Scientific publications

Gold nanoparticles were observed to move at a liquid/solid interface 3 orders of magnitude slower than expected for the movement in a bulk liquid by Brownian motion. The nanoscale movement was studied with scanning transmission electron microscopy (STEM) using a liquid enclosure consisting of microchips with silicon nitride windows. The experiments involved a variation of the electron dose, the coating of the nanoparticles, the surface charge of the enclosing membrane, the viscosity, and the liquid thickness. The observed slow movement was not a result of hydrodynamic hindrance near a wall but instead explained by the presence of a layer of ordered liquid exhibiting a viscosity 5 orders of magnitude larger than a bulk liquid. The increased viscosity presumably led to a dramatic slowdown of the movement. The layer was formed as a result of the surface charge of the silicon nitride windows. The exceptionally slow motion is a crucial aspect of electron microscopy of specimens in liquid, enabling a direct observation of the movement and agglomeration of nanoscale objects in liquid.

The formation of HER2 homodimers plays an important role in breast cancer aggressiveness and progression; however, little is known about its localization. We have studied the intra- and intercellular variation of HER2 at the single-molecule level in intact SKBR3 breast cancer cells. Whole cells were visualized in hydrated state with correlative fluorescence microscopy and environmental scanning electron microscopy (ESEM). The locations of individual HER2 receptors were detected using an anti-HER2 affibody in combination with a quantum dot (QD), a fluorescent nanoparticle. Fluorescence microscopy revealed considerable differences of HER2 membrane expression between individual cells and between different membrane regions of the same cell (that is, membrane ruffles and flat areas). Subsequent ESEM of the corresponding cellular regions provided images of individually labeled HER2 receptors. The high spatial resolution of 3 nm and the close proximity between the QD and the receptor allowed quantifying the stoichiometry of HER2 complexes, distinguishing between monomers, dimers, and higher-order clusters. Downstream data analysis based on calculating the pair correlation function from receptor positions showed that cellular regions exhibiting membrane ruffles contained a substantial fraction of HER2 in homodimeric state. Larger-order clusters were also present. Membrane areas with homogeneous membrane topography, on the contrary, displayed HER2 in random distribution. Second, HER2 homodimers appeared to be absent from a small subpopulation of cells exhibiting a flat membrane topography, possibly resting cells. Local differences in homodimer presence may point toward functional differences with possible relevance for studying metastasis and drug response.Keywords

We introduce a molecular toolkit for studying the dynamics in friction and adhesion from the single molecule level to effects of multivalency. As experimental model system we use supramolecular bonds established by the inclusion of ditopic adamantane connector molecules into two surface-bound cyclodextrin molecules, attached to a tip of an atomic force microscope (AFM) and to a flat silicon surface. The rupture force of a single bond does not depend on the pulling rate, indicating that the fast complexation kinetics of adamantane and cyclodextrin are probed in thermal equilibrium. In contrast, the pull-off force for a group of supramolecular bonds depends on the unloading rate revealing a non-equilibrium situation, an effect discussed as the combined action of multivalency and cantilever inertia effects. Friction forces exhibit a stick-slip characteristic which is explained by the cooperative rupture of groups of host-guest bonds and their rebinding. No dependence of friction on the sliding velocity has been observed in the accessible range of velocities due to fast rebinding and the negligible delay of cantilever response in AFM lateral force measurements.

Friction and adhesion between two [small beta]-cyclodextrin functionalized surfaces can be switched reversibly by external light stimuli. The interaction between the cyclodextrin molecules attached to the tip of an atomic force microscope and a silicon wafer surface is mediated by complexation of ditopic azobenzene guest molecules. At the single molecule level, the rupture force of an individual complex is 61 +/- 10 pN.

We report on a friction study at the nanometer scale using atomic force microscopy under electrochemical control. Friction arises from the interaction between two surfaces functionalized with cyclodextrin molecules. The interaction is mediated by connector molecules with (ferrocenylmethyl)ammonium end groups forming supramolecular complexes with the cyclodextrin molecules. With ferrocene connector molecules in solution, the friction increases by a factor of up to 12 compared to control experiments without connector molecules. The electrochemical oxidation of ferrocene to ferrocenium causes a decrease in friction owing to the lower stability of ferrocenium-cyclodextrin complex. Upon switching between oxidative and reduction potentials, a change in friction by a factor of 1.2-1.8 is observed. Isothermal titration calorimetry reveals fast dissociation and rebinding kinetics and thus an equilibrium regime for the friction experiments.

We combine non-contact atomic force microscopy (AFM) imaging and AFM indentation in ultra-high vacuum to quantitatively and reproducibly determine the hardness and deformation mechanisms of Pt(111) and a Pt57.5Cu14.7Ni5.3P22.5 metallic glass with unprecedented spatial resolution. Our results on plastic deformation mechanisms of crystalline Pt(111) are consistent with the discrete mechanisms established for larger scales: Plasticity is mediated by dislocation gliding and no rate dependence is observed. For the metallic glass we have discovered that plastic deformation at the nanometer scale is not discrete but continuous and localized around the indenter, and does not exhibit rate dependence. This contrasts with the observation of serrated, rate-dependent flow of metallic glasses at larger scales. Our results reveal a lower size limit for metallic glasses below which shear transformation mechanisms are not activated by indentation. In the case of metallic glass, we conclude that the energy stored in the stressed volume during nanometer-scale indentation is insufficient to account for the interfacial energy of a shear band in the glassy matrix.

Thermoplastic nanocomposites used for vibration welding are compounded on a twin-screw extruder by dilution of a concentrate masterbatch containing 14 vol% of filler. They are butt welded under different weld pressures by a linear vibration welding machine. By means of a quick ramp-down technology, this machine enables a very short vibration damping time of about 40 ms. The influence of different damping time on the weld strength of various materials is investigated. The experimental results are compared also with the results of simulation. In the case of nano-silica filled polypropylene, no impact of the damping time on the weld quality is detected and the possible reasons for this observation are explained.

Polyoxymethylene nanocomposites containing different contents of carbon nanotubes were produced by a two-step melt compounding process using a twin-screw extruder. The dispersion quality, thermal and mechanical properties, and the creep as well as the tribological behaviors of the nanocomposites were investigated. Morphological investigations show that the masterbatch dilution process significantly improves the dispersion quality of carbon nanotubes within polyoxymethylene matrix, and as a consequence, enhanced mechanical properties and creep resistance are gained. Furthermore, to predict the long-term property based on the short-term experimental data, the time-temperature superposition principle and Findley model were used. Master curves with extended time scale are constructed using time-temperature superposition principle to horizontally shift the short-term experimental data. The simulated results confirm the reinforced creep resistance by incorporation of the carbon nanotubes into the polymer matrix even at extended long time scale. By contrast, the tribological performance of polyoxymethylene was remarkably impaired after adding carbon nanotubes. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42639.

Although the research and development of nanocomposites for almost a decade focused on structural properties, these properties remained until today far below
expectations, which were forecast at the beginning of the new millennium. However, even if it is well known that the processing history has a major impact on the structure and properties of final components, this aspect was not subject of intensive research in the past. The talk focuses on the role of the manufacturing sequence on the morphology and properties of polypropylene based nanocomposites. In general it can be stated that the incorporation of nano-sized TiO2-fillers improves the some mechanical properties of the resulting nanocomposites as long as the production enables a good dispersion and distribution of the nanofiller agglomerates. However, with increasing filler loading, the morphology of injection molded parts changes: The size of the spherulites and the degree of crystallinity decreases while the crystallization/solidification proceeds faster. Simultaneously a slight improvement in the mechanical performance up to a certain filler loading can be found. However, improved mechanical properties of the nanocomposites in the final component cannot be exploited if its production in a subsequent welding step is required. The reason for the decrease in the mechanical properties is the decrease in the viscosity by the addition of the fillers, and thereby caused extreme flow processes and subsequent orientation of the fillers as well as the weakening of the filler/matrix-interphase in the welding zone. In summary, it
can be observed that nanocomposites increasingly offer great opportunities for applications where single-component materials reach their limits. The key to success is the processing. Therefore it is of crucial importance that the total manufacturing history is understood and controlled. Only then it is possible to sustainably exploit the potential of polymer nanocomposites in the application.