Prof. Dr. Tobias Kraus

We describe the self-assembly of silver nanocubes (AgNC) into dense bowl-shaped arrays using a template made from polystyrene nanospheres (PSNS). Interestingly, we found that most AgNCs were arranged facet-to-facet. When used as substrates for surface-enhanced Raman scattering (SERS), we observed that the SERS hot spot positions were located at the corners of the cubes. This was confirmed using the formation of a self-assembled monolayer (SAM) of 1-dodecanethiol (DDT) covering the cubes' facet surface, whilst the pinholes in the DDT SAM at the corners were subsequently filled with 2-mercaptopyridine (MPy). Due to the high enhancement from the densely arranged AgNCs, single molecule detection was achieved from this SERS substrate and evidenced using the bi-analyte Raman technique.

This Feature Article discusses two biomimetic aspects of functional particle surface assembly: the fabrication of biologically inspired structures from particles and the arrangement of particles on biomimetic templates. The first part discusses the creation of primary patterns by convective assembly and adsorption of particles that can be modified by a combination of etching and growth steps. Resulting structures mimic moth eyes, Lotus leaves, and the Gecko's adhesive structures, for example. The second part focusses on template assisted self-assembly (TASA) of particles. Herein, biological examples are inspiring in terms of structure formation related processes, rather than in terms of functionality. Template formation is a major bottleneck TASA. It is illustrated how bio-inspired wrinkling processes help overcoming this problem and can be employed for forming highly ordered functional nanoparticle assemblies.

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.

We exploit the strong optical anisotropy of metal nanorods to measure their mobility in a complex fluid. Gold rods in hot agarose solutions cause dynamic, depolarized scattering with an exponentially decaying autocorrelation. As the solution cools down, its decay constant increases. At a certain temperature, the autocorrelation drastically changes its shape and the dynamic contrast drops. We show that, at this temperature, the gelling liquid confines the rods and dampens their motion almost entirely. Depolarized scattering proves to be extraordinarily sensitive to the transition from Brownian to confined motion. We calculate true mobilities for the particles using Pusey and van Megen's correction of the Siegert relation for nonergodic systems. Multipoint measurements show that the rods are immobilized throughout the gel.

Crystalline and amorphous materials composed of the same atoms exhibit strikingly different properties. Likewise, the behavior of materials composed of mesoscale particles depends on the arrangement of their constituent particles. Here, we demonstrate control over particle arrangement during agglomeration. We obtain disordered and ordered agglomerates of the same alkyl thiol-coated gold nanoparticles depending on temperature and solvent. We find that ordered agglomeration occurs exclusively above the melting temperature of the ligand shells. Many-particle simulations show that the contact mechanics of the ligand shells dominate the order-disorder transition: Purely spherical particle-particle interactions yield order, whereas localized "stiction" between the ligand shells leads to disorder. This indicates that the "stickiness" and the packing of the agglomerates can be switched by the state of the ligand shells. It suggests that contact mechanics govern ordering in a wide range of nanoparticles.

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.

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.

The ability of nanoparticles to penetrate the stratum corneum was the focus of several studies. Yet, there are controversial issues available for particle penetration due to different experimental setups. Meanwhile, there is little known about the mechanism and determinants of their penetration. In this paper the penetration of four model gold nanoparticles of diameter 6 and 15 nm, differing in surface polarity and the nature of the vehicle, through human skin was studied using multiphoton microscopy. This is in an attempt to profoundly investigate the parameters governing particle penetration through human skin. Our results imply that nanoparticles at this size range permeate the stratum corneum in a similar manner to drug molecules, mainly through the intercellular pathways. However, due to their particulate nature, permeation is also dependent on the complex microstructure of the stratum corneum with its tortuous aqueous and lipidic channels, as shown from our experiments performed using skin of different grades of barrier integrity. The vehicle (toluene-versus-water) had a minimal effect on skin penetration of gold nanoparticles. Other considerations in setting up a penetration experiment for nanoparticles were also studied. The results obtained are important for designing a new transdermal carrier and for a basic understanding of skin-nanoparticle interaction.

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.

Purpose: To measure penetration and metabolic effects of ion-stabilized, polar, 15 nm gold nanoparticles in aqueous solution (AuNP-Aq) and sterically stabilized, non-polar, 6 nm gold nanoparticles in toluene (AuNP-TOL) on excised human skin. Methods: Gold 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. Results: Dermoscopy 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. Conclusions: Gold nanoparticles, 15 nm, in aqueous solution aggregated on the skin surface. Toluene treatment eliminated skin metabolism; skin treated with toluene/gold nanoparticles (6 nm) for 24 h, but not at 4 h, showed increased nanoparticle permeability. These results are of value to nanotoxicology.