TY - JOUR A1 - Bekir, Marek A1 - Jelken, Joachim A1 - Jung, Se-Hyeong A1 - Pich, Andrij A1 - Pacholski, Claudia A1 - Kopyshev, Alexey A1 - Santer, Svetlana T1 - Dual responsiveness of microgels induced by single light stimulus JF - Applied physics letters N2 - We report on the multiple response of microgels triggered by a single optical stimulus. Under irradiation, the volume of the microgels is reversibly switched by more than 20 times. The irradiation initiates two different processes: photo-isomerization of the photo-sensitive surfactant, which forms a complex with the anionic microgel, rendering it photo-responsive; and local heating due to a thermo-plasmonic effect within the structured gold layer on which the microgel is deposited. The photo-responsivity is related to the reversible accommodation/release of the photo-sensitive surfactant depending on its photo-isomerization state, while the thermo-sensitivity is intrinsically built in. We show that under exposure to green light, the thermo-plasmonic effect generates a local hot spot in the gold layer, resulting in the shrinkage of the microgel. This process competes with the simultaneous photo-induced swelling. Depending on the position of the laser spot, the spatiotemporal control of reversible particle shrinking/swelling with a predefined extent on a per-second base can be implemented. Y1 - 2021 U6 - https://doi.org/10.1063/5.0036376 SN - 0003-6951 SN - 1077-3118 VL - 118 IS - 9 PB - American Institute of Physics CY - Melville ER - TY - JOUR A1 - Kopyshev, Alexey A1 - Kanevche, Katerina A1 - Lomadze, Nino A1 - Pfitzner, Emanuel A1 - Loebner, Sarah A1 - Patil, Rohan R. A1 - Genzer, Jan A1 - Heberle, Joachim A1 - Santer, Svetlana T1 - Light-Induced Structuring of Photosensitive Polymer Brushes JF - ACS Applied polymer materials N2 - We investigate light-induced irreversible structuring of surface topographies in poly(3-sulfopropyl methacrylate/potassium salt) (PSPMK) brushes on flat solid substrates prepared by surface-initiated atom transfer radical polymerization. The brushes have been loaded with azobenzene-based surfactant comprised of positively charged headgroups and hydrophobic tail. The surfactant exhibits photoresponsive properties through photoisomerization from the trans to cis states leading to significant changes in physicochemical properties of grafted polymer chains. The azobenzene surfactant enables photoresponsive behavior without introducing irreversible changes to chemical composition of the parent polymer brush. Exposing these photosensitive brushes to irradiation with UV interference beams causes the polymer brush to form surface relief grating (SRG) patterns. The cationic surfactant penetrates only similar to 25% of the upper portion of the PSPMK brush, resulting in the formation of two sections within the brush: a photoresponsive upper layer and nonfunctional buried layer, which is not affected by the UV irradiation. Using nano-FTIR spectroscopy, we characterize locally the chemical composition of the polymer brush and confirm partial penetration of the surfactant within the film. Strong optomechanical stresses take place only within the upper layer of the brush that is impregnated with the surfactants and causes surface topography alternation due to a local rupture of grafted polymer chains. The cleaved polymer chains are then removed from the surface by using a good solvent, leaving behind topographical grating on top of the nonfunctional brush layer. We demonstrate that photostructured polymer brush can be used for reversible switching of brush topography by varying external humidity. KW - photosensitive polymer brushes KW - reversible and irreversible structuring of polymer brushes KW - photosensitive azobenzene containing surfactant KW - strong polyelectrolyte brush KW - SRG formation in polymer brushes Y1 - 2019 U6 - https://doi.org/10.1021/acsapm.9b00705 SN - 2637-6105 VL - 1 IS - 11 SP - 301 EP - 3026 PB - American Chemical Society CY - Washington ER -