@article{KopyshevGalvinPatiletal.2016,
  author    = {Kopyshev, Alexey and Galvin, Casey J. and Patil, Rohan R. and Genzer, Jan and Lomadze, Nino and Feldmann, David and Zakrevski, Juri and Santer, Svetlana},
  title     = {Light-Induced Reversible Change of Roughness and Thickness of Photosensitive Polymer Brushes},
  series = {Applied physics : A, Materials science \& processing},
  volume    = {8},
  journal   = {Applied physics : A, Materials science \& processing},
  publisher = {American Chemical Society},
  address   = {Washington},
  issn      = {1944-8244},
  doi       = {10.1021/acsami.6b06881},
  pages     = {19175 -- 19184},
  year      = {2016},
  abstract  = {We investigate light-induced changes in thickness and roughness of photosensitive polymer brushes containing azobenzene cationic surfactants by atomic force microscopy (AFM) in real time during light irradiation. Because the cis-state of azobenzene unit requires more free volume than its trans counterpart, the UV light-induced expansion of polymer thin films associated with the trans-to-cis isomerism of azobenzene groups is expected to occur. This phenomenon is well documented in physisorbed polymer films containing azobenzene groups. In contrast, photosensitive polymer brushes show a decrease in thickness under UV irradiation. We have found that the azobenzene surfactants in their trans-state form aggregates within the brush. Under irradiation, the surfactants undergo photoisomerization to the cis-state, which is more hydrophilic. As a consequence, the aggregates within the brush are disrupted, and the polymer brush contracts. When subsequently irradiated with blue light the polymer brush thickness returns back to its initial value. This behavior is related to isomerization of the surfactant to the more hydrophobic trans-state and subsequent formation of surfactant aggregates within the polymer brush. The photomechanical function of the dry polymer brush, i.e., contraction and expansion, was found to be reversible with repeated irradiation cycles and requires only a few seconds for switching. In addition to the thickness change, the roughness of the brush also changes reversibly between a few Angstroms (blue light) and several nanometers (UV light). Photosensitive polymer brushes represent smart films with light responsive thickness and roughness that could be used for generating dynamic fluctuating surfaces, the function of which can be turned on and off in a controllable manner on a nanometer length scale.},
  language  = {en}
}
@article{KopyshevKanevcheLomadzeetal.2019,
  author    = {Kopyshev, Alexey and Kanevche, Katerina and Lomadze, Nino and Pfitzner, Emanuel and Loebner, Sarah and Patil, Rohan R. and Genzer, Jan and Heberle, Joachim and Santer, Svetlana},
  title     = {Light-Induced Structuring of Photosensitive Polymer Brushes},
  series = {ACS Applied polymer materials},
  volume    = {1},
  journal   = {ACS Applied polymer materials},
  number    = {11},
  publisher = {American Chemical Society},
  address   = {Washington},
  issn      = {2637-6105},
  doi       = {10.1021/acsapm.9b00705},
  pages     = {301 -- 3026},
  year      = {2019},
  abstract  = {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.},
  language  = {en}
}