TY - JOUR A1 - Bonifacio, P. A1 - Rahmani, H. A1 - Whitmore, J. B. A1 - Wendt, Martin A1 - Centurion, Martin A1 - Molaro, P. A1 - Srianand, R. A1 - Murphy, M. T. A1 - Petitjean, P. A1 - Agafonova, I. I. A1 - Evans, T. M. A1 - Levshakov, S. A. A1 - Lopez, S. A1 - Martins, C. J. A. P. A1 - Reimers, D. A1 - Vladilo, G. T1 - Fundamental constants and high-resolution spectroscopy JF - Astronomische Nachrichten = Astronomical notes KW - atomic processes KW - cosmology: observations KW - elementary particles KW - line: formation KW - quasars: absorption lines KW - techniques: spectroscopic Y1 - 2014 U6 - https://doi.org/10.1002/asna.201312005 SN - 0004-6337 SN - 1521-3994 VL - 335 IS - 1 SP - 83 EP - 91 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Cherstvy, Andrey G. A1 - Chechkin, Aleksei V. A1 - Metzler, Ralf T1 - Particle invasion, survival, and non-ergodicity in 2D diffusion processes with space-dependent diffusivity JF - Soft matter N2 - We study the thermal Markovian diffusion of tracer particles in a 2D medium with spatially varying diffusivity D(r), mimicking recently measured, heterogeneous maps of the apparent diffusion coefficient in biological cells. For this heterogeneous diffusion process (HDP) we analyse the mean squared displacement (MSD) of the tracer particles, the time averaged MSD, the spatial probability density function, and the first passage time dynamics from the cell boundary to the nucleus. Moreover we examine the non-ergodic properties of this process which are important for the correct physical interpretation of time averages of observables obtained from single particle tracking experiments. From extensive computer simulations of the 2D stochastic Langevin equation we present an in-depth study of this HDP. In particular, we find that the MSDs along the radial and azimuthal directions in a circular domain obey anomalous and Brownian scaling, respectively. We demonstrate that the time averaged MSD stays linear as a function of the lag time and the system thus reveals a weak ergodicity breaking. Our results will enable one to rationalise the diffusive motion of larger tracer particles such as viruses or submicron beads in biological cells. Y1 - 2014 U6 - https://doi.org/10.1039/c3sm52846d SN - 1744-683X SN - 1744-6848 VL - 10 IS - 10 SP - 1591 EP - 1601 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Mkrtchian, Vanik E. A1 - Henkel, Carsten T1 - On non-equilibrium photon distributions in the Casimir effect JF - Annalen der Physik N2 - The electromagnetic field in a typical geometry of the Casimir effect is described in the Schwinger-Keldysh formalism. The main result is the photon distribution function (Keldysh Green function) in any stationary state of the field. A two-plate geometry with a sliding interface in local equilibrium is studied in detail, and full agreement with the results of Rytov fluctuation electrodynamics is found. KW - Casimir effect KW - van der Waals interaction KW - quantum friction KW - nonequilibrium electrodynamics of nanosystems Y1 - 2014 U6 - https://doi.org/10.1002/andp.201300135 SN - 0003-3804 SN - 1521-3889 VL - 526 IS - 1-2 SP - 87 EP - 101 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Liu, W. A1 - Tkachov, R. A1 - Komber, H. A1 - Senkovskyy, V. A1 - Schubert, M. A1 - Wei, Z. A1 - Facchetti, A. A1 - Neher, Dieter A1 - Kiriy, A. T1 - Chain-growth polycondensation of perylene diimide-based copolymers: a new route to regio-regular perylene diimide-based acceptors for all-polymer solar cells and n-type transistors JF - Polymer Chemistry N2 - Herein, we report the chain-growth tin-free room temperature polymerization method to synthesize n-type perylene diimide-dithiophene-based conjugated polymers (PPDIT2s) suitable for solar cell and transistor applications. The palladium/electron-rich tri-tert-butylphosphine catalyst is effective to enable the chain-growth polymerization of anion-radical monomer Br-TPDIT-Br/Zn to PPDIT2 with a molecular weight up to M-w approximate to 50 kg mol(-1) and moderate polydispersity. This is the second example of the polymerization of unusual anion-radical aromatic complexes formed in a reaction of active Zn and electron-deficient diimide-based aryl halides. As such, the discovered polymerization method is not a specific reactivity feature of the naphthalene-diimide derivatives but is rather a general polymerization tool. This is an important finding, given the significantly higher maximum external quantum efficiency that can be reached with PDI-based copolymers (32-45%) in all-polymer solar cells compared to NDI-based materials (15-30%). Our studies revealed that PPDIT2 synthesized by the new method and the previously published polymer prepared by step-growth Stille polycondensation show similar electron mobility and all-polymer solar cell performance. At the same time, the polymerization reported herein has several technological advantages as it proceeds relatively fast at room temperature and does not involve toxic tin-based compounds. Because several chain-growth polymerization reactions are well-suited for the preparation of well-defined multi-functional polymer architectures, the next target is to explore the utility of the discovered polymerization in the synthesis of end-functionalized polymers and block copolymers. Such materials would be helpful to improve the nanoscale morphology of polymer blends in all-polymer solar cells. Y1 - 2014 U6 - https://doi.org/10.1039/c3py01707a SN - 1759-9954 SN - 1759-9962 VL - 5 IS - 10 SP - 3404 EP - 3411 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Albrecht, Torsten A1 - Levermann, Anders T1 - Fracture-induced softening for large-scale ice dynamics JF - The Cryosphere : TC ; an interactive open access journal of the European Geosciences Union N2 - Floating ice shelves can exert a retentive and hence stabilizing force onto the inland ice sheet of Antarctica. However, this effect has been observed to diminish by the dynamic effects of fracture processes within the protective ice shelves, leading to accelerated ice flow and hence to a sea-level contribution. In order to account for the macroscopic effect of fracture processes on large-scale viscous ice dynamics (i.e., ice-shelf scale) we apply a continuum representation of fractures and related fracture growth into the prognostic Parallel Ice Sheet Model (PISM) and compare the results to observations. To this end we introduce a higher order accuracy advection scheme for the transport of the two-dimensional fracture density across the regular computational grid. Dynamic coupling of fractures and ice flow is attained by a reduction of effective ice viscosity proportional to the inferred fracture density. This formulation implies the possibility of non-linear threshold behavior due to self-amplified fracturing in shear regions triggered by small variations in the fracture-initiation threshold. As a result of prognostic flow simulations, sharp across-flow velocity gradients appear in fracture-weakened regions. These modeled gradients compare well in magnitude and location with those in observed flow patterns. This model framework is in principle expandable to grounded ice streams and provides simple means of investigating climate-induced effects on fracturing (e. g., hydro fracturing) and hence on the ice flow. It further constitutes a physically sound basis for an enhanced fracture-based calving parameterization. Y1 - 2014 U6 - https://doi.org/10.5194/tc-8-587-2014 SN - 1994-0416 SN - 1994-0424 VL - 8 IS - 2 SP - 587 EP - 605 PB - Copernicus CY - Göttingen ER - TY - JOUR A1 - Winkler, Roland G. A1 - Cherstvy, Andrey G. ED - Muller, M. T1 - Strong and weak polyelectrolyte adsorption onto oppositely charged curved surfaces JF - Advances in polymer science JF - Advances in Polymer Science N2 - Polyelectrolytes are macromolecules composed of charged monomers and exhibit unique properties due to the interplay of their flexibility and electrostatic interactions. In solution, they are attracted to oppositely charged surfaces and interfaces and exhibit a transition to an adsorbed state when certain conditions are met concerning the charge densities of the polymer and surface and the properties of the solution. In this review, we discuss two limiting cases for adsorption of flexible polyelectrolytes on curved surfaces: weak and strong adsorption. In the first case, adsorption is strongly influenced by the entropic degrees of freedom of a flexible polyelectrolyte. By contrast, in the strong adsorption limit, electrostatic interactions dominate, which leads to particular adsorption patterns, specifically on spherical surfaces. We discuss the corresponding theoretical approaches, applying a mean-field description for the polymer and the polymer-surface interaction. For weak adsorption, we discuss the critical adsorption behavior by exactly solvable models for planar and spherical geometries and a generic approximation scheme, which is additionally applied to cylindrical surfaces. For strong adsorption, we investigate various polyelectrolyte patterns on cylinders and spheres and evaluate their stability. The results are discussed in the light of experimental results, mostly of DNA adsorption experiments. Y1 - 2014 SN - 978-3-642-40734-5; 978-3-642-40733-8 U6 - https://doi.org/10.1007/12_2012_183 SN - 0065-3195 VL - 255 SP - 1 EP - 56 PB - Springer CY - Berlin ER - TY - JOUR A1 - Schleussner, Carl-Friedrich A1 - Runge, Jakob A1 - Lehmann, Jasvcha A1 - Levermann, Anders T1 - The role of the North Atlantic overturning and deep ocean for multi-decadal global-mean-temperature variability JF - Earth system dynamics Y1 - 2014 U6 - https://doi.org/10.5194/esd-5-103-2014 SN - 2190-4979 SN - 2190-4987 VL - 5 IS - 1 SP - 103 EP - 115 PB - Copernicus CY - Göttingen ER - TY - JOUR A1 - de Carvalho, Sidney J. A1 - Metzler, Ralf A1 - Cherstvy, Andrey G. T1 - Critical adsorption of polyelectrolytes onto charged Janus nanospheres JF - Physical chemistry, chemical physics : a journal of European Chemical Societies N2 - Based on extensive Monte Carlo simulations and analytical considerations we study the electrostatically driven adsorption of flexible polyelectrolyte chains onto charged Janus nanospheres. These net-neutral colloids are composed of two equally but oppositely charged hemispheres. The critical binding conditions for polyelectrolyte chains are analysed as function of the radius of the Janus particle and its surface charge density, as well as the salt concentration in the ambient solution. Specifically for the adsorption of finite-length polyelectrolyte chains onto Janus nanoparticles, we demonstrate that the critical adsorption conditions drastically differ when the size of the Janus particle or the screening length of the electrolyte are varied. We compare the scaling laws obtained for the adsorption-desorption threshold to the known results for uniformly charged spherical particles, observing significant disparities. We also contrast the changes to the polyelectrolyte chain conformations close to the surface of the Janus nanoparticles as compared to those for simple spherical particles. Finally, we discuss experimentally relevant physicochemical systems for which our simulations results may become important. In particular, we observe similar trends with polyelectrolyte complexation with oppositely but heterogeneously charged proteins. Y1 - 2014 U6 - https://doi.org/10.1039/c4cp02207f SN - 1463-9076 SN - 1463-9084 VL - 16 IS - 29 SP - 15539 EP - 15550 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Palyulin, Vladimir V. A1 - Ala-Nissila, Tapio A1 - Metzler, Ralf T1 - Polymer translocation: the first two decades and the recent diversification JF - Soft matter N2 - Probably no other field of statistical physics at the borderline of soft matter and biological physics has caused such a flurry of papers as polymer translocation since the 1994 landmark paper by Bezrukov, Vodyanoy, and Parsegian and the study of Kasianowicz in 1996. Experiments, simulations, and theoretical approaches are still contributing novel insights to date, while no universal consensus on the statistical understanding of polymer translocation has been reached. We here collect the published results, in particular, the famous-infamous debate on the scaling exponents governing the translocation process. We put these results into perspective and discuss where the field is going. In particular, we argue that the phenomenon of polymer translocation is non-universal and highly sensitive to the exact specifications of the models and experiments used towards its analysis. Y1 - 2014 U6 - https://doi.org/10.1039/c4sm01819b SN - 1744-683X SN - 1744-6848 VL - 10 IS - 45 SP - 9016 EP - 9037 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Di Florio, G. A1 - Bruendermann, E. A1 - Yadavalli, Nataraja Sekhar A1 - Santer, Svetlana A1 - Havenith, Martina T1 - Confocal raman microscopy and AFM study of the interface between the photosensitive polymer layer and multilayer graphene JF - Soft materials N2 - In this paper we report on the interaction between photosensitive azobenzene-containing polymer films and on top adsorbed graphene multilayers. The photosensitive polymer film changes its topography under irradiation with light interference patterns according to their polarization distribution. The multilayer graphene follows the deformation of the polymer film and stretches accordingly. Using confocal Raman microspectroscopy we can detect the appearance of additional peaks in the Raman spectrum of the photosensitive polymer film upon irradiation indicating a molecular interaction at the interface between the graphene multilayer and the polymer matrix. Multi-component analysis of the specific Raman bands shows that the interaction involves the graphene rings and the aromatic rings of the azobenzenes causing the strong adhesion between the two materials. KW - Graphene KW - Multilayer graphene KW - Photosensitive polymer film KW - Confocal Raman microscopy KW - AFM KW - Surface Relief Grating KW - Interfacial molecular interaction Y1 - 2014 U6 - https://doi.org/10.1080/1539445X.2014.945040 SN - 1539-445X SN - 1539-4468 VL - 12 SP - S98 EP - S105 PB - Taylor & Francis Group CY - Philadelphia ER -