TY - JOUR A1 - Arya, Pooja A1 - Feldmann, David A1 - Kopyshev, Alexey A1 - Lomadze, Nino A1 - Santer, Svetlana T1 - Light driven guided and self-organized motion of mesoporous colloidal particles JF - Soft matter N2 - 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. Y1 - 2019 U6 - https://doi.org/10.1039/c9sm02068c SN - 1744-683X SN - 1744-6848 VL - 16 IS - 5 SP - 1148 EP - 1155 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Arya, Pooja A1 - Jelken, Joachim A1 - Feldmann, David A1 - Lomadze, Nino A1 - Santer, Svetlana T1 - Light driven diffusioosmotic repulsion and attraction of colloidal particles JF - The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr N2 - In this paper, we introduce the phenomenon of light driven diffusioosmotic long-range attraction and repulsion of porous particles under irradiation with UV light. The change in the inter-particle interaction potential is governed by flow patterns generated around single colloids and results in reversible aggregation or separation of the mesoporous silica particles that are trapped at a solid surface. The range of the interaction potential extends to several times the diameter of the particle and can be adjusted by varying the light intensity. The "fuel" of the process is a photosensitive surfactant undergoing photo-isomerization from a more hydrophobic trans-state to a rather hydrophilic cis-state. The surfactant has different adsorption affinities to the particles depending on the isomerization state. The trans-isomer, for example, tends to accumulate in the negatively charged pores of the particles, while the cis-isomer prefers to remain in the solution. This implies that when under UV irradiation cis-isomers are being formed within the pores, they tend to diffuse out readily and generate an excess concentration near the colloid's outer surface, ultimately resulting in the initiation of diffusioosmotic flow. The direction of the flow depends strongly on the dynamic redistribution of the fraction of trans- and cis-isomers near the colloids due to different kinetics of photo-isomerization within the pores as compared to the bulk. The unique feature of the mechanism discussed in the paper is that the long-range mutual repulsion but also the attraction can be tuned by convenient external optical stimuli such as intensity so that a broad variety of experimental situations for manipulation of a particle ensemble can be realized. Y1 - 2020 U6 - https://doi.org/10.1063/5.0007556 SN - 0021-9606 SN - 1089-7690 VL - 152 IS - 19 PB - American Institute of Physics CY - Melville, NY ER - TY - JOUR A1 - Arya, Pooja A1 - Jelken, Joachim A1 - Lomadze, Nino A1 - Santer, Svetlana A1 - Bekir, Marek T1 - Kinetics of photo-isomerization of azobenzene containing surfactants JF - The journal of chemical physics : bridges a gap between journals of physics and journals of chemistry N2 - We report on photoisomerization kinetics of azobenzene containing surfactants in aqueous solution. The surfactant molecule consists of a positively charged trimethylammonium bromide head group, a hydrophobic spacer connecting via 6 to 10 CH2 groups to the azobenzene unit, and the hydrophobic tail of 1 and 3CH(2) groups. Under exposure to light, the azobenzene photoisomerizes from more stable trans- to metastable cis-state, which can be switched back either thermally in dark or by illumination with light of a longer wavelength. The surfactant isomerization is described by a kinetic model of a pseudo first order reaction approaching equilibrium, where the intensity controls the rate of isomerization until the equilibrated state. The rate constants of the trans-cis and cis-trans photoisomerization are calculated as a function of several parameters such as wavelength and intensity of light, the surfactant concentration, and the length of the hydrophobic tail. The thermal relaxation rate from cis- to trans-state is studied as well. The surfactant isomerization shows a different kinetic below and above the critical micellar concentration of the trans isomer due to steric hindrance within the densely packed micelle but does not depend on the spacer length. KW - genomic DNA conformation KW - water-interface KW - light photocontrol KW - driven KW - manipulation KW - photoisomerization KW - molecules Y1 - 2020 U6 - https://doi.org/10.1063/1.5135913 SN - 0021-9606 SN - 1089-7690 VL - 152 IS - 2 PB - American Institute of Physics CY - Melville ER - TY - JOUR A1 - Bekir, Marek A1 - Sharma, Anjali A1 - Umlandt, Maren A1 - Lomadze, Nino A1 - Santer, Svetlana T1 - How to make a surface act as a micropump JF - Advanced materials interfaces N2 - In this paper, the phenomenon of light-driven diffusioosmotic (DO) long-range attractive and repulsive interactions between micro-sized objects trapped near a solid wall is investigated. The range of the DO flow extends several times the size of microparticles and can be adjusted to point towards or away from the particle by varying irradiation parameters such as intensity or wavelength of light. The "fuel" of the light-driven DO flow is a photosensitive surfactant which can be photo-isomerized between trans and cis-states. The trans-isomer tends to accumulate at the interface, while the cis-isomer prefers to stay in solution. In combination with a dissimilar photo-isomerization rate at the interface and in bulk, this yields a concentration gradient of the isomers around single particles resulting in local light-driven diffusioosmotic (l-LDDO) flow. Here, the extended analysis of the l-LDDO flow as a function of irradiation parameters by introducing time-dependent development of the concentration excess of isomers near the particle surface is presented. It is also demonstrated that the l-LDDO can be generated at any solid/liquid interface being more pronounced in the case of strongly absorbing material. This phenomenon has plenty of potential applications since it makes any type of surface act as a micropump. KW - azobenzene containing surfactant KW - light-driven diffusioosmosis KW - rate of KW - photo-isomerization Y1 - 2022 U6 - https://doi.org/10.1002/admi.202102395 SN - 2196-7350 VL - 9 IS - 12 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Feldmann, David A1 - Arya, Pooja A1 - Lomadze, Nino A1 - Kopyshev, Alexey A1 - Santer, Svetlana T1 - Light-driven motion of self-propelled porous Janus particles JF - Applied physics letters N2 - 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. Y1 - 2019 U6 - https://doi.org/10.1063/1.5129238 SN - 0003-6951 SN - 1077-3118 VL - 115 IS - 26 PB - American Institute of Physics CY - Melville ER - TY - JOUR A1 - Feldmann, David A1 - Maduar, Salim R. A1 - Santer, Mark A1 - Lomadze, Nino A1 - Vinogradova, Olga I. A1 - Santer, Svetlana T1 - Manipulation of small particles at solid liquid interface: light driven diffusioosmosis JF - Scientific reports N2 - The strong adhesion of sub-micron sized particles to surfaces is a nuisance, both for removing contaminating colloids from surfaces and for conscious manipulation of particles to create and test novel micro/nano-scale assemblies. The obvious idea of using detergents to ease these processes suffers from a lack of control: the action of any conventional surface-modifying agent is immediate and global. With photosensitive azobenzene containing surfactants we overcome these limitations. Such photo-soaps contain optical switches (azobenzene molecules), which upon illumination with light of appropriate wavelength undergo reversible trans-cis photo-isomerization resulting in a subsequent change of the physico-chemical molecular properties. In this work we show that when a spatial gradient in the composition of trans-and cis-isomers is created near a solid-liquid interface, a substantial hydrodynamic flow can be initiated, the spatial extent of which can be set, e.g., by the shape of a laser spot. We propose the concept of light induced diffusioosmosis driving the flow, which can remove, gather or pattern a particle assembly at a solid-liquid interface. In other words, in addition to providing a soap we implement selectivity: particles are mobilized and moved at the time of illumination, and only across the illuminated area. Y1 - 2016 U6 - https://doi.org/10.1038/srep36443 SN - 2045-2322 VL - 6 SP - 25083 EP - 25091 PB - Nature Publ. Group CY - London ER - TY - JOUR A1 - Feldmann, David A1 - Maduar, Salim R. A1 - Santer, Mark A1 - Lomadze, Nino A1 - Vinogradova, Olga I. A1 - Santer, Svetlana T1 - Manipulation of small particles at solid liquid interface BT - light driven diffusioosmosis JF - Scientific reports N2 - The strong adhesion of sub-micron sized particles to surfaces is a nuisance, both for removing contaminating colloids from surfaces and for conscious manipulation of particles to create and test novel micro/nano-scale assemblies. The obvious idea of using detergents to ease these processes suffers from a lack of control: the action of any conventional surface-modifying agent is immediate and global. With photosensitive azobenzene containing surfactants we overcome these limitations. Such photo-soaps contain optical switches (azobenzene molecules), which upon illumination with light of appropriate wavelength undergo reversible trans-cis photo-isomerization resulting in a subsequent change of the physico-chemical molecular properties. In this work we show that when a spatial gradient in the composition of trans- and cis- isomers is created near a solid-liquid interface, a substantial hydrodynamic flow can be initiated, the spatial extent of which can be set, e.g., by the shape of a laser spot. We propose the concept of light induced diffusioosmosis driving the flow, which can remove, gather or pattern a particle assembly at a solid-liquid interface. In other words, in addition to providing a soap we implement selectivity: particles are mobilized and moved at the time of illumination, and only across the illuminated area. KW - genomic DNA conformation KW - photosensitive surfactants KW - optical manipulation KW - photocontrol KW - azobenzene KW - films KW - gradients KW - transport KW - tracking KW - brushes Y1 - 2016 U6 - https://doi.org/10.1038/srep36443 SN - 2045-2322 VL - 6 PB - Nature Publishing Group CY - London ER - TY - GEN A1 - Feldmann, David A1 - Maduar, Salim R. A1 - Santer, Mark A1 - Lomadze, Nino A1 - Vinogradova, Olga I. A1 - Santer, Svetlana T1 - Manipulation of small particles at solid liquid interface BT - light driven diffusioosmosis N2 - The strong adhesion of sub-micron sized particles to surfaces is a nuisance, both for removing contaminating colloids from surfaces and for conscious manipulation of particles to create and test novel micro/nano-scale assemblies. The obvious idea of using detergents to ease these processes suffers from a lack of control: the action of any conventional surface-modifying agent is immediate and global. With photosensitive azobenzene containing surfactants we overcome these limitations. Such photo-soaps contain optical switches (azobenzene molecules), which upon illumination with light of appropriate wavelength undergo reversible trans-cis photo-isomerization resulting in a subsequent change of the physico-chemical molecular properties. In this work we show that when a spatial gradient in the composition of trans- and cis- isomers is created near a solid-liquid interface, a substantial hydrodynamic flow can be initiated, the spatial extent of which can be set, e.g., by the shape of a laser spot. We propose the concept of light induced diffusioosmosis driving the flow, which can remove, gather or pattern a particle assembly at a solid-liquid interface. In other words, in addition to providing a soap we implement selectivity: particles are mobilized and moved at the time of illumination, and only across the illuminated area. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 293 KW - azobenzene KW - brushes KW - films KW - genomic DNA conformation KW - gradients KW - optical manipulation KW - photocontrol KW - photosensitive surfactants KW - tracking KW - transport Y1 - 2016 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-100338 ER - TY - JOUR A1 - Jelken, Joachim A1 - Pandiyarajan, Chinnayan Kannan A1 - Genzer, Jan A1 - Lomadze, Nino A1 - Santer, Svetlana T1 - Fabrication of flexible hydrogel sheets featuring periodically spaced circular holes with continuously adjustable size in realtime JF - ACS applied materials & interfaces N2 - We report on the formation of stimuli-responsive structured hydrogel thin films whose pattern geometry can be adjusted on demand and tuned reversibly by varying solvent quality or by changing temperature. The hydrogel films, similar to 100 nm in thickness, were prepared by depositing layers of random copolymers comprising N-isopropylacrylamide and ultraviolet (UV)-active methacryloyloxybenzophenone units onto solid substrates. A two-beam interference pattern technique was used to cross-link the selected areas of the film; any unreacted material was extracted using ethanol after UV light-assisted cross-linking. In this way, we produced nanoholes, perfectly ordered structures with a narrow size distribution, negligible tortuosity, adjustable periodicity, and a high density. The diameter of the circular holes ranged from a few micrometers down to several tens of nanometers; the hole periodicity could be adjusted readily by changing the optical period of the UV interference pattern. The holes were reversibly closed and opened by swelling/deswelling the polymer networks in the presence of ethanol and water, respectively, at various temperatures. The reversible regulation of the hole diameter can be repeated many times within a few seconds. The hydrogel sheet with circular holes periodically arranged may also be transferred onto different substrates and be employed as tunable templates for the deposition of desired substances. KW - photosensitive polymers KW - PNIPAm KW - hydrogels KW - UV cross-linking KW - stimuli-responsive structured polymer films KW - azobenzene-containing molecules Y1 - 2018 U6 - https://doi.org/10.1021/acsami.8b09580 SN - 1944-8244 VL - 10 IS - 36 SP - 30844 EP - 30851 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Kopyshev, Alexey A1 - Galvin, Casey J. A1 - Genzer, Jan A1 - Lomadze, Nino A1 - Santer, Svetlana T1 - Opto-mechanical scission of polymer chains in photosensitive diblock-copolymer brushes JF - Langmuir N2 - 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. Y1 - 2013 U6 - https://doi.org/10.1021/la403241t SN - 0743-7463 VL - 29 IS - 45 SP - 13967 EP - 13974 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Kopyshev, Alexey A1 - Galvin, Casey J. A1 - Genzer, Jan A1 - Lomadze, Nino A1 - Santer, Svetlana T1 - Polymer brushes modified by photosensitive azobenzene containing polyamines JF - Polymer : the international journal for the science and technology of polymers N2 - 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. KW - Photosensitive brushes KW - Photosensitive azobenzene containing polyamines Y1 - 2016 U6 - https://doi.org/10.1016/j.polymer.2016.03.050 SN - 0032-3861 SN - 1873-2291 VL - 98 SP - 421 EP - 428 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Kopyshev, Alexey A1 - Galvin, Casey J. A1 - Patil, Rohan R. A1 - Genzer, Jan A1 - Lomadze, Nino A1 - Feldmann, David A1 - Zakrevski, Juri A1 - Santer, Svetlana T1 - Light-Induced Reversible Change of Roughness and Thickness of Photosensitive Polymer Brushes JF - Applied physics : A, Materials science & processing N2 - 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. KW - photosensitive brushes KW - azobenzene containing surfactants KW - light driven reversible change of surface topography and thickness KW - domain memory in polymer brushes KW - orientation of azobenzenes in polymer brushes Y1 - 2016 U6 - https://doi.org/10.1021/acsami.6b06881 SN - 1944-8244 VL - 8 SP - 19175 EP - 19184 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Kopyshev, Alexey A1 - Lomadze, Nino A1 - Feldman, David A1 - Genzer, Jan A1 - Santer, Svetlana T1 - Making polymer brush photosensitive with azobenzene containing surfactants JF - Polymer : the international journal for the science and technology of polymers N2 - 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. KW - Azobenzene containing cationic surfactants KW - Photosensitive polymer brushes KW - Opto-mechanically induced scission of polymer chains Y1 - 2015 U6 - https://doi.org/10.1016/j.polymer.2015.09.023 SN - 0032-3861 VL - 79 SP - 65 EP - 72 PB - Elsevier Science CY - Oxford ER - TY - JOUR A1 - Loebner, Sarah A1 - Lomadze, Nino A1 - Kopyshev, Alexey A1 - Koch, Markus A1 - Guskova, Olga A1 - Saphiannikova, Marina A1 - Santer, Svetlana T1 - Light-Induced Deformation of Azobenzene-Containing Colloidal Spheres BT - Calculation and Measurement of Opto-Mechanical Stresses JF - The journal of physical chemistry : B, Condensed matter, materials, surfaces, interfaces & biophysical chemistry N2 - 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. Y1 - 2018 U6 - https://doi.org/10.1021/acs.jpcb.7b11644 SN - 1520-6106 VL - 122 IS - 6 SP - 2001 EP - 2009 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Loebner, Sarah A1 - Yadav, Bharti A1 - Lomadze, Nino A1 - Tverdokhleb, Nina A1 - Donner, Hendrik A1 - Saphiannikova, Marina A1 - Santer, Svetlana T1 - Local direction of optomechanical stress in azobenzene containing polymers during surface relief grating formation JF - Macromolecular materials and engineering N2 - In this work, it is revealed how the photoinduced deformation of azobenzene containing polymers relates to the local direction of optomechanical stresses generated during irradiation with interference patterns (IPs). It can be substantiated by the modeling approach proposed by Saphiannikova et al., which describes the directional photodeformations in glassy side-chain azobenzene polymers, and proves that these deformations arise from the reorientation of rigid backbone segments along the light polarization direction. In experiments and modeling, surface relief gratings in pre-elongated photosensitive colloids of few micrometers length are inscribed using different IPs such as SS, PP, +/- 45, SP, RL, and LR. The deformation of colloidal particles is studied in situ, whereby the local variation of polymer topography is assigned to the local distribution of the electrical field vector for all IPs. Experimentally observed shapes are reproduced exactly with modeling azopolymer samples as visco-plastic bodies in the finite element software ANSYS. Orientation approach correctly predicts local variations of the main axis of light-induced stress in each interference pattern for both initially isotropic and highly oriented materials. With this work, it is suggested that the orientation approach implements a self-sufficient and convincing mechanism to describe photoinduced deformation in azopolymer films that in principle does not require auxiliary assumptions. KW - azobenzene containing polymers KW - colloidal particles KW - direction of optomechanical stress KW - orientation approaches Y1 - 2022 U6 - https://doi.org/10.1002/mame.202100990 SN - 1438-7492 SN - 1439-2054 VL - 307 IS - 8 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Lomadze, Nino A1 - Kopyshev, Alexey A1 - Bargheer, Matias A1 - Wollgarten, Markus A1 - Santer, Svetlana T1 - Mass production of polymer nano-wires filled with metal nano-particles JF - Scientific reports N2 - 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. Y1 - 2017 U6 - https://doi.org/10.1038/s41598-017-08153-0 SN - 2045-2322 VL - 7 SP - 3759 EP - 3764 PB - Nature Publ. Group CY - London ER - TY - JOUR A1 - Lomadze, Nino A1 - Kopyshev, Alexey A1 - Bargheer, Matias A1 - Wollgarten, Markus A1 - Santer, Svetlana T1 - Mass production of polymer nanowires filled with metal nanoparticles JF - Scientific reports N2 - 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. Y1 - 2017 U6 - https://doi.org/10.1038/s41598-017-08153-0 SN - 2045-2322 VL - 7 PB - Springer Nature CY - London ER - TY - GEN A1 - Lomadze, Nino A1 - Kopyshev, Alexey A1 - Bargheer, Matias A1 - Wollgarten, Markus A1 - Santer, Svetlana T1 - Mass production of polymer nanowires filled with metal nanoparticles N2 - 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. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 387 Y1 - 2017 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-402712 ER - TY - JOUR A1 - Lomadze, Nino A1 - Kopyshev, Alexey A1 - Rühe, Jürgen A1 - Santer, Svetlana T1 - Light-Induced chain scission in photosensitive polymer brushes JF - Macromolecules : a publication of the American Chemical Society N2 - 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. Y1 - 2011 U6 - https://doi.org/10.1021/ma201016q SN - 0024-9297 VL - 44 IS - 18 SP - 7372 EP - 7377 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Lysyakova, Liudmila A1 - Lomadze, Nino A1 - Neher, Dieter A1 - Maximova, Ksenia A1 - Kabashin, Andrei V. A1 - Santer, Svetlana T1 - Light-Tunable Plasmonic Nanoarchitectures Using Gold Nanoparticle-Azobenzene-Containing Cationic Surfactant Complexes JF - The journal of physical chemistry : C, Nanomaterials and interfaces N2 - When arranged in a proper nanoaggregate architecture, gold nanoparticles can offer controllable plasmon-related absorption/scattering, yielding distinct color effects that depend critically on the relative orientation and distance between nanoparticle constituents. Herein, we report on the implementation of novel plasmonic nanoarchitectures based on complexes between gold nanoparticles and an azobenzene-modified cationic surfactant that can exhibit a light-tunable plasmonic response. The formation of such complexes becomes possible through the use of strongly negatively charged bare gold nanoparticles (similar to 10-nm diameter) prepared by the method of laser ablation in deionized water. Driven by electrostatic interactions, the cationic surfactant molecules attach and form a shell around the negatively charged nanoparticles, resulting in neutralization of the particle charge or even overcompensation beyond which the nanoparticles become positively charged. At low and high surfactant concentrations, Au nanoparticles are negatively and positively charged, respectively, and are represented by single species due to electric repulsion effects having absorption peaks around 523-527 nm, whereas at intermediate concentrations, the Au nanoparticles become neutral, forming nanoscale 100-nm clusterlike aggregates and exhibiting an additional absorption peak at gimel > 600 nm and a visible change in the color of the solution from red to blue. Because of the presence of the photosensitive azobenzene unit in the surfactant tail that undergoes trans-to-cis isomerization under irradiation with UV light, we then demonstrate a light-controlled nanoclustering of nanoparticles, yielding a switch in the plasmonic absorption band and a related change in the solution color. The formed hybrid architectures with a light-controlled plasmonic response could be important for a variety of tasks, including biomedical, surface-enhanced Raman spectroscopy (SERS), data transmission, and storage applications. Y1 - 2015 U6 - https://doi.org/10.1021/jp511232g SN - 1932-7447 VL - 119 IS - 7 SP - 3762 EP - 3770 PB - American Chemical Society CY - Washington ER -