Tobias Vossmeyer

A "Double-Diamond Superlattice" Built Up of Cd17S4(SCH2CH2OH)26 Clusters

A simple preparation of Cd17S4(SCH2CH2OH)26 clusters in aqueous solution leads to the formation of colorless blocky crystals. X-ray structure determinations revealed a superlattice framework built up of covalently linked clusters. This superlattice is best described as two enlarged and interlaced diamond or zinc blende lattices. Because both the superlattice and the clusters display the same structural features, the crystal structure resembles the self-similarities known from fractal geometry. The optical spectrum of the cluster solution displays a sharp transition around 290 nanometers with a large absorption coefficient (∼84,000 per molar per centimeter).

Combinatorial approaches toward patterning nanocrystals

A scheme for generating complex, spatially separated patterns of multiple types of semiconducting and/or metallic nanocrystals is presented. The process is based on lithographic patterning of organic monolayers that contain a photolabile protection group and are covalently bound to SiO2 surfaces. The process results in spatially and chemically distinct interaction sites on a single substrate. Nanocrystal assembly occurs with a high selectivity on just one type of site. We report on the production of binary, tertiary, and quatemary patterns of nanocrystals. We highlight and discuss the differences between nanocrystal/substrate assembly and molecule/substrate assembly. Finally, we investigate the assembled structures using photoluminescence and absorption spectroscopy.

Little Adjustments Significantly Improve the Turkevich Synthesis of Gold Nanoparticles

In this report, we show how the classical and widely used Turkevich synthesis can be improved significantly by simple adjustments. The gold nanoparticles (AuNPs) produced with the optimized protocol have a much narrower size distribution (5-8% standard deviation), and their diameters can be reproduced with unrivaled little variation (<3%). Moreover, large volumes of these particles can be produced in one synthesis; we routinely synthesize 1000 mL of ∼3.5 nM AuNPs. The key features of the improved protocol are the control of the pH by using a citrate buffer instead of a citrate solution as the reducing agent or stabilizer and optimized mixing of reagents. Further, the shape uniformity of the particles can be improved by addition of 0.02 mM EDTA. While the proposed protocol is as straightforward as the original Turkevich protocol, it is more tolerant against variations in precursor concentration.

Gold-nanoparticle/organic linker films: self-assembly, electronic and structural characterisation, composition and vapour sensitivity

Gold-nanoparticle/organic films were prepared via layer-by-layer self-assembly using dodecylamine-stabilised Au-nanoparticles and poly(propyleneimine) (PPI) dendrimers of generation one to five (G1-G5) or hexadecanedithiol (HDT) as linker compounds. TEM and FE-SEM images revealed that the bulk of the films consisted of nanoparticles with diameters of about 4 nm. XPS was used to study the chemical composition of the films. The C 1s and N 1s signals of an AuPPI-G4 film were interpreted qualitatively according to the dendrimer structure. The absence of the nitrogen signal in case of an AuHDT film indicated that the dodecylamine ligands were quantitatively exchanged during film assembly. About 76% of the sulfur atoms were bound to the nanoparticles. the remainder being present as free thiol (S H) groups. All films displayed linear current voltage characteristics and Arrhenius-type activation of charge transport. The conductivities of the AuPPI films decreased exponentially over approximately two orders of magnitude (6.8 x 10(-2) to 1.0 x 10(-3) ohms(-1) cm(-1)) with a five-fold increase of the dendrimer generation number. Dosing the films with solvent vapours caused their resistances to increase. Using different solvent vapours demonstrated that the sensitivity of this response was determined by the solubility properties of the linker compounds. Microgravimetric measurements showed that absorption of analyte was consistent with a Langmuir adsorption model. These measurements also revealed a linear correlation between the electrical response (deltaR/Rini) and the concentration of absorbed analyte. The absorption of d4-methanol from a saturated vapour atmosphere was studied by neutron reflectometry with an AuPPI-G4 film. This measurement indicated condensation of methanol on top of the film and a uniform distribution of the analyte across the film thickness.

Effect of the Spacer Structure on the Stability of Gold Nanoparticles Functionalized with Monodentate Thiolated Poly(ethylene glycol) Ligands

Poly(ethylene glycol)- (PEG-) based ligands are well-established for the stabilization of nanoparticles in aqueous solution and are especially interesting for applications in medicine and biotechnology because they are known to improve the pharmacokinetic properties of nanomaterials. In this study, we prepared gold nanoparticles (AuNPs) with ligand shells of different monodentate poly(ethylene glycol)-thiol (PEG-SH) ligands. These ligands differed only in the segment connecting the thiol group with the PEG moiety (Mw ≈ 2000 g/mol) through an ester bond, the spacer. All ligands were synthesized by straightforward esterification. Specifically, we used PEG ligands with a long (C10, PEGMUA) or short (C2, PEGMPA) alkylene spacer or a phenylene (PEGMPAA) spacer. The influence of the spacer on the stability of gold nanoparticle-PEG conjugates (AuNP@PEG) was tested by cyanide etching experiments, electrolyte-induced aggregation, and competitive ligand displacement with dithiothreitol (DTT). In the presence of 100 mM cyanide, AuNPs stabilized with PEGMPA or PEGMPAA were completely dissolved by oxidative etching within a few minutes, whereas AuNPs stabilized with PEGMUA needed more than 20 h to be completely etched. By complementary experiments, we deduced a simplified description for the etching process that takes into account the role of excess ligand. In the presence of free ligand, significantly fewer AuNPs are etched, suggesting a competition of etching and ligand binding to AuNPs. We also compared the stabilizing effect of PEGMUA with that of a bidentate PEG-thiol ligand (PEGLIP) and found a reversed stability against cyanide etching and DTT displacement, in agreement with previously reported observations. Our results clearly demonstrate the strong impact of the spacer structure on conjugate stability and provide valuable information for the rational design of more complex AuNP@PEG conjugates, which are of much interest in the context of biotechnology and medical applications.

Synthesis and thermal stability of zirconia and yttria-stabilized zirconia microspheres

HYPOTHESIS Zirconia microparticles produced by sol-gel synthesis have great potential for photonic applications. To this end, identifying synthetic methods that yield reproducible control over size uniformity is important. Phase transformations during thermal cycling can disintegrate the particles. Therefore, understanding the parameters driving these transformations is essential for enabling high-temperature applications. Particle morphology is expected to influence particle processability and stability. Yttria-doping should improve the thermal stability of the particles, as it does in bulk zirconia. EXPERIMENTS Zirconia and YSZ particles were synthesized by improved sol-gel approaches using fatty acid stabilizers. The particles were heated to 1500 °C, and structural and morphological changes were monitored by SEM, ex situ XRD and high-energy in situ XRD. FINDINGS Zirconia particles (0.4-4.3 μm in diameter, 5-10% standard deviation) synthesized according to the modified sol-gel approaches yielded significantly improved monodispersities. As-synthesized amorphous particles transformed to the tetragonal phase at ∼450 °C with a volume decrease of up to ∼75% and then to monoclinic after heating from ∼650 to 850 °C. Submicron particles disintegrated at ∼850 °C and microparticles at ∼1200 °C due to grain growth. In situ XRD revealed that the transition from the amorphous to tetragonal phase was accompanied by relief in microstrain and the transition from tetragonal to monoclinic was correlated with the tetragonal grain size. Early crystallization and smaller initial grain sizes, which depend on the precursors used for particle synthesis, coincided with higher stability. Yttria-doping reduced grain growth, stabilized the tetragonal phase, and significantly improved the thermal stability of the particles.

Freestanding films of crosslinked gold nanoparticles prepared via layer-by-layer spin-coating

A new, extremely efficient method for the fabrication of films comprised of gold nanoparticles (GNPs) crosslinked by organic dithiols is presented in this paper. The method is based on layer-by-layer spin-coating of both components, GNPs and crosslinker, and enables the deposition of films several tens of nanometers in thickness within a few minutes. X-ray diffraction and conductance measurements reveal the proper adjustment concentration of the crosslinker solution of the critical is in order to prevent the destabilization and coalescence of particles. UV/vis spectroscopy, atomic force microscopy, and conductivity measurements indicate that films prepared via layer-by-layer spin-coating are of comparable quality to coatings prepared via laborious layer-by-layer self-assembly using immersion baths. Because spin-coated films are not bound chemically to the substrate, they can be lifted-off by alkaline underetching and transferred onto 3d-electrodes to produce electrically addressable, freely suspended films. Comparative measurements of the sheet resistances indicate that the transfer process does not compromise the film quality.

Lithographic patterning of nanoparticle films self-assembled from organic solutions by using a water-soluble mask

A lithographic technique is described that enables the highly selective patterning of thin films from gold nanoparticles and organic linker molecules, which are formed via repetitive self-assembly from organic solution. The key element of this method is the application of a calcium oxide∕hydroxide mask, which withstands the application of organic solvents during film deposition and which prevents deposition of nanoparticles on protected parts of the substrate. After film assembly the mask is removed by dissolution in water at room temperature. The method was used to pattern chemiresistor-type vapor sensors based on gold nanoparticle∕nonanedithiol films. Comparative experiments with nonpatterned reference sensors reveal that the patterning process does not degrade the sensing properties of the films.

Intraspinal Delivery of Polyethylene Glycol-coated Gold Nanoparticles Promotes Functional Recovery After Spinal Cord Injury

Failure of the mammalian central nervous system (CNS) to regenerate effectively after injury leads to mostly irreversible functional impairment. Gold nanoparticles (AuNPs) are promising candidates for drug delivery in combination with tissue-compatible reagents, such as polyethylene glycol (PEG). PEG administration in CNS injury models has received interest for potential therapy, but toxicity and low bioavailability prevents clinical application. Here we show that intraspinal delivery of PEG-functionalized 40-nm-AuNPs at early stages after mouse spinal cord injury is beneficial for recovery. Positive outcome of hind limb motor function was accompanied by attenuated inflammatory response, enhanced motor neuron survival, and increased myelination of spared or regrown/sprouted axons. No adverse effects, such as body weight loss, ill health, or increased mortality were observed. We propose that PEG-AuNPs represent a favorable drug-delivery platform with therapeutic potential that could be further enhanced if PEG-AuNPs are used as carriers of regeneration-promoting molecules.

Tungsten band edge absorber/emitter based on a monolayer of ceramic microspheres.

We report on a band edge absorber/emitter design for high-temperature applications based on an unstructured tungsten substrate and a monolayer of ceramic microspheres. The absorber was fabricated as a monolayer of ZrO(2) microparticles on a tungsten layer with a HfO(2) nanocoating. The band edge of the absorption is based on critically coupled microsphere resonances. It can be tuned from visible to near-infrared range by varying the diameter of the microparticles. The absorption properties were found to be stable up to 1000°C.