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- ItemTime Optimization of Seed-Mediated Gold Nanotriangle Synthesis Based on Kinetic Studies(Basel : MDPI, 2021) Podlesnaia, Ekaterina; Csáki, Andrea; Fritzsche, WolfgangThe synthesis of shape-anisotropic plasmonic nanoparticles such as gold nanotriangles is of increasing interest. These particles have a high potential for applications due to their notable optical properties. A key challenge of the synthesis is usually the low reproducibility. Even the optimized seed-based methods often lack in the synthesis yield or are labor- and time-consuming. In this work, a seed-mediated synthesis with high reproducibility is replicated in order to determine the necessary reaction time for each step. Online monitoring of the reaction mixtures by UV–VIS spectroscopy is used as a powerful tool to track the evolution of the synthesis. The kinetics of the individual stages is elucidated by real-time investigations. As a consequence, the complete synthesis could be optimized and can now be realized in a single day instead of three without any loss in the resulting sample quality.
- ItemDNA-Biofunctionalization of CTAC-Capped Gold Nanocubes(Basel : MDPI, 2020) Slesiona, Nicole; Thamm, Sophie; Stolle, H. Lisa K.S.; Weißenborn, Viktor; Müller, Philipp; Csáki, Andrea; Fritzsche, WolfgangClinical diagnostics and disease control are fields that strongly depend on technologies for rapid, sensitive, and selective detection of biological or chemical analytes. Nanoparticles have become an integral part in various biomedical detection devices and nanotherapeutics. An increasing focus is laid on gold nanoparticles as they express less cytotoxicity, high stability, and hold unique optical properties with the ability of signal transduction of biological recognition events with enhanced analytical performance. Strong electromagnetic field enhancements can be found in close proximity to the nanoparticle that can be exploited to enhance signals for e.g., metal-enhanced fluorescence or Raman spectroscopy. Even stronger field enhancements can be achieved with sharp-edged nanoparticles, which are synthesized with the help of facet blocking agents, such as cetyltrimethylammonium bromide/chloride (CTAB/CTAC). However, chemical modification of the nanoparticle surface is necessary to reduce the particle’s cytotoxicity, stabilize it against aggregation, and to bioconjugate it with biomolecules to increase its biocompatibility and/or specificity for analytical applications. Here, a reliable two-step protocol following a ligand exchange with bis (p-sulfonatophenyl) phenyl phosphine (BSPP) as the intermediate capping-agent is demonstrated, which results in the reliable biofunctionalization of CTAC-capped gold nanocubes with thiol-modified DNA. The functionalized nanocubes have been characterized regarding their electric potential, plasmonic properties, and stability against high concentrations of NaCl and MgCl2.
- ItemShape-Dependent Catalytic Activity of Gold and Bimetallic Nanoparticles in the Reduction of Methylene Blue by Sodium Borohydride(Basel : MDPI, 2021) Stolle, Heike Lisa Kerstin Stephanie; Kluitmann, Jonas Jakobus; Csáki, Andrea; Köhler, Johann Michael; Fritzsche, WolfgangIn this study the catalytic activity of different gold and bimetallic nanoparticle solutions towards the reduction of methylene blue by sodium borohydride as a model reaction is investigated. By utilizing differently shaped gold nanoparticles, i.e., spheres, cubes, prisms and rods as well as bimetallic gold–palladium and gold–platinum core-shell nanorods, we evaluate the effect of the catalyst surface area as available gold surface area, the shape of the nanoparticles and the impact of added secondary metals in case of bimetallic nanorods. We track the reaction by UV/Vis measurements in the range of 190–850 nm every 60 s. It is assumed that the gold nanoparticles do not only act as a unit transferring electrons from sodium borohydride towards methylene blue but can promote the electron transfer upon plasmonic excitation. By testing different particle shapes, we could indeed demonstrate an effect of the particle shape by excluding the impact of surface area and/or surface ligands. All nanoparticle solutions showed a higher methylene blue turnover than their reference, whereby gold nanoprisms exhibited 100% turnover as no further methylene blue absorption peak was detected. The reaction rate constant k was also determined and revealed overall quicker reactions when gold or bimetallic nanoparticles were added as a catalyst, and again these were highest for nanoprisms. Furthermore, when comparing gold and bimetallic nanorods, it could be shown that through the addition of the catalytically active second metal platinum or palladium, the dye turnover was accelerated and degradation rate constants were higher compared to those of pure gold nanorods. The results explore the catalytic activity of nanoparticles, and assist in exploring further catalytic applications.
- ItemTime-resolved study of site-specific corrosion in a single crystalline silver nanoparticle(Berlin : SpringerOpen, 2019) Trautmann, Steffen; Dathe, André; Csáki, Andrea; Thiele, Matthias; Müller, Robert; Fritzsche, Wolfgang; Stranik, OndrejWe followed over 24 h a corrosion process in monocrystalline triangular-shaped nanoparticles at a single-particle level by atomic force microscopy and optical spectroscopy techniques under ambient laboratory conditions. The triangular-shaped form of the particles was selected, because the crystallographic orientation of the particles is well defined upon their deposition on a substrate. We observed that the particles already start to alter within this time frame. Surprisingly, the corrosion starts predominantly from the tips of the particles and it creates within few hours large protrusions, which strongly suppress the plasmon character of the particles. These observations support the crystallographic model of these particles consisting of a high-defect hexagonal closed packed layer, and they could help material scientists to design more stable silver nanoparticles. Moreover, this described technique can be used to reveal kinetics of the corrosion in the nanoscale of other materials.