TY  - JOUR
A1  - Titov, Evgenii
A1  - Sharma, Anjali
A1  - Lomadze, Nino
A1  - Saalfrank, Peter
A1  - Santer, Svetlana
A1  - Bekir, Marek
T1  - Photoisomerization of an azobenzene-containing surfactant within a micelle
JF  - ChemPhotoChem
N2  - Photosensitive azobenzene-containing surfactants have attracted great attention in past years because they offer a means to control soft-matter transformations with light. At concentrations higher than the critical micelle concentration (CMC), the surfactant molecules aggregate and form micelles, which leads to a slowdown of the photoinduced trans -> cis azobenzene isomerization. Here, we combine nonadiabatic dynamics simulations for the surfactant molecules embedded in the micelles with absorption spectroscopy measurements of micellar solutions to uncover the reasons responsible for the reaction slowdown. Our simulations reveal a decrease of isomerization quantum yields for molecules inside the micelles. We also observe a reduction of extinction coefficients upon micellization. These findings explain the deceleration of the trans -> cis switching in micelles of the azobenzene-containing surfactants.
KW  - azobenzene
KW  - micelles
KW  - photoswitches
KW  - rate constants
KW  - surfactants
KW  - surface hopping
Y1  - 2021
U6  - https://doi.org/10.1002/cptc.202100103
SN  - 2367-0932
VL  - 5
IS  - 10
SP  - 926
EP  - 932
PB  - Wiley-VCH
CY  - Weinheim
ER  - 
TY  - JOUR
A1  - Reifarth, Martin
A1  - Bekir, Marek
A1  - Bapolisi, Alain M.
A1  - Titov, Evgenii
A1  - Nusshardt, Fabian
A1  - Nowaczyk, Julius
A1  - Grigoriev, Dmitry
A1  - Sharma, Anjali
A1  - Saalfrank, Peter
A1  - Santer, Svetlana
A1  - Hartlieb, Matthias
A1  - Böker, Alexander
T1  - A dual pH- and light-responsive spiropyrane-based surfactant
BT  - investigations on Its switching behavior and remote control over emulsion stability
JF  - Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition
N2  - A cationic surfactant containing a spiropyrane unit is prepared exhibiting a dual-responsive adjustability of its surface-active characteristics. The switching mechanism of the system relies on the reversible conversion of the non-ionic spiropyrane (SP) to a zwitterionic merocyanine (MC) and can be controlled by adjusting the pH value and via light, resulting in a pH-dependent photoactivity: While the compound possesses a pronounced difference in surface activity between both forms under acidic conditions, this behavior is suppressed at a neutral pH level. The underlying switching processes are investigated in detail, and a thermodynamic explanation based on a combination of theoretical and experimental results is provided. This complex stimuli-responsive behavior enables remote-control of colloidal systems. To demonstrate its applicability, the surfactant is utilized for the pH-dependent manipulation of oil-in-water emulsions.
KW  - Dual-Responsiveness
KW  - Manipulation of Emulsion Stability
KW  - Spiropyrane
KW  - Surfactant
KW  - Switchable Surfactants
KW  - pH-Dependent Photoresponsivity
Y1  - 2022
U6  - https://doi.org/10.1002/anie.202114687
SN  - 1433-7851
SN  - 1521-3773
VL  - 61
IS  - 21
PB  - Wiley-VCH
CY  - Weinheim
ER  -