.7 mAh g–1 and 102.4 mAh g–1 after 200 cycles of charging–discharging. The Mg-ion diffusion rate for MAFMRO was 1.08 × 10–5 cm2 s–1, which was significantly improved, compared to traditional magnesium spinel anodes. This work highlights an approach for modification of spinel-type cathode materials and the high-value utilization of pelagic clay resources.
用于镁离子电池（MIB）阴极的尖晶石氧化物的氧化和晶格畸变导致其稳定性和循环性能不佳。在这里，利用富含稀土的浮游粘土的浸出液，通过发泡溶胶-凝胶/煅烧法制备了 i = 0.62 的高度反相尖晶石氧化物 Mg（Al，Fe，Mn，REE）2O4，其中掺入了稀土元素（REE），具有良好的比表面积。比容量、循环性能和倍率性能的测量结果表明，发泡尖晶石具有出色的 MIB 电化学性能。在电流密度为 100 mA h-1 时，初始放电和充电比容量分别为 125.7 mAh g-1 和 139.7 mAh g-1，在充放电循环 200 次后，可逆放电和充电比容量分别保持在 96.7 mAh g-1 和 102.4 mAh g-1。与传统的尖晶石镁阳极相比，MAFMRO 的镁离子扩散速率为 1.08 × 10-5 cm2 s-1，明显提高。这项工作为尖晶石型阴极材料的改性和浮游粘土资源的高值化利用提供了一种方法。
{"title":"Mg(Al, Fe, Mn, REE)2O4 Spinel Prepared from Pelagic REE-Rich Clays and Application as Magnesium-Ion-Battery Cathodes","authors":"Peiping Zhang, Tongtong Liu, Jibo Miao, Weikun Ning, Yanbin Sun, Fagui Qiu, Xuefa Shi, Shiding Miao","doi":"10.1021/acsami.4c09480","DOIUrl":"https://doi.org/10.1021/acsami.4c09480","url":null,"abstract":"The oxidation and lattice distortion of spinel oxides used for magnesium-ion battery (MIB) cathodes lead to poor stability and cycling performance. Herein, the highly inverted spinel oxide Mg(Al, Fe, Mn, REE)<sub>2</sub>O<sub>4</sub> of <i>i</i> = 0.62 with incorporated rare-earth elements (REE) and decent specific surface area was prepared by utilizing leachate of the pelagic rare-earth-rich clays via a foamed sol–gel/calcination method. Measurements of specific capacity, cycling performance, and multiplicity performance showed that the foamed spinel exhibited distinguished electrochemical performance of MIB. At the current density of 100 mA h<sup>–1</sup>, the initial discharge and charge specific capacity were 125.7 mAh g<sup>–1</sup> and 139.7 mAh g<sup>–1</sup>, and the reversible discharge and charge specific capacities were maintained as 96.7 mAh g<sup>–1</sup> and 102.4 mAh g<sup>–1</sup> after 200 cycles of charging–discharging. The Mg-ion diffusion rate for MAFMRO was 1.08 × 10<sup>–5</sup> cm<sup>2</sup> s<sup>–1</sup>, which was significantly improved, compared to traditional magnesium spinel anodes. This work highlights an approach for modification of spinel-type cathode materials and the high-value utilization of pelagic clay resources.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":null,"pages":null},"PeriodicalIF":9.5,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486770","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}
Marco Montalbano, Gianluigi Marra, Mariangela Longhi, Laura Prati, Elena Selli, Maria Vittoria Dozzi
The interplay on anatase TiO2 photoactivity between particle morphology and gold nanoparticles (NPs) deposition, via either deposition–precipitation (DP) or photodeposition (P), is here investigated by evaluating the photoactivity of Au modified anatase (Au/TiO2) nanocrystals with either a pseudospherical shape or a nanosheet structure in both reduction and oxidation test reactions. The presence of Au NPs on the anatase surface only slightly affects its photoactivity in Cr(VI) reduction, which is kinetically limited by the anodic half-reaction, whereas a larger exposure of highly oxidant {001} facets is beneficial for overcoming this rate-determining step. In the photocatalytic oxidation of both formic acid, proceeding through a direct mechanism, and rhodamine B (RhB) on surface fluorinated photocatalysts, occurring through a hydroxyl-radical-mediated mechanism, the presence of gold NPs produces a significant photoactivity increase only with spherically shaped photocatalysts, mainly exposing {101} facets. These results are rationalized in light of the preferential migration of photogenerated, oppositely charged carriers toward different crystal facets. In fact, when the Au/TiO2 material mainly exposes the more oxidant {001} facets, where photoproduced holes preferentially migrate, recombination between these latter and the electrons captured by Au NPs is favored. Instead, Au NPs on {101} facets efficiently capture photopromoted electrons, preferentially migrating toward such facets with a consequent improvement of photoproduced charge separation.
{"title":"Combined Role of {001} Facet-Enriched Morphology and Gold Nanoparticle Deposition on Anatase TiO2 Photoactivity","authors":"Marco Montalbano, Gianluigi Marra, Mariangela Longhi, Laura Prati, Elena Selli, Maria Vittoria Dozzi","doi":"10.1021/acsami.4c12465","DOIUrl":"https://doi.org/10.1021/acsami.4c12465","url":null,"abstract":"The interplay on anatase TiO<sub>2</sub> photoactivity between particle morphology and gold nanoparticles (NPs) deposition, via either deposition–precipitation (DP) or photodeposition (P), is here investigated by evaluating the photoactivity of Au modified anatase (Au/TiO<sub>2</sub>) nanocrystals with either a pseudospherical shape or a nanosheet structure in both reduction and oxidation test reactions. The presence of Au NPs on the anatase surface only slightly affects its photoactivity in Cr(VI) reduction, which is kinetically limited by the anodic half-reaction, whereas a larger exposure of highly oxidant {001} facets is beneficial for overcoming this rate-determining step. In the photocatalytic oxidation of both formic acid, proceeding through a direct mechanism, and rhodamine B (RhB) on surface fluorinated photocatalysts, occurring through a hydroxyl-radical-mediated mechanism, the presence of gold NPs produces a significant photoactivity increase only with spherically shaped photocatalysts, mainly exposing {101} facets. These results are rationalized in light of the preferential migration of photogenerated, oppositely charged carriers toward different crystal facets. In fact, when the Au/TiO<sub>2</sub> material mainly exposes the more oxidant {001} facets, where photoproduced holes preferentially migrate, recombination between these latter and the electrons captured by Au NPs is favored. Instead, Au NPs on {101} facets efficiently capture photopromoted electrons, preferentially migrating toward such facets with a consequent improvement of photoproduced charge separation.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":null,"pages":null},"PeriodicalIF":9.5,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142487008","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 rising incidence of infections caused by multidrug-resistant bacteria highlights the urgent need for innovative bacterial eradication strategies. Metal ions, such as Zn2+ and Co2+, have bactericidal effects by disrupting bacterial cell membranes and interfering with essential cellular processes. This has led to increased attention toward metal-organic frameworks (MOFs) as potential nonantibiotic bactericidal agents. However, the uniform and enhanced localized release of bactericidal metal ions remains a challenge. Herein, we introduce a nanoscale multipatterned Zn,Co-ZIF@FeOOH, featuring a multipod-like morphology with spiky corners, and dual-bactericidal metal ions. Compared to pure Zn,Co-ZIF, the multipod-like morphology of Zn,Co-ZIF@FeOOH exhibits enhanced adhesion toward bacterial surfaces via topological and multiple interactions of electrostatic interaction, significantly increasing the local release of Zn2+ and Co2+. Additionally, the spiky corners of the spindle-shaped FeOOH nanorods physically penetrate bacterial membranes, causing damage and further enhancing adhesion to bacteria. Nine Gram-negative and one Gram-positive bacteria were selected for in vitro test. Notably, the nanoscale multipatterned Zn,Co-ZIF@FeOOH exhibited high bactericidal efficacy against various multidrug-resistant bacteria, including extended-spectrum β-lactamase-producing (ESBL+) bacteria and carbapenem-resistant bacteria, performing well in both acidic and neutral environments. The wound healing activity of Zn,Co-ZIF@FeOOH was further demonstrated using female Balb/c mouse models infected with bacteria, where the materials show robust antibacterial efficacy and commendable biocompatibility. This study showcases the assembly of metal oxide/MOF composites for nanoscale multipatterning, aims at synergistic bacterial eradication and offers insights into developing nanomaterial-based strategies against multidrug-resistant bacteria.
{"title":"Nanoscale Multipatterning Zn,Co-ZIF@FeOOH for Eradication of Multidrug-Resistant Bacteria and Antibacterial Treatment of Wounds.","authors":"Jia Yi, Congcong Pei, Tangming Zhang, Qin Qin, Xiaoxia Gu, Yekan Li, Danping Ruan, Jingjing Wan, Liang Qiao","doi":"10.1021/acsami.4c10935","DOIUrl":"https://doi.org/10.1021/acsami.4c10935","url":null,"abstract":"<p><p>The rising incidence of infections caused by multidrug-resistant bacteria highlights the urgent need for innovative bacterial eradication strategies. Metal ions, such as Zn<sup>2+</sup> and Co<sup>2+</sup>, have bactericidal effects by disrupting bacterial cell membranes and interfering with essential cellular processes. This has led to increased attention toward metal-organic frameworks (MOFs) as potential nonantibiotic bactericidal agents. However, the uniform and enhanced localized release of bactericidal metal ions remains a challenge. Herein, we introduce a nanoscale multipatterned Zn,Co-ZIF@FeOOH, featuring a multipod-like morphology with spiky corners, and dual-bactericidal metal ions. Compared to pure Zn,Co-ZIF, the multipod-like morphology of Zn,Co-ZIF@FeOOH exhibits enhanced adhesion toward bacterial surfaces via topological and multiple interactions of electrostatic interaction, significantly increasing the local release of Zn<sup>2+</sup> and Co<sup>2+</sup>. Additionally, the spiky corners of the spindle-shaped FeOOH nanorods physically penetrate bacterial membranes, causing damage and further enhancing adhesion to bacteria. Nine Gram-negative and one Gram-positive bacteria were selected for in vitro test. Notably, the nanoscale multipatterned Zn,Co-ZIF@FeOOH exhibited high bactericidal efficacy against various multidrug-resistant bacteria, including extended-spectrum β-lactamase-producing (ESBL+) bacteria and carbapenem-resistant bacteria, performing well in both acidic and neutral environments. The wound healing activity of Zn,Co-ZIF@FeOOH was further demonstrated using female Balb/c mouse models infected with bacteria, where the materials show robust antibacterial efficacy and commendable biocompatibility. This study showcases the assembly of metal oxide/MOF composites for nanoscale multipatterning, aims at synergistic bacterial eradication and offers insights into developing nanomaterial-based strategies against multidrug-resistant bacteria.</p>","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":null,"pages":null},"PeriodicalIF":8.3,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142453171","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}
Multitarget tyrosine kinase inhibitors (TKIs) serve as first-line therapeutics in the systemic treatment of hepatocellular carcinoma (HCC), yet their clinical effectiveness is hampered by suboptimal pharmacokinetics and bioavailability. There is a critical need to enhance the circulation, tumor targeting, and infiltration of TKIs. In this context, we developed a silk fibroin (SF)-based nanomedicine that exploits the chemical versatility and conformation tunability of SF. Folic acid (FA) with affinity toward HCC cells is utilized to functionalize SF, simultaneously aiding in the pH-sensitive β-sheet transitions of SF. This dynamic conformation behavior is key to improving the nanomedicine’s circulation, biological adhesion, and tumor localization. By encapsulating Lenvatinib (Leva) TKI, the nanomedicine exhibits tumor-targeted accumulation and potent inhibition on HCC cell survival and angiogenesis, thereby amplifying Leva’s bioavailability and therapeutic impact. Owing to SF’s low immunogenicity and high reproducibility, this SF-based approach for TKI delivery holds substantial promise for advancing HCC systemic therapy.
多靶点酪氨酸激酶抑制剂（TKIs）是系统治疗肝细胞癌（HCC）的一线疗法，但其临床疗效却受到药代动力学和生物利用度不理想的影响。目前亟需加强 TKIs 的循环、肿瘤靶向性和浸润性。在此背景下，我们开发了一种基于丝纤维蛋白（SF）的纳米药物，利用了丝纤维蛋白的化学多功能性和构象可调性。我们利用对 HCC 细胞具有亲和力的叶酸（FA）对 SF 进行功能化，同时帮助 SF 实现对 pH 值敏感的β片转变。这种动态构象行为是改善纳米药物的循环、生物粘附性和肿瘤定位的关键。通过封装伦伐替尼（Leva）TKI，该纳米药物表现出了肿瘤靶向积累和对 HCC 细胞存活和血管生成的强效抑制作用，从而提高了 Leva 的生物利用度和治疗效果。由于 SF 的免疫原性低、可重复性高，这种基于 SF 的 TKI 给药方法有望推动 HCC 的系统治疗。
{"title":"Silk Fibroin-Based Lenvatinib Nanomedicine with Conformation Tunability for Systemic Treatment of Hepatocellular Carcinoma","authors":"Kaxi Yu, Yu Wang, Hong Sun, Yijie Lou, Hanxiao Bao, Xuanhao Wang, Jinguo Zhang, Junhui Shi, Guping Tang, Qiwen Wang, Hongzhen Bai","doi":"10.1021/acsami.4c16424","DOIUrl":"https://doi.org/10.1021/acsami.4c16424","url":null,"abstract":"Multitarget tyrosine kinase inhibitors (TKIs) serve as first-line therapeutics in the systemic treatment of hepatocellular carcinoma (HCC), yet their clinical effectiveness is hampered by suboptimal pharmacokinetics and bioavailability. There is a critical need to enhance the circulation, tumor targeting, and infiltration of TKIs. In this context, we developed a silk fibroin (SF)-based nanomedicine that exploits the chemical versatility and conformation tunability of SF. Folic acid (FA) with affinity toward HCC cells is utilized to functionalize SF, simultaneously aiding in the pH-sensitive β-sheet transitions of SF. This dynamic conformation behavior is key to improving the nanomedicine’s circulation, biological adhesion, and tumor localization. By encapsulating Lenvatinib (Leva) TKI, the nanomedicine exhibits tumor-targeted accumulation and potent inhibition on HCC cell survival and angiogenesis, thereby amplifying Leva’s bioavailability and therapeutic impact. Owing to SF’s low immunogenicity and high reproducibility, this SF-based approach for TKI delivery holds substantial promise for advancing HCC systemic therapy.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":null,"pages":null},"PeriodicalIF":9.5,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486825","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}
Passivation technology is crucial for reducing interface defects and impacting the performance of crystalline silicon (c-Si) solar cells. Concurrently, maintaining a thin passivation layer is essential for ensuring efficient carrier transport. With an ultrathin passivated contact structure, both Silicon Heterojunction (SHJ) cells and Tunnel Oxide Passivated Contact (TOPCon) solar cells achieve an efficiency surpassing 26%. To reduce production costs and simplify solar cell manufacturing processes, the rapid development of organic material passivation technology has emerged. However, its widespread industrial production is hindered by environmental safety concerns, such as strong acid corrosion and biological and ecological safety issues. Here, we discovered a low-cost self-assembled monolayer (SAM) hole-selective transport material known as 2PACz ([2-(9H-carbazol-9-yl) ethyl] phosphonic acid) with phosphate groups to form c-Si solar cells for the first time. The ultrathin film of 2PACz with phosphate groups can establish strong and stable P–O–Si bonds on the silicon surface. Meanwhile, like 2PACz, a uniform ultrathin film with a carbazole function group can offer electron-localizing and thus hole-selective properties, which provides ideas for studying dopant-free silicon solar cells. As a result of such interfacial passivation engineering, it plays an important role in repairing porous structures, such as pyramid-textured silicon surfaces, and cutting losses during the commercialization of c-Si solar cells. Crucially, this advancement offers insights for the development of new high-efficiency ultrathin film passivation methods in the postsilicon era.
{"title":"Ultrathin Self-Assembled Monolayer for Effective Silicon Solar Cell Passivation","authors":"Wenheng Li, Ziqi Zhao, Jianxin Guo, Bingbing Chen, Xiao Wang, Yuhua Bai, Jingwei Chen, Dehua Yang, Qing Gao, Xueliang Yang, Jianming Wang, Dengyuan Song, Shufang Wang, Xuning Zhang, Jianhui Chen","doi":"10.1021/acsami.4c10257","DOIUrl":"https://doi.org/10.1021/acsami.4c10257","url":null,"abstract":"Passivation technology is crucial for reducing interface defects and impacting the performance of crystalline silicon (c-Si) solar cells. Concurrently, maintaining a thin passivation layer is essential for ensuring efficient carrier transport. With an ultrathin passivated contact structure, both Silicon Heterojunction (SHJ) cells and Tunnel Oxide Passivated Contact (TOPCon) solar cells achieve an efficiency surpassing 26%. To reduce production costs and simplify solar cell manufacturing processes, the rapid development of organic material passivation technology has emerged. However, its widespread industrial production is hindered by environmental safety concerns, such as strong acid corrosion and biological and ecological safety issues. Here, we discovered a low-cost self-assembled monolayer (SAM) hole-selective transport material known as 2PACz ([2-(9H-carbazol-9-yl) ethyl] phosphonic acid) with phosphate groups to form c-Si solar cells for the first time. The ultrathin film of 2PACz with phosphate groups can establish strong and stable P–O–Si bonds on the silicon surface. Meanwhile, like 2PACz, a uniform ultrathin film with a carbazole function group can offer electron-localizing and thus hole-selective properties, which provides ideas for studying dopant-free silicon solar cells. As a result of such interfacial passivation engineering, it plays an important role in repairing porous structures, such as pyramid-textured silicon surfaces, and cutting losses during the commercialization of c-Si solar cells. Crucially, this advancement offers insights for the development of new high-efficiency ultrathin film passivation methods in the postsilicon era.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":null,"pages":null},"PeriodicalIF":9.5,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486685","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}
Acute kidney injury (AKI) represents a prevalent and complex clinical event, characterized by irreversible damage to renal tubular epithelial cells and high intensive care unit (ICU) admission rates and mortality. The kidneys are highly susceptible to oxidative stress, inflammation, pyroptosis, and programmed cell death. Pyroptosis poses a significant risk, exacerbating the damage and inflammation of renal tubular cells. Disulfiram (DSF), an FDA-approved medication for alcohol cessation, inhibits the pyroptotic pore-forming protein Gasdermin-D (GSDMD), positioning it as a potential solution for emergency relief against an inflammatory response. However, current obstacles include poor water solubility, rapid metabolism, and off-target effects. Inspired by this discovery, bovine serum albumin (BSA), which has already entered clinical application, has been utilized to produce safe and long-lasting nanoparticles (BSA@DSF NPs), addressing the challenges posed by DSF’s physicochemical properties. By targeting the GSDMD protein, the potent pro-inflammatory effects of pyroptosis were mitigated, leading to the alleviation of AKI induced by ischemia-reperfusion injury. This research offers a straightforward and efficient concept for treating AKI, potentially enhancing the transition to clinical practice.
{"title":"Prolonged Retention of Albumin Nanoparticles Alleviates Renal Ischemia-Reperfusion Injury through Targeted Pyroptosis","authors":"Lihao Guo, Hongmei Wang, Xiaoang Liu, Qian Liu, Jingtian Zhang, Dan Ding, Donghui Zheng","doi":"10.1021/acsami.4c13481","DOIUrl":"https://doi.org/10.1021/acsami.4c13481","url":null,"abstract":"Acute kidney injury (AKI) represents a prevalent and complex clinical event, characterized by irreversible damage to renal tubular epithelial cells and high intensive care unit (ICU) admission rates and mortality. The kidneys are highly susceptible to oxidative stress, inflammation, pyroptosis, and programmed cell death. Pyroptosis poses a significant risk, exacerbating the damage and inflammation of renal tubular cells. Disulfiram (DSF), an FDA-approved medication for alcohol cessation, inhibits the pyroptotic pore-forming protein Gasdermin-D (GSDMD), positioning it as a potential solution for emergency relief against an inflammatory response. However, current obstacles include poor water solubility, rapid metabolism, and off-target effects. Inspired by this discovery, bovine serum albumin (BSA), which has already entered clinical application, has been utilized to produce safe and long-lasting nanoparticles (BSA@DSF NPs), addressing the challenges posed by DSF’s physicochemical properties. By targeting the GSDMD protein, the potent pro-inflammatory effects of pyroptosis were mitigated, leading to the alleviation of AKI induced by ischemia-reperfusion injury. This research offers a straightforward and efficient concept for treating AKI, potentially enhancing the transition to clinical practice.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":null,"pages":null},"PeriodicalIF":9.5,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486694","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：