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Himalayan water resources attract a rapidly growing number of hydroelectric power projects (HPP) to satisfy Asia's soaring energy demands. Yet HPP operating or planned in steep, glacier-fed mountain rivers face hazards of glacial lake outburst floods (GLOFs) that can damage hydropower infrastructure, alter water and sediment yields, and compromise livelihoods downstream. Detailed appraisals of such GLOF hazards are limited to case studies, however, and a more comprehensive, systematic analysis remains elusive. To this end we estimate the regional exposure of 257 Himalayan HPP to GLOFs, using a flood-wave propagation model fed by Monte Carlo-derived outburst volumes of >2300 glacial lakes. We interpret the spread of thus modeled peak discharges as a predictive uncertainty that arises mainly from outburst volumes and dam-breach rates that are difficult to assess before dams fail. With 66% of sampled HPP are on potential GLOF tracks, up to one third of these HPP could experience GLOF discharges well above local design floods, as hydropower development continues to seek higher sites closer to glacial lakes. We compute that this systematic push of HPP into headwaters effectively doubles the uncertainty about GLOF peak discharge in these locations. Peak discharges farther downstream, in contrast, are easier to predict because GLOF waves attenuate rapidly. Considering this systematic pattern of regional GLOF exposure might aid the site selection of future Himalayan HPP. Our method can augment, and help to regularly update, current hazard assessments, given that global warming is likely changing the number and size of Himalayan meltwater lakes.
Himalayan water resources attract a rapidly growing number of hydroelectric power projects (HPP) to satisfy Asia's soaring energy demands. Yet HPP operating or planned in steep, glacier-fed mountain rivers face hazards of glacial lake outburst floods (GLOFs) that can damage hydropower infrastructure, alter water and sediment yields, and compromise livelihoods downstream. Detailed appraisals of such GLOF hazards are limited to case studies, however, and a more comprehensive, systematic analysis remains elusive. To this end we estimate the regional exposure of 257 Himalayan HPP to GLOFs, using a flood-wave propagation model fed by Monte Carlo-derived outburst volumes of >2300 glacial lakes. We interpret the spread of thus modeled peak discharges as a predictive uncertainty that arises mainly from outburst volumes and dam-breach rates that are difficult to assess before dams fail. With 66% of sampled HPP are on potential GLOF tracks, up to one third of these HPP could experience GLOF discharges well above local design floods, as hydropower development continues to seek higher sites closer to glacial lakes. We compute that this systematic push of HPP into headwaters effectively doubles the uncertainty about GLOF peak discharge in these locations. Peak discharges farther downstream, in contrast, are easier to predict because GLOF waves attenuate rapidly. Considering this systematic pattern of regional GLOF exposure might aid the site selection of future Himalayan HPP. Our method can augment, and help to regularly update, current hazard assessments, given that global warming is likely changing the number and size of Himalayan meltwater lakes.
Inspired by the application of ultrasonic cavitation based mechanical force (CMF) to open small channels in natural soft materials (skin or tissue), it is explored whether an artificial polymer network can be created, in which shape-changes can be induced by CMF. This concept comprises an interconnected macroporous rhodium-phosphine (Rh-P) coordination polymer network, in which a CMF can reversibly dissociate the Rh-P microphases. In this way, the ligand exchange of Rh-P coordination bonds in the polymer network is accelerated, resulting in a topological rearrangement of molecular switches. This rearrangement of molecular switches enables the polymer network to release internal tension under ultrasound exposure, resulting in a CMF-induced shape-memory capability. The interconnected macroporous structure with thin pore walls is essential for allowing the CMF to effectively permeate throughout the polymer network. Potential applications of this CMF-induced shape-memory polymer can be mechanosensors or ultrasound controlled switches.
The molecular ability to selectively and efficiently convert sunlight into other forms of energy like heat, bond change, or charge separation is truly remarkable. The decisive steps in these transformations often happen on a femtosecond timescale and require transitions among different electronic states that violate the Born-Oppenheimer approximation (BOA). Non-BOA transitions pose challenges to both theory and experiment. From a theoretical point of view, excited state dynamics and nonadiabatic transitions both are difficult problems (see Figure 1(a)). However, the theory on non-BOA dynamics has advanced significantly over the last two decades. Full dynamical simulations for molecules of the size of nucleobases have been possible for a couple of years and allow predictions of experimental observables like photoelectron energy or ion yield. The availability of these calculations for isolated molecules has spurred new experimental efforts to develop methods that are sufficiently different from all optical techniques. For determination of transient molecular structure, femtosecond X-ray diffraction and electron diffraction have been implemented on optically excited molecules.
In this thesis, the two prototype catalysts Fe(CO)₅ and Cr(CO)₆ are investigated with time-resolved photoelectron spectroscopy at a high harmonic setup. In both of these metal carbonyls, a UV photon can induce the dissociation of one or more ligands of the complex. The mechanism of the dissociation has been debated over the last decades. The electronic dynamics of the first dissociation occur on the femtosecond timescale.
For the experiment, an existing high harmonic setup was moved to a new location, was extended, and characterized. The modified setup can induce dynamics in gas phase samples with photon energies of 1.55eV, 3.10eV, and 4.65eV. The valence electronic structure of the samples can be probed with photon energies between 20eV and 40eV. The temporal resolution is 111fs to 262fs, depending on the combination of the two photon energies.
The electronically excited intermediates of the two complexes, as well as of the reaction product Fe(CO)₄, could be observed with photoelectron spectroscopy in the gas phase for the first time. However, photoelectron spectroscopy gives access only to the final ionic states. Corresponding calculations to simulate these spectra are still in development. The peak energies and their evolution in time with respect to the initiation pump pulse have been determined, these peaks have been assigned based on literature data. The spectra of the two complexes show clear differences. The dynamics have been interpreted with the assumption that the motion of peaks in the spectra relates to the movement of the wave packet in the multidimensional energy landscape. The results largely confirm existing models for the reaction pathways. In both metal carbonyls, this pathway involves a direct excitation of the wave packet to a metal-to-ligand charge transfer state and the subsequent crossing to a dissociative ligand field state. The coupling of the electronic dynamics to the nuclear dynamics could explain the slower dissociation in Fe(CO)₅ as compared to Cr(CO)₆.
Udmurt as an OV language
(2016)
This is the first study to investigate Hubert Haider's (2000, 2010, 2013, 2014) proposed systematic differences between OV and VO language in a family other than Germanic. Its aim is to gather evidence on whether basic word order is predictive of further properties of a language. The languages under investigation are the Finno-Ugric languages Udmurt (as an OV language) and Finnish (as a VO language). Counter to Kayne (1994), Haider proposes that the structure of a sentence with a head-final VP is fundamentally different from that of a sentence with a head-initial VP, e.g., OV languages do not exhibit a VP-shell structure, and they do not employ a TP layer with a structural subject position. Haider's proposed structural differences are said to result in the following empirically testable differences:
(a) VP: the availability of VP-internal adverbial intervention and scrambling only in OV-VPs;
(b) subjects: the lack of certain subject-object asymmetries in OV languages, i.e., lack of the subject condition and lack of superiority effects;
(c) V-complexes: the availability of partial predicate fronting only in OV languages; different orderings between selecting and selected verbs; the intervention of non-verbal material between verbs only in VO languages;
(d) V-particles: differences in the distribution of resultative phrases and verb particles.
Udmurt and Finnish behave in line with Haider's predictions with regard to the status of the subject, with regard to the order of selecting and selected verbs, and with regard to the availability of partial predicate fronting. Moreover, Udmurt allows for adverbial intervention and scrambling, as predicted, whereas the status of these properties in Finnish could not be reliably determined due to obligatory V-to-T. There is also counterevidence to Haider's predictions: Udmurt allows for non-verbal material between verbs, and the distribution of resultative phrases and verb particles is essentially as free as the distribution of adverbial phrases in both Finno-Ugric languages. As such, Haider's theory is not falsified by the data from Udmurt and Finnish (except for his theory on verb particles), but it is also not fully supported by the data.
The advantages of remote sensing using Unmanned Aerial Vehicles (UAVs) are a high spatial resolution of images, temporal flexibility and narrow-band spectral data from different wavelengths domains. This enables the detection of spatio-temporal dynamics of environmental variables, like plant-related carbon dynamics in agricultural landscapes. In this paper, we quantify spatial patterns of fresh phytomass and related carbon (C) export using imagery captured by a 12-band multispectral camera mounted on the fixed wing UAV Carolo P360. The study was performed in 2014 at the experimental area CarboZALF-D in NE Germany. From radiometrically corrected and calibrated images of lucerne (Medicago sativa), the performance of four commonly used vegetation indices (VIs) was tested using band combinations of six near-infrared bands. The highest correlation between ground-based measurements of fresh phytomass of lucerne and VIs was obtained for the Enhanced Vegetation Index (EVI) using near-infrared band b(899). The resulting map was transformed into dry phytomass and finally upscaled to total C export by harvest. The observed spatial variability at field- and plot-scale could be attributed to small-scale soil heterogeneity in part.
The advantages of remote sensing using Unmanned Aerial Vehicles (UAVs) are a high spatial resolution of images, temporal flexibility and narrow-band spectral data from different wavelengths domains. This enables the detection of spatio-temporal dynamics of environmental variables, like plant-related carbon dynamics in agricultural landscapes. In this paper, we quantify spatial patterns of fresh phytomass and related carbon (C) export using imagery captured by a 12-band multispectral camera mounted on the fixed wing UAV Carolo P360. The study was performed in 2014 at the experimental area CarboZALF-D in NE Germany. From radiometrically corrected and calibrated images of lucerne (Medicago sativa), the performance of four commonly used vegetation indices (VIs) was tested using band combinations of six near-infrared bands. The highest correlation between ground-based measurements of fresh phytomass of lucerne and VIs was obtained for the Enhanced Vegetation Index (EVI) using near-infrared band b(899). The resulting map was transformed into dry phytomass and finally upscaled to total C export by harvest. The observed spatial variability at field- and plot-scale could be attributed to small-scale soil heterogeneity in part.
In complement to the well-established zwitterionic monomers 3-((2-(methacryloyloxy)ethyl)dimethylammonio)propane-1-sulfonate (“SPE”) and 3-((3-methacrylamidopropyl)dimethylammonio)propane-1-sulfonate (“SPP”), the closely related sulfobetaine monomers were synthesized and polymerized by reversible addition-fragmentation chain transfer (RAFT) polymerization, using a fluorophore labeled RAFT agent. The polyzwitterions of systematically varied molar mass were characterized with respect to their solubility in water, deuterated water, and aqueous salt solutions. These poly(sulfobetaine)s show thermoresponsive behavior in water, exhibiting upper critical solution temperatures (UCST). Phase transition temperatures depend notably on the molar mass and polymer concentration, and are much higher in D2O than in H2O. Also, the phase transition temperatures are effectively modulated by the addition of salts. The individual effects can be in parts correlated to the Hofmeister series for the anions studied. Still, they depend in a complex way on the concentration and the nature of the added electrolytes, on the one hand, and on the detailed structure of the zwitterionic side chain, on the other hand. For the polymers with the same zwitterionic side chain, it is found that methacrylamide-based poly(sulfobetaine)s exhibit higher UCST-type transition temperatures than their methacrylate analogs. The extension of the distance between polymerizable unit and zwitterionic groups from 2 to 3 methylene units decreases the UCST-type transition temperatures. Poly(sulfobetaine)s derived from aliphatic esters show higher UCST-type transition temperatures than their analogs featuring cyclic ammonium cations. The UCST-type transition temperatures increase markedly with spacer length separating the cationic and anionic moieties from 3 to 4 methylene units. Thus, apparently small variations of their chemical structure strongly affect the phase behavior of the polyzwitterions in specific aqueous environments.
Water-soluble block copolymers were prepared from the zwitterionic monomers and the non-ionic monomer N-isopropylmethacrylamide (“NIPMAM”) by the RAFT polymerization. Such block copolymers with two hydrophilic blocks exhibit twofold thermoresponsive behavior in water. The poly(sulfobetaine) block shows an UCST, whereas the poly(NIPMAM) block exhibits a lower critical solution temperature (LCST). This constellation induces a structure inversion of the solvophobic aggregate, called “schizophrenic micelle”. Depending on the relative positions of the two different phase transitions, the block copolymer passes through a molecularly dissolved or an insoluble intermediate regime, which can be modulated by the polymer concentration or by the addition of salt. Whereas, at low temperature, the poly(sulfobetaine) block forms polar aggregates that are kept in solution by the poly(NIPMAM) block, at high temperature, the poly(NIPMAM) block forms hydrophobic aggregates that are kept in solution by the poly(sulfobetaine) block. Thus, aggregates can be prepared in water, which switch reversibly their “inside” to the “outside”, and vice versa.
The synthesis and photophysical properties of two new FRET pairs based on coumarin as a donor and DBD dye as an acceptor are described. The introduction of a bromo atom dramatically increases the two-photon excitation (2PE) cross section providing a 2PE-FRET system, which is also suitable for 2PE-FLIM.