Publikationen

Ultrathin gold nanowires (AuNWs) show prospects as components of materials for transparent and flexible electronics that exploit the wires’ high aspect ratio and mechanical flexibility. High junction resistances that are caused by the insulating oleylamine ligand shells and the wires’ intrinsic susceptibility to decomposition by the Rayleigh instability impede their use in the as-synthesized state. Treatment by H2/Ar  plasma has been shown to improve conductivity and stability. We study the effects of a plasma treatment on morphology, chemistry, and temperature stability of AuNW layers by electron microscopy, X-ray diffraction, and Raman spectroscopy. Plasma treatment effectively removes oleylamine and sinters the individual ultrathin wires to superstructures with enhanced conductivity and temperature stability. Bundles of single ultrathin AuNWs can be sintered to continuous superstructures with enhanced conductivity and stability by H2/Ar plasma treatment.

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.

This study outlines the synthetic and purification process used to obtain hyperbranched polyglycerol (HPG) within a molecular weight range not previously obtainable. Purified fractions with low polydispersity are achieved via successive precipitations from acetone. Furthermore, the use of the initiator molecule 5-hexyne-1-ol introduces alkyne functionality at the core of each HPG molecule. Alkyne-azide cycloaddition chemistry in combination with NMR and field flow fractionation analysis is used to verify the availability of the alkyne core for bioconjugation across the range of molecular weights.

We analyze the structure diagram for binary clusters of Lennard-Jones particles by means of a global optimization approach for a large range of cluster sizes, compositions, and interaction energies and present a publicly accessible database of 180 000 minimal energy structures (http://softmattertheory.lu/clusters.html). We identify a variety of structures such as core-shell clusters, Janus clusters, and clusters in which the minority species is located at the vertices of icosahedra. Such clusters can be synthesized from nanoparticles in agglomeration experiments and used as building blocks in colloidal molecules or crystals. We discuss the factors that determine the formation of clusters with specific structures.

Ultrathin gold nanowires are unusual colloidal objects that assemble into bundles with line contacts between parallel wires. Each molecule in the contact line interacts with many ligand and solvent molecules. We used X-ray scattering and electron microscopy to study how these interactions control assembly.

Metal-based nanoparticle inks for printed electronics usually require sintering to improve the poor electron transport at particle-particle interfaces. The ligands required for colloidal stability act as insulating barriers and must be removed in a post-deposition sintering step. This complicates the fabrication process and makes it incompatible with many flexible substrates. Here, we bind a conjugated, electrically conductive polymer on gold nanorods (AuNRs) as a ligand. The polymer, poly[2-(3-thienyl)-ethyloxy-4-butylsulfonate)] (PTEBS), provides colloidal stability and good electron transport properties to stable, sintering-free inks. We confirm that the polymer binds strongly through a multidentate binding motif and provides superior colloidal stability in polar solvents over months by IR and Raman spectrometry and zeta potential measurements. We demonstrate that the developed ligand exchange protocol is directly applicable to other polythiophenes such as poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS). Films of AuNRs coated with above polymers reached conductivities directly after deposition comparable to conventional metal inks after ligand removal and retained their conductivity for at least one year when stored under ambient conditions.

Fabrication of nanoparticle arrays on a substrate is one of the most concerned aspects for manipulating assembly of nanoparticles and preparing functional nanocomposites. Here, we studied in situ the assembly kinetics of polystyrene nanocolloids by using grazing incidence small-angle X-ray scattering. The structure formation of the nanoparticle film is monitored during air-brush spraying, which provides a rapid and scalable preparation. By optimizing the substrate temperature, the dispersion of the nanocolloids can be tailored to prepare monolayer film. The success of the monolayer preparations is attributed to the fast solvent evaporation which inhibits the aggregation of the nanocolloids. The present study may open a new avenue for the manufacture-friendly preparation of well-dispersed nanoparticle thin films.

Here, we applied optoRAF, an optogenetic tool for light-controlled clustering and activation of RAF proteins that mimics the natural occurring RAS-mediated dimerization. This versatile tool allows studying the effect on BRAF and CRAF homodimer- as well as heterodimer-induced RAF signaling. Vemurafenib and dabrafenib are two clinically approved inhibitors for BRAF that efficiently suppress the kinase activity of oncogenic BRAF (V600E). However in wild-type BRAF expressing cells, BRAF inhibitors can exert paradoxical activation of wild-type CRAF. Using optoRAF, vemurafenib was identified as paradoxical activator of BRAF and CRAF homo- and heterodimers. Dabrafenib enhanced activity of light-stimulated CRAF at low dose and inhibited CRAF signaling at high dose. Moreover, dabrafenib increased the protein level of CRAF proteins but not of BRAF proteins. Increased CRAF levels correlate with elevated RAF signaling in a dabrafenib-dependent manner, independent of light activation.

Here, we present a novel approach to increase the degree of miniaturization as well as the sensitivity of biosensor platforms by the optimization of microfluidic stop-flow techniques independent of the applied detection technique (e.g. electrochemical or optical). The readout of the labeled bioassays, immobilized in a microfluidic channel, under stop-flow conditions leads to a rectangular shaped peak signal. Data evaluation using the peak height allows for a high level miniaturization of the channel geometries. To study the main advantages and limitations of this method by numerical simulations, a universally applicable model system is introduced for the first time. Consequently, proof-of-principle experiments were successfully performed with standard and miniaturized versions of an electrochemical biosensor platform utilizing a repressor protein-based assay for tetracycline antibiotics. Herein, the measured current peak heights are the same despite the sextuple reduction of the channel dimensions. Thus, this results in a 22-fold signal amplification compared to the constant flow measurements in the case of the miniaturized version. © 2016 The Royal Society of Chemistry.

Scaffold proteins such as the multidomain protein CNK1 orchestrate the signalling network by integrating and controlling the underlying pathways. Using an optogenetic approach to stimulate CNK1 uncoupled from upstream effectors, we identified selective clusters of CNK1 that either stimulate RAF-MEK-ERK or AKT signalling depending on the light intensity applied. OptoCNK1 implemented in MCF7 cells induces differentiation at low light intensity stimulating ERK activity whereas stimulation of AKT signalling by higher light intensity promotes cell proliferation. CNK1 clustering in response to increasing EGF concentrations revealed that CNK1 binds to RAF correlating with ERK activation at low EGF dose. At higher EGF dose active AKT binds to CNK1 and phosphorylates and inhibits RAF. Knockdown of CNK1 protects CNK1 from this AKT/RAF crosstalk. In C2 skeletal muscle cells CNK1 expression is induced with the onset of differentiation. Hence, AKT-bound CNK1 counteracts ERK stimulation in differentiated but not in proliferating cells. Ectopically expressed CNK1 facilitates C2 cell differentiation and knockdown of CNK1 impaired the transcriptional network underlying C2 cell differentiation. Thus, CNK1 expression, CNK1 clustering and the thereto related differential signalling processes decide on proliferation and differentiation in a cell type-and cell stage-dependent manner by orchestrating AKT and RAF signalling. © 2016 The Author(s).