Size Exclusion Chromatography (SEC) on a semi-preparative scale (10 mg and more) was used to size-select ultrasmall gold nanoclusters (< 2 nm) from polydisperse mixtures. In particular, the ubiquitous byproducts of the etching process towards Au₃₈(SR)₂₄ (SR: thiolate) clusters were separated and gained in high monodispersity (based on mass spectrometry). The isolated fractions were characterized by UV/Vis spectroscopy, MALDI mass spectrometry and electron microscopy. Most notably, the separation of Au₃₈(SR)₂₄ and Au₄₀(SR)₂₄ clusters is demonstrated.

Ligand exchange on [Au₂₅(SCH₂CH₂Ph)₁₈^−] [TOA⁺] is studied with two chiral ligands R/S-BINAS and NILC/NIDC in THF with induction of metal-based optical activity. Under the applied condition the ligand exchange is only partial, showing that also within a mixed ligand shell significant optical activity can be induced. The ligand exchange resulted in the change of particle size as observed by UV−vis spectroscopy.

A combination of in situ attenuated total reflection infrared (ATR-IR) spectroscopy, UV−vis spectroscopy and transmission electron microscopy was used to study the adsorption of thiol-protected gold nanoparticles on TiO₂ films and the behavior of the resulting composite films upon UV irradiation. The gold nanoparticles were covered by charged thiols N-acetyl-l-cysteine and l-glutathione and had a mean core diameter of about 1 nm. The TiO₂ film was prepared by deposition of a slurry of TiO₂ nanoparticles with a particles size of 21 nm. The combination of the two spectroscopic techniques showed that the adsorption of the gold nanoparticles onto the TiO₂ films is significantly limited by intrafilm diffusion. Upon illumination the IR spectra revealed the removal of the adsorbed thiolates and the appearance of sulfates. These species were also observed when N-acetyl-l-cysteine adsorbed on TiO₂ was illuminated, i.e., in the absence of gold. In the latter case oxalate was observed in large quantity on the TiO₂ surface, in contrast to the illumination of the N-acetyl-l-cysteine-protected gold particles. This indicates a different pathway for the decomposition of the adsorbed thiol when adsorbed on the gold or directly on the TiO₂ surface. In situ UV−vis spectroscopy also shows the formation of larger particles upon illumination, which is confirmed by transmission electron microscopy.

Liquid-crystalline dendrons carrying either a thiol or disulfide function which display nematic, smectic A, columnar, or chiral nematic phases have been synthesized. Their mesomorphic properties are in agreement with the nature of the mesogenic units and structure of the dendrons. The first-generation poly(aryl ester) dendron containing two cyanobiphenyl mesogenic units was used to functionalize gold nanoparticles. For full coverage, a smectic-like supramolecular organization on the nanometer scale is observed, when the gold nanoparticles are spread onto carbon-coated copper grids. This result indicates that the dendritic ligands reported here act as self-organization promoters.

Chiral metal surfaces and nanoparticles have the potential to be used for the selective production, the resolution and the detection of enantiomers of a chiral compound, which renders them highly attractive in view of the tremendous consequences of homochirality on earth. Their capability to distinguish between enantiomers of a chemical compound relies on their structure and the ability to form intermolecular interactions. However, molecular-level understanding of the interactions that are at the origin of enantiodiscrimination is lagging behind due to the lack of powerful experimental techniques that are able to spot these interactions selectively with high sensitivity. In this article two techniques based on infrared spectroscopy are presented that are able to selectively target the chiral properties of nanoparticles and interfaces. These are the combination of attenuated total reflection infrared (ATR-IR) with modulation excitation spectroscopy (MES) to probe enantiodiscriminating interactions at chiral solid-liquid interfaces and vibrational circular dichroism (VCD), which is used to probe the structure of chirally modified metal nanoparticles.