20 results
Search Results
Now showing 1 - 10 of 20
- ItemCation-cation clusters in ionic liquids: Cooperative hydrogen bonding overcomes like-charge repulsion([London] : Macmillan Publishers Limited, part of Springer Nature, 2015) Knorr, Anne; Ludwig, RalfDirect spectroscopic evidence for H-bonding between like-charged ions is reported for the ionic liquid, 1-(2-hydroxyethyl)-3-methylimidazolium tetrafluoroborate. New infrared bands in the OH frequency range appear at low temperatures indicating the formation of H-bonded cation-cation clusters similar to those known for water and alcohols. Supported by DFT calculations, these vibrational bands can be assigned to attractive interaction between the hydroxyl groups of the cations. The repulsive Coulomb interaction is overcome by cooperative hydrogen bonding between ions of like charge. The transition energy from purely cation-anion interacting configurations to those including cation-cation H-bonds is determined to be 3–4 kJmol−1. The experimental findings and DFT calculations strongly support the concept of anti-electrostatic hydrogen bonds (AEHBs) as recently suggested by Weinhold and Klein. The like-charge configurations are kinetically stabilized with decreasing temperatures.
- ItemWorldwide variations in artificial skyglow([London] : Macmillan Publishers Limited, part of Springer Nature, 2015) Kyba, Christopher C.M.; Tong, Kai Pong; Bennie, Jonathan; Birriel, Ignacio; Birriel, Jennifer J.; Cool, Andrew; Danielsen, Arne; Davies, Thomas W.; den Outer, Peter N.; Edwards, William; Ehlert, Rainer; Falchi, Fabio; Fischer, Jürgen; Giacomelli, Andrea; Giubbilini, Francesco; Haaima, Marty; Hesse, Claudia; Heygster, Georg; Hölker, Franz; Inger, Richard; Jensen, Linsey J.; Kuechly, Helga U.; Kuehn, John; Langill, Phil; Lolkema, Dorien E.; Nagy, Matthew; Nievas, Miguel; Ochi, Nobuaki; Popow, Emil; Posch, Thomas; Puschnig, Johannes; Ruhtz, Thomas; Schmidt, Wim; Schwarz, Robert; Schwope, Axel; Spoelstra, Henk; Tekatch, Anthony; Trueblood, Mark; Walker, Constance E.; Weber, Michael; Welch, Douglas L.; Zamorano, Jaime; Gaston, Kevin J.Despite constituting a widespread and significant environmental change, understanding of artificial nighttime skyglow is extremely limited. Until now, published monitoring studies have been local or regional in scope and typically of short duration. In this first major international compilation of monitoring data we answer several key questions about skyglow properties. Skyglow is observed to vary over four orders of magnitude, a range hundreds of times larger than was the case before artificial light. Nearly all of the study sites were polluted by artificial light. A non-linear relationship is observed between the sky brightness on clear and overcast nights, with a change in behavior near the rural to urban landuse transition. Overcast skies ranged from a third darker to almost 18 times brighter than clear. Clear sky radiances estimated by the World Atlas of Artificial Night Sky Brightness were found to be overestimated by ~25%; our dataset will play an important role in the calibration and ground truthing of future skyglow models. Most of the brightly lit sites darkened as the night progressed, typically by ~5% per hour. The great variation in skyglow radiance observed from site-to-site and with changing meteorological conditions underlines the need for a long-term international monitoring program.
- ItemStrong magnetic frustration and anti-site disorder causing spin-glass behavior in honeycomb Li2RhO3([London] : Macmillan Publishers Limited, part of Springer Nature, 2015) Katukuri, Vamshi M.; Nishimoto, Satoshi; Rousochatzakis, Ioannis; Stoll, Hermann; van den Brink, Jeroen; Hozoi, LiviuWith large spin-orbit coupling, the electron configuration in d-metal oxides is prone to highly anisotropic exchange interactions and exotic magnetic properties. In 5d5 iridates, given the existing variety of crystal structures, the magnetic anisotropy can be tuned from antisymmetric to symmetric Kitaev-type, with interaction strengths that outsize the isotropic terms. By many-body electronic-structure calculations we here address the nature of the magnetic exchange and the intriguing spin-glass behavior of Li2RhO3, a 4d5 honeycomb oxide. For pristine crystals without Rh-Li site inversion, we predict a dimerized ground state as in the isostructural 5d5 iridate Li2IrO3, with triplet spin dimers effectively placed on a frustrated triangular lattice. With Rh-Li anti-site disorder, we explain the observed spin-glass phase as a superposition of different, nearly degenerate symmetry-broken configurations.
- ItemPhenotypic, Morphological and Adhesive Differences of Human Hematopoietic Progenitor Cells Cultured on Murine versus Human Mesenchymal Stromal Cells([London] : Macmillan Publishers Limited, part of Springer Nature, 2015) Reichert, Doreen; Friedrichs, Jens; Ritter, Steffi; Käubler, Theresa; Werner, Carsten; Bornhäuser, Martin; Corbeil, DenisXenogenic transplantation models have been developed to study human hematopoiesis in immunocompromised murine recipients. They still have limitations and therefore it is important to delineate all players within the bone marrow that could account for species-specific differences. Here, we evaluated the proliferative capacity, morphological and physical characteristics of human CD34+ hematopoietic stem and progenitor cells (HSPCs) after co-culture on murine or human bone marrow-derived mesenchymal stromal cells (MSCs). After seven days, human CD34+CD133– HSPCs expanded to similar extents on both feeder layers while cellular subsets comprising primitive CD34+CD133+ and CD133+CD34– phenotypes are reduced fivefold on murine MSCs. The number of migrating HSPCs was also reduced on murine cells suggesting that MSC adhesion influences cellular polarization of HSPC. We used atomic force microscopy-based single-cell force spectroscopy to quantify their adhesive interactions. We found threefold higher detachment forces of human HSPCs from murine MSCs compared to human ones. This difference is related to the N-cadherin expression level on murine MSCs since its knockdown abolished their differential adhesion properties with human HSPCs. Our observations highlight phenotypic, morphological and adhesive differences of human HSPCs when cultured on murine or human MSCs, which raise some caution in data interpretation when xenogenic transplantation models are used.
- ItemOptical pumping and readout of bismuth hyperfine states in silicon for atomic clock applications([London] : Macmillan Publishers Limited, part of Springer Nature, 2015) Saeedi, K.; Szech, M.; Dluhy, P.; Salvail, J.Z.; Morse, K.J.; Riemann, H.; Abrosimov, N.V.; Nötzel, N.; Litvinenko, K.L.; Murdin, B.N.; Thewalt, M.L.W.The push for a semiconductor-based quantum information technology has renewed interest in the spin states and optical transitions of shallow donors in silicon, including the donor bound exciton transitions in the near-infrared and the Rydberg, or hydrogenic, transitions in the mid-infrared. The deepest group V donor in silicon, bismuth, has a large zero-field ground state hyperfine splitting, comparable to that of rubidium, upon which the now-ubiquitous rubidium atomic clock time standard is based. Here we show that the ground state hyperfine populations of bismuth can be read out using the mid-infrared Rydberg transitions, analogous to the optical readout of the rubidium ground state populations upon which rubidium clock technology is based. We further use these transitions to demonstrate strong population pumping by resonant excitation of the bound exciton transitions, suggesting several possible approaches to a solid-state atomic clock using bismuth in silicon, or eventually in enriched 28Si.
- ItemMaximal rectification ratios for idealized bi-segment thermal rectifiers([London] : Macmillan Publishers Limited, part of Springer Nature, 2015) Shih, Tien-Mo; Gao, Zhaojing; Guo, Ziquan; Merlitz, Holger; Pagni, Patrick J.; Chen, ZhongThermal rectifiers whose forward heat fluxes are greater than reverse counterparts have been extensively studied. Here we have discovered, idealized and derived the ultimate limit of such rectification ratios, which are partially validated by numerical simulations, experiments and micro-scale Hamiltonian-oscillator analyses. For rectifiers whose thermal conductivities (κ) are linear with the temperature, this limit is simply a numerical value of 3. For those whose conductivities are nonlinear with temperatures, the maxima equal κmax/κmin, where two extremes denote values of the solid segment materials that can be possibly found or fabricated within a reasonable temperature range. Recommendations for manufacturing high-ratio rectifiers are also given with examples. Under idealized assumptions, these proposed rectification limits cannot be defied by any bi-segment thermal rectifiers.
- ItemUltrathin niobium nanofilms on fiber optical tapers--a new route towards low-loss hybrid plasmonic modes([London] : Macmillan Publishers Limited, part of Springer Nature, 2015) Wieduwilt, Torsten; Tuniz, Alessandro; Linzen, Sven; Goerke, Sebastian; Dellith, Jan; Hübner, Uwe; Schmidt, Markus A.Due to the ongoing improvement in nanostructuring technology, ultrathin metallic nanofilms have recently gained substantial attention in plasmonics, e.g. as building blocks of metasurfaces. Typically, noble metals such as silver or gold are the materials of choice, due to their excellent optical properties, however they also possess some intrinsic disadvantages. Here, we introduce niobium nanofilms (~10 nm thickness) as an alternate plasmonic platform. We demonstrate functionality by depositing a niobium nanofilm on a plasmonic fiber taper and observe a dielectric-loaded niobium surface-plasmon excitation for the first time, with a modal attenuation of only 3–4 dB/mm in aqueous environment and a refractive index sensitivity up to 15 μm/RIU if the analyte index exceeds 1.42. We show that the niobium nanofilm possesses bulk optical properties, is continuous, homogenous and inert against any environmental influence, thus possessing several superior properties compared to noble metal nanofilms. These results demonstrate that ultrathin niobium nanofilms can serve as a new platform for biomedical diagnostics, superconducting photonics, ultrathin metasurfaces or new types of optoelectronic devices.
- ItemBessel beam CARS of axially structured samples([London] : Macmillan Publishers Limited, part of Springer Nature, 2015) Heuke, Sandro; Zheng, Juanjuan; Akimov, Denis; Heintzmann, Rainer; Schmitt, Michael; Popp, JürgenWe report about a Bessel beam CARS approach for axial profiling of multi-layer structures. This study presents an experimental implementation for the generation of CARS by Bessel beam excitation using only passive optical elements. Furthermore, an analytical expression is provided describing the generated anti-Stokes field by a homogeneous sample. Based on the concept of coherent transfer functions, the underling resolving power of axially structured geometries is investigated. It is found that through the non-linearity of the CARS process in combination with the folded illumination geometry continuous phase-matching is achieved starting from homogeneous samples up to spatial sample frequencies at twice of the pumping electric field wave. The experimental and analytical findings are modeled by the implementation of the Debye Integral and scalar Green function approach. Finally, the goal of reconstructing an axially layered sample is demonstrated on the basis of the numerically simulated modulus and phase of the anti-Stokes far-field radiation pattern.
- ItemAn NMR Study of Biomimetic Fluorapatite - Gelatine Mesocrystals([London] : Macmillan Publishers Limited, part of Springer Nature, 2015) Vyalikh, Anastasia; Simon, Paul; Rosseeva, Elena; Buder, Jana; Scheler, Ulrich; Kniep, RüdigerThe mesocrystal system fluoroapatite—gelatine grown by double-diffusion is characterized by hierarchical composite structure on a mesoscale. In the present work we apply solid state NMR to characterize its structure on the molecular level and provide a link between the structural organisation on the mesoscale and atomistic computer simulations. Thus, we find that the individual nanocrystals are composed of crystalline fluorapatite domains covered by a thin boundary apatite-like layer. The latter is in contact with an amorphous layer, which fills the interparticle space. The amorphous layer is comprised of the organic matrix impregnated by isolated phosphate groups, Ca3F motifs and water molecules. Our NMR data provide clear evidence for the existence of precursor complexes in the gelatine phase, which were not involved in the formation of apatite crystals, proving hence theoretical predictions on the structural pre-treatment of gelatine by ion impregnation. The interfacial interactions, which may be described as the glue holding the composite materials together, comprise hydrogen bond interactions with the apatite PO43− groups. The reported results are in a good agreement with molecular dynamics simulations, which address the mechanisms of a growth control by collagen fibers and with experimental observations of an amorphous cover layer in biominerals.
- ItemDetection of vancomycin resistances in enterococci within 3 1/2 Hours([London] : Macmillan Publishers Limited, part of Springer Nature, 2015) Schröder, U.-Ch.; Beleites, C.; Assmann, C.; Glaser, U.; Hübner, U.; Pfister, W.; Fritzsche, W.; Popp, J.; Neugebauer, U.Vancomycin resistant enterococci (VRE) constitute a challenging problem in health care institutions worldwide. Novel methods to rapidly identify resistances are highly required to ensure an early start of tailored therapy and to prevent further spread of the bacteria. Here, a spectroscopy-based rapid test is presented that reveals resistances of enterococci towards vancomycin within 3.5 hours. Without any specific knowledge on the strain, VRE can be recognized with high accuracy in two different enterococci species. By means of dielectrophoresis, bacteria are directly captured from dilute suspensions, making sample preparation very easy. Raman spectroscopic analysis of the trapped bacteria over a time span of two hours in absence and presence of antibiotics reveals characteristic differences in the molecular response of sensitive as well as resistant Enterococcus faecalis and Enterococcus faecium. Furthermore, the spectroscopic fingerprints provide an indication on the mechanisms of induced resistance in VRE.