Gold nanoparticles (GNPs) are often used as colloidal carriers in numerous applications owing to their low-cost and size-controlled preparation as well as their straightforward surface functionalization with thiol containing molecules forming self-assembling monolayers (SAM). The quantification of the ligand density of such modified GNPs is technically challenging, yet of utmost importance for quality control in many applications. In this contribution, a new method for the determination of the surface coverage of GNPs with thiol containing ligands is proposed. It makes use of the measurement of the gold-to-sulfur (Au/S) ratio by inductively coupled plasma mass spectrometry (ICP–MS) and its dependence on the nanoparticle diameter. The simultaneous ICP–MS measurement of gold and sulfur was carefully validated and found to be a robust method with a relative standard uncertainty of lower than 10%. A major advantage of this method is the independence from sample preparation; for example, sample loss during the washing steps is not affecting the results. To demonstrate the utility of the straightforward method, GNPs of different diameters were synthesized and derivatized on the surface with bifunctional (lipophilic) ω-mercapto-alkanoic acids and (hydrophilic) mercapto-poly(ethylene glycol) (PEG)n-carboxylic acids, respectively, by self-assembling monolayer (SAM) formation. Thereby, a size-independent but ligand-chain length-dependent ligand density was found. The surface coverage increases from 4.3 to 6.3 molecules nm–2 with a decrease of ligand chain length from 3.52 to 0.68 nm. Furthermore, no significant difference between the surface coverage of hydrophilic and lipophilic ligands with approximately the same ligand length was found, indicating that sterical hindrance is of more importance than, for example, intermolecular strand interactions of Van der Waals forces as claimed in other studies.
The synthesis and characterization of ordered mesoporous In2O3 materials by structure replication from hexagonal mesoporous SBA‐15 silica and cubic KIT‐6 silica is presented. Variation of the synthesis parameters allows for different pore sizes and pore wall thicknesses in the products. The In2O3 samples turn out to be stable up to temperatures between 450 °C and 650 °C; such high thermal stability is necessary for their application as gas sensors. Test measurements show a high sensitivity to methane gas in concentrations relevant for explosion prevention. The sensitivity is shown to be correlated not only with the surface‐to‐volume ratio, but also with the nanoscopic structural properties of the materials.
Dinuclear copper peroxo complexes obtained from mononuclear copper(I) complexes showed extremely high stabilities under ambient conditions in the solid state and could be heated above 100 degrees C without decomposition. The increased stability could be explained with regard to their molecular structures. Furthermore, the four complexes investigated showed a high potential for aliphatic C-H bond oxidations: for example, technical-grade toluene was oxidized to benzaldehyde in yields of up to 20%.
The physical phenomena and engineering applications of martensitic phase transformations are the focus of intense ongoing research. The martensitic phase transformation and functional properties such as the shape-memory effect and superelasticity are strongly affected by the crystal size at the nanoscale. The current state of research on the impact of crystal size on the phase stability of the martensite is reviewed summarizing experimental results of various nanostructured martensitic materials and discussing the corresponding theoretical approaches. The review outlines the effects of crystal size on the complex morphology of the martensite, leading to interface structures not encountered in coarse-grained bulk materials. The unique shape-memory properties of martensitic materials can persist even at the nanoscale. Nanocrystalline martensitic materials can be processed to obtain tailored functional properties in combination with enhanced strength. Structural changes of metallic nanowires are similar to those arising by martensitic phase transformations and also can lead to shape-memory effects, as predicted by atomistic simulations.
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