Tobias Kraus

Nanoparticle printing with single-particle resolution

Bulk syntheses of colloids efficiently produce nanoparticles with unique and useful properties. Their integration onto surfaces is a prerequisite for exploiting these properties in practice. Ideally, the integration would be compatible with a variety of surfaces and particles, while also enabling the fabrication of large areas and arbitrarily high-accuracy patterns. Whereas printing routinely meets these demands at larger length scales, we have developed a novel printing process that enables positioning of sub-100-nm particles individually with high placement accuracy. A colloidal suspension is inked directly onto printing plates, whose wetting properties and geometry ensure that the nanoparticles only fill predefined topographical features. The dry particle assembly is subsequently printed from the plate onto plain substrates through tailored adhesion. We demonstrate that the process can create a variety of particle arrangements including lines, arrays and bitmaps, while preserving the catalytic and optical activity of the individual nanoparticles.

Templated Self-Assembly of Ultrathin Gold Nanowires by Nanoimprinting for Transparent Flexible Electronics

We fabricated flexible, transparent, and conductive metal grids as transparent conductive materials (TCM) with adjustable properties by direct nanoimprinting of self-assembling colloidal metal nanowires. Ultrathin gold nanowires (diameter below 2 nm) with high mechanical flexibility were confined in a stamp and readily adapted to its features. During drying, the wires self-assembled into dense bundles that percolated throughout the stamp. The high aspect ratio and the bundling yielded continuous, hierarchical superstructures that connected the entire mesh even at low gold contents. A soft sintering step removed the ligand barriers but retained the imprinted structure. The material exhibited high conductivities (sheet resistances down to 29 Ω/sq) and transparencies that could be tuned by changing wire concentration and stamp geometry. We obtained TCMs that are suitable for applications such as touch screens. Mechanical bending tests showed a much higher bending resistance than commercial ITO: conductivity dropped by only 5.6% after 450 bending cycles at a bending radius of 5 mm.

Gold Nanoparticle Penetration and Reduced Metabolism in Human Skin by Toluene

ABSTRACTPurposeTo measure penetration and metabolic effects of ion-stabilized, polar, 15xa0nm gold nanoparticles in aqueous solution (AuNP-Aq) and sterically stabilized, non-polar, 6xa0nm gold nanoparticles in toluene (AuNP-TOL) on excised human skin.MethodsGold nanoparticles were characterized with dynamic light scattering and transmission electron microscopy (TEM). Skin penetration studies were done on frozen or fresh excised skin using static Franz diffusion cells. Viable treated skin was assessed by dermoscopy, reflectance confocal microscopy (RCM), multiphoton tomography (MPT) with fluorescence lifetime imaging microscopy (FLIM), and TEM.ResultsDermoscopy and RCM showed large aggregates in the furrows of AuNP-Aq-treated skin. Treatment of thawed and viable skin only showed enhanced permeability to nanoparticles in the AuNP-TOL group with MPT and FLIM imaging to stratum spinosum of epidermis. TEM analysis revealed gold nanoparticles within AuNP-treated stratum corneum. FLIM analysis of NAD(P)H showed a significant decrease in total NAD(P)H in all toluene-treated groups.ConclusionsGold nanoparticles, 15xa0nm, in aqueous solution aggregated on the skin surface. Toluene treatment eliminated skin metabolism; skin treated with toluene/gold nanoparticles (6xa0nm) for 24xa0h, but not at 4xa0h, showed increased nanoparticle permeability. These results are of value to nanotoxicology.

Combined multiphoton imaging-pixel analysis for semiquantitation of skin penetration of gold nanoparticles

Interaction of nanoparticles with the skin barrier is a recent area of research that draws a lot of attention from the researchers. However, monitoring nanoparticles in or through the skin is mainly based on qualitative microscopical techniques. Yet, a quantitative approach is required for a better basic understanding. In response, a combined multiphoton-pixel analysis method was developed in this study for semiquantitation of gold nanoparticles penetration into different skin layers. The developed approach provides a useful tool for future studies focusing on skin penetration of nanoparticles for the aim of health risk assessment or for the design of topical and transdermal drug delivery systems.

Copper-containing SiCN precursor ceramics (Cu@SiCN) as selective hydrocarbon oxidation catalysts using air as an oxidant.

A molecular approach to metal-containing ceramics and their application as selective heterogeneous oxidation catalysts is presented. The aminopyridinato copper complex [Cu(2)(Ap(TMS))(2)] (Ap(TMS)H=(4-methylpyridin-2-yl)trimethylsilanylamine) reacts with poly(organosilazanes) via aminopyridine elimination, as shown for the commercially available ceramic precursor HTT 1800. The reaction was studied by (1)H and (13)C NMR spectroscopy. The liberation of the free, protonated ligand Ap(TMS)H is indicative of the copper polycarbosilazane binding. Crosslinking of the copper-modified poly(organosilazane) and subsequent pyrolysis lead to the copper-containing ceramics. The copper is reduced to copper metal during the pyrolysis step up to 1000 degrees C, as observed by solid-state (65)Cu NMR spectroscopy, SEM images, and energy-dispersive spectroscopy (EDS). Powder diffraction experiments verified the presence of crystalline copper. All Cu@SiCN ceramics show catalytic activity towards the oxidation of cycloalkanes using air as oxidant. The selectivity of the reaction increases with increasing copper content. The catalysts are recyclable. This study proves the feasibility of this molecular approach to metal-containing SiCN precursor ceramics by using silylaminopyridinato complexes. Furthermore, the catalytic results confirm the applicability of this new class of metal-containing ceramics as catalysts.

Role of the meniscus shape in large-area convective particle assembly.

Dense and uniform particle films are deposited using a robust version of the convective particle assembly process. We analyze how the shape of the gas-liquid interface and the three-phase contact line govern the stability of convective deposition and, thus, the achievable quality of films. Interference microscopy indicates that a highly curved meniscus cannot compensate for the ubiquitous perturbation during deposition. A moderately curved meniscus provides flexibility to compensate and localize perturbation and enables reliable homogeneous deposition. We analyze which setup geometry and meniscus velocity yield appropriate meniscus shapes. The quality of the resulting films is analyzed and compared to the deposition conditions. Uniform films over areas beyond the centimeter range are accessible using the optimized process, which is suitable for functional particle coatings and templates for microstructured materials.

Dendritic Gold Nanowire Growth Observed in Liquid with Transmission Electron Microscopy

The growth of nanoscale gold dendrites was studied in situ in a thin liquid film with transmission electron microscopy (TEM) using a liquid cell with silicon nitride (SiN) windows. Gold nanoparticle seeds were covered by a thin liquid layer containing precursor solution. Dendrite nucleation was induced by the electron beam leading to an initial burst of growth. The growth then settled at tip velocities between 0.1 and 2.0 nm/s for different dendrites. Tip velocities fluctuated as different dendrite geometries grew from the tips. Those dendrites showing granularities in their structure experienced the largest growth speed. Comparison of the observed velocities with diffusion-limited growth rates suggests that dendrite growth in thin films at this scale is limited by diffusion. The described method may find application in research on the mechanisms behind dendrite growth and also to study other types of anisotropic growth of nanomaterials driven by crystal and twin geometries.

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.

Nanoparticle clusters with Lennard-Jones geometries.

Noble gas and metal atoms form minimum-energy clusters. Here, we present analogous agglomerates of gold nanoparticles formed in oil-in-water emulsions. We exclude interfacial templating and nucleation-and-growth as formation mechanisms of these supraparticles. Similar to atomic clusters, the supraparticles form when a mobile precursor state can reconfigure until the nanoparticles interactions with each other and with the liquid-liquid interface are maximized. This formation mechanism is in striking contrast to that previously reported for microparticle clusters.

Crystallization Mechanisms in Convective Particle Assembly

Colloidal particles are continuously assembled into crystalline particle coatings using convective fluid flows. Assembly takes place inside a meniscus on a wetting reservoir. The shape of the meniscus defines the profile of the convective flow and the motion of the particles. We use optical interference microscopy, particle image velocimetry, and particle tracking to analyze the particles trajectory from the liquid reservoir to the film growth front and inside the deposited film as a function of temperature. Our results indicate a transition from assembly at a static film growth front at high deposition temperatures to assembly in a precursor film with high particle mobility at low deposition temperatures. A simple model that compares the convective drag on the particles to the thermal agitation explains this behavior. Convective assembly mechanisms exhibit a pronounced temperature dependency and require a temperature that provides sufficient evaporation. Capillary mechanisms are nearly temperature independent and govern assembly at lower temperatures. The model fits the experimental data with temperature and particle size as variable parameters and allows prediction of the transition temperatures. While the two mechanisms are markedly different, dried particle films from both assembly regimes exhibit hexagonal particle packings. We show that films assembled by convective mechanisms exhibit greater regularity than those assembled by capillary mechanisms.