The reductive desorption process of self-assembled monolayers of
1-hexadecanethiol, 1-propanethiol,
and 3-mercaptopropionic acid on Au(111) has been studied in 0.5 M
KOH solution by in-situ scanning
tunneling microscopy (STM) and cyclic voltammetry. In-situ STM
images of the monolayers at the potentials
between −0.2 V and the reduction potentials of each thiols show the
pits that are commonly seen in STM
images of thiol self-assembled monolayers. A drastic morphological
change takes place in the STM image
around the peak potential in a cyclic voltammogram for the reductive
desorption of adsorbed thiols. The
images indicate that 3-mercaptopropionic acid molecules diffuse away
from the surface after the reduction
because of its higher solubility, while 1-propanethiol and
1-hexadecanethiol molecules stay in the vicinity
of the surface forming aggregates. The partial recovery of the
1-hexadecanethiol monolayer after the
anodic scan, suggested by cyclic voltammograms, is confirmed by STM,
whereas 1-propanethiol aggregates
remain at the surface without being reoxidized. The difference in
the reoxidation behavior reflects the
different amphiphilic properties of the desorbed molecules and the
resultant molecular organizations
formed on the surface.
A diarylethene possessing one [4]thiaheterohelicene and one benzothiophene, the latter with a chiral methoxymethoxyethyl group on its C-3 position, was proved to work as a switch of specific optical rotation at a wavelength at which both colored and colorless forms have no absorption in solution. The difference of the specific optical rotation was 1300 degrees between the open form and the photostationary state. The specific optical rotation of one of the isolated optically active major colored forms was -4680 degrees. The conversion to the colored form was 64%, and the diastereomeric excess of photocyclization was 47%.
These results suggest that M (an active metabolite of erdosteine) may exert an antiinflammatory effect by scavenging inflammatory cells-derived reactive oxygen species.
Quantitative evaluation of Förster-type fluorescence resonance energy transfer (FRET) was undertaken by statistical investigations on perylene-cored anthracene dendrimers.
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