% IMPORTANT: The following is UTF-8 encoded. This means that in the presence
% of non-ASCII characters, it will not work with BibTeX 0.99 or older.
% Instead, you should use an up-to-date BibTeX implementation like “bibtex8” or
% “biber”.
@ARTICLE{Hardt:1024739,
author = {Hardt, Michael and Busse, Franziska and Raschke, Simon and
Honnigfort, Christian and Carrascosa-Tejedor, Javier and
Wenk, Paul and Gutfreund, Philipp and Campbell, Richard A.
and Heuer, Andreas and Braunschweig, Björn},
title = {{P}hoto-{R}esponsive {C}ontrol of {A}dsorption and
{S}tructure {F}ormation at the {A}ir–{W}ater {I}nterface
with {A}rylazopyrazoles},
journal = {Langmuir},
volume = {39},
number = {16},
issn = {0743-7463},
address = {Washington, DC},
publisher = {ACS Publ.},
reportid = {FZJ-2024-02405},
pages = {5861 - 5871},
year = {2023},
abstract = {Smart interfaces that are responsive to external triggers
such as light are of great interest for the development of
responsive or adaptive materials and interfaces. Using
alkyl-arylazopyrazole butyl sulfonate surfactants
(alkyl-AAP) that can undergo E/Z photoisomerization when
irradiated with green (E) and UV (Z) lights, we demonstrate
through a combination of experiments and computer
simulations that there can be surprisingly large changes in
surface tension and in the molecular structure and order at
air–water interfaces. Surface tensiometry, vibrational
sum-frequency generation (SFG) spectroscopy, and neutron
reflectometry (NR) are applied to the study of
custom-synthesized AAP surfactants with octyl- and
H-terminal groups at air–water interfaces as a function of
their bulk concentration and E/Z configuration. Upon
photoswitching, a drastic influence of the alkyl chain on
both the surface activity and the responsiveness of
interfacial surfactants is revealed from changes in the
surface tension, γ, where the largest changes in γ are
observed for octyl-AAP (Δγ ∼ 23 mN/m) in contrast to
H-AAP with Δγ < 10 mN/m. Results from vibrational SFG
spectroscopy and NR show that the interfacial composition
and the molecular order of the surfactants drastically
change with E/Z photoisomerization and surface coverage.
Indeed, from analysis of the S–O (head group) and C–H
vibrational bands (hydrophobic tail), a qualitative analysis
of orientational and structural changes of interfacial AAP
surfactants is provided. The experiments are complemented by
resolution of thermodynamic parameters such as equilibrium
constants from ultra-coarse-grained simulations, which also
capture details like island formation and interaction
parameters of interfacial molecules. Here, the interparticle
interaction (“stickiness”) and the interaction with the
surface are adjusted, closely reflecting experimental
conditions.},
cin = {IEK-12},
ddc = {540},
cid = {I:(DE-Juel1)IEK-12-20141217},
pnm = {1221 - Fundamentals and Materials (POF4-122) / DFG project
G:(GEPRIS)433682494 - SFB 1459: Intelligente Materie – Von
responsiven zu adaptiven Nanosystemen (433682494)},
pid = {G:(DE-HGF)POF4-1221 / G:(GEPRIS)433682494},
typ = {PUB:(DE-HGF)16},
pubmed = {37058525},
UT = {WOS:000974305400001},
doi = {10.1021/acs.langmuir.3c00294},
url = {https://juser.fz-juelich.de/record/1024739},
}