TY - JOUR A1 - Dodoo, S. A1 - Steitz, R. A1 - Laschewsky, André A1 - von Klitzing, Regine T1 - Effect of ionic strength and type of ions on the structure of water swollen polyelectrolyte multilayers JF - Physical chemistry, chemical physics : a journal of European Chemical Societies N2 - This study addresses the effect of ionic strength and type of ions on the structure and water content of polyelectrolyte multilayers. Polyelectrolyte multilayers of poly(sodium-4-styrene sulfonate) (PSS) and poly(diallyl dimethyl ammonium chloride) (PDADMAC) prepared at different NaF, NaCl and NaBr concentrations have been investigated by neutron reflectometry against vacuum, H2O and D2O. Both thickness and water content of the multilayers increase with increasing ionic strength and increasing ion size. Two types of water were identified, "void water" which fills the voids of the multilayers and does not contribute to swelling but to a change in scattering length density and "swelling water" which directly contributes to swelling of the multilayers. The amount of void water decreases with increasing salt concentration and anion radius while the amount of swelling water increases with salt concentration and anion radius. This is interpreted as a denser structure in the dry state and larger ability to swell in water (sponge) for multilayers prepared from high ionic strengths and/or salt solution of large anions. No exchange of hydration water or replacement of H by D was detected even after eight hours incubation time in water of opposing isotopic composition. Y1 - 2011 U6 - https://doi.org/10.1039/c0cp01357a SN - 1463-9076 VL - 13 IS - 21 SP - 10318 EP - 10325 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Füchsel, Gernot A1 - Klamroth, Tillmann A1 - Monturet, Serge A1 - Saalfrank, Peter T1 - Dissipative dynamics within the electronic friction approach the femtosecond laser desorption of H-2/D-2 from Ru(0001) JF - Physical chemistry, chemical physics : a journal of European Chemical Societies N2 - An electronic friction approach based on Langevin dynamics is used to describe the multidimensional (six-dimensional) dynamics of femtosecond laser induced desorption of H-2 and D-2 from a H(D)-covered Ru(0001) surface. The paper extends previous reduced-dimensional models, using a similar approach. In the present treatment forces and frictional coefficients are calculated from periodic density functional theory (DFT) and essentially parameter-free, while the action of femtosecond laser pulses on the metal surface is treated by using the two-temperature model. Our calculations shed light on the performance and validity of various adiabatic, non-adiabatic, and Arrhenius/Kramers type kinetic models to describe hot-electron mediated photoreactions at metal surfaces. The multidimensional frictional dynamics are able to reproduce and explain known experimental facts, such as strong isotope effects, scaling of properties with laser fluence, and non-equipartitioning of vibrational, rotational, and translational energies of desorbing species. Further, detailed predictions regarding translations are made, and the question for the controllability of photoreactions at surfaces with the help of vibrational preexcitation is addressed. Y1 - 2011 U6 - https://doi.org/10.1039/c0cp02086a SN - 1463-9076 VL - 13 IS - 19 SP - 8659 EP - 8670 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Bartlett, Nate C. -M. A1 - Jankunas, Justin A1 - Goswami, Tapas A1 - Zare, Richard N. A1 - Bouakline, Foudhil A1 - Althorpe, Stuart C. T1 - Differential cross sections for H + D-2 -> HD(v '=2, j '=0,3,6,9) + D at center-of-mass collision energies of 1.25, 1.61, and 1.97 eV JF - Physical chemistry, chemical physics : a journal of European Chemical Societies N2 - We have measured differential cross sections (DCSs) for the reaction H + D-2 -> HD- (v' = 2, j' = 0,3,6,9) + D at center-of-mass collision energies E-coll of 1.25, 1.61, and 1.97 eV using the photoloc technique. The DCSs show a strong dependence on the product rotational quantum number. For the HD(v' = 2, j' = 0) product, the DCS is bimodal but becomes oscillatory as the collision energy is increased. For the other product states, they are dominated by a single peak, which shifts from back to sideward scattering as j' increases, and they are in general less sensitive to changes in the collision energy. The experimental results are compared to quantum mechanical calculations and show good, but not fully quantitative agreement. Y1 - 2011 U6 - https://doi.org/10.1039/c0cp02460k SN - 1463-9076 VL - 13 IS - 18 SP - 8175 EP - 8179 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Belova, Valentina A1 - Shchukin, Dmitry G. A1 - Gorin, Dmitry A. A1 - Kopyshev, Alexey A1 - Moehwald, Helmuth T1 - A new approach to nucleation of cavitation bubbles at chemically modified surfaces JF - Physical chemistry, chemical physics : a journal of European Chemical Societies N2 - Cavitation at the solid surface normally begins with nucleation, in which defects or assembled molecules located at a liquid-solid interface act as nucleation centers and are actively involved in the evolution of cavitation bubbles. Here, we propose a simple approach to evaluate the behavior of cavitation bubbles formed under high intensity ultrasound (20 kHz, 51.3 W cm (2)) at solid surfaces, based on sonication of patterned substrates with a small roughness (less than 3 nm) and controllable surface energy. A mixture of octadecylphosphonic acid (ODTA) and octadecanethiol (ODT) was stamped on the Si wafer coated with different thicknesses of an aluminium layer (20-500 nm). We investigated the growth mechanism of cavitation bubble nuclei and the evolution of individual pits (defects) formed under sonication on the modified surface. A new activation behavior as a function of Al thickness, sonication time, ultrasonic power and temperature is reported. In this process cooperativity is introduced, as initially formed pits further reduce the energy to form bubbles. Furthermore, cavitation on the patterns is a controllable process, where up to 40-50 min of sonication time only the hydrophobic areas are active nucleation sites. This study provides a convincing proof of our theoretical approach on nucleation. Y1 - 2011 U6 - https://doi.org/10.1039/c1cp20218a SN - 1463-9076 VL - 13 IS - 17 SP - 8015 EP - 8023 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Horsch, Philipp A1 - Urbasch, Gunter A1 - Weitzel, Karl-Michael A1 - Kroener, Dominik T1 - Circular dichroism in ion yields employing femtosecond laser ionization-the role of laser pulse duration JF - Physical chemistry, chemical physics : a journal of European Chemical Societies N2 - The circular dichroism (CD) induced by femtosecond laser pulse excitation of 3-methylcyclopentanone has been investigated by means of experiment and theory as a function of the laser pulse duration. In the experiment the CD in ion yields is measured by femtosecond laser ionization via a one-photon resonant excited state. In the theoretical part the CD is calculated by solving laser driven quantum electron dynamics for the same resonant excitation based on ab initio electronic structure calculations employing a complete description of the electric field-electric dipole and magnetic field-magnetic dipole interactions. Both the experimentally measured CD in ion yields and the calculated CD in excited state populations exhibit a marked increase of the CD for pulse duration increasing from 50 fs to about 200 fs. Beyond 200 fs pulse duration the CD levels off. The combination of experimental and theoretical evidences indicates that the CD decreases with increasing laser intensity connected to the increased coupling between the excited states. Y1 - 2011 U6 - https://doi.org/10.1039/c0cp01903h SN - 1463-9076 VL - 13 IS - 6 SP - 2378 EP - 2386 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Richter, Rico A1 - Döllner, Jürgen Roland Friedrich T1 - Integrated real-time visualisation of massive 3D-Point clouds and geo-referenced textured dates JF - Photogrammetrie, Fernerkundung, Geoinformation Y1 - 2011 SN - 1432-8364 IS - 3 SP - 145 EP - 154 PB - Schweizerbart CY - Stuttgart ER - TY - JOUR A1 - Klaus, Valentin H. A1 - Kleinebecker, Till A1 - Hoelzel, Norbert A1 - Bluethgen, Nico A1 - Boch, Steffen A1 - Müller, Jörg A1 - Socher, Stephanie A. A1 - Prati, Daniel A1 - Fischer, Markus T1 - Nutrient concentrations and fibre contents of plant community biomass reflect species richness patterns along a broad range of land-use intensities among agricultural grasslands JF - Perspectives in plant ecology, evolution and systematics N2 - Understanding changes in biodiversity in agricultural landscapes in relation to land-use type and intensity is a major issue in current ecological research. In this context nutrient enrichment has been identified as a key mechanism inducing species loss in Central European grassland ecosystems. At the same time, insights into the linkage between agricultural land use and plant nutrient status are largely missing. So far, studies on the relationship between chemical composition of plant community biomass and biodiversity have mainly been restricted to wetlands and all these studies neglected the effects of land use. Therefore, we analyzed aboveground biomass of 145 grassland plots covering a gradient of land-use intensities in three regions across Germany. In particular, we explored relationships between vascular plant species richness and nutrient concentrations as well as fibre contents (neutral and acid detergent fibre and lignin) in the aboveground community biomass. We found the concentrations of several nutrients in the biomass to be closely linked to plant species richness and land use. Whereas phosphorus concentrations increased with land-use intensity and decreased with plant species richness, nitrogen and potassium concentrations showed less clear patterns. Fibre fractions were negatively related to nutrient concentrations in biomass, but hardly to land-use measures and species richness. Only high lignin contents were positively associated with species richness of grasslands. The N:P ratio was strongly positively related to species richness and even more so to the number of endangered plant species, indicating a higher persistence of endangered species under P (co-)limited conditions. Therefore, we stress the importance of low P supply for species-rich grasslands and suggest the N:P ratio in community biomass to be a useful proxy of the conservation value of agriculturally used grasslands. KW - Biodiversity exploratories KW - Fertilization KW - Grazing KW - Land use KW - Mowing KW - Nitrogen KW - Nutrient limitation KW - Phosphorus KW - Productivity Y1 - 2011 U6 - https://doi.org/10.1016/j.ppees.2011.07.001 SN - 1433-8319 VL - 13 IS - 4 SP - 287 EP - 295 PB - Elsevier CY - Jena ER - TY - JOUR A1 - Albert, Cécile H. A1 - Grassein, Fabrice A1 - Schurr, Frank Martin A1 - Vieilledent, Ghislain A1 - Violle, Cyrille T1 - When and how should intraspecific variability be considered in trait-based plant ecology? JF - Perspectives in plant ecology, evolution and systematics N2 - Trait-based studies have become extremely common in plant ecology. Trait-based approaches often rely on the tacit assumption that intraspecific trait variability (ITV) is negligible compared to interspecific variability, so that species can be characterized by mean trait values. Yet, numerous recent studies have challenged this assumption by showing that ITV significantly affects various ecological processes. Accounting for ITV may thus strengthen trait-based approaches, but measuring trait values on a large number of individuals per species and site is not feasible. Therefore, it is important and timely to synthesize existing knowledge on ITV in order to (1) decide critically when ITV should be considered, and (2) establish methods for incorporating this variability. Here we propose a practical set of rules to identify circumstances under which ITV should be accounted for. We formulate a spatial trait variance partitioning hypothesis to highlight the spatial scales at which ITV cannot be ignored in ecological studies. We then refine a set of four consecutive questions on the research question, the spatial scale, the sampling design, and the type of studied traits, to determine case-by-case if a given study should quantify ITV and test its effects. We review methods for quantifying ITV and develop a step-by-step guideline to design and interpret simulation studies that test for the importance of ITV. Even in the absence of quantitative knowledge on ITV, its effects can be assessed by varying trait values within species within realistic bounds around the known mean values. We finish with a discussion of future requirements to further incorporate ITV within trait-based approaches. This paper thus delineates a general framework to account for ITV and suggests a direction towards a more quantitative trait-based ecology. KW - Comparative ecology KW - Functional ecology KW - Genetic variability KW - Intraspecific functional variability KW - Phenotypic plasticity KW - Plant functional hairs KW - Within-species variability Y1 - 2011 U6 - https://doi.org/10.1016/j.ppees.2011.04.003 SN - 1433-8319 VL - 13 IS - 3 SP - 217 EP - 225 PB - Elsevier CY - Jena ER - TY - JOUR A1 - Knobloch, Jörn T1 - Postdemocracy and postsocialism the convergence of two crises by using the example of Russia JF - Österreichische Zeitschrift für Politikwissenschaft N2 - The article compares the postdemocracy with the postsocialism. At first the paper analyzes the debate of the postdemocracy and points out an analytical model of postdemocracy. Afterwards the paper searches for symptoms of the postdemocracy within the case of Russia which appears as one possible ideal type of postsocialism. The comparison shows that both post-phenomenons are two sides of one global process of transformation. However, the case of postsocialism acts as a trendsetter. The postsocialist Russia sets an example for the possible developments of the postdemocracy. KW - Postdemocracy KW - Postsocialism KW - Russia KW - power KW - depoliticization Y1 - 2011 SN - 1615-5548 VL - 40 IS - 2 SP - 169 EP - + PB - Facultas.wuv CY - Wien ER - TY - JOUR A1 - Wessig, Pablo A1 - Matthes, Annika A1 - Pick, Charlotte T1 - The photo-dehydro-Diels-Alder (PDDA) reaction JF - Organic & biomolecular chemistry : an international journal of synthetic, physical and biomolecular organic chemistry N2 - The photo-dehydro-Diels-Alder (PDDA) reaction is a valuable extension of the classical Diels-Alder (DA) reaction. The PDDA reaction differs from the DA reaction by the replacement of one of the C-C-double bonds of the diene moiety by a C-C triple bond and by the photochemical triggering of the reaction. This entails that, in contrast to the DA reaction, the PDDA reaction proceeds according to a multistage mechanism with biradicals and cycloallenes as intermediates. The PDDA reaction provides access to a considerable variety of compound classes. For example, 1-phenylnaphthlenes, 1,1'-binaphthyls, N-heterocyclic biaryls, and naphthalenophanes could be obtained by this reaction. Y1 - 2011 U6 - https://doi.org/10.1039/c1ob06066j SN - 1477-0520 VL - 9 IS - 22 SP - 7599 EP - 7605 PB - Royal Society of Chemistry CY - Cambridge ER -