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 - Umlandt, Maren A1 - Feldmann, David A1 - Schneck, Emanuel A1 - Santer, Svetlana A1 - Bekir, Marek T1 - Adsorption of photoresponsive surfactants at solid-liquid interfaces JF - Langmuir N2 - We report on the adsorption kinetics of azoben-zene-containing surfactants on solid surfaces of different hydrophobicity. The understanding of this processes is of great importance for many interfacial phenomena that can be actuated and triggered by light, since the surfactant molecules contain a photoresponsive azobenzene group in their hydrophobic tail. Three surfactant types are studied, differing in the spacer connecting the headgroup and the azobenzene unit by between 6 and 10 CH2 groups. Under irradiation with light of a suitable wavelength, the azobenzene undergoes reversible photoisomerization between two states, a nonpolar trans-state and a highly polar cis-state. Consequently, the surfactant molecule changes its hydrophobicity and thus affinity to a surface depending on the photoisomerization state of the azobenzene. The adsorption behavior on hydrophilic (glass) and hydrophobic (TeflonAF) surfaces is analyzed using quartz crystal microbalance with dissipation (QCM-D) and zeta-potential measurements. At equilibrium, the adsorbed surfactant amount is almost twice as large on glass compared to TeflonAF for both isomers. The adsorption rate for the trans-isomers on both surfaces is similar, but the desorption rate of the trans-isomers is faster at the glass-water interface than at the Teflon-water interface. This result demonstrates that the trans-isomers have higher affinity for the glass surface, so the trans-to-cis ratios on glass and TeflonAF are 80/1 and 2/1, respectively, with similar trends for all three surfactant types. Y1 - 2020 U6 - https://doi.org/10.1021/acs.langmuir.0c02545 SN - 0743-7463 SN - 1520-5827 VL - 36 IS - 46 SP - 14009 EP - 14018 PB - American Chemical Society CY - Washington ER - 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 - 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 - THES A1 - Feldmann, David T1 - Light-driven diffusioosmosis T1 - Licht-getriebene Diffusioosmose BT - the manipulation of colloids using azobenzene containing surfactant BT - Manipulation von Kolloiden mittels azobenzolhaltigen Tensiden N2 - The emergence of microfluidics created the need for precise and remote control of micron-sized objects. I demonstrate how light-sensitive motion can be induced at the micrometer scale by a simple addition of a photosensitive surfactant, which makes it possible to trigger hydrophobicity with light. With point-like laser irradiation, radial inward and outward hydrodynamic surface flows are remotely switched on and off. In this way, ensembles of microparticles can be moved toward or away from the irradiation center. Particle motion is analyzed according to varying parameters, such as surfactant and salt concentration, illumination condition, surface hydrophobicity, and surface structure. The physical origin of this process is the so-called light-driven diffusioosmosis (LDDO), a phenomenon that was discovered in the framework of this thesis and is described experimentally and theoretically in this work. To give a brief explanation, a focused light irradiation induces a local photoisomerization that creates a concentration gradient at the solid-liquid interface. To compensate for the change in osmotic pressure near the surface, a hydrodynamic flow along the surface is generated. Surface-surfactant interaction largely governs LDDO. It is shown that surfactant adsorption depends on the isomerization state of the surfactant. Photoisomerization, therefore, triggers a surfactant attachment or detachment from the surface. This change is considered to be one of the reasons for the formation of LDDO flow. These flows are introduced not only by a focused laser source but also by global irradiation. Porous particles show reversible repulsive and attractive interactions when dispersed in the solution of photosensitive surfactant. Repulsion and attraction is controlled by the irradiation wavelength. Illumination with red light leads to formation of aggregates, while illumination with blue light leads to the formation of a well-separated grid with equal interparticle distances, between 2µm and 80µm, depending on the particle surface density. These long-range interactions are considered to be a result of an increase or decrease of surfactant concentration around each particle, depending on the irradiation wavelength. Surfactant molecules adsorb inside the pores of the particles. A light-induced photoisomerization changes adsorption to the pores and drives surfactant molecules to the outside. The concentration gradients generate symmetric flows around each single particle resulting in local LDDO. With a break of the symmetry (i.e., by closing one side of the particle with a metal cap), one can achieve active self-propelled particle motion. N2 - Mit Aufkommen der Mikrofluidik entstand eine größere Nachfrage nach präziser und berührungsfreier Manipulation von mikrometergroßen Objekten. In dieser Arbeit wird gezeigt, wie Bewegung im Mikrometerbereich durch ein lichtschaltbares Tensid erzeugt werden kann, deren Hydrophobizität sich durch Beleuchtung ändert. Eine fokussierte punktförmige Laserbestrahlung erzeugt einen radial nach außen oder innen gerichteten Fluss an der Substratoberfläche je nach Laserwellenlänge. Mikropartikel die sich auf der Oberfläche befinden, bewegen sich dadurch passiv mit dem Fluss entweder zum Bestrahlungspunkt hin oder vom Bestrahlungspunkt weg. Die Partikelbewegung wird in Abhängigkeit von den folgenden Parametern untersucht: Tensid- und Salzkonzentration, Bestrahlungsbedingungen, Hydrophobizität der Oberfläche und Oberflächenstruktur. Der Grund für die Bewegung kann in einem Prozess gefunden werden, der sogenannten lichtgetriebenen Diffusioosmose (LDDO), die im Rahmen dieser Dissertation entdeckt und theoretisch sowie experimentell beschrieben wurde. Der Prozess kann wie folgt betrachtet werden: Die fokussierte Bestrahlung induziert eine lokale Photo-Isomerisation der Tensidmoleküle, die eine Monomer-Konzentrationsänderung zur Folge hat. Lokal entsteht ein hierdurch ein höherer osmotischer Druck an der Oberfläche. Um den Druckunterschied an der Oberfläche auszugleichen, wird ein hydrodynamischer Fluss nahe der Oberfläche erzeugt. Hierbei bestimmt vor allem die Wechselwirkung zwischen Tensid und Oberfläche den induzierten Fluss. Es wird gezeigt, dass die Oberflächenadsorption des Tensids vom Isomerisationszustand abhängt. Somit kann eine Bestrahlung ein Ablösen von oder Anhaften an der Oberfläche erzeugen. Diese Änderung der Oberflächenkonzentration kann als einer der Gründe für die Flussentstehung angesehen werden. Diese hydrodynamischen Oberflächenflüssen können nicht nur durch einen fokussierten Laser erzeugt werden, sondern auch durch eine gesamte Bestrahlung der Oberfläche. Hierbei zeigen poröse Partikel eine reversible Anziehung und Abstoßung, wenn sie sich in einer Tensidlösung und an einer Substratoberfläche befinden. Die Wechselwirkung kann hierbei durch die Bestrahlungswellenlänge kontrolliert werden. In Dunkelheit oder in rotem Licht ziehen sich die Partikel gegenseitig an, währenddessen sie sich unter blauer Bestrahlung abstoßen und ein Partikelnetz erzeugen mit äquidistanten Abständen zwischen den Partikeln. Die Partikelabstände hängen von der Partikeldichte an der Oberfläche ab und variieren zwischen 2µm und 80µm. Der Grund für die reversible Anziehung und Abstoßung wird ähnlich zu LDDO in einer lichtinduzierten Konzentrationsänderung gesehen. Tensidmoleküle adsorbieren innerhalb der Poren der Partikel. Durch eine lichtinduzierte Isomerisation werden die Moleküle ausgestoßen. Hierbei entsteht die Konzentrationsänderung um jedes poröse Partikel herum, währenddessen sie in LDDO um den Laserpunkt entsteht. Somit werden diffusioosmotische Flüsse symmetrisch um jedes Partikel erzeugt, wohingegen sie in LDDO nur um den Laserpunkt erzeugt werden.Demzufolge stoßen sich die Partikel durch eine hydrodynamische Wechselwirkung ab. Es wird gezeigt, dass aufgrund eines Symmetriebruchs durch ein Abdecken einer Partikelhälfte eine aktive selbstgetriebene Partikelbewegung erzeugt werden kann. KW - azobenzene surfactant KW - Diffusioosmosis KW - Janus particle KW - surface KW - solid-liquid interface KW - surface flow KW - micro swimmer KW - self-propelled particle KW - light-driven KW - particles KW - azobenzolhaltige Tenside KW - Diffusioosmose KW - Janus Partikel KW - Oberfläche KW - fest-flüssig Grenzfläche KW - Oberflächenfluss KW - Mikroschwimmer KW - selbst-getriebene Partikel KW - licht-getrieben KW - Partikel Y1 - 2018 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-417184 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 - 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 -