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Bioorthogonal metallocatalysis has opened up a xenobiotic route to perform nonenzymatic catalytic transformations in living settings. Despite their promising features, most metals are deactivated inside cells by a myriad of reactive biomolecules, including biogenic thiols, thereby limiting the catalytic functioning of these abiotic reagents. Here we report the development of cytocompatible alloyed AuPd nanoparticles with the capacity to elicit bioorthogonal depropargylations with high efficiency in biological media. We also show that the intracellular catalytic performance of these nanoalloys is significantly enhanced by protecting them following two different encapsulation methods. Encapsulation in mesoporous silica nanorods resulted in augmented catalyst reactivity, whereas the use of a biodegradable PLGA matrix increased nanoalloy delivery across the cell membrane. The functional potential of encapsulated AuPd was demonstrated by releasing the potent chemotherapy drug paclitaxel inside cancer cells. Nanoalloy encapsulation provides a novel methodology to develop nanoreactors capable of mediating new-to-life reactions in cells., UK Research & Innovation (UKRI), Engineering & Physical Sciences Research Council (EPSRC) EP/N021134/1, ERC (Advanced Grant CADENCE) ERC-2016-ADG-742684, European Commission European Commission Joint Research Centre H2020-MSCA-IF-2014-658833 H2020-MSCA-IF-2018-841990 H2020-MSCA-IF-2016-749299 H2020-MSCA-IF-2019-895664, Spanish Government RTI2018-099019-A-I00

Ethylene oxide is one of the most important raw materials in the chemical industry, with an annual production close to 35 million metric tons. Despite its importance, to date, no metal has been found that can compete with the original silver bulk material catalyst discovered in 1931. Recently, a few copper and copper–silver based nanostructures have demonstrated remarkable selectivity and activity, especially when coupled with an industrial chlorine promoter. The present work evaluates the mechanistic role of chlorine as an active promoter of the selective oxidation of ethylene to ethylene oxide in the presence of a silver–copper oxide hybrid nanocatalyst (AgCuO). Experimental kinetic studies combined with density functional theory (DFT) calculations provide insight into the influence that Ag/CuO-supported chlorine atoms have over the ethylene epoxidation reaction. Remarkably, the typically described indirect route via the formation of an oxametallacycle (OMC) is also accompanied by a direct route. Furthermore, the presence of chlorine seems to facilitate a more favorable adsorption energy for ethylene oxide (EO) than for acetaldehyde (AA), the main reaction by-product. As a result, complete oxidation of EO can be further prevented in the presence of this AgCuO hybrid heteronanostructure., We acknowledge financial support from the European Research Council ERC-Advanced Grant HECTOR (project number 267626) is gratefully acknowledged. The computations were performed on resources provided by the supercomputer “Caesaraugusta” (node of the Spanish Supercomputer Network) provided by BIFI (Universidad de Zaragoza). The TEM studies were conducted at the Laboratorio de Microscopias Avanzadas, Instituto de Nanociencia de Aragon, Universidad de Zaragoza, Spain. S.H. acknowledges funding from the Agencia Estatal de Investigación and the Ministerio de Ciencia, Innovación y Universidades, of Spain (PID2019-110430G B-C22), and from the EU FEDER Framework 2014-2020 and Consejería de Conocimiento, Investigación y Universidad of the Andalusian Government (FEDER-UPO-1265695).

Cancer represents a major public health issue and a primary cause of death for the mankind and the search for alternative cancer treatments that assist or alleviate the drawbacks of current cancer therapies remains imperative. Nanocatalytic medicine represents a new discipline that aims at exploiting the unique response of heterogeneous catalysts exposed to unconventional conditions such as those encountered in the tumor microenvironment (TME). Photo-triggered cancer therapies using light-activable catalytic materiales can stimulate and activate multiple biological processes and represent a very promising field of study. Herein, we evaluate the use of carbon nanodots with different composition (CNDs) retrieved by laser pyrolysis as potential near-infrared (NIR) photosensitizers able to activate P25 semiconductor nanostructured photocatalysts. We describe the enhanced photocatalytic response towards glucose conversion and reactive oxygen species (ROS) generation upon irradiation with NIR-LEDs when CNDs doped with heteroatoms were tested. The most active photocatalysts were evaluated in the presence of cancer cells and revealed a promising photodynamic effect under NIR irradiation. This work represents one of the scarce examples of a conventional inorganic photocatalyst containing TiO2 that is translated into a biomedical application with a successful outcome.

Platinum nanoparticles (Pt NPs) have a well-established role as a classic heterogeneous catalyst. Also, Pt has traditionally been employed as a component of organometallic drug formulations for chemotherapy. However, a new role in cancer therapy is emerging thanks to its outstanding catalytic properties, enabling novel approaches that are surveyed in this review. Herein, we critically discuss results already obtained and attempt to ascertain future perspectives for Pt NPs as catalysts able to modify key processes taking place in the tumour microenvironment (TME). In addition, we explore relevant parameters affecting the cytotoxicity, biodistribution and clearance of Pt nanosystems. We also analyze pros and cons in terms of biocompatibility and potential synergies that emerge from combining the catalytic capabilities of Pt with other agents such as co-catalysts, external energy sources (near-infrared light, X-ray, electric currents) and conventional therapies., The authors gratefully acknowledge funding from the European Commission (ERC Advanced Grant-742684 CADENCE).

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This article is part of the themed collection: Recent Open Access Articles, A metal–insulator transition is observed in spin–orbit-coupled IrO2 thin films upon reduction of the film thickness. In the epitaxially grown samples, the critical thickness (t ∼ 1.5–2.2 nm) is found to depend on growth orientation (001), (100) or (110). Interestingly from the applied point of view, the insulating behavior is found even in polycrystalline ultrathin films. By analyzing the experimental electrical response with various theoretical models, we find good fits to the Efros–Shklovskii-VRH and the Arrhenius-type behaviors, which suggests an important role of electron correlations in determining the electrical properties of IrO2. Our magnetic measurements also point to a significant role of magnetic order. Altogether, our results would point to a mixed Slater- and Mott-type of insulator., This work was partially supported by the Spanish MINECO projects MAT2014-54425-R (MINECO/FEDER, UE), MAT2017-82970-C2-R (AEI/FEDER, UE), MAT2017-83468-R (AEI/FEDER, UE), MAT2017-87134-C02-01-R (AEI/FEDER, UE) and MAT2017-87134-C02-02-R (AEI/FEDER, UE), the Spanish MICINN project PID2020-115159GB-I00 / AEI / 10.13039/501100011033 and by the Aragon Regional Government (Projects No. E12-20R and E28-20R). E. A-E acknowledges the Spanish MINECO and the European Social Fund for an FPI (Formación de Personal Investigador, 2015) grant. R. B. acknowledges funding support from the European Union's Horizon 2020 research and innovation program under the Marie Skłodowska-Curie grant agreement no. 665919. This research used resources of the APS, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. We acknowledge Diamond Light Source for time on I20-Scanning under Proposal SP-17266. The research leading to this result has been supported by the project CALIPSOplus under the Grant Agreement 730872 from the EU Framework Programme for Research and Innovation Horizon 2020. The authors acknowledge funding from the project Quantox of QuantERA ERA-NET Cofund of Quantum Technologies (Grant Agreement No. 731473) implemented within the European Union's Horizon 2020 Programme.

Heterogeneous catalysis has emerged as a promising alternative for the development of new cancer therapies. In addition, regarding the tumor microenvironment as a reactor with very specific chemical features has provided a new perspective in the search for catalytic nanoarchitectures with specific action against chemical species playing a key role in tumor metabolism. One of these species is glutathione (GSH), whose depletion is the cornerstone of emerging strategies in oncology, since this metabolite plays a pivotal regulatory role as antioxidant agent, dampening the harmful effects of intracellular reactive oxidative species (ROS). Herein, we present copper-iron oxide spinel nanoparticles that exhibit a versatile and selective catalytic response to reduce GSH levels while generating ROS in a cascade reaction. We demonstrate a clear correlation between GSH depletion and apoptotic cell death in tumor cells in the presence of the copper-iron nanocatalyst. Furthermore, we also provide a novel analytical protocol, alternative to state-of-the-art commercial kits, to accurately monitoring the concentration of GSH intracellular levels in both tumor and healthy cells. We observe a selective action of the nanoparticles, with lower toxicity in healthy cell lines, whose intrinsic GSH levels are lower, and intense apoptosis in tumor cells accompanied by a fast reduction of GSH levels., Financial support from the European Research Council (ERC-Advanced Grant CADENCE number 742684) is gratefully acknowledged. The TEM measurements were conducted at the Laboratorio de Microscopias Avanzadas, Instituto de Nanociencia de Aragon, Universidad de Zaragoza, Spain. The synthesis of materials has been performed by the Platform of Production of Biomaterials and Nanoparticles of the NANBIOSIS ICTS, more specifically by the Nanoparticle Synthesis Unit of the CIBER in BioEngineering, Biomaterials & Nanomedicine (CIBER-BBN). J.B-A. acknowledges the Spanish Government for an FPU predoctoral contract. We would also like to thank to the Scientific Services of the Aragon Institute of Health Sciences (IACS), specifically to the Cell culture, Microscopy, and Citometry Services and their specialist and the ICTS ELECMI.

The present work sheds light on a generally overlooked issue in the emerging field of bio-orthogonal catalysis within tumour microenvironments (TMEs): the interplay between homogeneous and heterogeneous catalytic processes. In most cases, previous works dealing with nanoparticle-based catalysis in the TME focus on the effects obtained (e.g. tumour cell death) and attribute the results to heterogeneous processes alone. The specific mechanisms are rarely substantiated and, furthermore, the possibility of a significant contribution of homogeneous processes by leached species – and the complexes that they may form with biomolecules – is neither contemplated nor pursued. Herein, we have designed a bimetallic catalyst nanoparticle containing Cu and Fe species and we have been able to describe the whole picture in a more complex scenario where both homogeneous and heterogeneous processes are coupled and fostered under TME relevant chemical conditions. We investigate the preferential leaching of Cu ions in the presence of a TME overexpressed biomolecule such as glutathione (GSH). We demonstrate that these homogeneous processes initiated by the released by Cu–GSH interactions are in fact responsible for the greater part of the cell death effects found (GSH, a scavenger of reactive oxygen species, is depleted and highly active superoxide anions are generated in the same catalytic cycle). The remaining solid CuFe nanoparticle becomes an active catalyst to supply oxygen from oxygen reduced species, such as superoxide anions (by-product from GSH oxidation) and hydrogen peroxide, another species that is enriched in the TME. This activity is essential to sustain the homogeneous catalytic cycle in the oxygen-deprived tumour microenvironment. The combined heterogeneous–homogeneous mechanisms revealed themselves as highly efficient in selectively killing cancer cells, due to their higher GSH levels compared to healthy cell lines., Financial support from the European Research Council (ERC Advanced Grant CADENCE number 742684) is gratefully acknowledged. The TEM measurements were conducted at the Laboratorio de Microscopias Avanzadas, Instituto de Nanociencia y Materiales de Aragon, Universidad de Zaragoza, Spain. The synthesis of materials has been performed by the Platform of Production of Biomaterials and Nanoparticles of the NANBIOSIS ICTS, more specifically by the Nanoparticle Synthesis Unit of the CIBER in BioEngineering, Biomaterials & Nanomedicine (CIBER-BBN). J. B.-A. acknowledges the Spanish Government for an FPU predoctoral contract. M. E. acknowledges the Diputacion General de Aragon (DGA) for a predoctoral contract. The authors thank Dr Javier Calzada and Dr Silvia Irusta for their help with UPLC and XPS data acquisition. E. P. U. thanks Gobierno de Aragón-FSE (Spain, grupo Aminoácidos y Péptidos, E19_20R) for funding.

The present work sheds light on a generally overlooked issue in the emerging field of bio-orthogonal catalysis within tumor microenvironments (TMEs): the interplay between homogeneous and heterogeneous catalytic processes. In most cases, previous works dealing with nanoparticle-based catalysis in the TME, focus on the effects obtained (e.g. tumor cell death) and attribute the results to heterogeneous processes alone. The specific mechanisms are rarely substantiated and, furthermore, the possibility of a significant contribution of homogeneous processes by leached species –and the complexes that they may form with biomolecules- is neither contemplated nor pursued. Herein, we have designed a bimetallic catalyst nanoparticle containing Cu and Fe species and we have been able to describe the whole picture in a more complex scenario where both homogeneous and heterogeneous processes are coupled and fostered under TME relevant chemical conditions. We investigate the preferential leaching of Cu ions in the presence of a TME overexpressed biomolecule such as glutathione (GSH). We demonstrate that these homogeneous processes initiated by the released by Cu-GSH interactions are in fact responsible for the greater part of the cell death effects found (GSH, a scavenger of reactive oxygen species is depleted and highly active superoxide anions are generated in the same catalytic cycle). The remaining solid CuFe nanoparticle becomes an active catalase-mimicking surrogate able to supply oxygen from oxygen reduced species, such as superoxide anions (by-product from GSH oxidation) and hydrogen peroxide, another species that is enriched in the TME. This enzyme-like activity is essential to sustain the homogeneous catalytic cycle in the oxygen-deprived tumor microenvironment. The combined heterogeneous-homogeneous mechanisms revealed themselves as highly efficient in selectively killing cancer cells, due to their higher GSH levels compared to healthy cell lines.

This article belongs to the Topic Emerging Material-Based Approaches to Chronic and Infectious Diseases., Inhalation therapy offers several advantages in respiratory disease treatment. Azithromycin is a macrolide antibiotic with poor solubility and bioavailability but with a high potential to be used to fight lung infections. The main objective of this study was to generate a new inhalable dry powder azithromycin formulation. To this end, an electrospray was used, yielding a particle size around 2.5 µm, which is considered suitable to achieve total deposition in the respiratory system. The physicochemical properties and morphology of the obtained microparticles were analysed with a battery of characterization techniques. In vitro deposition assays were evaluated after aerosolization of the powder at constant flow rate (100 L/min) and the consideration of the simulation of two different realistic breathing profiles (healthy and chronic obstructive pulmonary disease (COPD) patients) into a next generation impactor (NGI). The formulation was effective in vitro against two types of bacteria, Staphylococcus aureus and Pseudomonas aeruginosa. Finally, the particles were biocompatible, as evidenced by tests on the alveolar cell line (A549) and bronchial cell line (Calu-3)., Financial support from Nanbiosis platform, specifically Unit 9 (U9) and Unit 10 (U10) of the Biomedical Research Networking Center in Bioengineering, Biomaterials and Nanomedicine (CIBER-BBN).

Refers to: Zhi Du, Chun Liu, Hualong Song, Peter Scott, Zhenqi Liu, Jinsong Ren, Xiaogang Qu. Neutrophil-Membrane-Directed Bioorthogonal Synthesis of Inflammation-Targeting Chiral Drugs; Chem, Volume 6, Issue 8, 6 August 2020, Pages 2060-2072., Bioorthogonal nanofactories have emerged in the last decade to provide xenobiotic pathways that generate nonbiological substances in living environments. In this issue of Chem, Qu and co-workers incorporate asymmetric catalytic properties and chemotactic capabilities into novel nanodevices to achieve the stereo- and site-selective synthesis of the active enantiomer of ibuprofen at inflammation sites.

This work describes the synthesis of nitrogen‐doped carbon nanodots (CNDs) synthesized from ethylenediaminetetraacetic acid (EDTA) as a precursor and their application as luminescent agents with a dual‐mode theranostic role as near‐infrared (NIR) triggered imaging and photodynamic therapy agents. Interestingly, these fluorescent CNDs are more rapidly and selectively internalized by tumor cells and exhibit very limited cytotoxicity until remotely activated with a NIR illumination source. These CNDs are excellent candidates for phototheranostic purposes, for example, simultaneous imaging and therapy can be carried out on cancer cells by using their luminescent properties and the in situ generation of reactive oxidative species (ROS) upon excitation in the NIR range. In the presence of CNDs, NIR remote activation induces the in vitro killing of U251MG cells. Through the use of flow imaging cytometry, we have been able to successfully map and quantify the different types of cell deaths induced by the presence of intracellular superoxide anions (.O2−) and hydrogen peroxide (H2O2) ROS generated in situ upon NIR irradiation., The authors acknowledge the European Research Council for funding through an advanced grant research project (HECTOR grant number 267626; CADENCE grant number 742684) and a CIG‐Marie Curie Reintegration Grant (NANOLIGHT REA grant number 294094). M.C.O. acknowledges the Spanish Government for a FPU predoctoral fellowship.

Surface-enhanced Raman scattering (SERS) is a powerful spectroscopic technique for selective detection and quantification of molecules at extremely low concentrations. However, practical SERS applications for gaseous chemicals with small cross section is still in its early stages. We herein report a plasmonic-sorbent thin-film platform with integrated Raman internal standard with outstanding SERS sensing capabilities for chemical warfare agents (CWA) simulants. The thin film is constituted of close-packed core–shell Au@Ag nanorods individually encapsulated within a ZIF-8 framework (Au@Ag@ZIF-8). While the Au@Ag nanoparticles amplify the Raman signal of molecules located near their surface, the ZIF-8 framework plays a key role in the trapping of the dimethyl methylphosphonate (DMMP) or 2-chloroethyl ethyl sulfide (CEES) from the gas phase as well as Raman internal standard. The underlying adsorption mechanism of the molecules within the ZIF-8 framework as well as the interaction between DMMP and Ag surface are investigated by computational simulations. Outstanding SERS sensing capabilities of Au@Ag@ZIF-8 thin films, in terms of response time, quantification limit, reproducibility, and recyclability, are demonstrated for dimethyl methylphosphonate (DMMP) and 2-chloroethyl ethyl sulfide (CEES), selected as CWA simulants of sarin gas and mustard gas, respectively. A limit of detection (LOD) of 0.2 ppbV is reported for DMMP. Additionally, experiments performed with portable Raman equipment detect 2.5 ppmV for DMMP in ambient air and 76 ppbV for CEES in N2, with response times of 21 and 54 s, respectively. This proof of concept opens the door for handheld SERS-based gas sensing at ultralow concentrations in practical applications, such as homeland security, critical infrastructure protection, chemical process monitoring, or personalized medicine., The authors are grateful for financial support from the European Union’s Horizon 2020 research and innovation programme under grant agreement no. 883390 (H2020-SU-SECU-2019 SERSing Project), Spanish State Research Agency (CTQ2016-79419-R, MAT2016-77809-R, PID2019-108660RB-I00 and PID2019-108954RB-I00), Gobierno de Aragón (T57-17R p, Feder 2014-2020 “Construyendo Europa desde Aragón”), Xunta de Galicia (GRC ED431C 2016-048, FEDER 1014-2020), and CIBER-BNN (initiative funded by the VI National R&D&i Plan 2008–2011, Iniciativa Ingenio 2010, Consolider Program, CIBER Actions, and financed by the Instituto de Salud Carlos III with assistance from the European Regional Development Fund).

The most widespread method for the synthesis of 2D-2D heterostructures is the direct growth of one material on top of the other. Alternatively, one can manually stack flakes of different materials. Both methods are limited to one crystal/device at a time and involve interfacing the 2D materials through van der Waals forces, to the point that all these materials are known as van der Waals heterostructures. Synthetic chemistry is the paradigm of atomic-scale control, yet its toolbox remains unexplored for the construction of 2D-2D heterostructures. Here, we describe how to covalently connect 2H-MoS2 flakes to several single-layer graphene field-effect transistors simultaneously, and show that the final electronic properties of the MoS2-graphene heterostructure are dominated by the molecular interface. We use a bifunctional molecule with two chemically orthogonal anchor points, selective for sulphides and carbon-based materials. Our experiments highlight the potential of the chemical approach to build 2D-2D heterostructures beyond van der Waals.

Photocatalytic gas-phase hydrogenation of CO

The development of “fault-tolerant” quantum computers, unaffected by noise and decoherence, is one of the fundamental challenges in quantum technology. One of the approaches currently followed is the realization of “topologically protected” qubits which make use of quantum systems characterized by a degenerate ground state of composite particles, known as “non-Abelian anyons”, able to encode and manipulate quantum information in a non-local manner. In this paper, we discuss the potential of quasi-two-dimensional electron gas (q2DEG) at the interface between band insulating oxides, like LaAlO3 and SrTiO3, as an innovative technological platform for the realization of topological quantum systems. Being characterized by a unique combination of unconventional spin-orbit coupling, magnetism, and 2D-superconductivity, these systems naturally possess most of the fundamental characteristics needed for the realization of a topological superconductor. These properties can be widely tuned by electric field effect acting on the orbital splitting and occupation of the non-degenerate 3dxy and 3dxz,yz bands. The topological state in oxide q2DEGs quasi-one-dimensional nanochannels could be therefore suitably controlled, leading to conceptual new methods for the realization of a topological quantum electronics based on the tuning of the orbital degrees of freedom. Copyright © 2021 EPLA

Perovskite rare-earth titanates are prototypical Mott insulators in which ${\mathrm{Ti}}^{3+}$ ions with $3{d}^{1}$ electronic configuration exhibit ferromagnetic or antiferromagnetic spin order, depending on the rare-earth size. This peculiar magnetic behavior has, however, been barely studied with element-specific probes, either in bulk or in thin films. The recent finding of fingerprints of ferromagnetism in two-dimensional electron gases at oxide interfaces involving rare-earth titanates has produced a surge of the interest in these complex materials. Harnessing the interfacial magnetic states in these heterostructures calls for a better understanding of their insufficiently explored magnetic states in bulk and especially in thin film form. In this paper, we combine high-resolution transmission electron microscopy with x-ray absorption spectroscopy and x-ray magnetic circular dichroism (XMCD) to determine the structural, electronic, and magnetic structure of $\mathrm{GdTi}{\mathrm{O}}_{3}$ in bulk and thin film form. In both cases, we find that the sample surface is strongly overoxidized but a few nm below, Ti is mostly 3+ and shows a large XMCD. We provide evidence for the ferrimagnetic nature of $\mathrm{GdTi}{\mathrm{O}}_{3}$ with antialigned Gd and Ti sublattices and show that, just as in antiferromagnetic $\mathrm{LaTi}{\mathrm{O}}_{3}$ or ferromagnetic $\mathrm{YTi}{\mathrm{O}}_{3}$, Ti carries no orbital moment.

Electrospray was used as a one-step technique to generate inhalable ciprofloxacin-loaded chitosan sub-micron particles with potential use in the treatment of pulmonary infections. The effect of operating parameters was studied and the preparation method optimized. The final sizes of ciprofloxacin-loaded particles were 386.1 ± 248.5 nm and 501.1 ± 276.3 nm for high and low molecular weight chitosan, respectively. The high surface charge of the particles formed, around +45 mV, enhances their mucoadhesive properties. The particles were biocompatible with alveolar cell line (A549), and showed a high antimicrobial activity against two of the most common respiratory pathogens Staphylococcus aureus and Pseudomonas aeruginosa., Financial support from Nanbiosis platform and Biomedical Research Networking Center in Bioengineering, Biomaterials and Nanomedicine (CIBER-BBN). B. Arauzo thanks DGA predoctoral fellowship for personal researcher (2017–2021). Authors thank the “Advanced Microscopy Laboratory” of the “Institute of Nanoscience and Materials of Aragon - University of Zaragoza”, LMA-INMA, for access to their instruments.

Microwave-assisted gas-phase conversion on structured catalysts is emerging as a promising process intensification technology in the field of heterogeneous catalysis. The combination of selective heating and structured catalytic materials induces a temperature difference between the heated catalytic sample and the surrounding void regions to avoid non-selective gas-phase reactions. This operational principle allowed inhibiting thermal cracking in alkane dehydrogenation processes as well as retarding catalyst deactivation by coking in methane dehydroaromatization (MDA) processes. However, its effectiveness has not been reported so far out of the laboratory scale conditions. This work addresses the scaling of the microwave-assisted MDA process from lab scale experiments to a scaled-up configuration capable of stable operation with a 150-fold higher feeding rate. The scaling-up potential and main obstacles to overcome for this technology are critically discussed. In addition, a techno-economic assessment of the MW-MDA process is presented. The catalytic activity was kept for seven consecutive reaction cycles, i.e. 35 h MW-MDA, prior to a progressive decay due to permanent deactivation caused by zeolite dealumination and active metal loss. The scaled set-up operated for up to 295 consecutive hours under unmanned operation conducting 4 -h MDA-regeneration cycles on Mo/ZSM-5@SiC monoliths and resulting in 125-fold increase of converted methane and a 450-fold increase of benzene (0.17 LC6H6/h) in comparison with the laboratory scale tests. Scaled set-up experiments were run using only a 6-fold microwave input power, thus, highlighting the non-linearity between energy consumption and scaling factor for this technology and the importance of microwave cavity design., Financial support from the European Union’s Horizon 2020 Research and Innovation Programme (ADREM project – Grant Agreement No. 680777) is gratefully acknowledged.

Microwave-assisted catalysis is an emerging route for reactor modularization and decarbonization of chemical manufacturing with energy-intensive reactions. While laboratory-scale microwave-assisted heterogeneous catalytic reactors are being developed, hot spots and reactor stability under increased catalyst inventory remain impediments for high throughput processing. Here, we engineer the electromagnetic field-material interactions by introducing a packed monolith configuration, consisting of a microwave absorbing monolith filled with catalytic pellets. Electromagnetic simulations reveal the crucial role of monolith electrical conductivity in diminishing the local power dissipation between the pellets' contact points by absorbing the heat directly. Compared to traditional fixed beds, where hot spots form within minutes of operation, and catalyst-coated monoliths, whose active catalyst loading is limited, the proposed system is stable at all tested temperatures up to 900 °C and has a catalyst packing density near that of fixed beds. We demonstrate its versatility first on the ethane dehydrogenation to produce ethylene over a Ga2O3/Al2O3 catalyst. Repeatable performance over multiple cycles of reaction and regeneration highlights long-term operation. Second, the dry reforming of methane (CH4) is carried out over a commercial Rh/Al2O3 catalyst, achieving a high (~86%) CH4 conversion with an order of magnitude higher H2 throughput (~85 m3/kg/hr) than previous laboratory-scale reactors. By enhancing the catalyst inventory, packed monoliths create a potential avenue for broader adoption of microwave-assisted heterogeneous catalytic reactors., This work was supported by the Department of Energy's Office of Energy Efficiency and Renewable Energy Advanced Manufacturing Office under Award Number DE-EE0007888-8.3. The authors gratefully acknowledge Keiji Adachi from Ibiden USA for providing the SiC monolith sample and Jaynell Keely for assistance with graphics.

Research on proximity effects in superconductor/ferromagnetic hybrids has most often focused on how superconducting properties are affected—and can be controlled—by the effects of the ferromagnet’s exchange or magnetic fringe fields. The opposite, namely the possibility to craft, tailor and stabilize the magnetic texture in a ferromagnet by exploiting superconducting effects, has been more seldom explored. Here we show that the magnetic flux trapped in high-temperature superconducting YBa2Cu3O7-δ microstructures can be used to modify the magnetic reversal of a hard ferromagnet—a cobalt/platinum multilayer with perpendicular magnetic anisotropy—and to imprint unusual magnetic domain distributions in a controlled manner via the magnetic field history. The domain distributions imprinted in the superconducting state remain stable, in absence of an external magnetic field, even after increasing the temperature well above the superconducting critical temperature, at variance to what has been observed for soft ferromagnets with in-plane magnetic anisotropy. This opens the possibility of having non-trivial magnetic configuration textures at room temperature after being tailored below the superconducting transition temperature. The observed effects are well explained by micromagnetic simulations that demonstrate the role played by the magnetic field from the superconductor on the nucleation, propagation, and stabilization of magnetic domains.

Photocatalytic gas-phase hydrogenation of CO2 into alkanes was achieved over TiO2-supported Ni nanoparticles under LED irradiation at 365 nm, 460 nm and white light. The photocatalysts were prepared using photo-assisted deposition of Ni salts under LED irradiation at 365 nm onto TiO2 P25 nanoparticles in methanol as a hole scavenger. This procedure yielded 2 nm Ni particles decorating the surface of TiO2 with a nickel mass content of about 2%. Before the photocatalytic runs, Ni/TiO2 was submitted to thermal reduction at 400 °C in a 10% H2 atmosphere which induced O-defective TiO2−x substrates. The formation of oxygen vacancies, Ti3+ centers and metallic Ni sites upon photocatalytic CO2 hydrogenation was confirmed by operando EPR analysis. In situ XPS under reaction conditions suggested a strong metal–support interaction and the co-existence of zero and divalent Ni states. These photoactive species enhanced the photo-assisted reduction of CO2 below 300 °C to yield CO, CH4 and C2H6 as final products., Financial support from the Spanish Ministry of Science and Universities through the CTQ2016-77144-R research project is gratefully acknowledged. We thank Dr Irusta for her assistance in preliminary XPS measurements. The synthesis of materials was performed by the Platform of Production of Biomaterials and Nanoparticles of the NANBIOSIS ICTS, more specifically by the Nanoparticle Synthesis Unit of the CIBER in Bioengineering, Biomaterials & Nanomedicine (CIBER-BBN). The TEM studies were conducted at the Laboratorio de Microscopias Avanzadas, Instituto de Nanociencia de Aragon, Universidad de Zaragoza, Spain. The EPR characterization was performed at the Centre for Catalysis and Sustainable Chemistry, Technical University of Denmark, supported by the Department of Chemistry for a PhD project to D. N. and by the Carlsberg Foundation for instrumentation.

The use of exosomes as selective delivery vehicles of therapeutic agents, such as drugs or hyperthermia-capable nanoparticles, is being intensely investigated on account of their preferential tropism toward their parental cells. However, the methods used to introduce a therapeutic load inside exosomes often involve disruption of their membrane, which may jeopardize their targeting capabilities, attributed to their surface integrins. On the other hand, in recent years bio-orthogonal catalysis has emerged as a new tool with a myriad of potential applications in medicine. These bio-orthogonal processes, often based on Pd-catalyzed chemistry, would benefit from systems capable of delivering the catalyst to target cells. It is therefore highly attractive to combine the targeting capabilities of exosomes and the bio-orthogonal potential of Pd nanoparticles to create new therapeutic vectors. In this protocol, we provide detailed information on an efficient procedure to achieve a high load of catalytically active Pd nanosheets inside exosomes, without disrupting their membranes. The protocol involves a multistage process in which exosomes are first harvested, subjected to impregnation with a Pd salt precursor followed by a mild reduction process using gas-phase CO, which acts as both a reducing and growth-directing agent to produce the desired nanosheets. The technology is scalable, and the protocol can be conducted by any researcher having basic biology and chemistry skills in ~3 d., We gratefully acknowledge financial support from the ERC Advanced Grant CADENCE (grant no. ERC-2016-ADG-742684) and the EPSRC (Healthcare Technology Challenge award no. EP/N021134/1). M.S.-A. thanks the Spanish Government for an FPU PhD research fellowship. B.R.-R. thanks the EC (grant no. H2020-MSCA-IF-2014–658833). V.S. acknowledges the financial support of Ministerio de Ciencia, Innovación y Universidades, Programa Retos Investigación, Proyecto REF: RTI2018-099019-A-I00. M.A. acknowledges the financial support of the ERC Consolidator Grant programme (grant no. ERC-2013-CoG-614715). P.M.-D. also thanks Instituto de Salud Carlos III (PI19/01007). We also thank CIBER-BBN, an initiative funded by the VI National R&D&i Plan 2008–2011 financed by the Instituto de Salud Carlos III and by Fondo Europeo de Desarrollo Regional (Feder) ‘Una manera de hacer Europa’, with the assistance of the European Regional Development Fund. This study is also partially funded by the Aragon Government (T57_17R p) cofounded by Feder 2014–2020 ‘Building Europe from Aragon’.

This article is part of the themed collection: Editor’s Choice: Single-atom and nanocluster catalysis., One of the hallmarks of microwave irradiation is its selective heating mechanism. In the past 30 years, alternative designs of chemical reactors have been introduced, where the microwave (MW) absorber occupies a limited reactor volume but the surrounding environment is MW transparent. This advantage results in a different heating profile or even the possibility to quickly cool down the system. Simultaneous cooling–microwave heating has been largely adopted for organic chemical transformations. However, to the best of our knowledge there are no reports of its application in the field of nanocluster synthesis. In this work, we propose an innovative one-pot procedure for the synthesis of Cu nanoclusters. The cluster nucleation was selectively MW-activated inside the pores of a highly ordered mesoporous substrate. Once the nucleation event occurred, the crystallization reaction was instantaneously quenched, precluding the growth events and favoring the production of Cu clusters with a homogenous size distribution. Herein, we demonstrated that Cu nanoclusters could be successfully adopted for radical cascade annulations of N-alkoxybenzamides, resulting in various tricyclic and tetracyclic isoquinolones, which are widely present in lots of natural products and bioactive compounds. Compared to reported homogeneous methods, supported Cu nanoclusters provide a better platform for a green, sustainable and efficient heterogeneous approach for the synthesis of tricyclic and tetracyclic isoquinolones, avoiding a variety of toxic waste/byproducts and metal contamination in the final products., Liangliang Song appreciates the Postdoctoral Mandate (PDM) of KU Leuven. This project has received funding from the European Union's Horizon 2020 Research and Innovation Programme under the Marie Skłodowska-Curie grant agreement no. 721290. This publication reflects only the author's view, exempting the Community from any liability. Project website: http://cosmic-etn.eu/. LVM thanks the Hercules Foundation for supporting the purchase of the diffractometer through project AKUL/09/0035. We acknowledge the FWO [Fund for Scientific Research-Flanders (Belgium)] and the Research Council of KU Leuven (BOF) for financial support. We acknowledge the support of RUDN University Program 5-100. The microscopy works have been conducted in the Laboratorio de Microscopias Avanzadas at Instituto de Nanociencia de Aragón-Universidad de Zaragoza. Authors acknowledge the LMA-INA for offering access to their instruments and expertise.

Background Exosomes are endocytic-extracellular vesicles with a diameter around 100 nm that play an essential role on the communication between cells. In fact, they have been proposed as candidates for the diagnosis and the monitoring of different pathologies (such as Parkinson, Alzheimer, diabetes, cardiac damage, infection diseases or cancer). Results In this study, magnetic nanoparticles (Fe3O4NPs) were successfully functionalized with an exosome-binding antibody (anti-CD9) to mediate the magnetic capture in a microdevice. This was carried out under flow in a 1.6 mm (outer diameter) microchannel whose wall was in contact with a set of NdFeB permanent magnets, giving a high magnetic field across the channel diameter that allowed exosome separation with a high yield. To show the usefulness of the method, the direct capture of exosomes from whole blood of patients with pancreatic cancer (PC) was performed, as a proof of concept. The captured exosomes were then subjected to analysis of CA19-9, a protein often used to monitor PC patients. Conclusions Here, we describe a new microfluidic device and the procedure for the isolation of exosomes from whole blood, without any need of previous isolation steps, thereby facilitating translation to the clinic. The results show that, for the cases analyzed, the evaluation of CA19-9 in exosomes was highly sensitive, compared to serum samples.

The development of SERS substrates for chemical detection of specific analytes requires appropriate selection of plasmonic metal and the surface where it is deposited. Here we deposited Ag nanoplates on three substrates: i) conventional SiO2/Si wafer, ii) stainless steel mesh and iii) graphite foils. The SERS enhancement of the signal was studied for Rhodamine 6 G (R6 G) as common liquid phase probe molecule. We conducted a comprehensive study with λ = 532, 633 and 785 nm on all the substrates. The best substrate was investigated, at the optimum laser 785 nm, for gas phase detection of dimethyl methyl phosphonate (DMMP), simulant of the G-series nerve agents, at a concentration of 2.5 ppmV (14 mg/m3). The spectral fingerprint was clearly observed; with variations on the relative intensities of SERS Raman bands compared to bulk DMMP in liquid phase reflects the DMMP-Ag interactions. These interactions were simulated by Density Functional Theory (DFT) calculations and the simulated spectra matched with the experimental one. Finally, we were detected the characteristics DMMP fingerprint with hand-held portable equipment. These results open the way for the application of SERS technique on real scenarios where robust, light-weight, miniaturized and simple to use and cost-effective tools are required by first responders., Authors are grateful for financial support from the European Union’s Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grant agreement Nr. 823895; MICINN, Spain (CTQ2013-49068-C2-1-R and CTQ2016-79419-R); Gobierno de Aragón (T57-17R p), Feder 2014-2020 “Construyendo Europa desde Aragón”) and CIBER-BBN (initiative funded by the VI National R&D&i Plan 2008–2011, Iniciativa Ingenio 2010, Consolider Program, CIBER Actions and financed by the Instituto de Salud Carlos III with assistance from the European Regional Development Fund), Spain.

The Josephson effect results from the coupling of two superconductors across a spacer such as an insulator, a normal metal or a ferromagnet to yield a phase coherent quantum state. However, in junctions with ferromagnetic spacers, very long-range Josephson effects have remained elusive. Here we demonstrate extremely long-range (micrometric) high-temperature (tens of kelvins) Josephson coupling across the half-metallic manganite La0.7Sr0.3MnO3 combined with the superconducting cuprate YBa2Cu3O7. These planar junctions, in addition to large critical currents, display the hallmarks of Josephson physics, such as critical current oscillations driven by magnetic flux quantization and quantum phase locking effects under microwave excitation (Shapiro steps). The latter display an anomalous doubling of the Josephson frequency predicted by several theories. In addition to its fundamental interest, the marriage between high-temperature, dissipationless quantum coherent transport and full spin polarization brings opportunities for the practical realization of superconducting spintronics, and opens new perspectives for quantum computing. Josephson coupling over micrometres and at tens of kelvins is demonstrated across the half-metallic manganite La0.7Sr0.3MnO3 combined with the superconducting cuprate YBa2Cu3O7.

The promising potential of bioorthogonal catalysis in biomedicine is inspiring incremental efforts to design strategies that regulate drug activity in living systems. To achieve this, it is not only essential to develop customized inactive prodrugs and biocompatible metal catalysts but also the right physical environment for them to interact and enable drug production under spatial and/or temporal control. Toward this goal, here, we report the first inactive precursor of the potent broad-spectrum anticancer drug paclitaxel (a.k.a. Taxol) that is stable in cell culture and labile to Pd catalysts. This new prodrug is effectively uncaged in cancer cell culture by Pd nanosheets captured within agarose and alginate hydrogels, providing a biodegradable catalytic framework to achieve controlled release of one of the most important chemotherapy drugs in medical practice. The compatibility of bioorthogonal catalysis and physical hydrogels opens up new opportunities to administer and modulate the mobility of transition metal catalysts in living environs., R.C.-M. and L.A.C. thank Junta de Andalucıá (Spain) for funding project P12-FQM-790. L.A.C. thanks the Ministerio de Ciencia, Innovación y Universidades, for a Salvador de Madariaga visiting professor fellowship (PRX18/00017) and the Agencia Estatal de Investigación (Ministerio de Economia y Competitividad) and the European Regional Development Fund for cofunding project FIS2017-85954-R.

Microwave (MW) heating has been applied to increase the selectivity to propylene in the oxidative dehydrogenation (ODH) of propane. The preferential heating of the solid monolith (made of SiC, a good microwave susceptor), allows working with a lower gas phase temperature, reducing the formation of undesired by-products in the gas phase via homogeneous reactions. Conversion levels of ~ 21% and selectivity to propylene up to 70% have been achieved with MW-heated straight channel monolithic reactors coated with a VMgO catalyst. These competitive values contrast with the more limited performance delivered by the same catalytic system when it is subjected to conventional heating in a fixed-bed reactor configuration, thereby corroborating the advantage of working under a significant gas–solid temperature gap to minimize the extent of homogeneous reactions., Financial support from the European Research Council (ERC Advanced Grant HECTOR-267626) and the Regional Government of Aragon (DGA) is gratefully acknowledged. The CIBER-BBN (initiative funded by the VI National R&D&i Plan 2008-2011, Iniciativa Ingenio 2010, Consolider Program, CIBER Actions and financed by the Instituto de Salud Carlos III with assistance from the European Regional Development Fund) is gratefully acknowledged.

Special Issue: Chemical Functionalization of 2D Materials. This article also appears in: Chemical Functionalization of 2D Materials Society Volumes: Czech Republic., Most air‐stable 2D materials are relatively inert, which makes their chemical modification difficult. In particular, in the case of MoS2, the semiconducting 2 H‐MoS2 is much less reactive than its metallic counterpart, 1T‐MoS2. As a consequence, there are hardly any reliable methods for the covalent modification of 2 H‐MoS2. An ideal method for the chemical functionalization of such materials should be both mild, not requiring the introduction of a large number of defects, and versatile, allowing for the decoration with as many different functional groups as possible. Herein, a comprehensive study on the covalent functionalization of 2 H‐MoS2 with maleimides is presented. The use of a base (Et3N) leads to the in situ formation of a succinimide polymer layer, covalently connected to MoS2. In contrast, in the absence of base, functionalization stops at the molecular level. Moreover, the functionalization protocol is mild (occurs at room temperature), fast (nearly complete in 1 h), and very flexible (11 different solvents and 10 different maleimides tested). In practical terms, the procedures described here allow for the chemist to manipulate 2 H‐MoS2 in a very flexible way, decorating it with polymers or molecules, and with a wide range of functional groups for subsequent modification. Conceptually, the spurious formation of an organic polymer might be general to other methods of functionalization of 2D materials, where a large excess of molecular reagents is typically used., The European Research Council (ERC‐StG‐307609; ERC‐PoC‐ ERC‐AdG‐742684), MINECO (CTQ2017‐86060‐P and CTQ2016‐79419‐R) the Comunidad de Madrid (MAD2D‐CM S2013/ MIT‐3007) are gratefully acknowledged. IMDEA Nanociencia acknowledges support from the “Severo Ochoa” Programme for Centres of Excellence in R&D (MINECO, Grant SEV‐ 2016‐0686). Part of the work was carried out with the support of CEITEC Nano Research Infrastructure (ID LM2015041, MEYS CR, 2016–2019), CEITEC Brno University of Technology.

Natural gas is currently envisioned as a potential energy and hydrocarbon feedstock in the forthcoming years. To overcome the detrimental flaring of this natural gas and the partial release of its major component, methane, novel and more effective strategies are required. These include the development of new, efficient and seemingly stable catalysts able to rapidly convert methane into valuable feedstocks. We show a novel synthesis method of Mo/ZSM-5 based on a solvothermal synthesis under supercritical conditions and reducing atmosphere (SC-STS-E) to improve metal dispersion and enhance catalyst stability and durability during the methane dehydroaromatization (MDA) reaction. In contrast to the conventional impregnation method, SC-STS-E provides a super-high atom-like metal dispersion at the zeolite pores resulting in the most stable Mo/ZSM-5 catalyst for MDA with the highest long-term hydrocarbon yield (xCH4 = 11.6% and yC2+ = 8.9%, after 15 h on stream) among the catalysts reported in literature for this reaction., Financial support from the European Union’s Horizon 2020 Research and Innovation Programme (ADREM project – Grant Agreement No. 680777) is gratefully acknowledged.

Metal nanoclusters are becoming exciting candidates as highly efficient catalysts for heterogeneous processes in view of their extraordinary surface to volume ratio and the high concentration of un...

The term tunnel electroresistance (TER) denotes a fast, non-volatile, reversible resistance switching triggered by voltage pulses in ferroelectric tunnel junctions. It is explained by subtle mechanisms connected to the voltage-induced reversal of the ferroelectric polarization. Here we demonstrate that effects functionally indistinguishable from the TER can be produced in a simpler junction scheme—a direct contact between a metal and an oxide—through a different mechanism: a reversible redox reaction that modifies the oxide’s ground-state. This is shown in junctions based on a cuprate superconductor, whose ground-state is sensitive to the oxygen stoichiometry and can be tracked in operando via changes in the conductance spectra. Furthermore, we find that electrochemistry is the governing mechanism even if a ferroelectric is placed between the metal and the oxide. Finally, we extend the concept of electroresistance to the tunnelling of superconducting quasiparticles, for which the switching effects are much stronger than for normal electrons. Besides providing crucial understanding, our results provide a basis for non-volatile Josephson memory devices., The non-volatile switching of tunnel electroresistance in ferroelectric junctions provides the basis for memory and neuromorphic computing devices. Rouco et al. show tunnel electroresistance in superconductor-based junctions that arises from a redox rather than ferroelectric mechanism and is enhanced by superconductivity.

Despite the continuous developments in the synthesis of noble metal nanoparticles, the uniformity of particle size distribution still represents a critical aspect. A fast and homogeneous nucleation is a key requirement to achieve a monodisperse particle size distribution and in this scenario, the application of alternative energy sources may constitute a winning strategy for the development of highly active nanocatalysts with unique properties. Here we present several approaches to control the synthesis of Ag nanoparticles stabilized by an anionic template, and the results evidence the advantages of adopting unconventional heating techniques such as microwave heating. The fast and selective electromagnetic heating strongly reduced the nucleation and growth times, impacting on the homogeneity of the resulting particle size distribution. In this work, we have carried out the microwave-assisted synthesis of Ag nanoparticles and the resulting nanoparticles were compared to those synthesized under conventional heating using an oil bath, showing that the differences in temperature profile and heating rates between the two synthesis pathways had a clear effect on the size distribution of the resulting nanoparticles as well as on their stability under long term storage. Finally, the synthesized ultra-small Ag nanoparticles were deposited on a mesoporous substrate, reducing undesired Ostwald ripening and facilitating their reusability. This nanocatalyst was adopted for the abatement of 4-nitrophenol, a well-known carcinogenic pollutant with adverse effects on human beings and aquatic life. The catalytic results confirm the high activity of the catalyst thanks to the high dispersion achieved afforded by ultra-small Ag nanoparticles and the accessibility provided by the wide SBA-15 mesoporous channels., This project has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement No 721290.

The combination of 2D materials opens a wide range of possibilities to create new-generation structures with multiple applications. Covalently cross-linked approaches are a ground-breaking strategy for the formation of homo or heterostructures made by design. However, the covalent assembly of transition metal dichalcogenides flakes is relatively underexplored. Here, a simple covalent cross-linking method to build 2H-MoS2 -MoS2 homostructures is described, using commercially available bismaleimides. These assemblies are mainly connected vertically, basal plane to basal plane, creating specific molecular sized spaces between MoS2 sheets. Therefore, this straightforward approach gives access to the controlled connection of sulfide-based 2D materials.

The increasing presence of nanotechnology on the market entails a growing probability of finding ENMs in the environment. Nanoparticles aerosols are a yet unknown risk for human and environmental exposure that may normally occur at any point during the nanomaterial lifecycle. There is a research gap in standardized methods to assess the exposure to airborne nanoparticles in different environments. The controllable generation of nanoparticle aerosols has long been a challenging objective for researchers and industries dealing with airborne nanoparticles. In this work, a versatile system to generate nanoparticulate aerosols has been designed. The system allows the production of both i) instantaneous nanoparticle clouds and ii) continuous nanoparticle streams with quasi-stable values of particle concentration and size distribution. This novel device uses a compressed-air pressure pulse to disperse the target material into either the testing environment (instantaneous cloud formation) or a secondary chamber, from which a continuous aerosol stream can be drawn, with a tunable nanoparticle concentration. The system is robust, highly versatile and easy to operate, enabling reproducible generation of aerosols from a variety of sources. The system has been verified with four dry nanomaterials: TiO2, ZnO, CuO and CNT bundles.

The reproducibility of key nanomaterial features is essential in nanomedicine applications where small changes of physical characteristics often lead to a very different behavior. In this regard, continuous microreactors are often advocated as a means to achieve highly precise synthesis of nanomaterials. However, when the synthesis must take place at high temperatures the use of these devices becomes restricted in terms of materials and practical problems (e.g. plugging of microchannels). Here we present the continuous synthesis of ultrasmall superparamagnetic iron oxide nanoparticles (SPIONs) through a polyol-based process at high temperatures (>200 °C). The microfluidic reactor designed allows SPION production at residence times under 1 min, was able to work continuously for 8 h without channel blockage and reached high production yields by coupling microreactors using stacked plates. The effect of operating conditions was optimized to produce homogeneous particles with a narrow particle size distribution. In summary, the microreactor developed in this work enables easy-to scale up, reproducible continuous production of SPIONs.

The present work investigates the role of two types of carbon nanodots (CNDs) as novel sensitizers of TiO2 to create a visible-light driven photo-catalyst that is not only efficient for solar-driven pollution abatement, but also inexpensive, durable and environmentally-friendly. Two widely available green organic precursors, the Argentinean herb Mate and the Stevia plant have been selected as the carbogenic source to thermally induce the formation of different types of CNDs with different levels of N and P doping and tunable photoluminescence response in the UV–vis-near infrared (NIR) ranges. These CNDs have been successfully assembled with TiO2 to form heterogeneous photocatalysts that are highly active in the visible-light and NIR- driven photodegradation of 2,4-dichlorophenol (2,4-DCP), a persistent chlorinated organic compound present in numerous pesticide formulations.

Infection of orthopedic devices is a major complication in the postsurgical period generating important health issues and economic consequences. Prevention strategies could be based on local release of antibiotics from the orthopedic device itself to avoid adhesion and growth of bacteria. The purpose of this work is to demonstrate the efficiency to prevent these infections by a cefazolin-eluting, perforated stainless steel implant in an in vivo ovine model. The device was placed in the tibia of sheep, one group receiving cefazolin-loaded implants whereas the control group received empty implants. All implants were experimentally infected by direct inoculation of Staphylococcus aureus ATCC 6538. In vitro cytotoxicological studies were also performed to check the effect of antibiotic on cell viability, integrity, and cycle. Results showed that sheep receiving cefazolin-loaded devices were able to avoid implant-associated infections, with normal tissue healing process. The antibiotic release followed a local concentric pattern as demonstrated by high-performance liquid chromatography detection in tissues. The in vitro results indicate the lack of relevant cytotoxic effects for the maximum antibiotic concentration released by the device. These results demonstrate the efficiency and safety of cefazolin-eluting implants in an ovine model to prevent early postsurgical infections of orthopedic devices. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 106B: 1976-1986, 2018.