The role of pH, metal ions and their hydroxides in charge reversal of protein-coated nanoparticles

In this study, we investigated charge inversion of protein-coated Au nanoparticles caused by the addition of metal ions. The addition of hydrolyzable metal ions (Lewis acids) can induce drastic pH changes and depending on this pH, the metal ions (e.g. M3+) are readily converted into the hydrolyzed species (MOH2+, M(OH)2+) or even into hydroxides (M(OH)3). Adsorbed metal hydroxides were identified to cause the charge inversion of the NPs by using a combination of cryo-TEM, EFTEM and ζ-potential measurements

Formation mechanism for stable hybrid clusters of proteins and nanoparticles

Citrate-stabilized gold nanoparticles (AuNP) agglomerate in the presence of hemoglobin (Hb) at acidic pH. The extent of agglomeration strongly depends on the concentration ratio [Hb]/[AuNP]. Negligible agglomeration occurs at very low and very high [Hb]/[AuNP]. Full agglomeration and precipitation occur at [Hb]/[AuNP] corresponding to an Hb monolayer on the AuNP. Ratios above and below this value lead to the formation of an unexpected phase: stable, microscopic AuNP–Hb agglomerates. We investigated the kinetics of agglomeration with dynamic light scattering and the adsorption kinetics of Hb on planar gold with surface-acoustic wave-phase measurements. Comparing agglomeration and adsorption kinetics leads to an explanation of the complex behavior of this nanoparticle–protein mixture. Agglomeration is initiated either when Hb bridges AuNP or when the electrostatic repulsion between AuNP is neutralized by Hb. It is terminated when Hb has been depleted or when Hb forms multilayers on the agglomerates that stabilize microscopic clusters indefinitely

Mineralization of wood by calcium carbonate insertion for improved flame retardancy

Wood can be considered as a highly porous, three-dimensional organic scaffold. It can be mineralized to create hierarchically structured organic-inorganic hybrid materials with novel properties. In the present paper, the precipitation of CaCO3 mineral in Norway spruce and European beech wood has been studied by alternating impregnation with aqueous and alcoholic electrolyte solutions. Microstructural imaging by SEM and confocal Raman microscopy shows the distribution of calcite and vaterite as two CaCO3 polymorphs, which are deposited deep inside the cellular structure of the wood. The confined microenvironment of the wood cell wall seems to favor a formation of vaterite, as visible by XRD and Raman spectroscopy. In view of a practical application, the mineralization of wood opens up ways for sustainable wood-based hybrid materials with a significantly improved fire resistance, as proven via pyrolysis combustion flow calorimetry and cone calorimetry tests. Beyond that, this versatile solute-exchange approach provides an opportunity for the incorporation of a broad range of different mineral phases into wood for novel material property combinations

Enzymatic Catalysis at Nanoscale: Enzyme-Coated Nanoparticles as Colloidal Biocatalysts for Polymerization Reactions

Enzyme-catalyzed controlled radical polymerization represents a powerful approach for the polymerization of a wide variety of water-soluble monomers. However, in such an enzyme-based polymerization system, the macromolecular catalyst (i.e., enzyme) has to be separated from the polymer product. Here, we present a compelling approach for the separation of the two macromolecular species, by taking the catalyst out of the molecular domain and locating it in the colloidal domain, ensuring quasi-homogeneous catalysis as well as easy separation of precious biocatalysts. We report on gold nanoparticles coated with horseradish peroxidase that can catalyze the polymerization of various monomers (e.g., N-isopropylacrylamide), yielding thermoresponsive polymers. Strikingly, these biocatalyst-coated nanoparticles can be recovered completely and reused in more than three independent polymerization cycles, without significant loss of their catalytic activity

Nanoscopic interactions of colloidal particles can suppress millimetre drop splashing

The splashing of liquid drops onto a solid surface is important for a wide range of applications, including combustion and spray coating. As the drop hits the solid surface, the liquid is ejected into a thin horizontal sheet expanding radially over the substrate. Above a critical impact velocity, the liquid sheet is forced to separate from the solid surface by the ambient air, and breaks up into smaller droplets. Despite many applications involving complex fluids, their effects on splashing remain mostly unexplored. Here we show that the splashing of a nanoparticle dispersion can be suppressed at higher impact velocities by the interactions of the nanoparticles with the solid surface. Although the dispersion drop first shows the classical transition from deposition to splashing when increasing the impact velocity, no splashing is observed above a second higher critical impact velocity. This result goes against the commonly accepted understanding of splashing, that a higher impact velocity should lead to even more pronounced splashing. Our findings open new possibilities to deposit large amount of complex liquids at high speeds

Mineralization of wood by calcium carbonate insertion for improved flame retardancy

ISSN:0018-3830ISSN:1437-434

The role of pH, metal ions and their hydroxides in charge reversal of protein-coated nanoparticles

In this study, we investigated charge inversion of protein-coated Au nanoparticles caused by the addition of metal ions. The addition of hydrolyzable metal ions (Lewis acids) can induce drastic pH changes and depending on this pH, the metal ions (e.g. M3+) are readily converted into the hydrolyzed species (MOH2+, M(OH)2+) or even into hydroxides (M(OH)3). Adsorbed metal hydroxides were identified to cause the charge inversion of the NPs by using a combination of cryo-TEM, EFTEM and ζ-potential measurements.ISSN:1463-9084ISSN:1463-907

Mineralization of wood by calcium carbonate insertion for improved flame retardancy

Wood can be considered as a highly porous, three-dimensional organic scaffold. It can be mineralized to create hierarchically structured organic-inorganic hybrid materials with novel properties. In the present paper, the precipitation of CaCO3 mineral in Norway spruce and European beech wood has been studied by alternating impregnation with aqueous and alcoholic electrolyte solutions. Microstructural imaging by SEM and confocal Raman microscopy shows the distribution of calcite and vaterite as two CaCO3 polymorphs, which are deposited deep inside the cellular structure of the wood. The confined microenvironment of the wood cell wall seems to favor a formation of vaterite, as visible by XRD and Raman spectroscopy. In view of a practical application, the mineralization of wood opens up ways for sustainable wood-based hybrid materials with a significantly improved fire resistance, as proven via pyrolysis combustion flow calorimetry and cone calorimetry tests. Beyond that, this versatile solute-exchange approach provides an opportunity for the incorporation of a broad range of different mineral phases into wood for novel material property combinations.ISSN:0018-3830ISSN:1437-434

Colloidally Stable and Surfactant-Free Protein-Coated Gold Nanorods in Biological Media

In this work, we investigate the ligand exchange of cetyltrimethylammonium bromide (CTAB) with bovine serum albumin for gold nanorods. We demonstrate by surface-enhanced Raman scattering measurements that CTAB, which is used as a shape-directing agent in the particle synthesis, is completely removed from solution and particle surface. Thus, the protein-coated nanorods are suitable for bioapplications, where cationic surfactants must be avoided. At the same time, the colloidal stability of the system is significantly increased, as evidenced by spectroscopic investigation of the particle longitudinal surface plasmon resonance, which is sensitive to aggregation. Particles are stable at very high concentrations (cAu 20 mg/mL) in biological media such as phosphate buffer saline or Dulbecco’s Modified Eagle’s Medium and over a large pH range (2–12). Particles can even be freeze-dried (lyophilized) and redispersed. The protocol was applied to gold nanoparticles with a large range of aspect ratios and sizes with main absorption frequencies covering the visible and the near-IR spectral range from 600 to 1100 nm. Thus, these colloidally stable and surfactant-free protein-coated nanoparticles are of great interest for various plasmonic and biomedical applications.ISSN:1944-8244ISSN:1944-825

Propriétés acoustiques de Sonowood, bois densifié destiné à remplacer les bois tropicaux menacés pour la fabrication d'instruments de musique

Sonowood est un matériau en bois européen fabriqué selon un procédé novateur, qui a été développé en particulier pour la fabrication d'instruments de musique en remplacement de l'ébène et d'autres bois tropicaux denses, pour lesquels des restrictions de commerce de plus en plus importantes sont imposées. Le procédé développé par l'entreprise Swiss Wood Solutions, une start-up de l'ETH Zurich et de l'EMPA Dübendorf, consiste à comprimer le bois (résineux et feuillus) jusqu’à une densité de 1200 - 1400 kg/m3, ce qui correspond à la densité et à la dureté des bois tropicaux denses. Ce nouveau matériau permet de combiner la haute dureté et densité des bois exotiques aux propriétés des bois européens. Ainsi, les bois résineux comme l'épicéa présentent des vitesses de propagation du son très élevées dans le sens des fibres, qui sont conservées même après la modification. Cela peut être utilisé par exemple dans les touches et les cordiers des instruments à cordes afin d'optimiser le son de l'ensemble de l'instrument. Nous présenterons différentes propriétés de Sonowood (vitesse du son, module dyn. E, amortissement, etc.) qui influencent le son, en fonction de l'essence de bois et également en comparaison avec d'autres bois utilisés dans la fabrication d'instruments de musique