Herein, gas phase synthesis and characterization of multifunctional core@shell, Au@TiOx nanoparticles have been reported. The nanoparticles were produced via a one-step process using a multiple-ion cluster source under a controlled environment that guaranteed the purity of the nanoparticles. The growth of the Au cores (6 nm diameter) is stopped when they pass through the Ti plasma where they are covered by an ultra-thin (1 nm thick) and homogeneous titanium shell that is oxidized in-flight before the soft-landing of the nanoparticles. The Au cores were found to be highly crystalline with icosahedral (44%) and decahedral (66%) structures, whereas the shell, mainly composed of TiO2 (79%), was not ordered. The highly electrical insulating behaviour of the titanium oxide shell was confirmed by the charging effect produced during X-ray photoemission spectroscopy. ; This work was supported by the European ERC-2013-SyG 610256 NANOCOSMOS and European Union Seventh Framework Programme under grant agreement no. 604391 FET Graphene Flagship and by the Spanish Ministerio de Ciencia e Innovación under projects no. MAT2014-59772-C2-2-P and MAT2016-80394-R. A. M. acknowledges the Government of Aragon and the European Social Fund under the project grant number E/26 "Construyendo Europa desde Aragón" 2014–2020. ; Peer reviewed
13 pags., 8 figs. -- Open Access funded by Creative Commons Atribution Licence 4.0 ; The increasing demand for nanostructured materials is mainly motivated by their key role in a wide variety of technologically relevant fields such as biomedicine, green sustainable energy or catalysis. We have succeeded to scale-up a type of gas aggregation source, called a multiple ion cluster source, for the generation of complex, ultra-pure nanoparticles made of different materials. The high production rates achieved (tens of g/day) for this kind of gas aggregation sources, and the inherent ability to control the structure of the nanoparticles in a controlled environment, make this equipment appealing for industrial purposes, a highly coveted aspect since the introduction of this type of sources. Furthermore, our innovative UHV experimental station also includes in-flight manipulation and processing capabilities by annealing, acceleration, or interaction with background gases along with in-situ characterization of the clusters and nanoparticles fabricated. As an example to demonstrate some of the capabilities of this new equipment, herein we present the fabrication of copper nanoparticles and their processing, including the controlled oxidation (from Cu to CuO through CuO, and their mixtures) at different stages in the machine. ; This work was supported by the European Union [grant number ERC-2013-SyG 610256 NANOCOSMOS]; the Spanish MINECO [grant numbers MAT2017-85089-C2-1-R, MAT2014-54231-C4-1-P, MAT2014-54231- C4-4-P, MAT2014-59772-C2-2-P, FIS2016-77578-R, FIS2013-48087-C2-1P, FIS2016-77726-C3-1P and CSIC13-4E-1775]. ; Peer Reviewed
Nanostructured silver (Ag) and gold (Au) are widely known to be potent biocidal and cytotoxic agents as well as biocompatible nanomaterials. It has been recently reported that combining both metals in a specific chemical composition causes a significant enhancement in their antibacterial activity against antibiotic-resistant bacterial strains, as well as in their anticancer effects, while preserving cytocompatibility properties. In this work, Ag/Au bimetallic nanoparticles over a complete atomic chemical composition range were prepared at 10 at% through a green, highly reproducible, and simple approach using starch as a unique reducing and capping agent. The noble metal nanosystems were thoroughly characterized by different analytical techniques, including UV-visible and FT-IR spectroscopies, XRD, TEM/EDS, XPS and ICP-MS. Moreover, absorption spectra simulations for representative colloidal Ag/Au-NP samples were conducted using FDTD modelling. The antibacterial properties of the bimetallic nanoparticles were determined against multidrug-resistant Escherichia coli and methicillin-resistant Staphylococcus aureus, showing a clear dose-dependent inhibition even at the lowest concentration tested (5 µg/mL). Cytocompatibility assays showed a medium range of toxicity at low and intermediate concentrations (5 and 10 µg/mL), while triggering an anticancer behavior, even at the lowest concentration tested, in a process involving reactive oxygen species production per the nanoparticle Au:Ag ratio. In this manner, this study provides promising evidence that the presently fabricated Ag/Au-NPs should be further studied for a wide range of antibacterial and anticancer applications. ; The groups at CSIC and Tecnologico de Monterrey acknowledge the i-Link+2019 program (ref. LINKB20024 "NANOBIO-ROJA") for financial support. AM acknowledges the Spanish Ministry of Science (RYC2018-024561-I), the regional government of Aragon (E13_20R), the European Union's Horizon 2020 research and innovation programme (823717– ESTEEM3) and the National Natural Science Foundation of China (NSFC- 21835002). ; Peer reviewed
Cancer and antimicrobial resistance to antibiotics are two of the most worrying healthcare concerns that humanity is facing nowadays. Some of the most promising solutions for these healthcare problems may come from nanomedicine. While the traditional synthesis of nanomaterials is often accompanied by drawbacks such as high cost or the production of toxic by-products, green nanotechnology has been presented as a suitable solution to overcome such challenges. In this work, an approach for the synthesis of tellurium (Te) nanostructures in aqueous media has been developed using aloe vera (AV) extracts as a unique reducing and capping agent. Te-based nanoparticles (AV-TeNPs), with sizes between 20 and 60 nm, were characterized in terms of physicochemical properties and tested for potential biomedical applications. A significant decay in bacterial growth after 24 h was achieved for both Methicillin-resistant Staphylococcus aureus and multidrug-resistant Escherichia coli at a relative low concentration of 5 µg/mL, while there was no cytotoxicity towards human dermal fibroblasts after 3 days of treatment. AV-TeNPs also showed anticancer properties up to 72 h within a range of concentrations between 5 and 100 µg/mL. Consequently, here, we present a novel and green approach to produce Te-based nanostructures with potential biomedical applications, especially for antibacterial and anticancer applications. ; This work was supported by the Chemical Engineering Department at Northeastern University. M.K., L.D.G., and G.G. would like to thank the Center for Integrative Nanotechnology Sciences (CINS) of UA Little Rock for the use of their T.E.M. J.L. C.-D. thanks the School of Engineering and Sciences at Tecnológico de Monterrey through the Research Group on Photonics and Quantum Systems for financial support. A.D.J. was supported by the Northeastern Future Faculty Fellowship. L.M. acknowledges the European Union (grant number ERC-2013-SyG 610256 NANOCOSMOS) and Comunidad de Madrid (S2018/NMT-4367 FotoArt-CM). The groups at CSIC and Tecnológico de Monterrey acknowledge the i-Link+2019 program (ref. LINKB20024 "NANOBIO-ROJA") for financial support. The authors also acknowledge the service from the MiNa Laboratory at IMN funded by Comunidad de Madrid (S2018/NMT-4291 TEC2SPACE), MINECO (CSIC13-4E-1794), and the EU (FEDER, FSE). ; Peer reviewed
Technologically useful and robust graphene-based interfaces for devices require the introduction of highly selective, stable, and covalently bonded functionalities on the graphene surface, whilst essentially retaining the electronic properties of the pristine layer. This work demonstrates that highly controlled, ultrahigh vacuum covalent chemical functionalization of graphene sheets with a thiol-terminated molecule provides a robust and tunable platform for the development of hybrid nanostructures in different environments. We employ this facile strategy to covalently couple two representative systems of broad interest: metal nanoparticles, via S–metal bonds, and thiol-modified DNA aptamers, via disulfide bridges. Both systems, which have been characterized by a multitechnique approach, remain firmly anchored to the graphene surface even after several washing cycles. Atomic force microscopy images demonstrate that the conjugated aptamer retains the functionality required to recognize a target protein. This methodology opens a new route to the integration of high-quality graphene layers into diverse technological platforms, including plasmonics, optoelectronics, or biosensing. With respect to the latter, the viability of a thiol-functionalized chemical vapor deposition graphene-based solution-gated field-effect transistor array was assessed. ; This work was supported by the European Union's Horizon 2020 research and innovation programme under grant agreement No 696656 (Graphene Flagship-core 1) and no 785219 (Graphene Flagship −core 2); UE FP7 ideas: ERC (grant ERC-2013-SYG-610256 Nanocosmos) and Spanish MINECO grants MAT2014-54231-C4-1-P, MAT2014-54231-C4-4-P, MAT2017-85089-C2-1-R, MAT2014-59772-C2-2-P, and BIO2016-79618-R (funded by EU under the FEDER programme), as well as the Nanoavansens program from the Community of Madrid (S2013/MIT-3029). This work has made use of the Spanish ICTS Network MICRONANOFABS partially supported by MINECO and also the ICTS NANBIOSIS, more specifically the Micro-Nano Technology Unit of the CIBER in Bioengineering, Biomaterials & Nanomedicine (CIBER-BBN) at the IMB-CNM. We are grateful to Matthias Muntwiler for his assistance with experiments in the PEARL beamline in the SLS facility. Finally, we acknowledge the TEM and ICP services at the CNB and ICMM institutes, respectively. CSS acknowledges the MINECO for a Juan de la Cierva Incorporación grant (IJCI-2014-19291). M. Marciello is grateful to the Comunidad de Madrid (CM) and European Social Fund (ESF) for supporting her research work through the I+D Collaborative Programme in Biomedicine NIETO-CM (B2017-BMD3731). ; Peer reviewed
8 pags, 4 figs. -- The online version contains supplementary material available at https://doi.org/10.1038/s41467-021-26184-0 ; Development of sustainable processes for hydrocarbons synthesis is a fundamental challenge in chemistry since these are of unquestionable importance for the production of many essential synthetic chemicals, materials and carbon-based fuels. Current industrial processes rely on non-abundant metal catalysts, temperatures of hundreds of Celsius and pressures of tens of bars. We propose an alternative gas phase process under mild reaction conditions using only atomic carbon, molecular hydrogen and an inert carrier gas. We demonstrate that the presence of CH2 and H radicals leads to efficient C-C chain growth, producing micron-length fibres of unbranched alkanes with an average length distribution between C23-C33. Ab-initio calculations uncover a thermodynamically favourable methylene coupling process on the surface of carbonaceous nanoparticles, which is kinematically facilitated by a trap-and-release mechanism of the reactants and nanoparticles that is confirmed by a steady incompressible flow simulation. This work could lead to future alternative sustainable synthetic routes to critical alkane-based chemicals or fuels. ; We thank Jose Criado for the artwork schematics of the system, in figures 4 and S1; Funding: We thank the European Research Council for funding support under Synergy grant ERC-2013-SyG, G.A. 610256 (NANOCOSMOS). Also, we acknowledge partial support from the Spanish MINECO through grants PID2020-113142RB-C21, PID2019106315RB-I00, and PID2019-106315RB-I00, EU ERC CoG HyMAP 648319, and from the regional government through project S2018-NMT-4367 (FotoArt-CM). AM acknowledges to the Spanish Ministry of Science (RYC2018-024561-I), to the Regional Government of Aragon (DGA E13_20R), to the National Natural Science Foundation of China (NFSC-21850410448, NSFC-21835002), and to the The Centre for Highresolution Electron Microscopy (ChEM), supported by SPST of ShanghaiTech University under contract No. EM02161943. S.K. and G.H. acknowledge funding from the Turbulent Superstructures Program of the German National Science Foundation (DFG) ; Peer reviewed
