@article{YadavalliLindeKopyshevetal.2013, author = {Yadavalli, Nataraja Sekhar and Linde, Felix and Kopyshev, Alexey and Santer, Svetlana}, title = {Soft matter beats hard matter - rupturing of thin metallic films induced by mass transport in photosensitive polymer films}, series = {ACS applied materials \& interfaces}, volume = {5}, journal = {ACS applied materials \& interfaces}, number = {16}, publisher = {American Chemical Society}, address = {Washington}, issn = {1944-8244}, doi = {10.1021/am4006132w}, pages = {7743 -- 7747}, year = {2013}, abstract = {The interface between thin films of metal and polymer materials play a significant role in modern flexible microelectronics viz., metal contacts on polymer substrates, printed electronics and prosthetic devices. The major emphasis in metal polymer interface is on studying how the externally applied stress in the polymer substrate leads to the deformation and cracks in metal film and vice versa. Usually, the deformation process involves strains varying over large lateral dimensions because of excessive stress at local imperfections. Here we show that the seemingly random phenomena at macroscopic scales can be rendered rather controllable at submicrometer length scales. Recently, we have created a metal polymer interface system with strains varying over periods of several hundred nanometers. This was achieved by exploiting the formation of surface relief grating (SRG) within the azobenzene containing photosensitive polymer film upon irradiation with light interference pattern. Up to a thickness of 60 nm, the adsorbed metal film adapts neatly to the forming relief, until it ultimately ruptures into an array of stripes by formation of highly regular and uniform cracks along the maxima and minima of the polymer topography. This surprising phenomenon has far-reaching implications. This is the first time a direct probe is available to estimate the forces emerging in SRG formation in glassy polymers. Furthermore, crack formation in thin metal films can be studied literally in slow motion, which could lead to substantial improvements in the design process of flexible electronics. Finally, cracks are produced uniformly and at high density, contrary to common sense. This could offer new strategies for precise nanofabrication procedures mechanical in character.}, language = {en} } @article{SimonovaIvanovMeleshkoetal.2020, author = {Simonova, Maria and Ivanov, Ivan and Meleshko, Tamara and Kopyshev, Alexey and Santer, Svetlana and Yakimansky, Alexander and Filippov, Alexander}, title = {Self-assembly of molecular brushes with polyimide backbone and amphiphilic block copolymer side chains in selective solvents}, series = {Polymers}, volume = {12}, journal = {Polymers}, number = {12}, publisher = {MDPI}, address = {Basel}, issn = {2073-4360}, doi = {10.3390/polym12122922}, pages = {15}, year = {2020}, abstract = {Three-component molecular brushes with a polyimide backbone and amphiphilic block copolymer side chains with different contents of the "inner" hydrophilic (poly(methacrylic acid)) and "outer" hydrophobic (poly(methyl methacrylate)) blocks were synthesized and characterized by molecular hydrodynamics and optics methods in solutions of chloroform, dimethylformamide, tetrahydrofuran and ethanol. The peculiarity of the studied polymers is the amphiphilic structure of the grafted chains. The molar masses of the molecular brushes were determined by static and dynamic light scattering in chloroform in which polymers form molecularly disperse solutions. Spontaneous self-assembly of macromolecules was detected in dimethylformamide, tetrahydrofuran and ethanol. The aggregates size depended on the thermodynamic quality of the solvent as well as on the macromolecular architectural parameters. In dimethylformamide and tetrahydrofuran, the distribution of hydrodynamic radii of aggregates was bimodal, while in ethanol, it was unimodal. Moreover, in ethanol, an increase in the poly(methyl methacrylate) content caused a decrease in the hydrodynamic radius of aggregates. A significant difference in the nature of the blocks included in the brushes determines the selectivity of the used solvents, since their thermodynamic quality with respect to the blocks is different. The macromolecules of the studied graft copolymers tend to self-organization in selective solvents with formation of a core-shell structure with an insoluble solvophobic core surrounded by the solvophilic shell of side chains.}, language = {en} } @article{KopyshevGalvinGenzeretal.2016, author = {Kopyshev, Alexey and Galvin, Casey J. and Genzer, Jan and Lomadze, Nino and Santer, Svetlana}, title = {Polymer brushes modified by photosensitive azobenzene containing polyamines}, series = {Polymer : the international journal for the science and technology of polymers}, volume = {98}, journal = {Polymer : the international journal for the science and technology of polymers}, publisher = {Elsevier}, address = {Oxford}, issn = {0032-3861}, doi = {10.1016/j.polymer.2016.03.050}, pages = {421 -- 428}, year = {2016}, abstract = {This paper describes a strategy for preparing photosensitive polymeric grafts on flat solid surfaces by loading diblock-copolymer or homopolymer brushes with cationic azobenzene-containing surfactants. In contrast to previous work, we utilize photosensitive surfactants that bear positively-charged polyamine head groups whose charge varies between 1(+) and 3(+). Poly(methylmethacrylate-b-methacrylic acid) (PMMA-b-PMAA) brushes were prepared by employing atom transfer radical polymerization, where the bottom poly(methyl methacrylate) block was grown first followed by the synthesis of t-butyl methacrylate block that after de-protection yielded poly(methacrylic acid). We used PMMA-b-PMAA brushes with constant grafting density and length of the PMMA block, and three different lengths of the PMAA block. The azobenzene-based surfactants attached only to the PMAA block. The degree of binding (i.e., the number of surfactant molecules per binding site on the brush backbone) of the surfactants to the brush depends strongly on the valence of the surfactant head-group; within the brushes the concentration of the surfactant carrying unit charge is larger than that of multivalent surfactants. We detect pronounced response of the brush topography on irradiation with UV interference pattern even at very low degree of binding (as small as 0.08) of multi-valence surfactant. Areas on the sample that receive the highest UV dose exhibit chain scission. By removing the ruptured chains from the substrate via good solvent, one uncovers a surface topographical relief grating, whose spatial arrangement follows the intensity distribution of the UV light on the sample during irradiation. Due to strong coupling of the multi-valence surfactants to the polymer brush, it was possible in some cases to completely remove the polyelectrolyte block from the PMMA layer. The application of multi-valence azobenzene surfactants for triggering brush photosensitive has important advantage over usage of surfactant with unit charge because relative to single-valence surfactants much lower concentrations of the multivalent surfactant are needed to achieve comparable response upon UV irradiation. (C) 2016 Elsevier Ltd. All rights reserved.}, language = {en} } @article{SchimkaLomadzeRabeetal.2017, author = {Schimka, Selina and Lomadze, Nino and Rabe, Maren and Kopyshev, Alexey and Lehmann, Maren and von Klitzing, Regine and Rumyantsev, Artem M. and Kramarenko, Elena Yu. and Santer, Svetlana}, title = {Photosensitive microgels containing azobenzene surfactants of different charges}, series = {Physical chemistry, chemical physics : a journal of European Chemical Societies}, volume = {19}, journal = {Physical chemistry, chemical physics : a journal of European Chemical Societies}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1463-9076}, doi = {10.1039/c6cp04555c}, pages = {108 -- 117}, year = {2017}, abstract = {We report on light sensitive microgel particles that can change their volume reversibly in response to illumination with light of different wavelengths. To make the anionic microgels photosensitive we add surfactants with a positively charged polyamine head group and an azobenzene containing tail. Upon illumination, azobenzene undergoes a reversible photo-isomerization reaction from a trans- to a cis-state accompanied by a change in the hydrophobicity of the surfactant. Depending on the isomerization state, the surfactant molecules are either accommodated within the microgel (trans- state) resulting in its shrinkage or desorbed back into water (cis-isomer) letting the microgel swell. We have studied three surfactants differing in the number of amino groups, so that the number of charges of the surfactant head varies between 1 and 3. We have found experimentally and theoretically that the surfactant concentration needed for microgel compaction increases with decreasing number of charges of the head group. Utilization of polyamine azobenzene containing surfactants for the light triggered remote control of the microgel size opens up a possibility for applications of light responsive microgels as drug carriers in biology and medicine.}, language = {en} } @misc{SchimkaLomadzeRabeetal.2017, author = {Schimka, Selina and Lomadze, Nino and Rabe, Maren and Kopyshev, Alexey and Lehmann, Maren and von Klitzing, Regine and Rumyantsev, Artem M. and Kramarenko, Elena Yu. and Santer, Svetlana}, title = {Photosensitive microgels containing azobenzene surfactants of different charges}, series = {Postprints der Universit{\"a}t Potsdam : Mathematisch-Naturwissenschaftliche Reihe}, journal = {Postprints der Universit{\"a}t Potsdam : Mathematisch-Naturwissenschaftliche Reihe}, number = {461}, issn = {1866-8372}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-413528}, year = {2017}, abstract = {We report on light sensitive microgel particles that can change their volume reversibly in response to illumination with light of different wavelengths. To make the anionic microgels photosensitive we add surfactants with a positively charged polyamine head group and an azobenzene containing tail. Upon illumination, azobenzene undergoes a reversible photo-isomerization reaction from a trans- to a cis-state accompanied by a change in the hydrophobicity of the surfactant. Depending on the isomerization state, the surfactant molecules are either accommodated within the microgel (trans-state) resulting in its shrinkage or desorbed back into water (cis-isomer) letting the microgel swell. We have studied three surfactants differing in the number of amino groups, so that the number of charges of the surfactant head varies between 1 and 3. We have found experimentally and theoretically that the surfactant concentration needed for microgel compaction increases with decreasing number of charges of the head group. Utilization of polyamine azobenzene containing surfactants for the light triggered remote control of the microgel size opens up a possibility for applications of light responsive microgels as drug carriers in biology and medicine.}, language = {en} } @article{SchuhLomadzeRueheetal.2011, author = {Schuh, Christian and Lomadze, Nino and R{\"u}he, J{\"u}rgen and Kopyshev, Alexey and Santer, Svetlana}, title = {Photomechanical degrafting of Azo-functionalized Poly(methacrylic acid) (PMAA) brushes}, series = {The journal of physical chemistry : B, Condensed matter, materials, surfaces, interfaces \& biophysical chemistry}, volume = {115}, journal = {The journal of physical chemistry : B, Condensed matter, materials, surfaces, interfaces \& biophysical chemistry}, number = {35}, publisher = {American Chemical Society}, address = {Washington}, issn = {1520-6106}, doi = {10.1021/jp2041229}, pages = {10431 -- 10438}, year = {2011}, abstract = {We report on the preparation and characterization of photosensitive polymer brushes. The brushes are synthesized through polymer analogous attachment of azobenzene groups to surface-attached poly(methacrylic acid) (PMAA) chains. The topography of the photosensitive brushes shows a strong reaction upon irradiation with UV light. While homogeneous illumination leaves the polymer topography unchanged, irradiation of the samples with interference patterns with periodically varying light intensity leads to the formation of surface relief gratings (SRG). The height of the stripes of the grating can be controlled by adjusting the irradiation time. The SRG pattern can be erased through solvent treatment when the periodicity of the stripe pattern is less than the length of the fully stretched polymer chains. In the opposite case, photomechanical scission of receding polymer chains is observed during SRG formation, and the inscribed patterns are permanent.}, language = {en} } @article{KopyshevGalvinGenzeretal.2013, author = {Kopyshev, Alexey and Galvin, Casey J. and Genzer, Jan and Lomadze, Nino and Santer, Svetlana}, title = {Opto-mechanical scission of polymer chains in photosensitive diblock-copolymer brushes}, series = {Langmuir}, volume = {29}, journal = {Langmuir}, number = {45}, publisher = {American Chemical Society}, address = {Washington}, issn = {0743-7463}, doi = {10.1021/la403241t}, pages = {13967 -- 13974}, year = {2013}, abstract = {In this paper we report on an opto-mechanical scission of polymer chains within photosensitive diblock-copolymer brushes grafted to flat solid substrates. We employ surface-initiated polymerization of methylmethacrylate (MMA) and t-butyl methacrylate (tBMA) to grow diblock-copolymer brushes of poly(methylmethacrylate-b-t-butyl methacrylate) following the atom transfer polymerization (ATRP) scheme. After the synthesis, deprotection of the PtBMA block yields poly(methacrylic acid) (PMAA). To render PMMA-b-PMAA copolymers photosensitive, cationic azobenzene containing surfactants are attached to the negatively charged outer PMAA block. During irradiation with an ultraviolet (UV) interference pattern, the extent of photoisomerization of the azobenzene groups varies spatially and results in a topography change of the brush, i.e., formation of surface relief gratings (SRG). The SRG formation is accompanied by local rupturing of the polymer chains in areas from which the polymer material recedes. This opto-mechanically induced scission of the polymer chains takes place at the interfaces of the two blocks and depends strongly on the UV irradiation intensity. Our results indicate that this process may be explained by employing classical continuum fracture mechanics, which might be important for tailoring the phenomenon for applying it to poststructuring of polymer brushes.}, language = {en} } @inproceedings{SchuhPruckerLomadzeetal.2012, author = {Schuh, Christian and Prucker, Oswald and Lomadze, Nino and Kopyshev, Alexey and Santer, Svetlana and Ruehe, Juergen}, title = {Nanogradient polymer brushes}, series = {Abstracts of papers : joint conference / The Chemical Institute of Cananda, CIC, American Chemical Society, ACS}, volume = {243}, booktitle = {Abstracts of papers : joint conference / The Chemical Institute of Cananda, CIC, American Chemical Society, ACS}, publisher = {American Chemical Society}, address = {Washington}, issn = {0065-7727}, pages = {1}, year = {2012}, language = {en} } @article{LomadzeKopyshevBargheeretal.2017, author = {Lomadze, Nino and Kopyshev, Alexey and Bargheer, Matias and Wollgarten, Markus and Santer, Svetlana}, title = {Mass production of polymer nanowires filled with metal nanoparticles}, series = {Scientific reports}, volume = {7}, journal = {Scientific reports}, publisher = {Springer Nature}, address = {London}, issn = {2045-2322}, doi = {10.1038/s41598-017-08153-0}, year = {2017}, abstract = {Despite the ongoing progress in nanotechnology and its applications, the development of strategies for connecting nano-scale systems to micro- or macroscale elements is hampered by the lack of structural components that have both, nano- and macroscale dimensions. The production of nano-scale wires with macroscale length is one of the most interesting challenges here. There are a lot of strategies to fabricate long nanoscopic stripes made of metals, polymers or ceramics but none is suitable for mass production of ordered and dense arrangements of wires at large numbers. In this paper, we report on a technique for producing arrays of ordered, flexible and free-standing polymer nano-wires filled with different types of nano-particles. The process utilizes the strong response of photosensitive polymer brushes to irradiation with UV-interference patterns, resulting in a substantial mass redistribution of the polymer material along with local rupturing of polymer chains. The chains can wind up in wires of nano-scale thickness and a length of up to several centimeters. When dispersing nano-particles within the film, the final arrangement is similar to a core-shell geometry with mainly nano-particles found in the core region and the polymer forming a dielectric jacket.}, language = {en} } @misc{LomadzeKopyshevBargheeretal.2017, author = {Lomadze, Nino and Kopyshev, Alexey and Bargheer, Matias and Wollgarten, Markus and Santer, Svetlana}, title = {Mass production of polymer nanowires filled with metal nanoparticles}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-402712}, pages = {10}, year = {2017}, abstract = {Despite the ongoing progress in nanotechnology and its applications, the development of strategies for connecting nano-scale systems to micro- or macroscale elements is hampered by the lack of structural components that have both, nano- and macroscale dimensions. The production of nano-scale wires with macroscale length is one of the most interesting challenges here. There are a lot of strategies to fabricate long nanoscopic stripes made of metals, polymers or ceramics but none is suitable for mass production of ordered and dense arrangements of wires at large numbers. In this paper, we report on a technique for producing arrays of ordered, flexible and free-standing polymer nano-wires filled with different types of nano-particles. The process utilizes the strong response of photosensitive polymer brushes to irradiation with UV-interference patterns, resulting in a substantial mass redistribution of the polymer material along with local rupturing of polymer chains. The chains can wind up in wires of nano-scale thickness and a length of up to several centimeters. When dispersing nano-particles within the film, the final arrangement is similar to a core-shell geometry with mainly nano-particles found in the core region and the polymer forming a dielectric jacket.}, language = {en} } @article{LomadzeKopyshevBargheeretal.2017, author = {Lomadze, Nino and Kopyshev, Alexey and Bargheer, Matias and Wollgarten, Markus and Santer, Svetlana}, title = {Mass production of polymer nano-wires filled with metal nano-particles}, series = {Scientific reports}, volume = {7}, journal = {Scientific reports}, publisher = {Nature Publ. Group}, address = {London}, issn = {2045-2322}, doi = {10.1038/s41598-017-08153-0}, pages = {3759 -- 3764}, year = {2017}, abstract = {Despite the ongoing progress in nanotechnology and its applications, the development of strategies for connecting nano-scale systems to micro-or macroscale elements is hampered by the lack of structural components that have both, nano-and macroscale dimensions. The production of nano-scale wires with macroscale length is one of the most interesting challenges here. There are a lot of strategies to fabricate long nanoscopic stripes made of metals, polymers or ceramics but none is suitable for mass production of ordered and dense arrangements of wires at large numbers. In this paper, we report on a technique for producing arrays of ordered, flexible and free-standing polymer nano-wires filled with different types of nano-particles. The process utilizes the strong response of photosensitive polymer brushes to irradiation with UV-interference patterns, resulting in a substantial mass redistribution of the polymer material along with local rupturing of polymer chains. The chains can wind up in wires of nano-scale thickness and a length of up to several centimeters. When dispersing nano-particles within the film, the final arrangement is similar to a core-shell geometry with mainly nano-particles found in the core region and the polymer forming a dielectric jacket.}, language = {en} } @article{KopyshevLomadzeFeldmanetal.2015, author = {Kopyshev, Alexey and Lomadze, Nino and Feldman, David and Genzer, Jan and Santer, Svetlana}, title = {Making polymer brush photosensitive with azobenzene containing surfactants}, series = {Polymer : the international journal for the science and technology of polymers}, volume = {79}, journal = {Polymer : the international journal for the science and technology of polymers}, publisher = {Elsevier Science}, address = {Oxford}, issn = {0032-3861}, doi = {10.1016/j.polymer.2015.09.023}, pages = {65 -- 72}, year = {2015}, abstract = {We report on rendering polyelectrolyte brushes photosensitive by loading them with azobenzene-containing cationic surfactants. Planar poly(methacrylic acid) (PMAA) brushes are synthesized using the "grafting from" free-radical polymerization scheme followed by exposure to a solution of photosensitive surfactants consisting of positively-charged head groups and hydrophobic tails into which azobenzene moieties are inserted. In this study the length of the hydrophobic methylene spacer connecting the azobenzene and the charged head group ranges from 4 to 10 CH2 groups. Under irradiation with UV light, the photo-isomerization of azobenzene integrated into a surfactant results in a change in size, geometry, dipole moment and free volume of the whole molecule. When the brush loaded with photosensitive surfactants is exposed to irradiation with UV interference patterns, the topography of the brush deforms following the distribution of the light intensity, exhibiting surface relief gratings (SRG). Since SRG formation is accompanied by a local rupturing of polymer chains in areas from which the polymer material is receding, most of the polymer material is removed from the surface during treatment with good solvent, leaving behind characteristic patterns of lines or dots. The azobenzene molecules still integrated within the polymer film can be removed by washing the brush with water. The remaining nano-structured brush can then be re-used for further functionalization. Although the opto-mechanically induced rupturing occurs for all surfactants, larger species do not penetrate deep enough into the brush such that after rupturing a leftover layer of polymer material remains on the substrate. This indicates that rupturing occurs predominantly in regions of high surfactant density.}, language = {en} } @article{KopyshevLomadzeFeldmannetal.2015, author = {Kopyshev, Alexey and Lomadze, Nino and Feldmann, David and Genzer, Jan and Santer, Svetlana}, title = {Making polymer brush photosensitive with azobenzene containing surfactants}, series = {Polymer : the international journal for the science and technology of polymers}, volume = {79}, journal = {Polymer : the international journal for the science and technology of polymers}, publisher = {Elsevier}, address = {Oxford}, issn = {0032-3861}, doi = {10.1016/j.polymer.2015.09.023}, pages = {65 -- 72}, year = {2015}, abstract = {We report on rendering polyelectrolyte brushes photosensitive by loading them with azobenzene-containing cationic surfactants. Planar poly( methacrylic acid) (PMAA) brushes are synthesized using the "grafting from" free-radical polymerization scheme followed by exposure to a solution of photosensitive surfactants consisting of positively-charged head groups and hydrophobic tails into which azobenzene moieties are inserted. In this study the length of the hydrophobic methylene spacer connecting the azobenzene and the charged head group ranges from 4 to 10 CH2 groups. Under irradiation with UV light, the photo-isomerization of azobenzene integrated into a surfactant results in a change in size, geometry, dipole moment and free volume of the whole molecule. When the brush loaded with photosensitive surfactants is exposed to irradiation with UV interference patterns, the topography of the brush deforms following the distribution of the light intensity, exhibiting surface relief gratings (SRG). Since SRG formation is accompanied by a local rupturing of polymer chains in areas from which the polymer material is receding, most of the polymer material is removed from the surface during treatment with good solvent, leaving behind characteristic patterns of lines or dots. The azobenzene molecules still integrated within the polymer film can be removed by washing the brush with water. The remaining nano-structured brush can then be re-used for further functionalization. Although the opto-mechanically induced rupturing occurs for all surfactants, larger species do not penetrate deep enough into the brush such that after rupturing a leftover layer of polymer material remains on the substrate. This indicates that rupturing occurs predominantly in regions of high surfactant density.}, 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} } @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{LoebnerLomadzeKopyshevetal.2018, author = {Loebner, Sarah and Lomadze, Nino and Kopyshev, Alexey and Koch, Markus and Guskova, Olga and Saphiannikova, Marina and Santer, Svetlana}, title = {Light-Induced Deformation of Azobenzene-Containing Colloidal Spheres}, series = {The journal of physical chemistry : B, Condensed matter, materials, surfaces, interfaces \& biophysical chemistry}, volume = {122}, journal = {The journal of physical chemistry : B, Condensed matter, materials, surfaces, interfaces \& biophysical chemistry}, number = {6}, publisher = {American Chemical Society}, address = {Washington}, issn = {1520-6106}, doi = {10.1021/acs.jpcb.7b11644}, pages = {2001 -- 2009}, year = {2018}, abstract = {We report on light-induced deformation of colloidal spheres consisting of azobenzene-containing polymers. The colloids of the size between 60 nm and 2 mu m in diameter were drop casted on a glass surface and irradiated with linearly polarized light. It was found that colloidal particles can be deformed up to ca. 6 times of their initial diameter. The maximum degree of deformation depends on the irradiation wavelength and intensity, as well as on colloidal particles size. On the basis of recently proposed theory by Toshchevikov et al. [J. Phys. Chem. Lett. 2017, 8, 1094], we calculated the optomechanical stresses (ca. 100 MPa) needed for such giant deformations and compared them with the experimental results.}, language = {en} } @article{LomadzeKopyshevRueheetal.2011, author = {Lomadze, Nino and Kopyshev, Alexey and R{\"u}he, J{\"u}rgen and Santer, Svetlana}, title = {Light-Induced chain scission in photosensitive polymer brushes}, series = {Macromolecules : a publication of the American Chemical Society}, volume = {44}, journal = {Macromolecules : a publication of the American Chemical Society}, number = {18}, publisher = {American Chemical Society}, address = {Washington}, issn = {0024-9297}, doi = {10.1021/ma201016q}, pages = {7372 -- 7377}, year = {2011}, abstract = {We report on a process inducing photomechanical fracture of chemical bonds in photosensitive PMAA polymer brushes. The photosensitive PMAA polymer brushes were prepared by covalent attachment of azobenzene groups to poly(methylacrylic acid) (PMAA) chains generated by surface-initiated polymerization. While homogeneous irradiation leaves the polymer topography unchanged, the azo-PMAA brushes show a strong response upon irradiation with UV interference patterns. The photoisomerization process in the surface-attached polymer films results in the irreversible formation of surface relief gratings (SRG), which are strongly enhanced upon washing with a good solvent for the polymer. The photomechanical forces during mass transport induced by the irradiation lead to the scission of covalent bounds and accordingly to a degrafting of the polymer chains in areas where the polymer is receding from. It is observed that the number of ruptured chains depends strongly on the amount of azo side chains in the polymer.}, language = {en} } @article{FeldmannAryaLomadzeetal.2019, author = {Feldmann, David and Arya, Pooja and Lomadze, Nino and Kopyshev, Alexey and Santer, Svetlana}, title = {Light-driven motion of self-propelled porous Janus particles}, series = {Applied physics letters}, volume = {115}, journal = {Applied physics letters}, number = {26}, publisher = {American Institute of Physics}, address = {Melville}, issn = {0003-6951}, doi = {10.1063/1.5129238}, pages = {5}, year = {2019}, abstract = {We introduce a versatile mechanism of light-driven self-propelled motion applied to porous Janus-type particles. The mechanism is based on the generation of local light-driven diffusio-osmotic (l-LDDO) flow around each single porous particle subjected to suitable irradiation conditions. The photosensitivity is introduced by a cationic azobenzene containing surfactant, which undergoes a photoisomerization reaction from a more hydrophobic trans-state to a rather hydrophilic cis-state under illumination with light. The negatively charged porous silica particles are dispersed in a corresponding aqueous solution and absorb molecules in their trans-state but expel them in their cis-state. During illumination with blue light triggering both trans-cis and cis-trans isomerization at the same time, the colloids start to move due to the generation of a steady-state diffusive flow of cis-isomers out of and trans-isomers into the particle. This is because a hemi-spherical metal cap partially sealing the colloid breaks the symmetry of the otherwise radially directed local flow around the particle, leading to self-propelled motion. Janus particles exhibit superdiffusive motion with a velocity of similar to 0.5 mu m/s and a persistence length of ca. 50 mu m, confined to microchannels the direction can be maintained up to 300 mu m before rotational diffusion reverts it. Particles forming dimers of different shapes can be made to travel along circular trajectories. The unique feature of this mechanism is that the strength of self-propulsion can be tuned by convenient external optical stimuli (intensity and irradiation wavelength) such that a broad variety of experimental situations can be realized in a spatiotemporal way and in situ.}, language = {en} } @article{AryaFeldmannKopyshevetal.2020, author = {Arya, Pooja and Feldmann, David and Kopyshev, Alexey and Lomadze, Nino and Santer, Svetlana}, title = {Light driven guided and self-organized motion of mesoporous colloidal particles}, series = {Soft matter}, volume = {16}, journal = {Soft matter}, number = {5}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1744-683X}, doi = {10.1039/c9sm02068c}, pages = {1148 -- 1155}, year = {2020}, abstract = {We report on guided and self-organized motion of ensembles of mesoporous colloidal particles that can undergo dynamic aggregation or separation upon exposure to light. The forces on particles involve the phenomenon of light-driven diffusioosmosis (LDDO) and are hydrodynamic in nature. They can be made to act passively on the ensemble as a whole but also used to establish a mutual interaction between particles. The latter scenario requires a porous colloid morphology such that the particle can act as a source or sink of a photosensitive surfactant, which drives the LDDO process. The interplay between the two modes of operation leads to fascinating possibilities of dynamical organization and manipulation of colloidal ensembles adsorbed at solid-liquid interfaces. While the passive mode can be thought of to allow for a coarse structuring of a cloud of colloids, the inter-particle mode may be used to impose a fine structure on a 2D particle grid. Local flow is used to impose and tailor interparticle interactions allowing for much larger interaction distances that can be achieved with, e.g., DLVO type of forces, and is much more versatile.}, language = {en} } @article{BekirJelkenJungetal.2021, author = {Bekir, Marek and Jelken, Joachim and Jung, Se-Hyeong and Pich, Andrij and Pacholski, Claudia and Kopyshev, Alexey and Santer, Svetlana}, title = {Dual responsiveness of microgels induced by single light stimulus}, series = {Applied physics letters}, volume = {118}, journal = {Applied physics letters}, number = {9}, publisher = {American Institute of Physics}, address = {Melville}, issn = {0003-6951}, doi = {10.1063/5.0036376}, pages = {6}, year = {2021}, abstract = {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.}, language = {en} } @article{ZakrevskyyKopyshevLomadzeetal.2011, author = {Zakrevskyy, Yuriy and Kopyshev, Alexey and Lomadze, Nino and Morozova, Elena and Lysyakova, Liudmila and Kasyanenko, Nina and Santer, Svetlana}, title = {DNA compaction by azobenzene-containing surfactant}, series = {Physical review : E, Statistical, nonlinear and soft matter physics}, volume = {84}, journal = {Physical review : E, Statistical, nonlinear and soft matter physics}, number = {2}, publisher = {American Physical Society}, address = {College Park}, issn = {1539-3755}, doi = {10.1103/PhysRevE.84.021909}, pages = {9}, year = {2011}, abstract = {We report on the interaction of cationic azobenzene-containing surfactant with DNA investigated by absorption and fluorescence spectroscopy, dynamic light scattering, and atomic force microscopy. The properties of the surfactant can be controlled with light by reversible switching of the azobenzene unit, incorporated into the surfactant tail, between a hydrophobic trans (visible irradiation) and a hydrophilic cis (UV irradiation) configuration. The influence of the trans-cis isomerization of the azobenzene on the compaction process of DNA molecules and the role of both isomers in the formation and colloidal stability of DNA-surfactant complexes is discussed. It is shown that the trans isomer plays a major role in the DNA compaction process. The influence of the cis isomer on the DNA coil configuration is rather small. The construction of a phase diagram of the DNA concentration versus surfactant/DNA charge ratio allows distancing between three major phases: colloidally stable and unstable compacted globules, and extended coil conformation. There is a critical concentration of DNA above which the compacted globules can be hindered from aggregation and precipitation by adding an appropriate amount of the surfactant in the trans configuration. This is because of the compensation of hydrophobicity of the globules with an increasing amount of the surfactant. Below the critical DNA concentration, the compacted globules are colloidally stable and can be reversibly transferred with light to an extended coil state.}, language = {en} } @article{KoenigPapkeKopyshevetal.2013, author = {K{\"o}nig, Tobias and Papke, Thomas and Kopyshev, Alexey and Santer, Svetlana}, title = {Atomic force microscopy nanolithography fabrication of metallic nano-slits using silicon nitride tips}, series = {Journal of materials science}, volume = {48}, journal = {Journal of materials science}, number = {10}, publisher = {Springer}, address = {New York}, issn = {0022-2461}, doi = {10.1007/s10853-013-7188-x}, pages = {3863 -- 3869}, year = {2013}, abstract = {In this paper, we report on the properties of nano-slits created in metal thin films using atomic force microscope (AFM) nanolithography (AFM-NL). We demonstrate that instead of expensive diamond AFM tips, it is also possible to use low cost silicon nitride tips. It is shown that depending on the direction of scratching, nano-slits of different widths and depths can be fabricated at constant load force. We elucidate the reasons for this behavior and identify an optimal direction and load force for scratching a gold layer.}, language = {en} }