2017, Nagendra, Baku, Rosely, C. V. Sijla, Leuteritz, Andreas, Reuter, Uta, Gowd, E. Bhoje

Sonication-assisted delamination of layered double hydroxides (LDHs) resulted in smaller-sized LDH nanoparticles (∼50-200 nm). Such delaminated Co-Al LDH, Zn-Al LDH, and Co-Zn-Al LDH solutions were used for the preparation of highly dispersed isotactic polypropylene (iPP) nanocomposites. Transmission electron microscopy and wide-angle X-ray diffraction results revealed that the LDH nanoparticles were well dispersed within the iPP matrix. The intention of this study is to understand the influence of the intralayer metal composition of LDH on the various properties of iPP/LDH nanocomposites. The sonicated LDH nanoparticles showed a significant increase in the crystallization rate of iPP; however, not much difference in the crystallization rate of iPP was observed in the presence of different types of LDH. The dynamic mechanical analysis results indicated that the storage modulus of iPP was increased significantly with the addition of LDH. The incorporation of different types of LDH showed no influence on the storage modulus of iPP. But considerable differences were observed in the flame retardancy and thermal stability of iPP with the type of LDH used for the preparation of nanocomposites. The thermal stability (50% weight loss temperature (T0.5)) of the iPP nanocomposite containing three-metal LDH (Co-Zn-Al LDH) is superior to that of the nanocomposites made of two-metal LDH (Co-Al LDH and Zn-Al LDH). Preliminary studies on the flame-retardant properties of iPP/LDH nanocomposites using microscale combustion calorimetry showed that the peak heat release rate was reduced by 39% in the iPP/Co-Zn-Al LDH nanocomposite containing 6 wt % LDH, which is higher than that of the two-metal LDH containing nanocomposites, iPP/Co-Al LDH (24%) and iPP/Zn-Al LDH (31%). These results demonstrated that the nanocomposites prepared using three-metal LDH showed better thermal and flame-retardant properties compared to the nanocomposites prepared using two-metal LDH. This difference might be due to the better char formation capability of three-metal LDH compared to that of two-metal LDH.

2017, Kreuzer, Lucas Philipp, Männel, Max Julius, Schubert, Jonas, Höller, Roland P. M., Chanana, Munish

Enzyme-catalyzed controlled radical polymerization represents a powerful approach for the polymerization of a wide variety of water-soluble monomers. However, in such an enzyme-based polymerization system, the macromolecular catalyst (i.e., enzyme) has to be separated from the polymer product. Here, we present a compelling approach for the separation of the two macromolecular species, by taking the catalyst out of the molecular domain and locating it in the colloidal domain, ensuring quasi-homogeneous catalysis as well as easy separation of precious biocatalysts. We report on gold nanoparticles coated with horseradish peroxidase that can catalyze the polymerization of various monomers (e.g., N-isopropylacrylamide), yielding thermoresponsive polymers. Strikingly, these biocatalyst-coated nanoparticles can be recovered completely and reused in more than three independent polymerization cycles, without significant loss of their catalytic activity.

2017-4-12, Chang, Ching-Hao, Ortix, Carmine

Snake orbits are trajectories of charge carriers curving back and forth that form at an interface where either the magnetic field direction or the charge carrier type are inverted. In ballistic samples, their presence is manifested in the appearance of magnetoconductance oscillations at small magnetic fields. Here we show that signatures of snake orbits can also be found in the opposite diffusive transport regime. We illustrate this by studying the classical magnetotransport properties of carbon tubular structures subject to relatively weak transversal magnetic fields where snake trajectories appear in close proximity to the zero radial field projections. In carbon nanoscrolls, the formation of snake orbits leads to a strongly directional dependent positive magnetoresistance with an anisotropy up to 80%.

2016, de Kanter, Martinus, Meyer-Kirschner, Julian, Viell, Jörn, Mitsos, Alexander, Kather, Michael, Pich, Andrij, Janzen, Christoph

A novel probe head design is introduced, which enables in-line monitoring of particle sizes in undiluted stirred fluids using dynamic light scattering. The novel probe head separates a small sample volume of 0.65 ml from the bulk liquid by means of an impeller. In this sample volume, particle sizing is performed using a commercially available fiber-optical backscatter probe. While conventional light scattering measurements in stirred media fail due to the superposition of Brownian’ motion and forced convection, undistorted measurements are possible with the proposed probe head. One measurement takes approximately 30 s used for liquid exchange by rotation of the impeller and for collection of scattered light. The probe head is applied for in-line monitoring of the particle growth during microgel synthesis by precipitation polymerization in a one liter laboratory reactor. The in-line measurements are compared to off-line measurements and show a good agreement.

2014, Schwenkbier, Lydia, Pollok, Sibyll, König, Stephan, Urban, Matthias, Werres, Sabine, Cialla-May, Dana, Weber, Karina, Popp, Jürgen

Rapid detection and accurate identification of plant pathogens in the field is an ongoing challenge. In this study, we report for the first time on the development of a helicase-dependent isothermal amplification (HDA) in combination with on-chip hybridization for the detection of selected Phytophthora species. The HDA approach allows efficient amplification of the yeast GTP-binding protein (Ypt1) target gene region at one constant temperature in a miniaturized heating device. The assay's specificity was determined by on-chip DNA hybridization and subsequent silver nanoparticle deposition. The silver deposits serve as stable endpoint signals that enable the visual as well as the electrical readout. Our promising results point to the direction of a near future on-site application of the combined techniques for a reliable detection of Phytophthora species.

2017-2-2, Natarajan, Tamil Selvan, Stöckelhuber, Klaus Werner, Malanin, Mikhail, Eichhorn, Klaus-Jochen, Formanek, Petr, Reuter, Uta, Wießner, Sven, Heinrich, Gert, Das, Amit

This is the first study on the impact of ice crystals on glass transition and mechanical behavior of soft cross-linked elastomers. A hydrophilic elastomer such as epichlorohydrin-ethylene oxide-allyl glycidyl ether can absorb about ∼40 wt % of water. The water-swollen cross-linked network exhibits elastic properties with more than 1500% stretchability at room temperature. Coincidently, the phase transition of water into solid ice crystals inside of the composites allows the reinforcement of the soft elastomer mechanically at lower temperatures. Young's modulus of the composites measured at -20 °C remarkably increased from 1.45 to 3.14 MPa, whereas at +20 °C, the effect was opposite and the Young's modulus decreased from 0.6 to 0.03 MPa after 20 days of water treatment. It was found that a part of the absorbed water, ∼74% of the total absorbed water, is freezable and occupies nearly 26 vol % of the composites. Simultaneously, these solid ice crystals are found to be acting as a reinforcing filler at lower temperatures. The size of these ice crystals is distributed in a relatively narrow range of 400-600 nm. The storage modulus (E′) of the ice crystal-filled composites increased from 3 to 13 MPa at -20 °C. The glass transition temperature (-37 °C) of the soft cross-linked elastomer was not altered by the absorption of water. However, a special transition (melting of ice) occurred at temperatures close to 0 °C as observed in the dynamic mechanical analysis of the water-swollen elastomers. The direct polymer/filler (ice crystals) interaction was demonstrated by strain sweep experiments and investigated using Fourier transform infrared spectroscopy. This type of cross-linked rubber could be integrated into a smart rubber application such as in adaptable mechanics, where the stiffness of the rubber can be altered as a function of temperature without affecting the mechanical stretchability either below or above 0 °C (above the glass temperature region) of the rubber.

2017-6-7, Reindl, Marcus, Jöns, Klaus D., Huber, Daniel, Schimpf, Christian, Huo, Yongheng, Zwiller, Val, Rastelli, Armando, Trotta, Rinaldo

Photonic quantum technologies are on the verge of finding applications in everyday life with quantum cryptography and quantum simulators on the horizon. Extensive research has been carried out to identify suitable quantum emitters and single epitaxial quantum dots have emerged as near-optimal sources of bright, on-demand, highly indistinguishable single photons and entangled photon-pairs. In order to build up quantum networks, it is essential to interface remote quantum emitters. However, this is still an outstanding challenge, as the quantum states of dissimilar “artificial atoms” have to be prepared on-demand with high fidelity and the generated photons have to be made indistinguishable in all possible degrees of freedom. Here, we overcome this major obstacle and show an unprecedented two-photon interference (visibility of 51 ± 5%) from remote strain-tunable GaAs quantum dots emitting on-demand photon-pairs. We achieve this result by exploiting for the first time the full potential of a novel phonon-assisted two-photon excitation scheme, which allows for the generation of highly indistinguishable (visibility of 71 ± 9%) entangled photon-pairs (fidelity of 90 ± 2%), enables push-button biexciton state preparation (fidelity of 80 ± 2%) and outperforms conventional resonant two-photon excitation schemes in terms of robustness against environmental decoherence. Our results mark an important milestone for the practical realization of quantum repeaters and complex multiphoton entanglement experiments involving dissimilar artificial atoms.

2017, Wiedensohler, A., Wiesner, A., Weinhold, K., Birmili, W., Hermann, M., Merkel, M., Müller, T., Pfeifer, S., Schmidt, A., Tuch, T., Velarde, F., Quincey, P., Seeger, S., Nowak, A.

Mobility particle size spectrometers (MPSS) belong to the essential instruments in aerosol science that determine the particle number size distribution (PNSD) in the submicrometer size range. Following calibration procedures and target uncertainties against standards and reference instruments are suggested for a complete MPSS quality assurance program: (a) calibration of the CPC counting efficiency curve (within 5% for the plateau counting efficiency; within 1 nm for the 50% detection efficiency diameter), (b) sizing calibration of the MPSS, using a certified polystyrene latex (PSL) particle size standard at 203 nm (within 3%), (c) intercomparison of the PNSD of the MPSS (within 10% and 20% of the dN/dlogDP concentration for the particle size range 20–200 and 200–800 nm, respectively), and (d) intercomparison of the integral PNC of the MPSS (within 10%). Furthermore, following measurement uncertainties have been investigated: (a) PSL particle size standards in the range from 100 to 500 nm match within 1% after sizing calibration at 203 nm. (b) Bipolar diffusion chargers based on the radioactive nuclides Kr85, Am241, and Ni63 and a new ionizer based on corona discharge follow the recommended bipolar charge distribution, while soft X-ray-based charges may alter faster than expected. (c) The use of a positive high voltage supply show a 10% better performance than a negative one. (d) The intercomparison of the integral PNC of an MPSS against the total number concentration is still within the target uncertainty at an ambient pressure of approximately 500 hPa. Copyright © 2018 Published with license by American Association for Aerosol Research.

2016, Viell, Jörn, Inouye, Hideyo, Szekely, Noemi K., Frielinghaus, Henrich, Marks, Caroline, Wang, Yumei, Anders, Nico, Spiess, Antje C., Makowski, Lee

Background: The valorization of biomass for chemicals and fuels requires efficient pretreatment. One effective strategy involves the pretreatment with ionic liquids which enables enzymatic saccharification of wood within a few hours under mild conditions. This pretreatment strategy is, however, limited by water and the ionic liquids are rather expensive. The scarce understanding of the involved effects, however, challenges the design of alternative pretreatment concepts. This work investigates the multi length-scale effects of pretreatment of wood in 1-ethyl-3-methylimidazolium acetate (EMIMAc) in mixtures with water using spectroscopy, X-ray and neutron scattering. Results: The structure of beech wood is disintegrated in EMIMAc/water mixtures with a water content up to 8.6 wt%. Above 10.7 wt%, the pretreated wood is not disintegrated, but still much better digested enzymatically compared to native wood. In both regimes, component analysis of the solid after pretreatment shows an extraction of few percent of lignin and hemicellulose. In concentrated EMIMAc, xylan is extracted more efficiently and lignin is defunctionalized. Corresponding to the disintegration at macroscopic scale, SANS and XRD show isotropy and a loss of crystallinity in the pretreated wood, but without distinct reflections of type II cellulose. Hence, the microfibril assembly is decrystallized into rather amorphous cellulose within the cell wall. Conclusions: The molecular and structural changes elucidate the processes of wood pretreatment in EMIMAc/water mixtures. In the aqueous regime with >10.7 wt% water in EMIMAc, xyloglucan and lignin moieties are extracted, which leads to coalescence of fibrillary cellulose structures. Dilute EMIMAc/water mixtures thus resemble established aqueous pretreatment concepts. In concentrated EMIMAc, the swelling due to decrystallinization of cellulose, dissolution of cross-linking xylan, and defunctionalization of lignin releases the mechanical stress to result in macroscopic disintegration of cells. The remaining cell wall constituents of lignin and hemicellulose, however, limit a recrystallization of the solvated cellulose. These pretreatment mechanisms are beyond common pretreatment concepts and pave the way for a formulation of mechanistic requirements of pretreatment with simpler pretreatment liquors. © 2016 Viell et al.

2015, Stroganov, Vladislav, Al-Hussein, Mahmoud, Sommer, Jens-Uwe, Janke, Andreas, Zakharchenko, Svetlana, Ionov, Leonid

We discovered a new and unexpected effect of reversible actuation of ultrathin semicrystalline polymer films. The principle was demonstrated on the example of thin polycaprolactone-gelatin bilayer films. These films are unfolded at room temperature, fold at temperature above polycaprolactone melting point, and unfold again at room temperature. The actuation is based on reversible switching of the structure of the hydrophobic polymer (polycaprolactone) upon melting and crystallization. We hypothesize that the origin of this unexpected behavior is the orientation of polycaprolactone chains parallel to the surface of the film, which is retained even after melting and crystallization of the polymer or the “crystallization memory effect”. In this way, the crystallization generates a directed force, which causes bending of the film. We used this effect for the design of new generation of fully biodegradable thermoresponsive polymeric actuators, which are highly desirable for bionano-technological applications such as reversible encapsulation of cells and design of swimmers.