TY - JOUR A1 - Goulet-Hanssens, Alexis A1 - Utecht, Manuel A1 - Mutruc, Dragos A1 - Titov, Evgenii A1 - Schwarz, Jutta A1 - Grubert, Lutz A1 - Bleger, David A1 - Saalfrank, Peter A1 - Hecht, Stefan T1 - Electrocatalytic Z -> E Isomerization of Azobenzenes JF - Journal of the American Chemical Society N2 - A variety of azobenzenes were synthesized to study the behavior of their E and Z isomers upon electrochemical reduction. Our results show that the radical anion of the Z isomer is able to rapidly isomerize to the corresponding E configured counterpart with a dramatically enhanced rate as compared to the neutral species. Due to a subsequent electron transfer from the formed E radical anion to the neutral Z starting material the overall transformation is catalytic in electrons; i.e., a substoichiometric amount of reduced species can isomerize the entire mixture. This pathway greatly increases the efficiency of (photo)switching while also allowing one to reach photostationary state compositions that are not restricted to the spectral separation of the individual azobenzene isomers and their quantum yields. In addition, activating this radical isomerization pathway with photoelectron transfer agents allows us to override the intrinsic properties of an azobenzene species by triggering the reverse isomerization direction (Z -> E) by the same wavelength of light, which normally triggers E -> Z isomerization. The behavior we report appears to be general, implying that the metastable isomer of a photoswitch can be isomerized to the more stable one catalytically upon reduction, permitting the optimization of azobenzene switching in new as well as indirect ways. Y1 - 2017 U6 - https://doi.org/10.1021/jacs.6b10822 SN - 0002-7863 VL - 139 IS - 1 SP - 335 EP - 341 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Georgiev, Vasil N. A1 - Grafmüller, Andrea A1 - Bléger, David A1 - Hecht, Stefan A1 - Kunstmann, Sonja A1 - Barbirz, Stefanie A1 - Lipowsky, Reinhard A1 - Dimova, Rumiana T1 - Area increase and budding in giant vesicles triggered by light BT - behind the scene JF - Advanced science N2 - Biomembranes are constantly remodeled and in cells, these processes are controlled and modulated by an assortment of membrane proteins. Here, it is shown that such remodeling can also be induced by photoresponsive molecules. The morphological control of giant vesicles in the presence of a water-soluble ortho-tetrafluoroazobenzene photoswitch (F-azo) is demonstrated and it is shown that the shape transformations are based on an increase in membrane area and generation of spontaneous curvature. The vesicles exhibit budding and the buds can be retracted by using light of a different wavelength. In the presence of F-azo, the membrane area can increase by more than 5% as assessed from vesicle electrodeformation. To elucidate the underlying molecular mechanism and the partitioning of F-azo in the membrane, molecular dynamics simulations are employed. Comparison with theoretically calculated shapes reveals that the budded shapes are governed by curvature elasticity, that the spontaneous curvature can be decomposed into a local and a nonlocal contribution, and that the local spontaneous curvature is about 1/(2.5 mu m). The results show that exo- and endocytotic events can be controlled by light and that these photoinduced processes provide an attractive method to change membrane area and morphology. KW - azobenzene KW - lipid membranes KW - molecular dynamics KW - photoswitch KW - vesicles Y1 - 2018 U6 - https://doi.org/10.1002/advs.201800432 SN - 2198-3844 VL - 5 IS - 8 PB - Wiley CY - Hoboken ER - TY - GEN A1 - Georgiev, Vasil N. A1 - Grafmüller, Andrea A1 - Bléger, David A1 - Hecht, Stefan A1 - Kunstmann, Ruth Sonja A1 - Barbirz, Stefanie A1 - Lipowsky, Reinhard A1 - Dimova, Rumiana T1 - Area increase and budding in giant vesicles triggered by light BT - behind the scene T2 - Postprints der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe N2 - Biomembranes are constantly remodeled and in cells, these processes are controlled and modulated by an assortment of membrane proteins. Here, it is shown that such remodeling can also be induced by photoresponsive molecules. The morphological control of giant vesicles in the presence of a water-soluble ortho-tetrafluoroazobenzene photoswitch (F-azo) is demonstrated and it is shown that the shape transformations are based on an increase in membrane area and generation of spontaneous curvature. The vesicles exhibit budding and the buds can be retracted by using light of a different wavelength. In the presence of F-azo, the membrane area can increase by more than 5% as assessed from vesicle electrodeformation. To elucidate the underlying molecular mechanism and the partitioning of F-azo in the membrane, molecular dynamics simulations are employed. Comparison with theoretically calculated shapes reveals that the budded shapes are governed by curvature elasticity, that the spontaneous curvature can be decomposed into a local and a nonlocal contribution, and that the local spontaneous curvature is about 1/(2.5 mu m). The results show that exo- and endocytotic events can be controlled by light and that these photoinduced processes provide an attractive method to change membrane area and morphology. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 733 KW - azobenzene KW - lipid membranes KW - molecular dynamics KW - photoswitch KW - vesicles Y1 - 2019 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-426298 SN - 1866-8372 VL - 5 IS - 733 ER -