Nanoscale Horizons最新文献

{"title":"Ab initio investigation of hot electron transfer in CO2 plasmonic photocatalysis in the presence of hydroxyl adsorbate†","authors":"Zelio Fusco, Dirk Koenig, Sean C. Smith and Fiona Jean Beck","doi":"10.1039/D4NH00046C","DOIUrl":"10.1039/D4NH00046C","url":null,"abstract":"<p >Photoreduction of carbon dioxide (CO<small>₂</small>) on plasmonic structures is of great interest in photocatalysis to aid selectivity. While species commonly found in reaction environments and associated intermediates can steer the reaction down different pathways by altering the potential energy landscape of the system, they are often not addressed when designing efficient plasmonic catalysts. Here, we perform an atomistic study of the effect of the hydroxyl group (OH) on CO<small>₂</small> activation and hot electron generation and transfer using first-principles calculations. We show that the presence of OH is essential in breaking the linear symmetry of CO<small>₂</small>, which leads to a charge redistribution and a decrease in the O<img>C<img>O angle to 134°, thereby activating CO<small>₂</small>. Analysis of the partial density of states (pDOS) demonstrates that the OH group mediates the orbital hybridization between Au and CO<small>₂</small> resulting in more accessible states, thus facilitating charge transfer. By employing time-dependent density functional theory (TDDFT), we quantify the fraction of hot electrons directly generated into hybridized molecular states at resonance, demonstrating a broader energy distribution and an 11% increase in charge-transfer in the presence of OH groups. We further show that the spectral overlap between excitation energy and plasmon resonance plays a critical role in efficiently modulating electron transfer processes. These findings contribute to the mechanistic understanding of plasmon-mediated reactions and demonstrate the importance of co-adsorbed species in tailoring the electron transfer processes, opening new avenues for enhancing selectivity.</p>","PeriodicalId":93,"journal":{"name":"Nanoscale Horizons","volume":null,"pages":null},"PeriodicalIF":9.7,"publicationDate":"2024-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140580368","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"N-Formylation modifies membrane damage associated with PSMα3 interfacial fibrillation†","authors":"Laura Bonnecaze, Katlyn Jumel, Anthony Vial, Lucie Khemtemourian, Cécile Feuillie, Michael Molinari, Sophie Lecomte and Marion Mathelié-Guinlet","doi":"10.1039/D4NH00088A","DOIUrl":"10.1039/D4NH00088A","url":null,"abstract":"<p >The virulence of <em>Staphylococcus aureus</em>, a multi-drug resistant pathogen, notably depends on the expression of the phenol soluble modulins α3 (PSMα3) peptides, able to self-assemble into amyloid-like cross-α fibrils. Despite remarkable advances evidencing the crucial, yet insufficient, role of fibrils in PSMα3 cytotoxic activities towards host cells, the relationship between its molecular structures, assembly propensities, and modes of action remains an open intriguing problem. In this study, combining atomic force microscopy (AFM) imaging and infrared spectroscopy, we first demonstrated <em>in vitro</em> that the charge provided by the N-terminal capping of PSMα3 alters its interactions with model membranes of controlled lipid composition without compromising its fibrillation kinetics or morphology. N-formylation eventually dictates PSMα3-membrane binding <em>via</em> electrostatic interactions with the lipid head groups. Furthermore, PSMα3 insertion within the lipid bilayer is favoured by hydrophobic interactions with the lipid acyl chains only in the fluid phase of membranes and not in the gel-like ordered domains. Strikingly, our real-time AFM imaging emphasizes how intermediate protofibrillar entities, formed along PSMα3 self-assembly and promoted at the membrane interface, likely disrupt membrane integrity <em>via</em> peptide accumulation and subsequent membrane thinning in a peptide concentration and lipid-dependent manner. Overall, our multiscale and multimodal approach sheds new light on the key roles of N-formylation and intermediate self-assembling entities, rather than mature fibrils, in dictating deleterious interactions of PSMα3 with membrane lipids, likely underscoring its ultimate cellular toxicity <em>in vivo</em>, and in turn <em>S. aureus</em> pathogenesis.</p>","PeriodicalId":93,"journal":{"name":"Nanoscale Horizons","volume":null,"pages":null},"PeriodicalIF":8.0,"publicationDate":"2024-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/nh/d4nh00088a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140580466","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Recent advances in fluorescence and afterglow of CDs in matrices","authors":"Qiang Fu, Kangzhi Lu, Shouhong Sun and Zhanhua Dong","doi":"10.1039/D4NH00093E","DOIUrl":"10.1039/D4NH00093E","url":null,"abstract":"<p >Carbon dots (CDs) are novel nanomaterials with dimensions less than 10 nm that have attracted much attention due to their outstanding optical properties. However, the development of solid-state fluorescence and afterglow methods has been relatively slow, although the properties of these materials under liquid conditions have been extensively studied. In recent years, embedding CDs in a matrix has been shown to prevent aggregation quenching and inhibit nonradiative transitions, thus realizing solid-state fluorescence and afterglow, which has greatly broadened the research and application areas of CDs. In terms of hydrogen bonding, ionic bonding, covalent bonding and spatial confinement, the interactions between CDs and matrices can effectively realize and improve the solid-state fluorescence and afterglow effects of CDs. Recent applications of CDs in matrices in optoelectronics, information security, sensing, biotherapeutics and imaging are also summarized. Finally, we summarize the challenges and developments of CDs in matrices.</p>","PeriodicalId":93,"journal":{"name":"Nanoscale Horizons","volume":null,"pages":null},"PeriodicalIF":8.0,"publicationDate":"2024-04-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140580372","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Iodine passivation facilitates on-surface synthesis of robust regular conjugated two-dimensional organogold networks on Au(111)†","authors":"Arash Badami-Behjat, Gianluca Galeotti, Rico Gutzler, Dominik L. Pastoetter, Wolfgang M. Heckl, Xinliang Feng and Markus Lackinger","doi":"10.1039/D3NH00496A","DOIUrl":"10.1039/D3NH00496A","url":null,"abstract":"<p >Two-dimensional conjugated organogold networks with anthra-tetrathiophene repeat units are synthesized by thermally activated debrominative coupling of 2,5,9,12-tetrabromoanthra[1,2-<em>b</em>:4,3-<em>b</em>′:5,6-<em>b</em>′′:8,7-<em>b</em>′′′]tetrathiophene (TBATT) precursor molecules on Au(111) surfaces under ultra-high vacuum (UHV) conditions. Performing the reaction on iodine-passivated Au(111) surfaces promotes formation of highly regular structures, as revealed by scanning tunneling microscopy (STM). In contrast, coupling on bare Au(111) surfaces results in less regular networks due to the simultaneous expression of competing intermolecular binding motifs in the absence of error correction. The carbon–Au–carbon bonds confer remarkable robustness to the organogold networks, as evidenced by their high thermal stability. In addition, as suggested by density functional theory (DFT) calculations and underscored by scanning tunneling spectroscopy (STS), the organogold networks exhibit a small electronic band gap in the order of 1.0 eV due to their high π-conjugation.</p>","PeriodicalId":93,"journal":{"name":"Nanoscale Horizons","volume":null,"pages":null},"PeriodicalIF":9.7,"publicationDate":"2024-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/nh/d3nh00496a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140580370","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A microphysiological system for handling graphene related materials under flow conditions†","authors":"Alodia Lacueva-Aparicio, Viviana Jehová González, Ana Rosa Remacha, Daniel Woods, Eduardo Prado, Ignacio Ochoa, Sara Oliván and Ester Vázquez","doi":"10.1039/D4NH00064A","DOIUrl":"10.1039/D4NH00064A","url":null,"abstract":"<p >The field of nanotechnology has developed rapidly in recent decades due to its broad applications in many industrial and biomedical fields. Notably, 2D materials such as graphene-related materials (GRMs) have been extensively explored and, as such, their safety needs to be assessed. However, GRMs tend to deposit quickly, present low stability in aqueous solutions, and adsorb to plastic materials. Consequently, traditional approaches based on static assays facilitate their deposition and adsorption and fail to recreate human physiological conditions. Organ-on-a-chip (OOC) technology could, however, solve these drawbacks and lead to the development of microphysiological systems (MPSs) that mimic the microenvironment present in human tissues. In light of the above, in the present study a microfluidic system under flow conditions has been optimised to minimise graphene oxide (GO) and few-layer graphene (FLG) adsorption and deposition. For that purpose, a kidney-on-a-chip was developed and optimised to evaluate the effects of exposure to GO and FLG flakes at a sublethal dose under fluid flow conditions. In summary, MPSs are an innovative and precise tool for evaluating the effects of exposure to GRMs and other type of nanomaterials.</p>","PeriodicalId":93,"journal":{"name":"Nanoscale Horizons","volume":null,"pages":null},"PeriodicalIF":9.7,"publicationDate":"2024-04-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/nh/d4nh00064a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140580477","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Heterointerface engineering of layered double hydroxide/MAPbBr3 heterostructures enabling tunable synapse behaviors in a two-terminal optoelectronic device†","authors":"Qian Chen, Jiacheng Cao, Zhiwei Yang, Zeyi Wang, Jian Wang, Shilong Yu, Chenjie Hao, Nana Wang, Hai Li and Xiao Huang","doi":"10.1039/D4NH00066H","DOIUrl":"10.1039/D4NH00066H","url":null,"abstract":"<p >Solution-processable semiconductor heterostructures enable scalable fabrication of high performance electronic and optoelectronic devices with tunable functions <em>via</em> heterointerface control. In particular, artificial optical synapses require interface manipulation for nonlinear signal processing. However, the limited combinations of materials for heterostructure construction have restricted the tunability of synaptic behaviors with simple device configurations. Herein, MAPbBr<small>₃</small> nanocrystals were hybridized with MgAl layered double hydroxide (LDH) nanoplates through a room temperature self-assembly process. The formation of such heterostructures, which exhibited an epitaxial relationship, enabled effective hole transfer from MAPbBr<small>₃</small> to LDH, and greatly reduced the defect states in MAPbBr<small>₃</small>. Importantly, the ion-conductive nature of LDH and its ability to form a charged surface layer even under low humidity conditions allowed it to attract and trap holes from MAPbBr<small>₃</small>. This imparted tunable synaptic behaviors and short-term plasticity (STP) to long-term plasticity (LTP) transition to a two-terminal device based on the LDH-MAPbBr<small>₃</small> heterostructures. The further neuromorphic computing simulation under varying humidity conditions showcased their potential in learning and recognition tasks under ambient conditions. Our work presents a new type of epitaxial heterostructure comprising metal halide perovskites and layered ion-conductive materials, and provides a new way of realizing charge-trapping induced synaptic behaviors.</p>","PeriodicalId":93,"journal":{"name":"Nanoscale Horizons","volume":null,"pages":null},"PeriodicalIF":9.7,"publicationDate":"2024-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140580367","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Polydopamine-encapsulated zinc peroxide nanoparticles to target the metabolism-redox circuit against tumor adaptability for mild photothermal therapy†","authors":"Yue Qiao, Xiaodan Jia, Yue Wang, Lin Liu, Mengchao Zhang and Xiue Jiang","doi":"10.1039/D4NH00070F","DOIUrl":"10.1039/D4NH00070F","url":null,"abstract":"<p >Regulating the metabolism-redox circuit of cancer cells has emerged as an attractive strategy to improve the therapeutic outcome, while often confronting the glaring issue of resistance due to the multiple adaptive responses of tumor cells. This study presents a simple yet efficient approach to regulate this circuit simultaneously against tumor adaptability by utilizing polydopamine-encapsulated zinc peroxide nanoparticles (ZnO<small>₂</small>@PDA NPs). The nanoparticles could deliver large amounts of Zn<small>²⁺</small> and H<small>₂</small>O<small>₂</small> into tumor cells to unfold an intracellular self-amplifying loop for breaking the balance in zinc and redox homeostasis by H<small>₂</small>O<small>₂</small>-mediated endogenous Zn<small>²⁺</small> release from metallothioneins due to its oxidation by H<small>₂</small>O<small>₂</small> and Zn<small>²⁺</small>-induced <em>in situ</em> H<small>₂</small>O<small>₂</small> production by disturbing mitochondrial respiration, ultimately disrupting tumor adaptability to exogenous stimuli. The elevated levels of Zn<small>²⁺</small> and H<small>₂</small>O<small>₂</small> also inhibited adenosine triphosphate (ATP) generation from glycolysis and mitochondrial respiration to disrupt energy adaptability. Furthermore, insufficient ATP supply could reduce glutathione and heat shock protein expression, thereby sensitizing oxidative stress and enabling PDA-mediated mild photothermal therapy (PTT). Consequently, this trinity nanoplatform, which integrated dual-starvation therapy, amplified oxidative stress, and mild PTT, demonstrated outstanding therapeutic effects and a facile strategy.</p>","PeriodicalId":93,"journal":{"name":"Nanoscale Horizons","volume":null,"pages":null},"PeriodicalIF":9.7,"publicationDate":"2024-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140580373","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A nanoengineered vanadium oxide composite as a high-performance anode for aqueous Li-ion hybrid batteries†","authors":"Ailun Huang, Zhiyin Yang, Xueying Chang, Cheng-Wei Lin and Richard B. Kaner","doi":"10.1039/D3NH00579H","DOIUrl":"10.1039/D3NH00579H","url":null,"abstract":"<p >Aqueous lithium-ion batteries (LIBs) have received increasing attention as a promising solution for stationary energy storage systems due to their low environmental impact, non-flammability and low cost. Despite recent progress in electrolyte development and cathode manufacturing, the lack of anode materials with high specific capacity presents difficult challenges for a wide range of applications. In this study, we propose a novel synthetic strategy to fabricate a pseudocapacitive V<small>₂</small>O<small>₅</small>/graphene composite as a highly functional anode material for aqueous LIBs. The designed synthesis combines a fast laser-scribing step with controlled calcination to tune the morphology and oxidation state of the electrochemically active vanadium oxide species while obtaining a highly conductive graphene scaffold. The optimized V<small>₂</small>O<small>₅</small>/graphene anode shows an outstanding specific capacity of 158 mA h g<small>⁻¹</small> in three-electrode measurements. When the V<small>₂</small>O<small>₅</small>/graphene anode is paired with an LiMn<small>₂</small>O<small>₄</small> cathode, the charge storage mechanism of the full cell is revealed to be dominantly surface-controlled, resulting in remarkable rate performance. Specifically, the full cell can reach a specific capacity of 151 and 107 mA h (g anode)<small>⁻¹</small> at C/6 and 3C, respectively. Moreover, this hybrid battery can achieve a high power density and an energy density of 650 W kg<small>⁻¹</small> at 15.6 W h kg<small>⁻¹</small> and 81.5 W h kg<small>⁻¹</small> at 13.6 W kg<small>⁻¹</small>, respectively, outperforming most aqueous LIBs reported in the literature. This innovative strategy provides a pathway to incorporate pseudocapacitive electrodes for improving aqueous lithium-ion storage systems, enabling safe operation of large-scale energy storage without compromising their electrochemical performance.</p>","PeriodicalId":93,"journal":{"name":"Nanoscale Horizons","volume":null,"pages":null},"PeriodicalIF":8.0,"publicationDate":"2024-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140580462","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Chiroptically active quantum nanonails†","authors":"Finn Purcell-Milton, Vera A. Kuznetsova, Xue Bai, Áine Coogan, Marina Martínez-Carmona, Jorge A. Garcia, A. Louise Bradley and Yurii K. Gun’ko","doi":"10.1039/D4NH00015C","DOIUrl":"10.1039/D4NH00015C","url":null,"abstract":"<p >In recent years, extensive research efforts have been dedicated to the investigation of CdSe/CdS-based quantum-confined nanostructures, driven by their distinctive properties. The morphologies of these nanostructures have been shown to directly affect their properties, an area which has proven to be an important field of study. Herein, we report a new morphology of CdSe/CdS core–shell heterostructures in the form of a ‘nanonail’ – a modified nanorod-like morphology, in which a distinctive triangular head can be observed at one end of the structure. In-depth studies of this morphology reveal a material with tuneable rod length and width, as well as exceptional photoluminescent properties. Following this, we have demonstrated the ability to induce chiroptical activity <em>via</em> ligand exchange, revealing the important role of the specific morphology, shell thickness and chiral ligand concentration in the effect of ligand induced chirality. In addition, the cellular uptake and cytotoxicity of obtained chiral nanostructures were evaluated on human lung-derived A549 cancer cells, revealing a significant enantioselectivity in biological activity. Finally, analysis on monolayers of the material demonstrate the complete absence of FRET processes. Overall, this CdSe/CdS heterostructure is another tuneable morphology of a very important nanomaterial, one which shows great advantages and a range of potential applications.</p>","PeriodicalId":93,"journal":{"name":"Nanoscale Horizons","volume":null,"pages":null},"PeriodicalIF":9.7,"publicationDate":"2024-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/nh/d4nh00015c?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140580618","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Graphene oxide–DNA/graphene oxide–PDDA sandwiched membranes with neuromorphic function†","authors":"Jia Hui Bong, Sergey Grebenchuk, Konstantin G. Nikolaev, Celestine P. T Chee, Kou Yang, Siyu Chen, Denis Baranov, Colin R. Woods, Daria V. Andreeva and Kostya S. Novoselov","doi":"10.1039/D3NH00570D","DOIUrl":"10.1039/D3NH00570D","url":null,"abstract":"<p >The behavior of polyelectrolytes in confined spaces has direct relevance to the protein mediated ion transport in living organisms. In this paper, we govern lithium chloride transport by the interface provided by polyelectrolytes, polycation, poly(diallyldimethylammonium chloride) (PDDA) and, polyanion, double stranded deoxyribonucleic acid (dsDNA), in confined graphene oxide (GO) membranes. Polyelectrolyte–GO interfaces demonstrate neuromorphic functions that were successfully applied with nanochannel ion interactions contributed, resulting in ion memory effects. Excitatory and inhibitory post-synaptic currents were tuned continuously as the number of pulses applied increased accordingly, increasing decay times. Furthermore, we demonstrated the short-term memory of a trained vs untrained device in computation. On account of its simple and safe production along with its robustness and stability, we anticipate our device to be a low dimensional building block for arrays to embed artificial neural networks in hardware for neuromorphic computing. Additionally, incorporating such devices with sensing and actuating parts for a complete feedback loop produces robotics with its own ability to learn by modifying actuation based on sensing data.</p>","PeriodicalId":93,"journal":{"name":"Nanoscale Horizons","volume":null,"pages":null},"PeriodicalIF":9.7,"publicationDate":"2024-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/nh/d3nh00570d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140292162","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}