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Faceted colloidal nanoparticles are currently of immense interest due to their unique electronic, optical, and catalytic properties. However, continuous flow synthesis that enables rapid formation of faceted nanoparticles of single or multi-elemental composition is not trivial. We present a continuous flow synthesis route for the synthesis of uniformly sized Pd nanocubes and PdPt core-shell nanoparticles in a single-phase microfluidic reactor, which enables rapid formation of shaped nanoparticles with a reaction time of 3 min. The PdPt core-shell nanoparticles feature a dendritic, high surface area with the Pt shell covering the Pd core, as verified using high-resolution scanning transmission electron microscopy and energy dispersive X-ray spectroscopy. The Pd nanocubes and PdPt core-shell particles are catalytically tested during NO2 reduction in the presence of H2 in a flow pocket reactor. The Pd nanocubes exhibited low-temperature activity (i.e.

[Image: see text] The ongoing quest to develop single-particle methods for the in situ study of heterogeneous catalysts is driven by the fact that heterogeneity in terms of size, shape, grain structure, and composition is a general feature among nanoparticles in an ensemble. This heterogeneity hampers the generation of a deeper understanding for how these parameters affect catalytic properties. Here we present a solution that in a single benchtop experimental setup combines single-particle plasmonic nanospectroscopy with mass spectrometry for gas phase catalysis under reaction conditions at high temperature. We measure changes in the surface state of polycrystalline platinum model catalyst particles in the 70 nm size range and the corresponding bistable kinetics during the carbon monoxide oxidation reaction via the peak shift of the dark-field scattering spectrum of a closely adjacent plasmonic nanoantenna sensor and compare these changes with the total reaction rate measured by the mass spectrometer from an ensemble of nominally identical particles. We find that the reaction kinetics of simultaneously measured individual Pt model catalysts are dictated by the grain structure and that the superposition of the individual nanoparticle response can account for the significant broadening observed in the corresponding nanoparticle ensemble data. In a wider perspective our work enables in situ plasmonic nanospectroscopy in controlled gas environments at high temperature to investigate the role of the surface state on transition metal catalysts during reaction and of processes such as alloying or surface segregation in situ at the single-nanoparticle level for model catalysts in the few tens to hundreds of nanometer size range.

peer-reviewed The development of cheap and robust heterogeneous catalysts for the Meerwein-Ponndorf-Verley (MPV) reduction is desirable due to the difficulties in product isolation and catalyst recovery associated with the traditional use of homogeneous catalysts for MPV. Herein, we show that microwave heated γ-Al2O3 can be used for the reduction of aldehydes to alcohols. The reaction is efficient and has a broad substrates scope (19 entries). The products can be isolated by simple filtration, and the catalyst can be regenerated. With the use of microwave heating, we can direct the heating to the catalyst rather than to the whole reaction medium. Furthermore, DFT was used to study the reaction mechanism, and we can conclude that a dual-site mechanism is operative where the aldehyde and 2-propoxide are situated on two adjacent Al sites during the reduction. Additionally, volcano plots were used to rationalize the reactivity of Al2O3 in comparison to other metal oxides.

Microparticles can be considered building units for functional systems, but their assembly into larger structures typically involves complex methods. In this work, we show that a large variety of macro-agglomerate clusters (“supra-particles”) can be obtained, by systematically varying the initial particle concentration in an evaporating droplet, spanning more than 3 decades. The key is the use of robust superhydrophobic substrates: in this study we make use of a recently discovered kind of patterned surface with fractal-like microstructures which dramatically reduce the contact of the droplet with the solid substrate. Our results show a clear transition from quasi-2D to 3D clusters as a function of the initial particle concentration, and a clear transition from unstable to stable 3D spheroids as a function of the evaporation rate. The origin of such shape transitions can respectively be found in the dynamic wetting of the fractal-like structure, but also in the enhanced mechanical stability of the particle agglomerate as its particle packing fraction increases.

The scientific community is exploiting the use of silver nanoparticles (AgNPs) in nanomedicine and other AgNPs combination like with biomaterials to reduce microbial contamination. In the field of nanomedicine and biomaterials, AgNPs are used as an antimicrobial agent. One of the most effective approaches for the production of AgNPs is green synthesis. Lysiloma acapulcensis (L. acapulcensis) is a perennial tree used in traditional medicine in Mexico. This tree contains abundant antimicrobial compounds. In the context of antimicrobial activity, the use of L. acapulcensis extracts can reduce silver to AgNPs and enhance its antimicrobial activity. In this work, we demonstrate such antimicrobial activity effect employing green synthesized AgNPs with L. acapulcensis. The FTIR and LC–MS results showed the presence of chemical groups that could act as either (i) reducing agents stabilizing the AgNPs or (ii) antimicrobial capping agents enhancing antimicrobial properties of AgNPs. The synthesized AgNPs with L. acapulcensis were crystalline with a spherical and quasi-spherical shape with diameters from 1.2 to 62 nm with an average size diameter of 5 nm. The disk diffusion method shows the magnitude of the susceptibility over four pathogenic microorganisms of clinical interest. The antimicrobial potency obtained was as follows: E. coli ≥ S. aureus ≥ P. aeruginosa > C. albicans. The results showed that green synthesized (biogenic) AgNPs possess higher antimicrobial potency than chemically produced AgNPs. The obtained results confirm a more significant antimicrobial effect of the biogenic AgNPs maintaining low-cytotoxicity than the AgNPs produced chemically.

In this study, the antifungal activity of AgNPs was tested against C. tropicalis (pathogen fungi) and S. boulardii (probiotic). The effectiveness of the AgNPs was assessed by comparing their antifungal activity with a triazole antifungal drug fluconazole and amphotericin B. The AgNPs have a polygonal-like shape (average size of 35 ± 15 nm) with 1.2% wt. of metallic silver stabilized with 18.8% wt. of polyvinylpyrrolidone (PVP) in 80% wt. of distilled water. The results revealed that 35 μg/mL of fluconazole inhibits 55–60% of both fungal cell growth. As for amphotericin B, 5 μg/mL is sufficient to inhibit more than 95% of both fungal cells. For AgNPs, 25 μg/mL was needed to inhibit 90% of the C. tropicalis cell growth, but remarkably, 50% of the S. boulardii cell population remains viable, which can potentiate cell reproduction. Our results could initiate the development of AgNPs possessing selective specificity against pathogenic fungal species.

The global threat of antimicrobial resistance is driving an urgent need for novel antimicrobial strategies. Functional surfaces are essential to prevent spreading of infection and reduce surface contamination. In this study we have fabricated and characterized multiscale-functional nanotopographies with three levels of functionalization: (1) nanostructure topography in the form of silicon nanowires, (2) covalent chemical modification with (3-aminopropyl)triethoxysilane, and (3) incorporation of chlorhexidine digluconate. Cell viability assays were carried out on two model microorganisms E. coli and S. aureus over these nanotopographic surfaces. Using SEM we have identified two growth modes producing distinctive multicellular structures, i.e. in plane growth for E. coli and out of plane growth for S. aureus. We have also shown that these chemically modified SiNWs arrays are effective in reducing the number of planktonic and surface-attached microorganisms.

Three-layer core-shell-nanoparticle nanoarchitectures exhibit properties not achievable by single-element nanostructures alone and have great potential to enable rationally designed functionality. However, nanofabrication strategies for crafting core-shell-nanoparticle structure arrays on surfaces are widely lacking, despite the potential of basically unlimited material combinations. Here we present a nanofabrication approach that overcomes this limitation. Using it, we produce a library of nanoarchitectures composed of a metal core and an oxide/nitride shell that is decorated with few-nanometer-sized particles with widely different material combinations. This is enabled by resolving a long-standing challenge in this field, namely the ability to grow a shell layer around a nanofabricated core without prior removal of the lithographically patterned mask, and the possibility to subsequently grow smaller metal nanoparticles locally on the shell only in close proximity of the core. Focusing on the application of such nanoarchitectures in plasmonics, we show experimentally and by Finite-Difference Time-Domain (FDTD) simulations that these structures exhibit significant optical absorption enhancement in small metal nanoparticles grown on the few nanometer thin dielectric shell layer around a plasmonic core, and derive design rules to maximize the effect by the tailored combination of the core and shell materials. We predict that these structures will find application in plasmon-mediated catalysis and nanoplasmonic sensing and spectroscopy.

Soft substrates decorated with micropillar arrays are known to be sensitive to deflection due to capillary action. In this work, we demonstrate that micropillared epoxy surfaces are sensitive to single drops of bacterial suspensions. The micropillars can show significant deformations upon evaporation, just as capillary action does in soft substrates. The phenomenon has been studied with five bacterial strains: S. epidermidis, L. sakei, P. aeruginosa, E. coli, and B. subtilis. The results reveal that only droplets containing motile microbes with flagella stimulate micropillar bending, which leads to significant distortions and pillar aggregations forming dimers, trimers, and higher order clusters. Such deformation is manifested in characteristic patterns that are left on the microarrayed surface following evaporation and can be easily identified even by the naked eye. Our findings could lay the ground for the design and fabrication of mechanically responsive substrates, sensitive to specific types of microorganisms.

Photo-responsive antibacterial surfaces combining both on-demand photo-switchable activity and sustained biocidal release were prepared using sequential chemical grafting of nano-objects with different geometries and functions. The multi-layered coating developed incorporates a monolayer of near-infrared active silica-coated gold nanostars (GNS) decorated by silver nanoparticles (AgNP). This modular approach also enables us to unravel static and photo-activated contributions to the overall antibacterial performance of the surfaces, demonstrating a remarkable synergy between these two mechanisms. Complementary microbiological and imaging evaluations on both planktonic and surface-attached bacteria provided new insights on these distinct but cooperative effects.

We evaluate the effect of epoxy surface structuring on the evaporation of water droplets containing Staphylococcus epidermidis (S. epidermidis). During evaporation, droplets with S. epidermidis cells yield to complex wetting patterns such as the zipping-wetting1-3 and the coffee-stain effects. Depending on the height of the microstructure, the wetting fronts propagate circularly or in a stepwise manner, leading to the formation of octagonal or square-shaped deposition patterns.4,5 We observed that the shape of the dried droplets has considerable influence on the local spatial distribution of S. epidermidis deposited between micropillars. These changes are attributed to an unexplored interplay between the zipping-wetting1 and the coffee-stain6 effects in polygonally shaped droplets containing S. epidermidis. Induced capillary flows during evaporation of S. epidermidis are modeled with polystyrene particles. Bacterial viability measurements for S. epidermidis show high viability of planktonic cells, but low biomass deposition on the microstructured surfaces. Our findings provide insights into design criteria for the development of microstructured surfaces on which bacterial propagation could be controlled, limiting the use of biocides.

Hydrogen–air mixtures are highly flammable. Hydrogen sensors are therefore of paramount importance for timely leak detection during handling. However, existing solutions do not meet the stringent performance targets set by stakeholders, while deactivation due to poisoning, for example by carbon monoxide, is a widely unsolved problem. Here we present a plasmonic metal–polymer hybrid nanomaterial concept, where the polymer coating reduces the apparent activation energy for hydrogen transport into and out of the plasmonic nanoparticles, while deactivation resistance is provided via a tailored tandem polymer membrane. In concert with an optimized volume-to-surface ratio of the signal transducer uniquely offered by nanoparticles, this enables subsecond sensor response times. Simultaneously, hydrogen sorption hysteresis is suppressed, sensor limit of detection is enhanced, and sensor operation in demanding chemical environments is enabled, without signs of long-term deactivation. In a wider perspective, our work suggests strategies for next-generation optical gas sensors with functionalities optimized by hybrid material engineering. Sensing hydrogen by the change in plasmonic response upon metal hydride formation is safe, but trace gas poisoning and low sensitivity can occur. Here, a PdAu alloy/polymer sensor is poison resistant and can sense 3 ppm H2 with a response time of 1 s.

The research described in this thesis aimed to explore new concepts in catalysis with the use of a homemade ATR-IR silicon-based microreactor. During this journey we have performed multidisciplinary research at the interface between physics and chemistry. New insights in the fabrication, integration and characterization of ATR-IR microreactors were generated. Excitingly, a goal of this project is achieved with the fabrication of an E-field device which allows the study of catalytic chemical reactions with ATR-IR spectroscopy. This work shows promising potential for the application of microreactor technology to study in sity chemical processes influenced by external electrical fields.

Surfaces that exhibit contact angles close to 180° for both polar and non-polar solvents are rare. Here we report the fabrication of such “omniphobic” surfaces by photolithography. We investigate their stability against a so-called wetting transition during evaporation of millimetric water droplets by systematically varying the shape and surface roughness of the micropillars on the surface. We show that a low edge curvature of the top of the micropillars strongly delays the transition, while it completely disappears when the surface roughness is increased. We compare these experimental findings with existing models that describe the Cassie–Baxter to Wenzel transition and conclude that new models are needed which include the hurdle of an energy barrier for the wetting transition. Our results reveal that by increasing the roughness of the micropillars we do not affect the apparent equilibrium contact angle of the droplets. The dynamic robustness of the surface is, however, dramatically enhanced by an increase of the surface roughness.

Evaporation-driven particle self-assembly can be used to generate three-dimensional microstructures. We present a new method to create these colloidal microstructures, in which we can control the amount of particles and their packing fraction. To this end, we evaporate colloidal dispersion droplets on a special type of superhydrophobic micro-structured surface, on which the droplet re- mains in Cassie-Baxter state during the entire evaporative process. The remainders of the droplet consist of a massive spherical cluster of the microspheres, with diameters ranging from a few tens up to several hundreds of microns. We present scaling arguments to show how the final particle packing fraction of these balls depends on the dynamics of the droplet evaporation., Comment: Manuscript Submitted to Physical Review Letters, 29th February 2012

Co-axial electrospinning was applied for the structuring of non-woven webs of TiO2 nanofibers loaded with Ag, Au, and CuO nanoparticles. The composite layers were tested in an electrochromic half-cell assembly. A clear correlation between the nanoparticle composition and electrochromic effect in the nanofibrous composite is observed: TiO2 loaded with Ag reveals a black-brown color, Au shows a dark-blue color, and CuO shows a dark-green color. For electrochromic applications, the Au/TiO2 layer is the most promising choice, with a color modulation time of 6 s, transmittance modulation of 40%, coloration efficiency of 20 cm2/C, areal capacitance of 300 F/cm2, and cyclic stability of over 1000 cycles in an 18 h period. In this study, an unexplored path for the rational design of TiO2-based electrochromic device is offered with unique color-switching and optical efficiency gained by the fibrous layer. It is also foreseen that co-axial electrospinning can be an alternative nanofabrication technique for smart colored windows.