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- ItemNanometer-thick lateral polyelectrolyte micropatterns induce macrosopic electro-osmotic chaotic fluid instabilities([London] : Macmillan Publishers Limited, part of Springer Nature, 2014) Wessling, M.; Morcillo, L. Garrigós; Abdu, S.Electro-convective vortices in ion concentration polarization under shear flow have been of practical relevance for desalination processes using electrodialysis. The phenomenon has been scientifically disregarded for decades, but is recently embraced by a growing fluid dynamics community due its complex superposition of multi-scale gradients in electrochemical potential and space charge interacting with emerging complex fluid momentum gradients. While the visualization, quantification and fundamental understanding of the often-chaotic fluid dynamics is evolving rapidly due to sophisticated simulations and experimentation, little is known whether these instabilities can be induced and affected by chemical topological heterogeneity in surface properties. In this letter, we report that polyelectrolyte layers applied as micropatterns on ion exchange membranes induce and facilitate the electro-osmotic fluid instabilities. The findings stimulate a variety of fundamental questions comparable to the complexity of today's turbulence research.
- ItemCubosomes from hierarchical self-assembly of poly(ionic liquid) block copolymers([London] : Nature Publishing Group UK, 2017) He, Hongkun; Rahimi, Khosrow; Zhong, Mingjiang; Mourran, Ahmed; Luebke, David R.; Nulwala, Hunaid B.; Möller, Martin; Matyjaszewski, KrzysztofCubosomes are micro- and nanoparticles with a bicontinuous cubic two-phase structure, reported for the self-assembly of low molecular weight surfactants, for example, lipids, but rarely formed by polymers. These objects are characterized by a maximum continuous interface and high interface to volume ratio, which makes them promising candidates for efficient adsorbents and host-guest applications. Here we demonstrate self-assembly to nanoscale cuboidal particles with a bicontinuous cubic structure by amphiphilic poly(ionic liquid) diblock copolymers, poly(acrylic acid)-block-poly(4-vinylbenzyl)-3-butyl imidazolium bis(trifluoromethylsulfonyl)imide, in a mixture of tetrahydrofuran and water under optimized conditions. Structure determining parameters include polymer composition and concentration, temperature, and the variation of the solvent mixture. The formation of the cubosomes can be explained by the hierarchical interactions of the constituent components. The lattice structure of the block copolymers can be transferred to the shape of the particle as it is common for atomic and molecular faceted crystals.
- ItemTime-resolved structural evolution during the collapse of responsive hydrogels: The microgel-to-particle transition(Washington, DC [u.a.] : Assoc., 2018) Keidel, Rico; Ghavami, Ali; Lugo, Dersy M.; Lotze, Gudrun; Virtanen, Otto; Beumers, Peter; Pedersen, Jan Skov; Bardow, Andre; Winkler, Roland G.; Richtering, WalterAdaptive hydrogels, often termed smart materials, are macromolecules whose structure adjusts to external stimuli. Responsive micro- and nanogels are particularly interesting because the small length scale enables very fast response times. Chemical cross-links provide topological constraints and define the three-dimensional structure of the microgels, whereas their porous structure permits fast mass transfer, enabling very rapid structural adaption of the microgel to the environment. The change of microgel structure involves a unique transition from a flexible, swollen finite-size macromolecular network, characterized by a fuzzy surface, to a colloidal particle with homogeneous density and a sharp surface. In this contribution, we determine, for the first time, the structural evolution during the microgel-to-particle transition. Time-resolved small-angle x-ray scattering experiments and computer simulations unambiguously reveal a two-stage process: In a first, very fast process, collapsed clusters form at the periphery, leading to an intermediate, hollowish core-shell structure that slowly transforms to a globule. This structural evolution is independent of the type of stimulus and thus applies to instantaneous transitions as in a temperature jump or to slower stimuli that rely on the uptake of active molecules from and/or exchange with the environment. The fast transitions of size and shape provide unique opportunities for various applications as, for example, in uptake and release, catalysis, or sensing.
- ItemCharge transfer to ground-state ions produces free electrons([London] : Nature Publishing Group UK, 2017) You, D.; Fukuzawa, H.; Sakakibara, Y.; Takanashi, T.; Ito, Y.; Maliyar, G G.; Motomura, K.; Nagaya, K.; Nishiyama, T.; Asa, K.; Sato, Y.; Saito, N.; Oura, M.; Schöffler, M.; Kastirke, G.; Hergenhahn, U.; Stumpf, V.; Gokhberg, K.; Kuleff, A.I.; Cederbaum, L.S.; Ueda, KInner-shell ionization of an isolated atom typically leads to Auger decay. In an environment, for example, a liquid or a van der Waals bonded system, this process will be modified, and becomes part of a complex cascade of relaxation steps. Understanding these steps is important, as they determine the production of slow electrons and singly charged radicals, the most abundant products in radiation chemistry. In this communication, we present experimental evidence for a so-far unobserved, but potentially very important step in such relaxation cascades: Multiply charged ionic states after Auger decay may partially be neutralized by electron transfer, simultaneously evoking the creation of a low-energy free electron (electron transfer-mediated decay). This process is effective even after Auger decay into the dicationic ground state. In our experiment, we observe the decay of Ne2+ produced after Ne 1s photoionization in Ne-Kr mixed clusters.
- ItemMulti-shell hollow nanogels with responsive shell permeability([London] : Macmillan Publishers Limited, part of Springer Nature, 2016) Schmid, Andreas J.; Dubbert, Janine; Rudov, Andrey A.; Pedersen, Jan Skov; Lindner, Peter; Karg, Matthias; Potemkin, Igor I.; Richtering, WalterWe report on hollow shell-shell nanogels with two polymer shells that have different volume phase transition temperatures. By means of small angle neutron scattering (SANS) employing contrast variation and molecular dynamics (MD) simulations we show that hollow shell-shell nanocontainers are ideal systems for controlled drug delivery: The temperature responsive swelling of the inner shell controls the uptake and release, while the thermoresponsive swelling of the outer shell controls the size of the void and the colloidal stability. At temperatures between 32 °C < T < 42 °C, the hollow nanocontainers provide a significant void, which is even larger than the initial core size of the template and they possess a high colloidal stability due to the steric stabilization of the swollen outer shell. Computer simulations showed, that temperature induced switching of the permeability of the inner shell allows for the encapsulation in and release of molecules from the cavity.
- ItemHybrid nanostructured particles via surfactant-free double miniemulsion polymerization([London] : Nature Publishing Group UK, 2018) Zhao, Yongliang; Liu, Junli; Chen, Zhi; Zhu, Xiaomin; Möller, MartinDouble emulsions are complex fluid systems, in which droplets of a dispersed liquid phase contain even smaller dispersed liquid droplets. Particularly, water-in-oil-in-water double emulsions provide significant advantages over simple oil-in-water emulsions for microencapsulation, such as carrier of both aqueous and oily payloads and sustained release profile. However, double emulsions are thermodynamically unstable systems consisting typically of relatively large droplets. Here we show that nanoscale water-in-oil-in-water double emulsions can be prepared by adding a silica precursor polymer, hyperbranched polyethoxysiloxane, to the oil phase without any additional surfactants. The resulting double miniemulsions are transformed to robust water@SiO2@polymer@SiO2 nanocapsules via conversion of the precursor to silica and polymerization of the oil phase. Other intriguing nanostructures like nanorattles and Janus-like nanomushrooms can also be obtained by changing preparation conditions. This simple surfactant-free double miniemulsion polymerization technique opens a promising avenue for mass production of various complex hybrid nanostructures that are amenable to numerous applications.
- ItemAntioxidant and hydrophilic poly(lactic acid) fibers obtained through their modification with amines and ferulic acid(New York, NY [u.a.] : Wiley, 2017) Wojciechowska, Dorota; Herczyńska, Lucyna; Simon, Frank; Puchalski, Michał; Stawski, DawidThe ferulic acid (FA) is a natural antioxidant, abundantly present in plants, which acts as the plant's immune system. In order to take advantage of its properties, a method has been developed, which combines antioxidant FA with bio-based biodegradable poly(lactic acid) fibers and biocompatible hydrophilic polyallylamine, enabling the production of versatile base material that could be used for active anti-inflammatory wound dressings. The fibers are first subjected to aminolysis in order to obtain amino moieties on the surface, able to react with the molecules of FA. Next, the FA was attached to the aminolyzed fibers surface with use of 1-ethyl-3–(3-dimethylaminopropyl) carbodiimide and N-hydroxysuccinimide. The anti-inflammatory properties of the modified fibers were assessed using 2,2-diphenyl-1-picrylhydrazyl radical scavenging assay. Presence of FA on the fibers’ surface was investigated through X-ray photoelectron spectroscopy analysis and Folin–Ciocalteu (total phenolic content) test.
- ItemPrograming stimuli-responsiveness of gelatin with electron beams: Basic effects and development of a hydration-controlled biocompatible demonstrator(London : Nature Publishing Group, 2017) Riedel, Stefanie; Heyart, Benedikt; Apel, Katharina S.; Mayr, Stefan G.Biomimetic materials with programmable stimuli responsiveness constitute a highly attractive material class for building bioactuators, sensors and active control elements in future biomedical applications. With this background, we demonstrate how energetic electron beams can be utilized to construct tailored stimuli responsive actuators for biomedical applications. Composed of collagen-derived gelatin, they reveal a mechanical response to hydration and changes in pH-value and ion concentration, while maintaining their excellent biocompatibility and biodegradability. While this is explicitly demonstrated by systematic characterizing an electron-beam synthesized gelatin-based actuator of cantilever geometry, the underlying materials processes are also discussed, based on the fundamental physical and chemical principles. When applied within classical electron beam lithography systems, these findings pave the way for a novel class of highly versatile integrated bioactuators from micro-to macroscales.
- ItemManipulation of small particles at solid liquid interface: Light driven diffusioosmosis([London] : Macmillan Publishers Limited, part of Springer Nature, 2016) Feldmann, David; Maduar, Salim R.; Santer, Mark; Lomadze, Nino; Vinogradova, Olga I.; Santer, SvetlanaThe 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.
- ItemCompetition between proton transfer and intermolecular Coulombic decay in water([London] : Nature Publishing Group UK, 2018) Richter, Clemens; Hollas, Daniel; Saak, Clara-Magdalena; Förstel, Marko; Miteva, Tsveta; Mucke, Melanie; Björneholm, Olle; Sisourat, Nicolas; Slavíček, Petr; Hergenhahn, UweIntermolecular Coulombic decay (ICD) is a ubiquitous relaxation channel of electronically excited states in weakly bound systems, ranging from dimers to liquids. As it is driven by electron correlation, it was assumed that it will dominate over more established energy loss mechanisms, for example fluorescence. Here, we use electron–electron coincidence spectroscopy to determine the efficiency of the ICD process after 2a1 ionization in water clusters. We show that this efficiency is surprisingly low for small water clusters and that it gradually increases to 40–50% for clusters with hundreds of water units. Ab initio molecular dynamics simulations reveal that proton transfer between neighboring water molecules proceeds on the same timescale as ICD and leads to a configuration in which the ICD channel is closed. This conclusion is further supported by experimental results from deuterated water. Combining experiment and theory, we infer an intrinsic ICD lifetime of 12–52 fs for small water clusters.