@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{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{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{ZakrevskyyRichterZakrevskaetal.2012, author = {Zakrevskyy, Yuriy and Richter, Marcel and Zakrevska, Svitlana and Lomadze, Nino and von Klitzing, Regine and Santer, Svetlana}, title = {Light-controlled reversible manipulation of microgel particle size using azobenzene-containing surfactant}, series = {Advanced functional materials}, volume = {22}, journal = {Advanced functional materials}, number = {23}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1616-301X}, doi = {10.1002/adfm.201200617}, pages = {5000 -- 5009}, year = {2012}, abstract = {The light-induced reversible switching of the swelling of microgel particles triggered by photo-isomerization and binding/unbinding of a photosensitive azobenzene-containing surfactant is reported. The interactions between the microgel (N-isopropylacrylamide, co-monomer: allyl acetic acid, crosslinker: N,N'-methylenebisacrylamide) and the surfactant are studied by UV-Vis spectroscopy, dynamic and electrophoretic light scattering measurements. Addition of the surfactant above a critical concentration leads to contraction/collapse of the microgel. UV light irradiation results in trans-cis isomerization of the azobenzene unit incorporated into the surfactant tail and causes an unbinding of the more hydrophilic cis isomer from the microgel and its reversible swelling. The reversible contraction can be realized by blue light irradiation that transfers the surfactant back to the more hydrophobic trans conformation, in which it binds to the microgel. The phase diagram of the surfactant-microgel interaction and transitions (aggregation, contraction, and precipitation) is constructed and allows prediction of changes in the system when the concentration of one or both components is varied. Remote and reversible switching between different states can be realized by either UV or visible light irradiation.}, 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{YadavalliSaphiannikovaLomadzeetal.2013, author = {Yadavalli, Nataraja Sekhar and Saphiannikova, Marina and Lomadze, Nino and Goldenberg, Leonid M. and Santer, Svetlana}, title = {Structuring of photosensitive material below diffraction limit using far field irradiation}, series = {Applied physics : A, Materials science \& processing}, volume = {113}, journal = {Applied physics : A, Materials science \& processing}, number = {2}, publisher = {Springer}, address = {New York}, issn = {0947-8396}, doi = {10.1007/s00339-013-7945-3}, pages = {263 -- 272}, year = {2013}, abstract = {In this paper, we report on in-situ atomic force microscopy (AFM) studies of topographical changes in azobenzene-containing photosensitive polymer films that are irradiated with light interference patterns. We have developed an experimental setup consisting of an AFM combined with two-beam interferometry that permits us to switch between different polarization states of the two interfering beams while scanning the illuminated area of the polymer film, acquiring corresponding changes in topography in-situ. This way, we are able to analyze how the change in topography is related to the variation of the electrical field vector within the interference pattern. It is for the first time that with a rather simple experimental approach a rigorous assignment can be achieved. By performing in-situ measurements we found that for a certain polarization combination of two interfering beams [namely for the SP (a dagger center dot, a dagger") polarization pattern] the topography forms surface relief grating with only half the period of the interference patterns. Exploiting this phenomenon we are able to fabricate surface relief structures with characteristic features measuring only 140 nm, by using far field optics with a wavelength of 491 nm. We believe that this relatively simple method could be extremely valuable to, for instance, produce structural features below the diffraction limit at high-throughput, and this could significantly contribute to the search of new fabrication strategies in electronics and photonics industry.}, 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} } @article{ZakrevskyyTitovLomadzeetal.2014, author = {Zakrevskyy, Yuriy and Titov, Evgenii and Lomadze, Nino and Santer, Svetlana}, title = {Phase diagrams of DNA-photosensitive surfactant complexes: Effect of ionic strength and surfactant structure}, series = {The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr}, volume = {141}, journal = {The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr}, number = {16}, publisher = {American Institute of Physics}, address = {Melville}, issn = {0021-9606}, doi = {10.1063/1.4899281}, pages = {8}, year = {2014}, abstract = {Realization of all-optically controlled and efficient DNA compaction is the major motivation in the study of interactions between DNA and photosensitive surfactants. In this article, using recently published approach of phase diagram construction [Y. Zakrevskyy, P. Cywinski, M. Cywinska, J. Paasche, N. Lomadze, O. Reich, H.-G. Lohmannsroben, and S. Santer, J. Chem. Phys. 140, 044907 (2014)], a strategy for substantial reduction of compaction agent concentration and simultaneous maintaining the light-induced decompaction efficiency is proposed. The role of ionic strength (NaCl concentration), as a very important environmental parameter, and surfactant structure (spacer length) on the changes of positions of phase transitions is investigated. Increase of ionic strength leads to increase of the surfactant concentration needed to compact DNA molecule. However, elongation of the spacer results to substantial reduction of this concentration. DNA compaction by surfactants with longer tails starts to take place in diluted solutions at charge ratios Z < 1 and is driven by azobenzene-aggregation compaction mechanism, which is responsible for efficient decompaction. Comparison of phase diagrams for different DNA-photosensitive surfactant systems allowed explanation and proposal of a strategy to overcome previously reported limitations of the light-induced decompaction for complexes with increasing surfactant hydrophobicity. (C) 2014 AIP Publishing LLC.}, language = {en} } @article{RichterZakrevskyyEiseleetal.2014, author = {Richter, Marcel and Zakrevskyy, Yuriy and Eisele, Michael and Lomadze, Nino and Santer, Svetlana and von Klitzing, Regine}, title = {Effect of pH, co-monomer content, and surfactant structure on the swelling behavior of microgel-azobenzene-containing surfactant complex}, series = {Polymer : the international journal for the science and technology of polymers}, volume = {55}, journal = {Polymer : the international journal for the science and technology of polymers}, number = {25}, publisher = {Elsevier}, address = {Oxford}, issn = {0032-3861}, doi = {10.1016/j.polymer.2014.10.027}, pages = {6513 -- 6518}, year = {2014}, abstract = {The contraction/swelling transition of anionic PNIPAM-co-AAA particles can be manipulated by light using interactions with cationic azobenzene-containing surfactant. In this study the influence of pH-buffers and their concentrations, the charge density (AAA content) in microgel particles as well as the spacer length of the surfactant on the complex formation between the microgel and surfactant is investigated. It is shown that the presence of pH buffer can lead to complete blocking of the interactions in such complexes and the resulting microgel contraction/swelling response. There is a clear competition between the buffer ions and the surfactant molecules interacting with microgel particles. When working in pure water solutions with fixed concentration (charge density) of microgel, the contraction/swelling of the particles is controlled only by relative concentration (charge ratio) of the surfactant and AAA groups of the microgel. Furthermore, the particle contraction is more efficient for shorter spacer length of the surfactant. The onset point of the contraction process is not affected by the surfactant hydrophobicity. This work provides new insight into the interaction between microgel particles and photo-sensitive surfactants, which offers high potential in new sensor systems. (C) 2014 Elsevier Ltd. All rights reserved.}, language = {en} } @article{ZakrevskyyRoxlauBrezesinskietal.2014, author = {Zakrevskyy, Yuriy and Roxlau, Julian and Brezesinski, Gerald and Lomadze, Nino and Santer, Svetlana}, title = {Photosensitive surfactants: Micellization and interaction with DNA}, series = {The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr}, volume = {140}, journal = {The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr}, number = {4}, publisher = {American Institute of Physics}, address = {Melville}, issn = {0021-9606}, doi = {10.1063/1.4862678}, pages = {8}, year = {2014}, abstract = {Recently, photosensitive surfactants have re-attracted considerable attention. It has been shown that their association with oppositely charged biologically important polyelectrolytes, such as DNA or microgels, can be efficiently manipulated simply by light exposure. In this article, we investigate the self-assembly of photosensitive surfactants as well as their interactions with DNA by calorimetric and spectroscopic methods. Critical micelle concentration (CMC), standard micellization enthalpy, entropy, and Gibbs energy were determined in different conditions (ionic strengths and temperatures) for a series of cationic surfactants with an azobenzene group in their tail. It is shown, that aggregation forces of photosensitive units play an important role in the micellization giving the major contribution to the micellization enthalpy. The onset of the aggregation can be traced from shift of the absorption peak position in the UV-visible spectrum. Titration UV-visible spectroscopy is used as an alternative, simple, and sensitive approach to estimate CMC. The titration UV-visible spectroscopy was also employed to investigate interactions (CAC: critical aggregation concentration, precipitation, and colloidal stabilization) in the DNA-surfactant complex.}, language = {en} }