Nanoscale最新文献

{"title":"Atomistic modelling of electron beam induced structural transformations in deposited metal clusters","authors":"Ioannis Bounas, Alexey V. Verkhovtsev, Theodoros Pavloudis, Gennady B. Sushko, Joseph Kioseoglou, Richard E. Palmer, Andrey V. Solov'yov","doi":"10.1039/d4nr04448g","DOIUrl":"https://doi.org/10.1039/d4nr04448g","url":null,"abstract":"Structural transformations in gold clusters deposited on a graphite substrate induced by the focused electron beam of a scanning transmission electron microscope are investigated using the classical molecular dynamics (MD) approach. The particular case study concerns Au<small>₃₀₉</small> clusters softly deposited on few-layer graphite and exposed to a 300 keV electron beam. Two mechanisms of energy transfer to the cluster during the irradiation are considered: (i) through the relaxation of collective electronic excitations and (ii) through the momentum transfer by the energetic primary electrons. A relativistic MD approach implemented in the MBN Explorer software package is used to simulate the collisions of energetic primary electrons with cluster atoms and to evaluate the amount of energy transferred to the cluster for different collision geometries. Characteristic times for the occurrence of these energy deposition events are estimated for realistic experimental irradiation conditions. The MD simulations of the cluster dynamics after irradiation show that the cluster temperature decreases rapidly during the first few tens of picoseconds, and the cluster cools down to a temperature close to its initial temperature within several hundred picoseconds. This time period is comparable to the characteristic time between two successive energy transfer events induced by plasmon excitations in the deposited cluster. A large number of successive energy transfer events (on the order of ∼10<small>³</small>–10<small>⁴</small>) during irradiation can cumulatively lead to substantial heating of the deposited cluster and induce its structural transformations.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"207 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143083556","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Spacer engineering in nanoparticle–peptide conjugates boosts targeting specificity for tumor-associated antigens","authors":"María de los Angeles Ramírez, Jolie Bou-Gharios, Barbara Freis, Julien Draussin, Clémence Cheignon, Loic J. Charbonnière, Sophie Laurent, Thomas Gevart, Adeline Gasser, Sebastian Jung, Fabien Rossetti, Olivier Tillement, Georges Noel, Xavier Pivot, Alexandre Detappe, Sylvie Bégin-Colin, Sébastien Harlepp","doi":"10.1039/d4nr02931c","DOIUrl":"https://doi.org/10.1039/d4nr02931c","url":null,"abstract":"Developing and synthesizing nano-objects capable of enabling early targeted diagnosis and ensuring effective tumor treatment represents a significant challenge in the theranostic field. Among various nanoparticles (NPs), iron oxide nanoparticles (IONPs) have made significant contributions to advancing this field. However, a key challenge lies in achieving selective recognition of specific cell types. In oncology, the primary goal is to develop innovative strategies to enhance NP uptake by tumors, primarily through active targeting. This involves adding targeting ligands (TL) to the NP surface to facilitate tumor accumulation and increase retention within the tumor microenvironment. Despite biofunctionalization strategies, overall tumor uptake remains modest at only 5–7% of the injected dose per gram. In this work, we demonstrate the effect of spacing between the NPs and the TL to improve their availability and thus the tumor uptake of the complex. This proof-of-concept study targets the epidermal growth factor receptor (EGFR) using a peptide as a targeting ligand. Specifically, we characterized the PEG-peptide coupled to dendronized IONPs, including the density of grafted TL. These nano-objects underwent <em>in vitro</em> evaluation to assess their ability to specifically target and be internalized by tumor cells. Therapeutically, compared to non-functionalized NPs, the presence of the TL with a PEG linker enhanced targeting efficacy and increased internalization, leading to improved photothermal efficacy.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"40 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143083557","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Gold nanozymes for efficient degradation of organic dye pollutants: outperforming natural enzymes","authors":"Giulia Mirra, Lorenzo Cursi, MARINA VERONESI, Luca Boselli, Pier Paolo Pompa","doi":"10.1039/d4nr05137h","DOIUrl":"https://doi.org/10.1039/d4nr05137h","url":null,"abstract":"Nanozymes (NZs) are raising increasing interest as effective tools for the degradation of organic pollutants dispersed in the environment. In particular, noble-metal NZs are extremely efficient and versatile, thanks to their multi-enzymatic activities, wide pH operational range, and thermal stability. However, whilst multifunctionality can be a key asset of NZs in some applications (e.g., by intrinsic self-cascade/tandem reactions), the “internal” competition between their different catalytic activities may strongly limit their specific efficiency towards some targets. In this scenario, a deep comprehension of their catalytic mechanisms and careful optimization of the operating conditions are crucial to disclose their full potential and maximize their performances. Here, we analyzed the ability of gold, palladium, and platinum NZs to degrade model organic pollutants of industrial relevance, i.e. rhodamine B, methylene blue, and methyl orange. Interestingly, we found that AuNZ is very efficient in degrading all three dyes via peroxidase-like activity, unlike the natural enzyme (horseradish peroxidase - HRP), which displayed weak degradative capabilities. On the other hand, Pd and PtNZs experience the internal competitive catalase-like reaction, strongly limiting their dye degradation performances. The mechanism underlying AuNZ ability to degrade the synthetic dyes was investigated, revealing the preferential reactivity with the aromatic structures of the molecules. We also developed a proof-of-concept AuNZ-based dye-degrading filter system, showing excellent dye removal capability and good recyclability, even in real environmental samples.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"133 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143083561","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis of MXene/Carbon Composites via Controlled Etching of Ti3SiC2 in gaseous etch-ant CCl₄","authors":"Yu Wang, Xudong Wang, Mian Li, Zhifang Chai, Qing Huang","doi":"10.1039/d4nr04736b","DOIUrl":"https://doi.org/10.1039/d4nr04736b","url":null,"abstract":"The study investigates the structural evolution of Ti3SiC2 using gaseous etchant CCl4 as an etchant, emphasizing its ability to selectively etch Si and Ti atoms to form MXene (Ti3C2Cl2) /carbon composite and carbide-derived carbon (CDC). Under specific conditions, a complete conversion to MXene is accomplished at a Ti3SiC2: CCl4 molar ratio of 1:3.5 , whereas higher CCl4 concentrations lead to further oxidation of Ti3C2Cl2 and formation of lamella CDC. This method presents a alternative chemical ething route to synthesize MXenes. Importantly, the production of CDC using CCl₄ as an etchant could obtain Carbon/MXene hybrides with significant implications for promising energy storage applications.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"47 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143084045","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Nanofiber-shaped Co3O4@In2O3 composite for high-performance enzymeless glucose sensing","authors":"Xinda Xu, Chao Zhang, Woochul Yang, Yujia Li, Bing Li, Yuvaraj Haldorai, Zhen-Yu Jiang, Wanfeng Xie","doi":"10.1039/d4nr04274c","DOIUrl":"https://doi.org/10.1039/d4nr04274c","url":null,"abstract":"Cobalt tetraoxide (Co3O4) holds great potential for enzymeless glucose detection due to its strong redox capabilities. However, its poor electrical conductivity limits the charge transfer and hence weakens its catalytic activity when utilized as the electrode of electrochemical sensors, such as enzymeless glucose sensor. In this study, we developed an indium oxide (In2O3)-wrapped Co3O4 nanofibers (Co3O4@In2O3 NFs) based electrochemical sensor for the enzymeless glucose detection, with an ultra-low limit of detection (LoD) of 8.85 nM (S/N = 3), a wide detection ranging from 10 nM to 118 μM, and a high sensitivity of 1197.5 μA mM-1cm-2. In addition, this sensor exhibits good selectivity, reproducibility, and long-term stability for over 30 days. The sensing performance of bare Co3O4 NFs towards glucose has been significantly enhanced by incorporating in high conductive In2O3, which is mainly attributed to the synergistic combination of the electrocatalytic activity of Co3O4 NFs, as the delicately designed core, and the excellent conductivity of In2O3, as the shell. Thus, this novel Co3O4@In2O3 NFs composites modified electrochemical has a huge potential to be further developed for the enzymeless glucose analysis in practical clinical settings.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"56 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143083559","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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 molecular strategy for creating functional vesicles with balancing structural stability and stimuli-responsiveness","authors":"Shoi Sasaki, Hibiki Ueno, Noriyoshi Arai, Kouichi Asakura, Taisuke Banno","doi":"10.1039/d5nr00151j","DOIUrl":"https://doi.org/10.1039/d5nr00151j","url":null,"abstract":"Vesicles, closed bilayer structures composed of amphiphiles, have attracted considerable attention as functional materials. Structural stability and stimulus responsiveness are required for next-generation functional vesicles. However, there is a dilemma between these properties because the desired membrane structure varies in terms of structural stability and stimulus sensitivity. Herein, we propose a new approach for the development of giant vesicles (GVs) through the molecular design and synthesis of amphiphiles with or without amide linkages, forming hydrogen bonding. From the <small>¹</small>H NMR analysis and fluorescence spectra of the environment-responsive probes, intermolecular hydrogen bonding between the amide linkages in the membrane contributed to the enhanced structural stability of the GVs. Moreover, by adding amphiphiles containing a photoresponsive azobenzene moiety to GVs composed of amphiphiles with or without amide linkages, a distinct mechanism of photoresponsive deformation was observed: the former exhibited large and irreversible deformation, while the latter showed modest and reversible manner due to the photoisomerisation of azobenzene under ultraviolet and subsequent visible light illumination. This difference was also attributed to the membrane structure affected by intermolecular hydrogen bonding. Based on these results, the finding provides the molecular methodology for developing highly functional vesicles.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"10 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143084046","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Hollow gold–platinum nanoshells as a delivery platform for Ce6: cascading catalysis for enhanced multimodal therapy in tumor ablation and antitumor immunity","authors":"Jia-Hao Feng, Mei-Lian Zhang, Yi-Ming Zou, Xiao-Yan Tang, Xiao-Tong Chen, Wei Meng, Ming Chen, Rong-Tian Li, Jin-Xiang Chen","doi":"10.1039/d4nr04627g","DOIUrl":"https://doi.org/10.1039/d4nr04627g","url":null,"abstract":"Precious metal nanozymes are renowned for their enzyme-mimicking properties, which can modulate the tumor microenvironment (TME) and enhance treatment. However, their small size often leads to aggregation and their single and limited catalytic potential impedes antitumor and immune-activating capabilities. To address these limitations, we developed a nanocomposite with multiple enzyme activities that synergistically enhances photodynamic and photothermal therapy (PDT and PTT), significantly boosting antitumor efficacy and immune response. Our approach involved using UiO-66-NH<small>₂</small> to facilitate the growth of gold–platinum bimetallic nanozymes, resulting in a core–shell structure of UiO-66-NH<small>₂</small>@AuPt (UAuPt). The UiO-66-NH<small>₂</small> was then etched to create hollow gold–platinum bimetallic (HAuPt) nanoshells and further encapsulated with PEG-SH and the photosensitizer Ce6 to form the HAuPt@Ce6-PEG-SH (HCP) nanocomposite. Regarding the HCP nanocomposite, its absorption capability in the near-infrared second (NIR-II) region makes it a suitable photothermal agent for PTT, while Ce6 serves as the active agent for PDT. Furthermore, the gold nanoparticles (Au NPs) and platinum nanoparticles (Pt NPs) exhibit glucose oxidase (GOD)-, catalase (CAT)-, and peroxidase (POD)-like activities. This triple-enzyme activity forms an efficient cascade catalytic system, leading to refined remodeling of the TME and efficient enhancement of PTT and PDT. Moreover, the combination therapy triggers tumor-associated macrophage (TAM) polarization and immunogenic cell death (ICD), which not only promotes dendritic cell (DC) maturation but also stimulates T cell activation and the release of tumor-specific immune factors. This cascade ultimately results in a robust antitumor immune response. The <em>in vitro</em> and <em>in vivo</em> results demonstrated a significant antitumor efficacy and immune response, promising efficient nanozymes for therapeutic advancement.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"8 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143083560","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"DNA Origami-Templated Individual Gold Nanocluster: Probing The Photophysical Dynamics Using Single Molecule Fluorescence Spectroscopy","authors":"Tapasi Sen, Shikha Rai, Vishaldeep Kaur, Charanleen Kaur, Mridu Sharma","doi":"10.1039/d4nr04887c","DOIUrl":"https://doi.org/10.1039/d4nr04887c","url":null,"abstract":"Single-molecule fluorescence microscopy demands ultrahigh stability of single fluorophore with less photobleaching and essentially no intensity fluctuations on experimentally relevant time scales. In this respect, there is a need to design fluorescent probes with excellent photostability and long-lived dark transient states. Herein, we report the site-specific synthesis of gold nanocluster (Au NC) on DNA origami. Rectangular DNA origami bearing poly-cytosine sequence in the centre was used as a template to guide the in situ synthesis of Au NC. The photophysical properties of DNA-templated AuNCs were extensively studied using single-molecule confocal fluorescence microscopy, which revealed the average on-time and off-time of 0.08 seconds and 0.05 seconds, respectively. The photon antibunching measurements confirmed the existence of single Au NC in the confocal volume and fluorescence transient studies revealed excellent brightness and remarkable photostability with long survival times and less blinking. Such DNA-templated Au NCs with ultrahigh photostability, intense brightness, and low toxicity has tremendous potential to be used as probes in single-molecule dynamics measurements in biologically relevant timescales. The precise addressability of DNA origami nanostructures provides the controlled attachment of various biomolecules specifically at a predesigned location on the origami template, allowing such platforms to be used as single nanocatalysis as well as performing imaging and sensing studies on single molecule level.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"42 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143083597","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"SPIN-STATE SWITCHING AT THE SINGLE-MOLECULE LEVEL BY DISTORTION OF THE COORDINATION SPHERE: VALIDATION BASED ON QUANTUM-CHEMISTRY CALCULATIONS","authors":"Iman Jaber El lala, Nicolas Montenegro-Pohlhammer, Rocío Sánchez-de-Armas, Carmen J. Calzado","doi":"10.1039/d4nr04935g","DOIUrl":"https://doi.org/10.1039/d4nr04935g","url":null,"abstract":"Different strategies have been proposed to trigger the spin switching in single-molecule junctions based on spin-crossover complexes. Here, we report on a computational study aimed to validate one of the hypothesized mechanisms consisting of the distortion of the coordination sphere of the molecule. We focus on a series of heteroleptic [FeII(tpy)2]+2 complexes in a mechanically controlled break junction setup, displaying voltage-dependent bistabilities, related to the switching of the FeII centre between the LS and HS states. Our model for the molecular junction can explain the hysteretic behaviour found in some of the junctions, with a mechanism close to the hypothesized one, but without the requirement of long-range interactions between the electrodes and different parts of the molecule. Our results predict the existence of a switching field able to foster the required distortion driving the switching between the LS and HS states.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"21 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143077329","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"~ 5-fold Thermoelectric Figure of Merit of Sustainable 3D-CuNi Interconnected Nanonetworks due to Ultralow Lattice Thermal onductivity","authors":"Cristina V. Manzano, Olga Caballero-Calero, Daniele Casari, Amit Sharma, Alba Díaz-Lobo, Xavier Maeder, Marisol S. Martín-González","doi":"10.1039/d4nr05292g","DOIUrl":"https://doi.org/10.1039/d4nr05292g","url":null,"abstract":"The pursuit of efficient thermoelectric materials, particularly those composed of low-toxicity and earth-abundant elements, has intensified in recent years. This study introduces an approach to increase the thermoelectric properties of CuNi alloys through the synergistic application of two nanostructuring techniques: the incorporation of saccharine in the electrolyte to achieve a crystallite size reduction to 23-26 nm, and the utilization of three-dimensional (3D) anodic aluminum oxide (3D-AAO) templates to fabricate nanowires networks. For comparison purposes we successfully electrodeposited CuNi films, one-dimensional (1D) nanowire arrays, and modulated nanowire arrays, together with 3D-nanonetworks, maintaining a consistent composition of Cu0.60Ni0.40 across all samples. Notably, while the electrical conductivity and Seebeck coefficient remained consistent between the nanocrystalline CuNi films and the 3D-nanonetworks, a significant reduction in thermal conductivity was observed, decreasing from 29 W/m·K for the bulk material, to 10.9 ± 1.1 W/m·K for nanocrystalline films, to 5.3 ± 0.5 W/m·K for the 3D-nanonetworks, and to 4.9 ± 0.6 W/m·K for free-standing 3D CuNi nanonetworks. This reduction is attributed to enhanced phonon scattering within the 3D architecture together with the nanocrystalline size inside the nanowires. The figure of merit (zT) exhibited an impressive increase of more than four times (4.4) for 3D-CuNi nanonetworks within AAO templates, and of 4.8 time for free-standing 3D-CuNi nanonetworks, when compared to bulk. Our findings underscore the potential of dual nanostructuring strategies to optimize the thermoelectric performance of environmentally friendly, stable, and abundant materials like CuNi, paving the way for advancements in sustainable energy technologies.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"38 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143077336","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}