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- ItemProbing carbonyl-water hydrogen-bond interactions in thin polyoxazoline brushes(Melville, NY : AIP Publishing, 2016) Kroning, Annika; Furchner, Andreas; Adam, Stefan; Uhlmann, Petra; Hinrichs, KarstenTemperature-responsive oxazoline-based polymer brushes have gained increased attention as biocompatible surfaces. In aqueous environment, they can be tuned between hydrophilic and hydrophobic behavior triggered by a temperature stimulus. This transition is connected with changes in molecule–solvent interactions and results in a switching of the brushes between swollen and collapsed states. This work studies the temperature-dependent interactions between poly(2-oxazoline) brushes and water. In detail, thermoresponsive poly(2-cyclopropyl-2-oxazoline), nonresponsive hydrophilic poly(2-methyl-2-oxazoline), as well as a copolymer of the two were investigated with in situ infrared ellipsometry. Focus was put on interactions of the brushes' carbonyl groups with water molecules. Different polymer–water interactions could be observed and assigned to hydrogen bonding between C=O groups and water molecules. The switching behavior of the brushes in the range of 20–45 °C was identified by frequency shifts and intensity changes of the amide I band.
- ItemPerspectives on the future of ice nucleation research: Research needs and Unanswered questions identified from two international workshops(Basel, Switzerland : MDPI AG, 2017) Coluzza, Ivan; Creamean, Jessie; Rossi, Michel J.; Wex, Heike; Alpert, Peter Aaron; Bianco, Valentino; Boose, Yvonne; Dellago, Christoph; Felgitsch, Laura; Fröhlich-Nowoisky, Janine; Herrmann, Hartmut; Jungblut, Swetlana; Kanji, Zamin A.; Menzl, Georg; Moffett, Bruce; Moritz, Clemens; Mutzel, Anke; Pöschl, Ulrich; Schauperl, Michael; Scheel, Jan; Stopelli, Emiliano; Stratmann, Frank; Grothe, Hinrich; Schmale, David G.There has been increasing interest in ice nucleation research in the last decade. To identify important gaps in our knowledge of ice nucleation processes and their impacts, two international workshops on ice nucleation were held in Vienna, Austria in 2015 and 2016. Experts from these workshops identified the following research needs: (1) uncovering the molecular identity of active sites for ice nucleation; (2) the importance of modeling for the understanding of heterogeneous ice nucleation; (3) identifying and quantifying contributions of biological ice nuclei from natural and managed environments; (4) examining the role of aging in ice nuclei; (5) conducting targeted sampling campaigns in clouds; and (6) designing lab and field experiments to increase our understanding of the role of ice-nucleating particles in the atmosphere. Interdisciplinary teams of scientists should work together to establish and maintain a common, unified language for ice nucleation research. A number of commercial applications benefit from ice nucleation research, including the production of artificial snow, the freezing and preservation of water-containing food products, and the potential modulation of weather. Additional work is needed to increase our understanding of ice nucleation processes and potential impacts on precipitation, water availability, climate change, crop health, and feedback cycles.
- ItemFreshwater resources under success and failure of the Paris climate agreement(Göttingen : Copernicus Publ., 2019) Heinke, Jens; Müller, Christoph; Lannerstad, Mats; Gerten, Dieter; Lucht, WolfgangPopulation growth will in many regions increase the pressure on water resources and likely increase the number of people affected by water scarcity. In parallel, global warming causes hydrological changes which will affect freshwater supply for human use in many regions. This study estimates the exposure of future population to severe hydrological changes relevant from a freshwater resource perspective at different levels of global mean temperature rise above pre-industrial level (ΔTglob). The analysis is complemented by an assessment of water scarcity that would occur without additional climate change due to population change alone; this is done to identify the population groups that are faced with particularly high adaptation challenges. The results are analysed in the context of success and failure of implementing the Paris Agreement to evaluate how climate mitigation can reduce the future number of people exposed to severe hydrological change. The results show that without climate mitigation efforts, in the year 2100 about 4.9 billion people in the SSP2 population scenario would more likely than not be exposed to severe hydrological change, and about 2.1 billion of them would be faced with particularly high adaptation challenges due to already prevailing water scarcity. Limiting warming to 2 °C by a successful implementation of the Paris Agreement would strongly reduce these numbers to 615 million and 290 million, respectively. At the regional scale, substantial water-related risks remain at 2 °C, with more than 12% of the population exposed to severe hydrological change and high adaptation challenges in Latin America and the Middle East and north Africa region. Constraining δTglob to 1.5 °C would limit this share to about 5% in these regions. ©2019 Author(s).
- ItemMechanism for potential strengthening of Atlantic overturning prior to collapse(München : European Geopyhsical Union, 2014) Ehlert, D.; Levermann, A.The Atlantic meridional overturning circulation (AMOC) carries large amounts of heat into the North Atlantic influencing climate regionally as well as globally. Palaeo-records and simulations with comprehensive climate models suggest that the positive salt-advection feedback may yield a threshold behaviour of the system. That is to say that beyond a certain amount of freshwater flux into the North Atlantic, no meridional overturning circulation can be sustained. Concepts of monitoring the AMOC and identifying its vicinity to the threshold rely on the fact that the volume flux defining the AMOC will be reduced when approaching the threshold. Here we advance conceptual models that have been used in a paradigmatic way to understand the AMOC, by introducing a density-dependent parameterization for the Southern Ocean eddies. This additional degree of freedom uncovers a mechanism by which the AMOC can increase with additional freshwater flux into the North Atlantic, before it reaches the threshold and collapses: an AMOC that is mainly wind-driven will have a constant upwelling as long as the Southern Ocean winds do not change significantly. The downward transport of tracers occurs either in the northern sinking regions or through Southern Ocean eddies. If freshwater is transported, either atmospherically or via horizontal gyres, from the low to high latitudes, this would reduce the eddy transport and by continuity increase the northern sinking which defines the AMOC until a threshold is reached at which the AMOC cannot be sustained. If dominant in the real ocean this mechanism would have significant consequences for monitoring the AMOC.
- ItemWater Dynamics in the Hydration Shells of Biomolecules(Washington, DC : ACS Publ., 2017) Laage, Damien; Elsaesser, Thomas; Hynes, James T.The structure and function of biomolecules are strongly influenced by their hydration shells. Structural fluctuations and molecular excitations of hydrating water molecules cover a broad range in space and time, from individual water molecules to larger pools and from femtosecond to microsecond time scales. Recent progress in theory and molecular dynamics simulations as well as in ultrafast vibrational spectroscopy has led to new and detailed insight into fluctuations of water structure, elementary water motions, electric fields at hydrated biointerfaces, and processes of vibrational relaxation and energy dissipation. Here, we review recent advances in both theory and experiment, focusing on hydrated DNA, proteins, and phospholipids, and compare dynamics in the hydration shells to bulk water.
- ItemExcited-state relaxation of hydrated thymine and thymidine measured by liquid-jet photoelectron spectroscopy: experiment and simulation(Washington, DC : ACS Publications, 2015) Buchner, Franziska; Nakayama, Akira; Yamazaki, Shohei; Ritze, Hans-Hermann; Lübcke, AndreaTime-resolved photoelectron spectroscopy is performed on thymine and thymidine in aqueous solution to study the excited-state relaxation dynamics of these molecules. We find two contributions with sub-ps lifetimes in line with recent excited-state QM/MM molecular dynamics simulations (J. Chem. Phys.2013, 139, 214304). The temporal evolution of ionization energies for the excited ππ* state along the QM/MM molecular dynamics trajectories were calculated and are compatible with experimental results, where the two contributions correspond to the relaxation paths in the ππ* state involving different conical intersections with the ground state. Theoretical calculations also show that ionization from the nπ* state is possible at the given photon energies, but we have not found any experimental indication for signal from the nπ* state. In contrast to currently accepted relaxation mechanisms, we suggest that the nπ* state is not involved in the relaxation process of thymine in aqueous solution.
- ItemCompetition between excited state proton and OH- transport via a short water wire: Solvent effects open the gate(London [u.a.] : Royal Society of Chemistry, 2014) Bekçioǧlu, G.; Allolio, C.; Ekimova, M.; Nibbering, E.T.J.; Sebastiani, D.We investigate the acid-base proton exchange reaction in a microsolvated bifunctional chromophore by means of quantum chemical calculations. The UV/vis spectroscopy shows that equilibrium of the keto-and enol-forms in the electronic ground state is shifted to the keto conformation in the excited state. A previously unknown mechanism involving a hydroxide ion transport along a short water wire is characterized energetically, which turns out to be competitive with the commonly assumed proton transport. Both mechanisms are shown to have a concerted character, as opposed to a step-wise mechanism. The alternative mechanism of a hydrogen atom transport is critically examined, and evidence for strong solvent dependence is presented. Specifically, we observe electrostatic destabilization of the corresponding πσ* state by the aqueous solvent. As a consequence, no conical intersections are found along the reaction pathway.
- ItemTime-resolved photoelectron spectroscopy of adenine and adenosine in aqueous solution(London [u.a.] : Royal Society of Chemistry, 2013) Buchner, F.; Ritze, H.-H.; Lahl, J.; Lübcke, A.Time-resolved photoelectron spectroscopy is applied to study the excited state dynamics of the DNA base adenine and its ribonucleoside adenosine in aqueous solution for pump and probe photon energies in the range between 4.66 eV and 5.21 eV. We follow the evolution of the prepared excited state on the potential energy surface and retrieve lifetimes of the S1 state under different excitation conditions.
- ItemGround-penetrating radar insight into a coastal aquifer: the freshwater lens of Borkum Island(Munich : EGU, 2013) Igel, J.; Günther, T.; Kuntzer, M.Freshwater lenses, as important resource for drinking water, are sensitive to climate changes and sea level rise. To simulate this impact on the groundwater systems, hydraulic subsurface models have to be designed. Geophysical techniques can provide information for generating realistic models. The aim of our work is to show how ground-penetrating radar (GPR) investigations can contribute to such hydrological simulations. In the pilot area, Borkum island, GPR was used to map the shape of the groundwater table (GWT) and to characterise the aquifer. In total, 20 km of constant offset (CO) profiles were measured with centre frequencies of 80 and 200 MHz. Wave velocities were determined by common midpoint (CMP) measurements and vertical radar profiling (VRP) in a monitoring well. The 80 MHz CO data show a clear reflection at the groundwater table, whereas the reflection is weaker for the 200 MHz data. After correcting the GPR water tables for the capillary rise, they are in good accordance with the pressure heads of the observation wells in the area. In the centre of the island, the groundwater table is found up to 3.5 m above sea level, however it is lower towards the coastline and marshland. Some local depressions are observed in the region of dune valleys and around pumping stations of the local water supplier. GPR also reveals details within the sediments and highly-permeable aeolian sands can be distinguished from less-permeable marine sediments. Further, a silt loam layer below the water table could be mapped on a large area. The reflection characteristics indicates scattered erosion channels in this layer that cause it to be an aquitard with some leakage. GPR provides a high resolution map of the groundwater table and insight into the stratigraphy of the sediments and their hydraulic properties. This is valuable complementary information to the observation of sparsely distributed monitoring wells as input to hydraulic simulation.
- ItemMediterranean irrigation under climate change: More efficient irrigation needed to compensate for increases in irrigation water requirements(Göttingen : Copernicus GmbH, 2016) Fader, M.; Shi, S.; Von Bloh, W.; Bondeau, A.; Cramer, W.