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Ocean Drilling Program (ODP) Site 982 provided a key sediment section at Rockall Plateau for reconstructing northeast Atlantic paleoceanography and monitoring benthic delta O-18 stratigraphy over the late Pliocene to Quaternary onset of major Northern Hemisphere glaciation. A renewed hole-specific inspection of magnetostratigraphic reversals and the addition of epibenthic delta O-18 records for short Pliocene sections in holes 982A, B, and C, crossing core breaks in the delta O-18 record published for Hole 982B, now imply a major revision of composite core depths. After tuning to the orbitally tuned reference record LR04, the new composite delta O-18 record results in a hiatus, where the Kaena magnetic subchron might have been lost, and in a significant age reduction for all proxy records by 130 to 20 ky over the time span 3.2-2.7 million years ago (Ma). Our study demonstrates the general significance of reliable composite-depth scales and delta O-18 stratigraphies in ODP sediment records for generating ocean-wide correlations in paleoceanography. The new concept of age control makes the late Pliocene trends in SST (sea surface temperature) and atmospheric pCO(2) at Site 982 more consistent with various paleoclimate trends published from elsewhere in the North Atlantic.
Teaching patterns and trends
(2012)
1. Outline 2. Definition 3. Why is it important (or not) to teach about patterns and trends? What are the strengths and weaknesses of teaching patterns and trends? 4. How were patterns and trends offered in the original assignments? 5. What did the student teacher change in practice? How did it go? 6. Suggestions for improving patterns and trends
The European Values Education (EVE) project is a large-scale, cross-national, and longitudinal survey research programme on basic human values. The main topic of its second stage was religion in Europe. Student teachers of several universities in Europe worked together in multicultural exchange groups. Their results are presented in this issue.
Coastal regions of the North East Atlantic and Mediterranean Seas have four known species of driftwood talitrids. Records are extremely scanty, often limited to the type locality and dating to 1950. We were able to study three of them, all belonging to the genus Macarorchestia, using fresh and archived samples including type material. Allometric and molecular analyses support: (1) a close relationship among all the three classically defined Macarorchestia species, (2) Macarorchestia was well separated from non-driftwood taxa, and (3) a putative new driftwood talitrid discovered during this study was not closely related to Macarorchestia. Genetic divergence between the new species and Macarorchestia remyi is as high as the average distance among a number of talitrid species included in the study for comparison. A key is provided to identify all three of the presently known species of Macarorchestia, using morphological characters employed in the allometric study.
We present ultrafast x-ray diffraction (UXRD) experiments on different photoexcited oxide superlattices. All data are successfully simulated by dynamical x-ray diffraction calculations based on a microscopic model, that accounts for the linear response of phonons to the excitation laser pulse. Some Bragg reflections display a highly nonlinear strain dependence. The origin of linear and two distinct nonlinear response phenomena is discussed in a conceptually simpler model using the interference of envelope functions that describe the diffraction efficiency of the average constituent nanolayers. The combination of both models facilitates rapid and accurate simulations of UXRD experiments.
Bacteriophages use specific tail proteins to recognize host cells. It is still not understood to molecular detail how the signal is transmitted over the tail to initiate infection. We have analysed in vitro DNA ejection in long-tailed siphovirus 9NA and short-tailed podovirus P22 upon incubation with Salmonella typhimurium lipopolysaccharide (LPS). We showed for the first time that LPS alone was sufficient to elicit DNA release from a siphovirus in vitro. Crystal structure analysis revealed that both phages use similar tailspike proteins for LPS recognition. Tailspike proteins hydrolyse LPS O antigen to position the phage on the cell surface. Thus we were able to compare in vitro DNA ejection processes from two phages with different morphologies with the same receptor under identical experimental conditions. Siphovirus 9NA ejected its DNA about 30 times faster than podovirus P22. DNA ejection is under control of the conformational opening of the particle and has a similar activation barrier in 9NA and P22. Our data suggest that tail morphology influences the efficiencies of particle opening given an identical initial receptor interaction event.
The validity of the Taft equation: log(k(R)/k(CH3)) = rho*sigma* + delta E-S was studied with the aid of NBO computational results concerning cyclohexyl esters RCOOC6H11 [R = Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, Isobutyl, sec-Butyl, tert-Butyl, Neopentyl, CH(CH2CH3)(2), CH(CH3)C(CH3)(3), C(CH3)(2)CH2CH3, C(CH3)(2)C(CH3)(3), CH(CH3)(Np), CH(iPr)(tBu), C(Me)(Et)(iPr), C(Et)(2)(tBu) or C(Et)(iPr)(tBu)]. It was proved that the sigma*(alkyl) value is a composite substitutent constant including the polar and steric contributions. A novel computational sigma(q)* substituent constant scale is presented based on the NBO atomic charges of the alpha-carbon and the computational total steric exchange energies E(ster) of the cyclohexyl esters specified above. The method used offers a useful way to calculate sigma*(alkyl) values for alkyl groups for which experimental Taft's polar sigma* parameters are not available.
The Richardson-Lucy deconvolution algorithm was applied to astronomical images in the very high-energy regime with photon energies above 100 GeV. Through a systematic study with respect to source significance, background level and source morphology we were able to derive optimal deconvolution parameters. The results presented show that deconvolution makes it possible to study structural details well below the angular resolution of the very high-energy gamma-ray experiment. (C) 2012 Elsevier B.V. All rights reserved.
Metabolic networks are characterized by complex interactions and regulatory mechanisms between many individual components. These interactions determine whether a steady state is stable to perturbations. Structural kinetic modeling (SKM) is a framework to analyze the stability of metabolic steady states that allows the study of the system Jacobian without requiring detailed knowledge about individual rate equations. Stability criteria can be derived by generating a large number of structural kinetic models (SK-models) with randomly sampled parameter sets and evaluating the resulting Jacobian matrices. Until now, SKM experiments applied univariate tests to detect the network components with the largest influence on stability. In this work, we present an extended SKM approach relying on supervised machine learning to detect patterns of enzyme-metabolite interactions that act together in an orchestrated manner to ensure stability. We demonstrate its application on a detailed SK-model of the Calvin-Benson cycle and connected pathways. The identified stability patterns are highly complex reflecting that changes in dynamic properties depend on concerted interactions between several network components. In total, we find more patterns that reliably ensure stability than patterns ensuring instability. This shows that the design of this system is strongly targeted towards maintaining stability. We also investigate the effect of allosteric regulators revealing that the tendency to stability is significantly increased by including experimentally determined regulatory mechanisms that have not yet been integrated into existing kinetic models.
A silicon analog of quinolizidine 3,3,7,7-tetramethylhexahydro-1H-[1,4,2]oxazasilino[4,5-d][1,4,2]oxazasilin-9a-yl)methanol 3 was synthesized. X-ray diffraction analysis confirmed the trans configuration and low temperature NMR spectroscopy both the flexibility (barrier of interconversion 5.8 kcal mol(-1)) and the conformational equilibrium (chair-chair and chair-twist conformers) of the compound. The relative stability of the different isomers/conformers of 3 was calculated also at the MP2/6-311G(d,p) level of theory. Intra- and intermolecular hydrogen bonding in 3 and the appropriate equilibrium between free and self-associated molecules was studied in solvents of different polarity. Both the N-methyl quaternary ammonium salt and the O-trimethylsilyl derivative of 3 could be obtained and their structure determined.
A new di-manganese complex with "back-to-back" 1,4-bis(2,2':6,2 ''-terpyridin-4'-yl) benzene ligation has been synthesized and characterised by a variety of techniques. The back-to-back ligation presents a novel new mononuclear manganese catalytic centre that functions as a heterogeneous catalysis for the evolution of oxygen in the presence of an exogenous oxidant. We discuss the synthesis and spectroscopic characterizations of this complex and propose a mechanism for oxygen evolution activity of the compound in the presence of oxone. The di-manganese complex also shows efficient and selective catalytic oxidation of sulfides in the presence of H2O2. Density functional theory calculations were used to assess the structural optimization of the complex and a proposed reaction pathway with oxone. The calculations show that middle benzene ring is distorted respect to both of metallic centers, and this in turn leads to negligible resonance of electrons between two sides of complex. The calculations also indicate the unpaired electron located on oxyl-ligand emphasizes the radical mechanism of water oxidation for the system.
Syntheses of thiazolidine-fused heterocycles via exo-mode cyclizations of vinylogous N-acyliminium ions incorporating heteroatom-based nucleophiles have been examined and discussed. The formation of (5,6)-membered systems was feasible with all nucleophiles tried (O, S and N), while the closing of the five-membered ring was restricted to O- and S-nucleophiles. The closure of a four-membered ring failed. Instead, the bicyclic (5,6)-membered acetal derivative and the tricyclic system with an eight-membered central ring were obtained from the substrates containing O and S nucleophilic moieties, respectively. The reaction outcome and stereochemistry are rationalized using quantum chemical calculations at B3LYP/6-31G(d) level. The exclusive cis-stereoselectivity in the formation of (5,6)- and (5,5)-membered systems results from thermodynamic control, whereas the formation of the eight-membered ring was kinetically controlled.
Syntheses of thiazolidine-fused heterocycles via exo-mode cyclizations of vinylogous N-acyliminium ions incorporating heteroatom-based nucleophiles have been examined and discussed. The formation of (5,6)-membered systems was feasible with all nucleophiles tried (O, S and N), while the closing of the five-membered ring was restricted to O- and S-nucleophiles. The closure of a four-membered ring failed. Instead, the bicyclic (5,6)-membered acetal derivative and the tricyclic system with an eight-membered central ring were obtained from the substrates containing O and S nucleophilic moieties, respectively. The reaction outcome and stereochemistry are rationalized using quantum chemical calculations at B3LYP/6-31G(d) level. The exclusive cis-stereoselectivity in the formation of (5,6)- and (5,5)-membered systems results from thermodynamic control, whereas the formation of the eight-membered ring was kinetically controlled.
A simple and efficient method for the conversion of alcohols and phenols to primary O-thiocarbamates and S- thiocarbamates in the absence of solvent (solvent-free condition) using silica sulfuric acid (SiO2OSO3H) as a solid acid is described. The products are easily distinguished by IR, NMR and X-ray data. X-ray data of the compounds reveal a planar trigonal orientation of the NH2 nitrogen atom with the partial C,N double-bond character and the CS or CO groups in synperiplanar position with CarylO and CalkylS moieties, respectively. Moreover, the OCSNH2 group which is perpendicular to the plane of the benzene ring in 1c and the central thiocarbamate SCONH2 group in 2b are essentially planar.
A simple and efficient method for the conversion of alcohols and phenols to primary O-thiocarbamates and S-thiocarbamates in the absence of solvent (solvent-free condition) using silica sulfuric acid (equivalent to SiO2-OSO3H) as a solid acid is described. The products are easily distinguished by IR, NMR and X-ray data. X-ray data of the compounds reveal a planar trigonal orientation of the NH2 nitrogen atom with the partial C,N double-bond character and the C=S or C=O groups in synperiplanar position with C-aryl-O and C-alkyl-S moieties, respectively. Moreover, the -O-CS-NH2 group which is perpendicular to the plane of the benzene ring in 1c and the central thiocarbamate -S-CO-NH2 group in 2b are essentially planar.
Mesoporous carbon/iron carbide hybrid materials with surface areas reaching 800 m(2) g(-1) were synthesized via an exotemplating route using monolithic mesoporous silica as template and the ionic liquid 1-butyl-3-methylimidazolium tetrachloridoferrate(III) [Bmim][FeCl4] as carbon and iron source. After heat treatment (750 degrees C under argon) of the [Bmim][FeCl4] precursor confined within the silica matrix, the silica exotemplate was removed with HF leaving the mesoporous C/Fe3C hybrid behind. The surface areas and the pore sizes depend on the exotemplate and the surface areas a significantly larger than any other surface area reported for C/Fe3C hybrid materials so far. The approach is thus a prototype for the synthesis of high-surface area iron carbide-based hybrid materials with potential application in catalysis.
The synthesis of ultrafine gold nanoparticles in presence of maltose-modified hyperbranched poly(ethyleneimines) (PEI) is described. The polymer acted as both a reducing and stabilising agent in the particle formation process. The nanoparticles were characterized by means of dynamic light scattering (DLS), transmission electron microscopy (TEM), analytical ultracentrifugation (AUC), small-angle x-ray scattering (SAXS), and small-angle neutron scattering (SANS). The mechanism of nanoparticle formation can be described in two steps. The reduction process of the Au3+ ions located in the inner coil region of the hyperbranched PEI led to the formation of a compact gold core, and is accompanied by a collapse of the polymer coil. Therefore, in the subsequent reduction process a gold-polymer hybrid shell is formed. By using the PEI of higher molar mass, core-shell gold nanoparticles of about 3.6 nm size with a more narrow size distribution and special fluorescence behavior could be synthesized.
A sequential ruthenium-catalyzed ring-closing metathesis-transfer hydrogenation sequence has been established as a synthesis of chromanes starting from 2-(allyloxy)styrenes. The sequence requires only one precatalyst, the first-generation Grubbs catalyst, which is converted into a ruthenium hydride species in situ. Propan-2-ol serves as a chemical trigger for the formation of the ruthenium hydride and as hydrogen source.
The synthesis of 7-methoxy-8-(4-methyl-3-furyl)-2H-chromen-2-one, a natural product with antileishmanial activity recently isolated from the plant Galipea panamensis, is described. The key step is a Suzuki-Miyaura coupling of a furan-3-boronic acid and an 8-halocoumarin, which is advantageously synthesized using a ring-closing metathesis reaction. Several non-natural analogues are also available along these lines.
A facile one-pot synthesis for preparing thermosensitive, luminescent gold nanodots with diameters of 1-2 nm is presented. The influence of the alkyl chain length of the surface ligands (alkyl thiols) on the optical properties of the gold nanodots was investigated. The synthesized gold nanodots show strong thermosensitive photoluminescence. A photoluminescence quantum yield of 16.6% was observed at room temperature, which could be improved to a value of 28.6% when cooling the gold nanodot solutions to -7 degrees C. The synthesized thermosensitive, luminescent gold nanodots are interesting candidates for optoelectronic devices, medical imaging, sensing, or security labels.
The esters of 4-hydroxy-cyclohexanone and a series of carboxylic acids R-COOH with R of different electronic and steric influence (R=Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, sec-Bu, t-Bu, CF3, CH2Cl, CHCl2, CCl3, CH2Br, CHBr2, and CBr3) were synthesized and the conformational equilibria studied by 1H and 13C NMR spectroscopy at 103 K and at 295 K, respectively. The geometry of optimized structures of the axial/equatorial chair conformers was computed at the ab initio MO and DFT levels of theory. Only one preferred conformation was obtained for the axial and the equatorial conformer as well. When comparing the conformational equilibria of the cyclohexanone esters with those of the corresponding cyclohexyl esters a certain polarity contribution of the cyclohexanone framework was revealed, which is independent of the substituent effects and increases the stability of the axial conformers by a constant amount.
The esters of 4-hydroxy-cyclohexanone and a series of carboxylic acids R-COOH with R of different electronic and steric influence (R=Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, sec-Bu, t-Bu, CF3, CH2Cl, CHCl2, CCl3, CH2Br, CHBr2, and CBr3) were synthesized and the conformational equilibria studied by H-1 and C-13 NMR spectroscopy at 103 K and at 295 K, respectively. The geometry of optimized structures of the axial 'equatorial chair conformers was computed at the ab initio MO and DFT levels of theory. Only one preferred conformation was obtained for the axial and the equatorial conformer as well. When comparing the conformational equilibria of the cyclohexanone esters with those of the corresponding cyclohexyl esters a certain polarity contribution of the cyclohexanone framework was revealed, which is independent of the substituent effects and increases the stability of the axial conformers by a constant amount.
A number of N-substituted 2,2-dimethyl-1,4,2-oxazasilinanes 1 were synthesized and studied by variable temperature dynamic H-1 and C-13 NMR spectroscopy, room temperature N-15 NMR spectroscopy and theoretical calculations at the DFT and MP2 levels of theory. Both the preferred conformers were assigned and the barrier to the ring inversion of the saturated six-membered ring determined. From 1 the corresponding methyl iodide salts were produced, their structure studied by X-ray analysis and found to be in excellent agreement with the results of the theoretical calculations.
1,3-Dimethyl-3-phenyl-1,3-azasilinane was synthesized and its conformational behavior was studied by the low temperature NMR spectroscopy and quantum chemical calculations. The compound was shown to exist as an equilibrium mixture of the PhaxMeeq and PheqMeax chair conformers with the N-methyl substituent in equatorial position. The barrier to ring inversion was also determined.
1,3-Dimethyl-3-phenyl-1,3-azasilinane was synthesized and its conformational behavior was studied by the low temperature NMR spectroscopy and quantum chemical calculations. The compound was shown to exist as an equilibrium mixture of the PhaxMeeq and PheqMeax chair conformers with the N-methyl substituent in equatorial position. The barrier to ring inversion was also determined.
1-Isopropyl-3-methyl-3-phenyl-1,3-azasilinane 1 and 1-isopropyl-3,3-dimethyl-1,3-azasilinane 2 were synthesized and a detailed analysis of their NMR spectra, conformational equilibria and ring inversion processes is presented. Low temperature H-1/C-13 NMR spectroscopy, iteration of the H-1 NMR spectra and quantum chemical calculations showed slight predominance of the PheqMeax over the PhaxMeeq conformer of 1 at low temperature. The barrier for the chair to chair interconversion of both compounds was measured to be 8.25 kcal/mol.
Purpose: The formation of photoresponsive hydrogels were reported by irradiation of star-shaped poly(ethylene glycol)s with terminal cinnamylidene acetic acid (CAA) groups, which are capable of a photoinduced [2+2] cycloaddition. In this study we explored whether oligo(ethylene glycol) s and oligo(propylene glycol)s of varying molecular architecture (linear or star-shaped) or molecular weights could be functionalized with CAA as terminal groups by esterification or by amide formation.
Methods: Oligo(ethylene glycol) (OEG) and oligo(propylene glycol) (OPG) with varying molecular architecture (linear, star-shaped) and weight average molecular weights between 1000 and 5000 g.mol(-1) were functionalized by means of esterification of hydroxyl or amine endgroups with cinnamylidene acetic acid (CAA) or cinnamylidene acetyl chloride (CAC) as telechelic endgroups. The chemical structure, thermal properties, and molecular weights of the oligoethers obtained were determined by NMR spectroscopy, UV spectroscopy, DSC, and MALDI-TOF.
Results: CAA-functionalized linear and star-shaped OEGs or OPGs could be obtained with a degree of functionalization higher than 90%. In MALDI-TOF measurements an increase in Mw of about 150 g.mol(-1) (for each terminal end) after the functionalization reaction was observed. OEGCAA and OPGCAA showed an increase in glass transition temperature (T-g) from about -70 degrees C to -50 degrees C, compared to the unfunctionalized oligoethers. In addition, the melting temperature (T-m) of OEGCAA decreased from about 55 C to 30 degrees C, which can be accounted for by the hampered crystallization of the precursors because of the bulky CAA end groups as well as by the loss of the hydroxyl telechelic end groups.
Conclusion: The synthesis of photoresponsive oligoethers containing cinnamylidene acetic acid as telechelic endgroup was reported and high degrees of functionalization could be achieved. Such photosensitive oligomers are promising candidates as reactive precursors, for the preparation of biocompatible high molecular weight polymers and polymer networks.
Novel substituted pyrimidines were synthesized from methyl 2,4-dioxo-4-phenyl-butanoate (I-A) and urea, followed by Mitsunobu coupling of I-A with benzyl or allyl alcohol to give the corresponding 2-hydroxypyrimidine ethers in good yields. Saponification of I-A, followed by reaction with benzyl or allyl amines in the presence of TBTU yielded 2-hydroxy-6-phenyl-pyrimidine 4-carboxamides. AChE and BuChE assays revealed 2-hydroxy-6-phenyl-pyrimidine-4-carboxyallyamide as the most active compound, IC50=90 mu M, with no inhibition of BuChE.
Syntheses and conformational analyses of new naphth[1,2-e][1,3]oxazino[3,2-c]quinazolin-13-ones
(2012)
The syntheses of naphth[1,2-e][1,3]oxazino[3,2-c]quinazolin-13-one derivatives (3a-f) were achieved by the solvent-free heating of benzyloxycarbonyl-protected intermediates (2a-f) with MeONa. For intermediates 2a-f, prepared by the reactions of substituted aminonaphthols with benzyl N-(2-formylphenyl)carbamate, not only the expected trans ring form B and chain form A1, but also the rearranged chain form A2 as a new tautomer were detected in DMSO at room temperature. The quantity of A2 in the tautomeric mixture was changed with time. Conformational analyses of the target heterocycles 3a-f by NMR spectroscopy and accompanying theoretical calculations at the DFT level of theory revealed that the oxazine ring preferred a twisted chair conformation and the quinazolone ring was planar. Besides the conformations, both the configurations at C-7a and C-15 and the preferred rotamers of the 1-naphthyl substituent at C-15 were assigned, which allowed evaluation of the aryl substituent-dependent steric hindrance in this part of the molecules. Configurational assignments were corroborated by quantifying the ring current effect of 15-aryl in terms of spatial NICS.
Syntheses and conformational analyses of new naphth[1,2-e][1,3]oxazino[3,2-c] quinazolin-13-ones
(2012)
The syntheses of naphth[1,2-e][1,3]oxazino[3,2-c]quinazolin-13-one derivatives (3a-f) were achieved by the solvent-free heating of benzyloxycarbonyl-protected intermediates (2a-f) with MeONa. For intermediates 2a-f, prepared by the reactions of substituted aminonaphthols with benzyl N-(2-formylphenyl)carbamate, not only the expected trans ring form B and chain form A(1), but also the rearranged chain form A(2) as a new tautomer were detected in DMSO at room temperature. The quantity of A(2) in the tautomeric mixture was changed with time.
Conformational analyses of the target heterocycles 3a-f by NMR spectroscopy and accompanying theoretical calculations at the DFT level of theory revealed that the oxazine ring preferred a twisted chair conformation and the quinazolone ring was planar. Besides the conformations, both the configurations at C-7a and C-15 and the preferred rotamers of the 1-naphthyl substituent at C-15 were assigned, which allowed evaluation of the aryl substituent-dependent steric hindrance in this part of the molecules. Configurational assignments were corroborated by quantifying the ring current effect of 15-aryl in terms of spatial NICS.
Electroactive polymers can be used for actuators with many desirable features, including high electromechanical energy density, low weight, compactness, direct voltage control, and complete silence during actuation. These features may enable personalized robotics with much higher ability to delicately manipulate their surroundings than can be achieved with currently available actuators; however, much work is still necessary to enhance the electroactive materials. Electric field-driven actuator materials are improved by an increase in permittivity and by a reduction in stiffness. Here, a synergistic enhancement method based on a macromolecular plasticizing filler molecule with a combination of both high dipole moment and compatibilizer moieties, synthesized to simultaneously ensure improvement of electromechanical properties and compatibility with the host matrix is presented. Measurements show an 85% increase in permittivity combined with 290% reduction in mechanical stiffness. NMR measurements confirm the structure of the filler while DSC measurements confirm that it is compatible with the host matrix at all the mixture ratios investigated. Actuation strain measurements in the pure shear configuration display an increase in sensitivity to the electrical field of more than 450%, confirming that the filler molecule does not only improve dielectric and mechanical properties, it also leads to a synergistic enhancement of actuation properties by simple means.
We present a setup for ultrafast x-ray diffraction (UXRD) based at the storage ring BESSY II, in particular, a pump laser that excites the sample using 250 fs laser-pulses at repetition rates ranging from 208 kHz to 1.25 MHz. We discuss issues connected to the high heat-load and spatio-temporal alignment strategies in the context of a UXRD experiment at high repetition rates. The spatial overlap between laser pump and x-ray probe pulse is obtained with 10 mu m precision and transient lattice changes can be recorded with an accuracy of delta a/a(0) = 10(-6). We also compare time-resolved x-ray diffraction signals from a laser excited LSMO/STO superlattice with phonon dynamics simulations. From the analysis we determine the x-ray pulse duration to 120 ps in standard operation mode and below 10 ps in low-alpha mode.
The switching kinetics of thin thermo-responsive hydrogel films of poly(monomethoxy-diethyleneglycol-acrylate) (PMDEGA) are investigated. Homogeneous and smooth PMDEGA films with a thickness of 35.9 nm are prepared on silicon substrates by spin coating. As probed with white light interferometry, PMDEGA films with a thickness of 35.9 nm exhibit a phase transition temperature of the lower critical solution temperature (LCST) type of 40 degrees C. In situ neutron reflectivity is performed to investigate the thermo-responsive behavior of these PMDEGA hydrogel films in response to a sudden thermal stimulus in deuterated water vapor atmosphere. The collapse transition proceeds in a complex way which can be seen as three steps. The first step is the shrinkage of the initially swollen film by a release of water. In the second step the thickness remains constant with water molecules embedded in the film. In the third step, perhaps due to a conformational rearrangement of the collapsed PMDEGA chains, water is reabsorbed from the vapor atmosphere, thereby giving rise to a relaxation process. Both the shrinkage and relaxation processes can be described by a simple model of hydrogel deswelling.
Sustainable management of semi-arid African savannas under environmental and political change
(2012)
Drylands cover about 40% of the earth’s land surface and provide the basis for the livelihoods of 38% of the global human population. Worldwide, these ecosystems are prone to heavy degradation. Increasing levels of dryland degradation result a strong decline of ecosystem services. In addition, in highly variable semi-arid environments changing future environmental conditions will potentially have severe consequences for productivity and ecosystem dynamics. Hence, global efforts have to be made to understand the particular causes and consequences of dryland degradation and to promote sustainable management options for semi-arid and arid ecosystems in a changing world. Here I particularly address the problem of semi-arid savanna degradation, which mostly occurs in form of woody plant encroachment. At this, I aim at finding viable sustainable management strategies and improving the general understanding of semi-arid savanna vegetation dynamics under conditions of extensive livestock production. Moreover, the influence of external forces, i.e. environmental change and land reform, on the use of savanna vegetation and on the ecosystem response to this land use is assessed. Based on this I identify conditions and strategies that facilitate a sustainable use of semi-arid savanna rangelands in a changing world. I extended an eco-hydrological model to simulate rangeland vegetation dynamics for a typical semi-arid savanna in eastern Namibia. In particular, I identified the response of semi-arid savanna vegetation to different land use strategies (including fire management) also with regard to different predicted precipitation, temperature and CO2 regimes. Not only environmental but also economic and political constraints like e.g. land reform programmes are shaping rangeland management strategies. Hence, I aimed at understanding the effects of the ongoing process of land reform in southern Africa on land use and the semi-arid savanna vegetation. Therefore, I developed and implemented an agent-based ecological-economic modelling tool for interactive role plays with land users. This tool was applied in an interdisciplinary empirical study to identify general patterns of management decisions and the between-farm cooperation of land reform beneficiaries in eastern Namibia. The eco-hydrological simulations revealed that the future dynamics of semi-arid savanna vegetation strongly depend on the respective climate change scenario. In particular, I found that the capacity of the system to sustain domestic livestock production will strongly depend on changes in the amount and temporal distribution of precipitation. In addition, my simulations revealed that shrub encroachment will become less likely under future climatic conditions although positive effects of CO2 on woody plant growth and transpiration have been considered. While earlier studies predicted a further increase in shrub encroachment due to increased levels of atmospheric CO2, my contrary finding is based on the negative impacts of temperature increase on the drought sensitive seedling germination and establishment of woody plant species. Further simulation experiments revealed that prescribed fires are an efficient tool for semi-arid rangeland management, since they suppress woody plant seedling establishment. The strategies tested have increased the long term productivity of the savanna in terms of livestock production and decreased the risk for shrub encroachment (i.e. savanna degradation). This finding refutes the views promoted by existing studies, which state that fires are of minor importance for the vegetation dynamics of semi-arid and arid savannas. Again, the difference in predictions is related to the bottleneck at the seedling establishment stage of woody plants, which has not been sufficiently considered in earlier studies. The ecological-economic role plays with Namibian land reform beneficiaries showed that the farmers made their decisions with regard to herd size adjustments according to economic but not according to environmental variables. Hence, they do not manage opportunistically by tracking grass biomass availability but rather apply conservative management strategies with low stocking rates. This implies that under the given circumstances the management of these farmers will not per se cause (or further worsen) the problem of savanna degradation and shrub encroachment due to overgrazing. However, as my results indicate that this management strategy is rather based on high financial pressure, it is not an indicator for successful rangeland management. Rather, farmers struggle hard to make any positive revenue from their farming business and the success of the Namibian land reform is currently disputable. The role-plays also revealed that cooperation between farmers is difficult even though obligatory due to the often small farm sizes. I thus propose that cooperation needs to be facilitated to improve the success of land reform beneficiaries.
The need to reduce humankind reliance on fossil fuels by exploiting sustainably the planet renewable resources is a major driving force determining the focus of modern material research. For this reason great interest is nowadays focused on finding alternatives to fossil fuels derived products/materials. For the short term the most promising substitute is undoubtedly biomass, since it is the only renewable and sustainable alternative to fossil fuels as carbon source. As a consequence efforts, aimed at finding new synthetic approaches to convert biomass and its derivatives into carbon-based materials, are constantly increasing. In this regard, hydrothermal carbonisation (HTC) has shown to be an effective means of conversion of biomass-derived precursors into functional carbon materials. However the attempts to convert raw biomass, in particular lignocellulosic one, directly into such products have certainly been rarer. Unlocking the direct use of these raw materials as carbon precursors would definitely be beneficial in terms of HTC sustainability. For this reason, in this thesis the HTC of carbohydrate and protein-rich biomass was systematically investigated, in order to obtain more insights on the potentials of this thermochemical processing technique in relation to the production of functional carbon materials from crude biomass. First a detailed investigation on the HTC conversion mechanism of lignocellulosic biomass and its single components (i.e. cellulose, lignin) was developed based on a comparison with glucose HTC, which was adopted as a reference model. In the glucose case it was demonstrated that varying the HTC temperature allowed tuning the chemical structure of the synthesised carbon materials from a highly cross-linked furan-based structure (T = 180oC) to a carbon framework composed of polyaromatic arene-like domains. When cellulose or lignocellulosic biomass was used as carbon precursor, the furan rich structure could not be isolated at any of the investigated processing conditions. These evidences were indicative of a different HTC conversion mechanism for cellulose, involving reactions that are commonly observed during pyrolytic processes. The evolution of glucose-derived HTC carbon chemical structure upon pyrolysis was also investigated. These studies revealed that upon heat treatment (Investigated temperatures 350 – 900 oC) the furan-based structure was progressively converted into highly curved aromatic pre-graphenic domains. This thermal degradation process was observed to produce an increasingly more hydrophobic surface and considerable microporosity within the HTC carbon structure. In order to introduce porosity in the HTC carbons derived from lignocellulosic biomass, KOH chemical activation was investigated as an HTC post-synthesis functionalisation step. These studies demonstrated that HTC carbons are excellent precursors for the production of highly microporous activated carbons (ACs) and that the porosity development upon KOH chemical activation is dependent on the chemical structure of the HTC carbon, tuned by employing different HTC temperatures. Preliminary testing of the ACs for CO2 capture or high pressure CH4 storage yielded very promising results, since the measured uptakes of both adsorbates (i.e. CO2 and CH4) were comparable to top-performing and commercially available adsorbents, usually employed for these end-applications. The combined use of HTC and KOH chemical activation was also employed to produce highly microporous N-doped ACs from microalgae. The hydrothermal treatment of the microalgae substrate was observed to cause the depletion of the protein and carbohydrate fractions and the near complete loss (i.e. 90%) of the microalgae N-content, as liquid hydrolysis/degradation products. The obtained carbonaceous product showed a predominantly aliphatic character indicating the presence of alkyl chains presumably derived from the lipid fractions. Addition of glucose to the initial reaction mixture was found out to be extremely beneficial, because it allowed the fixation of a higher N amount, in the algae derived HTC carbons (i.e. 60%), and the attainment of higher product yields (50%). Both positive effects were attributed to Maillard type cascade reactions taking place between the monosaccharides and the microalgae derived liquid hydrolysis/degradation products, which were in this way recovered from the liquid phase. KOH chemical activation of the microalgae/glucose mixture derived HTC carbons produced highly microporous N-doped carbons. Although the activation process led to a major reduction of the N-content, the retained N-amount in the ACs was still considerable. These features render these materials ideal candidates for supercapacitors electrodes, since they provide extremely high surface areas, for the formation of electric double-layer, coupled to abundant heteroatom doping (i.e. N and O) necessary to obtain a pseudocapacitance contribution.
Metal surfaces with disorder or with nanostructure modifications are studied, allowing for a localized charge layer (CL) in addition to continuous charges (CC) in the bulk, both charges having a compressional or diffusive nonlocal response. The notorious problem of "additional boundary conditions" is resolved with the help of a Boltzmann equation that involves the scattering between the two charge types. Depending on the strength of this scattering, the oscillating charges can be dominantly CC or CL; the surface plasmon (SP) resonance acquires then a relatively small linewidth, in agreement with a large set of data. With a few parameters our model describes a large variety of SP dispersions corresponding to observed data.
It is well-known that surface plasmon generated near fields of suitably irradiated metal nano-structures can induce a patterning in an azobenzene-modified photosensitive polymer film placed on top. The change in the topography usually follows closely and permanently the underlying near field intensity pattern. With this approach, one can achieve a multitude of morphologies by additionally changing light intensity, polarization and the kind of metal used for nano-structuring. In this paper, we demonstrate that below a critical value of the polymer film thickness, the receding polymer material induces a change in refractive index of the glass-metal-polymer system, modifying the near field intensity distribution and causing a back-reaction on the flow of polymer material. This has a profound influence on the smallest size of topographical features that can be imprinted into the polymer.
With ongoing miniaturization of electronic devices, the need for individually addressable, switchable molecules arises. An example are azobenzenes on surfaces which have been shown to be switchable between trans and cis forms. Here, we examine the "direct" (rather than substrate-mediated) channel of the trans -> cis photoisomerization after pi pi* excitation of tetra-tert-butyl-azobenzene physisorbed on surfaces mimicking Au(111) and Bi(111), respectively. In spirit of the direct channel, the electronic structure of the surface is neglected, the latter merely acting as a rigid platform which weakly interacts with the molecule via Van-der-Waals forces. Starting from thermal ensembles which represent the trans-form, sudden excitations promote the molecules to pi pi*-excited states which are non-adiabatically coupled among themselves and to a n pi*-excited and the ground state, respectively. After excitation, relaxation to the ground state by internal conversion takes place, possibly accompanied by isomerization. The process is described here by "on the fly" semiclassical surface hopping dynamics in conjunction with a semiempirical Hamiltonian (AM1) and configuration-interaction type methods. It is found that steric constraints imposed by the substrate lead to reduced but non-vanishing, trans -> cis reaction yields and longer internal conversion times than for the isolated molecule. Implications for recent experiments for azobenzenes on surfaces are discussed.
Materials for biomedical applications are often chosen for their bulk properties. Other requirements such as a hemocompatible surface shall be fulfilled by suitable chemical functionalization. Here we show, that linear, side-chain methylated oligoglycerols (OGMe) are more stable to oxidation than oligo(ethylene glycol) (OEG). Poly(ether imide) (PEI) membranes functionalized with OGMes perform at least as good as, and partially better than, OEG functionalized PEI membranes in view of protein resistance as well as thrombocyte adhesion and activation. Therefore, OGMes are highly potent surface functionalizing molecules for improving the hemocompatibility of polymers.
The southwest margin of the Central Anatolian Plateau has experienced multiple phases of topographic growth, including the formation of localized highs prior to the Late Miocene that were later affected by wholesale uplift of the plateau margin. Our new biostratigraphic data limit the age of uplifted marine sediments at the southwest plateau margin at 1.5 km elevation to <7.17 Ma, and regional lithostratigraphic correlations imply that the age is <6.7 Ma. Single-grain CA-TIMS U-Pb zircon analyses from a reworked ash within the marine sediments yield dates as young as 10.6 Ma, indicating a maximum age that is consistent with the biostratigraphy. Our structural measurements within the uplifted region and fault inversion modeling agree with previous findings in surrounding regions, with early contraction followed by strike-slip and extensional deformation during uplift. Focal mechanisms from shallow earthquakes show that the extensional phase has continued to the present. Broad similarities in the change in the tectonic stress regime (after 8 Ma) and the onset of surface uplift (after 7 Ma) imply that deep-seated process(es) caused post-7 Ma uplift. The geometry of lithospheric slabs beneath the plateau margin, Pliocene to recent alkaline volcanism, and the uplift pattern with accompanying normal faulting point toward slab tearing and localized heating at the base of the lithosphere as a probable mechanism for post-7 Ma uplift of the southwest margin. Considering previous work in the region, there appears to be an important link between slab dynamics and surface uplift throughout the Anatolian Plateau’s southern margin.
Suppression of the near-infrared OH night-sky lines with fibre Bragg gratings - first results
(2012)
The background noise between 1 and 1.8 ?mu m in ground-based instruments is dominated by atmospheric emission from hydroxyl molecules. We have built and commissioned a new instrument, the Gemini Near-infrared OH Suppression Integral Field Unit (IFU) System (GNOSIS), which suppresses 103 OH doublets between 1.47 and 1.7?mu m by a factor of 1000 with a resolving power of 10?000. We present the first results from the commissioning of GNOSIS using the IRIS2 spectrograph at the Anglo-Australian Telescope. We present measurements of sensitivity, background and throughput. The combined throughput of the GNOSIS fore-optics, grating unit and relay optics is 36?per cent, but this could be improved to 46?per cent with a more optimal design. We measure strong suppression of the OH lines, confirming that OH suppression with fibre Bragg gratings will be a powerful technology for low-resolution spectroscopy. The integrated OH suppressed background between 1.5 and 1.7 mu m is reduced by a factor of 9 compared to a control spectrum using the same system without suppression. The potential of low-resolution OH-suppressed spectroscopy is illustrated with example observations of Seyfert galaxies and a low-mass star. The GNOSIS background is dominated by detector dark current below 1.67 mu m and by thermal emission above 1.67 mu m. After subtracting these, we detect an unidentified residual interline component of 860 +/- 210 photons s-1 m-2?arcsec-2?mu m-1, comparable to previous measurements. This component is equally bright in the suppressed and control spectra. We have investigated the possible source of the interline component, but were unable to discriminate between a possible instrumental artefact and intrinsic atmospheric emission. Resolving the source of this emission is crucial for the design of fully optimized OH suppression spectrographs. The next-generation OH suppression spectrograph will be focused on resolving the source of the interline component, taking advantage of better optimization for a fibre Bragg grating feed incorporating refinements of design based on our findings from GNOSIS. We quantify the necessary improvements for an optimal OH suppressing fibre spectrograph design.
This paper presents the state of the art in the development of Semantic-Web-enabled software using object-oriented programming languages. Object triple mapping (OTM) is a frequently used method to simplify the development of such software. A case study that is based on interviews with developers of OTM frameworks is presented at the core of this paper. Following the results of the case study, the formalization of OTM is kept separate from optional but desirable extensions of OTM with regard to metadata, schema matching, and integration into the Semantic-Web infrastructure. The material that is presented is expected to not only explain the development of Semantic-Web software by the usage of OTM, but also explain what properties of Semantic-Web software made developers come up with OTM. Understanding the latter will be essential to get nonexpert software developers to use Semantic-Web technologies in their software.
The Low Earth Orbit (LEO) experiment Biology and Mars Experiment (BIOMEX) is an interdisciplinary and international space research project selected by ESA. The experiment will be accommodated on the space exposure facility EXPOSE-R2 on the International Space Station (ISS) and is foreseen to be launched in 2013. The prime objective of BIOMEX is to measure to what extent biomolecules, such as pigments and cellular components, are resistant to and able to maintain their stability under space and Mars-like conditions. The results of BIOMEX will be relevant for space proven biosignature definition and for building a biosignature data base (e.g. the proposed creation of an international Raman library). The library will be highly relevant for future space missions such as the search for life on Mars. The secondary scientific objective is to analyze to what extent terrestrial extremophiles are able to survive in space and to determine which interactions between biological samples and selected minerals (including terrestrial, Moon- and Mars analogs) can be observed under space and Mars-like conditions. In this context, the Moon will be an additional platform for performing similar experiments with negligible magnetic shielding and higher solar and galactic irradiation compared to LEO. Using the Moon as an additional astrobiological exposure platform to complement ongoing astrobiological LEO investigations could thus enhance the chances of detecting organic traces of life on Mars. We present a lunar lander mission with two related objectives: a lunar lander equipped with Raman and PanCam instruments which can analyze the lunar surface and survey an astrobiological exposure platform. This dual use of testing mission technology together with geo- and astrobiological analyses will significantly increase the science return, and support the human preparation objectives. It will provide knowledge about the Moon's surface itself and, in addition, monitor the stability of life-markers, such as cells, cell components and pigments, in an extraterrestrial environment with much closer radiation properties to the surface of Mars. The combination of a Raman data base of these data together with data from LEO and space simulation experiments, will lead to further progress on the analysis and interpretation of data that we will obtain from future Moon and Mars exploration missions.
Deformation experiments on hydrous melt-bearing dunite (olivine+4 vol% orthopyroxene+4 vol% clinopyroxene with less than 2.5 vol% of the melt phase) were conducted at pressures of 1.3-5.7 GPa and temperatures of 1270-1490 K in order to explore the effect of intergranular fluids on the plastic flow of olivine in Earth's upper mantle. The strain rate was proportional to steady-state creep strength to the 2.1 power, and the creep strength markedly increased with increase in grain size. Developments of the crystallographic preferred orientation of olivine and flattening of olivine grains were hardly observed even after 33-55% shortening of the samples. These observations show that grain boundary sliding (GBS) dominated the deformation of olivine (i.e., superplasticity). The creep strength of hydrous melt-bearing dunite was 2-5 times lower than that of melt-free dunite. The dependence of creep rate on melt fraction is known to be expressed empirically as (epsilon) over dot(phi) = (epsilon) over dot(0) exp(alpha phi), where alpha is a constant and phi is the melt fraction. The experimentally obtained value of alpha was in the range of 150-230, corresponding to 5-7 times the reported values for the olivine-basalt system at 0.3 GPa (i.e., creep strength of dunite was efficiently reduced by the hydrous melt). Superplasticity is the dominant creep mechanism of olivine in fluid-bearing fine-grained peridotites under low-temperature and high-stress conditions (i.e., peridotite shear zones in the upper mantle). Superplasticity induced by geological fluids would play an important role in the shear localization (and thus initiation of subduction) in the upper mantle.
Polarization of the electromagnetic wavefield has significant implications for the acquisition and interpretation of ground-penetrating radar (GPR) data. Based on the geometrical and physical properties of the subsurface scatterer and the physical properties of its surrounding material, strong polarization phenomena might occur. Here, we develop an attribute-based analysis approach to extract and characterize buried utility pipes using two broadside antenna configurations. First, we enhance and extract the utilities by making use of their distinct symmetric nature through the application of a symmetry-enhancing image-processing algorithm known as phase symmetry. Second, we assess the polarization characteristics by calculating two attributes (polarization angle and linearity) using principal component analysis. Combination of attributes derived from these steps into a novel depolarization attribute allows one to efficiently detect and distinguish different utilities present within 3-D GPR data. The performance of our analysis approach is illustrated using synthetic examples and evaluated using field examples (including a dual-configuration 3-D data set) collected across a field site, where detailed ground-truth information is available. Our results demonstrate that the proposed approach allows for a more detailed extraction and combination of utility relevant information compared to approaches relying on single-component data and, thus, eases the interpretation of multicomponent GPR data sets.
This study investigates phenomena that have been claimed to be indicative of Specific Language Impairment (SLI) in German, focusing on subject-verb agreement marking. Longitudinal data from fourteen German-speaking children with SLI, seven monolingual and seven Turkish-German successive bilingual children, were examined. We found similar patterns of impairment in the two participant groups. Both the monolingual and the bilingual children with SLI had correct (present vs. preterit) tense marking and produced syntactically complex sentences such as embedded clauses and wh-questions, but were limited in reliably producing correct agreement-marked verb forms. These contrasts indicate that agreement marking is impaired in German-speaking children with SLI, without any necessary concurrent deficits in either the CP-domain or in tense marking. Our results also show that it is possible to identify SLI from an early successive bilingual child's performance in one of her two languages.
This study investigates phenomena that have been claimed to be indicative of Specific Language Impairment (SLI) in German, focusing on subject-verb agreement marking. Longitudinal data from fourteen German-speaking children with SLI, seven monolingual and seven Turkish-German successive bilingual children, were examined. We found similar patterns of impairment in the two participant groups. Both the monolingual and the bilingual children with SLI had correct (present vs. preterit) tense marking and produced syntactically complex sentences such as embedded clauses and wh-questions, but were limited in reliably producing correct agreement-marked verb forms. These contrasts indicate that agreement marking is impaired in German-speaking children with SLI, without any necessary concurrent deficits in either the CP-domain or in tense marking. Our results also show that it is possible to identify SLI from an early successive bilingual child's performance in one of her two languages.
Ostracodes (Ostracoda, Crustacea) are aquatic micro-crustaceans with a significant representation in the fossil record. If the environmental influence on the species composition of their communities is robustly quantified, past changes in ostracode communities reflected in fossil assemblages can be used for paleo-environmental reconstruction. We analyzed ostracode assemblages in recently deposited surface sediments from 56 lakes in western and central Mongolia, and simultaneously recorded local water chemistry and solute concentration in order to elucidate the distribution of individual ostracode species in relation to these broad environmental gradients. Multivariate analysis indicated that the species variation in ostracode assemblages could be mainly attributed to variations in percent calcium (%Ca) relative to total cation content, mean annual precipitation, calcium concentration, alkalinity, percent bicarbonate relative to total anion content, and mean July temperature. This matches well with the results of a similar analysis on presence/absence data of living ostracodes in nearshore samples, even though some differences exist between the faunal composition of both datasets. The documented response of ostracode species to environmental variation tracks the typical solute evolutionary pathway for surface waters in this region, characterized by calcite precipitation and consequent depletion in dissolved calcium. Hence, the best quantitative inference model (WA-PLS model with R-jack(2) = 0.70, RMSEP = 0.40) for paleolimnological application was obtained for %Ca. Comparison between this model and a specific conductance (SC) inference model based on the same dataset, and based on ostracode datasets from different regions, indicated that the %Ca inference model suffers less than the SC inference model from a step-change in reconstructed values. The statistical power of different inference models based on Mongolian ostracodes are variously affected by the common dominance of a single euryhaline species (Limnocythere inopinata), limited faunal turnover in the freshwater portion of the salinity gradient, and the bimodal frequency distribution of SC among regional lakes. The latter probably represents true scarcity of lakes with intermediate salinity rather than a biased representation in our dataset. In a broader context of ostracode ecology, and with respect to regional paleolimnological applications, we highlight the potential of fossil Mongolian ostracode assemblages to trace past hydrological shifts associated with changes in groundwater inflow.
Structuring process models
(2012)
One can fairly adopt the ideas of Donald E. Knuth to conclude that process modeling is both a science and an art. Process modeling does have an aesthetic sense. Similar to composing an opera or writing a novel, process modeling is carried out by humans who undergo creative practices when engineering a process model. Therefore, the very same process can be modeled in a myriad number of ways. Once modeled, processes can be analyzed by employing scientific methods. Usually, process models are formalized as directed graphs, with nodes representing tasks and decisions, and directed arcs describing temporal constraints between the nodes. Common process definition languages, such as Business Process Model and Notation (BPMN) and Event-driven Process Chain (EPC) allow process analysts to define models with arbitrary complex topologies. The absence of structural constraints supports creativity and productivity, as there is no need to force ideas into a limited amount of available structural patterns. Nevertheless, it is often preferable that models follow certain structural rules. A well-known structural property of process models is (well-)structuredness. A process model is (well-)structured if and only if every node with multiple outgoing arcs (a split) has a corresponding node with multiple incoming arcs (a join), and vice versa, such that the set of nodes between the split and the join induces a single-entry-single-exit (SESE) region; otherwise the process model is unstructured. The motivations for well-structured process models are manifold: (i) Well-structured process models are easier to layout for visual representation as their formalizations are planar graphs. (ii) Well-structured process models are easier to comprehend by humans. (iii) Well-structured process models tend to have fewer errors than unstructured ones and it is less probable to introduce new errors when modifying a well-structured process model. (iv) Well-structured process models are better suited for analysis with many existing formal techniques applicable only for well-structured process models. (v) Well-structured process models are better suited for efficient execution and optimization, e.g., when discovering independent regions of a process model that can be executed concurrently. Consequently, there are process modeling languages that encourage well-structured modeling, e.g., Business Process Execution Language (BPEL) and ADEPT. However, the well-structured process modeling implies some limitations: (i) There exist processes that cannot be formalized as well-structured process models. (ii) There exist processes that when formalized as well-structured process models require a considerable duplication of modeling constructs. Rather than expecting well-structured modeling from start, we advocate for the absence of structural constraints when modeling. Afterwards, automated methods can suggest, upon request and whenever possible, alternative formalizations that are "better" structured, preferably well-structured. In this thesis, we study the problem of automatically transforming process models into equivalent well-structured models. The developed transformations are performed under a strong notion of behavioral equivalence which preserves concurrency. The findings are implemented in a tool, which is publicly available.
This article studies the problem of transforming a process model with an arbitrary topology into an equivalent well-structured process model. While this problem has received significant attention, there is still no full characterization of the class of unstructured process models that can be transformed into well-structured ones, nor an automated method for structuring any process model that belongs to this class. This article fills this gap in the context of acyclic process models. The article defines a necessary and sufficient condition for an unstructured acyclic process model to have an equivalent well-structured process model under fully concurrent bisimulation, as well as a complete structuring method. The method has been implemented as a tool that takes process models captured in the BPMN and EPC notations as input. The article also reports on an empirical evaluation of the structuring method using a repository of process models from commercial practice.
Structuring overmany length scales is a design strategy widely used in Nature to create materials with unique functional properties. We here present a comprehensive analysis of an adult sea urchin spine, and in revealing a complex, hierarchical structure, showhow Nature fabricates a material which diffracts as a single crystal of calcite and yet fractures as a glassy material. Each spine comprises a highly oriented array of Mg-calcite nanocrystals in which amorphous regions and macromolecules are embedded. It is postulated that this mesocrystalline structure forms via the crystallization of a dense array of amorphous calcium carbonate (ACC) precursor particles. A residual surface layer of ACC and/or macromolecules remains around the nanoparticle units which creates the mesocrystal structure and contributes to the conchoidal fracture behavior. Nature's demonstration of howcrystallization of an amorphous precursor phase can create a crystalline material with remarkable properties therefore provides inspiration for a novel approach to the design and synthesis of synthetic composite materials.
On 12 September 2007, an M-w 8.4 earthquake occurred within the southern section of the Mentawai segment of the Sumatra subduction zone, where the subduction thrust had previously ruptured in 1833 and 1797. Traveltime data obtained from a temporary local seismic network, deployed between December 2007 and October 2008 to record the aftershocks of the 2007 event, was used to determine two-dimensional (2-D) and three-dimensional (3-D) velocity models of the Mentawai segment. The seismicity distribution reveals significant activity along the subduction interface and within two clusters in the overriding plate either side of the forearc basin. The downgoing slab is clearly distinguished by a dipping region of high Vp (8.0 km/s), which can be a traced to similar to 50 km depth, with an increased Vp/Vs ratio (1.75 to 1.90) beneath the islands and the western side of the forearc basin, suggesting hydrated oceanic crust. Above the slab, a shallow continental Moho of less than 30 km depth can be inferred, suggesting that the intersection of the continental mantle with the subducting slab is much shallower than the downdip limit of the seismogenic zone despite localized serpentinization being present at the toe of the mantle wedge. The outer arc islands are characterized by low Vp (4.5-5.8 km/s) and high Vp/Vs (greater than 2.0), suggesting that they consist of fluid saturated sediments. The very low rigidity of the outer forearc contributed to the slow rupture of the M-w 7.7 Mentawai tsunami earthquake on 25 October 2010.
The structural and dynamical properties of oil-in-water (O/W) microemulsions (MEs) modified with telechelic polymers of different functionality (e.g., number of hydrophobically modified arms, f) were studied by means of dynamic light scattering (DLS), small-angle neutron scattering (SANS), and high frequency rheology measurements as a function of the polymer architecture and the amount of added polymer. For this purpose, we employed tailor-made hydrophobically end-capped poly(N,N-dimethylacrylamide) star polymers of a variable number of endcaps, f, of different alkyl chain lengths, synthesized by the reversible addition-fragmentation chain transfer method. The addition of the different end-capped polymers to an uncharged ME of O/W droplets leads to a large enhancement of the viscosity of the systems. SANS experiments show that the O/W ME droplets are not changed upon the addition of the polymer, and its presence only changes the interdroplet interactions. The viscosity increases largely upon addition of a polymer, and this enhancement depends pronouncedly on the alkyl length of the hydrophobic sticker as it controls the residence time in a ME droplet. Similarly, the high frequency modulus G(0) depends on the amount of added polymer but not on the sticker length. G(0) was found to be directly proportional to f - 1. The onset of network formation is shifted to a lower number of stickers per ME droplet with increasing f, and the network formation becomes more effective. Thus, the dynamics of network formation are controlled by the polymer architecture. The effect on the dynamics seen by DLS is even more pronounced. Upon increasing the polymer concentration, slower relaxation modes appear that become especially pronounced with increasing number of arms. The relaxation dynamics are correlated to the rheological relaxation, and both are controlled by the polymer architecture.
Structure and the conformational properties of 1,3,3-trimethyl-1,3-azasilinane have been studied. According to gas electron diffraction (GED), the molecule exists in a slightly distorted chair conformation with the N-Me group in equatorial position. High-level quantum chemical calculations excellently, reproduce the experimental geometry. Employing variable temperature H-1 and C-13 NMR spectroscopy down to 103 K, the conformational equilibrium could be frozen and the barrier to ring inversion determined.
Structurally diverse polyamides obtained from monomers derived via the Ugi multicomponent reaction
(2012)
The combination of the Ugi four-component reaction (Ugi-4CR) with acyclic diene metathesis (ADMET) or thiolene polymerization led to the formation of poly-1-(alkylcarbamoyl) carboxamides, a new class of substituted polyamides with amide moieties in the polymer backbone, as well as its side chains. 10-Undecenoic acid, obtained by pyrolysis of ricinoleic acid, the main fatty acid of castor oil, was used as the key renewable building block. The use of different primary amines, as well as isonitriles (isocyanides) for the described Ugi reactions provided monomers with high structural diversity. Furthermore, the possibility of versatile post-modification of functional groups in the side chains of the corresponding polymers should be of considerable interest in materials science. The obtained monomers were polymerized by ADMET, as well as thiolene, chemistry and all polymers were fully characterized. Finally, ortho-nitrobenzylamide-containing polyamides obtained by this route were shown to be photoresponsive and exhibited a dramatic change of their properties upon irradiation with light.
We have analyzed the O-antigen polysaccharide of the previously uncharacterized Escherichia coli strain TD2158 which is a host of bacteriophage HK620. This bacteriophage recognizes and cleaves the polysaccharide with its tailspike protein (TSP). The polysaccharide preparation as well as oligosaccharides obtained from HK620TSP endoglycosidase digests were analyzed with NMR spectroscopy. Additionally, sugar analysis was performed on the O-antigen polysaccharide and MALDI-TOF MS was used in oligosaccharide analysis. The present study revealed a heterogeneous polysaccharide with a hexasaccharide repeating unit of the following structure:
alpha-D-Glcp-(1 -> 6) vertical bar vertical bar 2)-alpha-L-Rhap-(1 -> 6)-alpha-D-Glcp-(1 -> 4)-alpha-D-Galp-(1 -> 3)-alpha-D-GlcpNAc- (1 ->vertical bar beta-D-Glcp/beta-D-GlcpNAc-(1 -> 3)
A repeating unit with a D-GlcNAc substitution of D-Gal has been described earlier as characteristic for serogroup O18A1. Accordingly, we termed repeating units with D-Glc substitution at D-Gal as O18A2. NMR analyses of the polysaccharide confirmed that O18A1- and O18A2-type repeats were present in a 1:1 ratio. However, HK620TSP preferentially bound the D-GlcNAc- substituted O18A1-type repeating units in its high affinity binding pocket with a dissociation constant of 140 mu M and disfavored the O18A2-type having a beta-D-Glcp-(1 -> 3)-linked group. As a result, in hexasaccharide preparations, O18A1 and O18A2 repeats were present in a 9: 1 ratio stressing the clear preference of O18A1- type repeats to be cleaved by HK620TSP.
Structural dynamics of photoexcited nanolayered perovskites studied by ultrafast x-ray diffraction
(2012)
This publication-based thesis represents a contribution to the active research field of ultrafast structural dynamics in laser-excited nanostructures. The investigation of such dynamics is mandatory for the understanding of the various physical processes on microscopic scales in complex materials which have great potentials for advances in many technological applications. I theoretically and experimentally examine the coherent, incoherent and anharmonic lattice dynamics of epitaxial metal-insulator heterostructures on timescales ranging from femtoseconds up to nanoseconds. To infer information on the transient dynamics in the photoexcited crystal lattices experimental techniques using ultrashort optical and x-ray pulses are employed. The experimental setups include table-top sources as well as large-scale facilities such as synchrotron sources. At the core of my work lies the development of a linear-chain model to simulate and analyze the photoexcited atomic-scale dynamics. The calculated strain fields are then used to simulate the optical and x-ray response of the considered thin films and multilayers in order to relate the experimental signatures to particular structural processes. This way one obtains insight into the rich lattice dynamics exhibiting coherent transport of vibrational energy from local excitations via delocalized phonon modes of the samples. The complex deformations in tailored multilayers are identified to give rise to highly nonlinear x-ray diffraction responses due to transient interference effects. The understanding of such effects and the ability to precisely calculate those are exploited for the design of novel ultrafast x-ray optics. In particular, I present several Phonon Bragg Switch concepts to efficiently generate ultrashort x-ray pulses for time-resolved structural investigations. By extension of the numerical models to include incoherent phonon propagation and anharmonic lattice potentials I present a new view on the fundamental research topics of nanoscale thermal transport and anharmonic phonon-phonon interactions such as nonlinear sound propagation and phonon damping. The former issue is exemplified by the time-resolved heat conduction from thin SrRuO3 films into a SrTiO3 substrate which exhibits an unexpectedly slow heat conductivity. Furthermore, I discuss various experiments which can be well reproduced by the versatile numerical models and thus evidence strong lattice anharmonicities in the perovskite oxide SrTiO3. The thesis also presents several advances of experimental techniques such as time-resolved phonon spectroscopy with optical and x-ray photons as well as concepts for the implementation of x-ray diffraction setups at standard synchrotron beamlines with largely improved time-resolution for investigations of ultrafast structural processes. This work forms the basis for ongoing research topics in complex oxide materials including electronic correlations and phase transitions related to the elastic, magnetic and polarization degrees of freedom.
In landscapes which are predominately characterised by agriculture, natural ecosystems are often reduced to a mosaic of scattered patches of natural vegetation. Species with formerly connected distribution ranges now have restricted gene flow among populations. This has isolating effects upon population structure, because species are often confined by their limited dispersal capabilities. In this study, we test the effects of habitat fragmentation, precipitation, and isolation of populations on the genetic structure (AFLP) and fitness of the Asteraceae Catananche lutea. Our study area is an agro-dominated ecosystem in the desert-Mediterranean transition zone of the Southern Judea Lowlands in Israel. Our analysis revealed an intermediate level of intra-population genetic diversity across the study site with reduced genetic diversity on smaller scale. Although the size of the whole study area was relatively small (20 x 45 km), we found isolation by distance to be effective. We detected a high level of genetic differentiation among populations but genetic structure did not reflect spatial patterns. Population genetic diversity was correlated neither with position along the precipitation gradient nor with different seed types or other plant fitness variables in C. lutea.
Here we demonstrate how a surface plasmon (SP) generated near field pattern in the vicinity of a nano-scale pin hole can be used to generate reversible topography changes in a photosensitive polymer film above the opening. This can be achieved by simply changing the polarization state of the plasmon generating incoming light. In the case of linear polarization, the near field intensity pattern causes the film to laterally expand/contract according to the direction of the polarization. For circular polarization, two pronounced rims corresponding to maxima in the topography are observed. In all cases, the topographical variation is in close agreement with the SP intensity distribution computed from finite difference time domain simulation. Our results demonstrate the versatility of using SP near fields to imprint a variety of structures into photosensitive polymer films using only a single metallic mask.
Both aftershocks and geodetically measured postseismic displacements are important markers of the stress relaxation process following large earthquakes. Postseismic displacements can be related to creep-like relaxation in the vicinity of the coseismic rupture by means of inversion methods. However, the results of slip inversions are typically non-unique and subject to large uncertainties. Therefore, we explore the possibility to improve inversions by mechanical constraints. In particular, we take into account the physical understanding that postseismic deformation is stress-driven, and occurs in the coseismically stressed zone. We do joint inversions for coseismic and postseismic slip in a Bayesian framework in the case of the 2004 M6.0 Parkfield earthquake. We perform a number of inversions with different constraints, and calculate their statistical significance. According to information criteria, the best result is preferably related to a physically reasonable model constrained by the stress-condition (namely postseismic creep is driven by coseismic stress) and the condition that coseismic slip and large aftershocks are disjunct. This model explains 97% of the coseismic displacements and 91% of the postseismic displacements during day 1-5 following the Parkfield event, respectively. It indicates that the major postseismic deformation can be generally explained by a stress relaxation process for the Parkfield case. This result also indicates that the data to constrain the coseismic slip model could be enriched postseismically. For the 2004 Parkfield event, we additionally observe asymmetric relaxation process at the two sides of the fault, which can be explained by material contrast ratio across the fault of similar to 1.15 in seismic velocity.
The aim of the present contribution was to examine the factors influencing the prosodic processing in a language with predictable word stress. For Polish, a language with fixed penultimate stress but several well-defined exceptions, difficulties in the processing and representation of prosodic information have been reported (e.g., Peperkamp and Dupoux, 2002). The present study utilized event-related potentials (ERPs) to investigate the factors influencing prosodic processing in Polish. These factors are (i) the predictability of stress and (ii) the prosodic structure in terms of metrical feet. Polish native speakers were presented with correctly and incorrectly stressed Polish words and instructed to judge the correctness of the perceived stress patterns. For some stress violations, an early negativity was found which was interpreted as a reflection of an error-detection mechanism. In addition, exceptional stress patterns (=antepenultimate stress) and post-lexical (=initial) stress evoked a task-related positivity effect (P300) whose amplitude and latency is correlated with the degree of anomaly and deviation from an expectation. In contrast, violations involving the default (=penultimate stress) did not produce such an effect. This asymmetrical result is interpreted to reflect that Polish native speakers are less sensitive to the default pattern than to the exceptional or post-lexical patterns. Behavioral results are orthogonal to the electrophysiological results showing that Polish speakers had difficulties to reject any kind of stress violation. Thus, on a meta-linguistic level Polish speakers appeared to be stress-"deaf" for any kind of stress manipulation, whereas the neural reactions differentiate between the default and lexicalized patterns.
The majority of cases of community-acquired pneumonia are caused by Streptococcus pneumoniae and most studies on pneumococcal host interaction are based on cell culture or animal experiments. Thus, little is known about infections in human lung tissue.
Cyclooxygenase-2 and its metabolites play an important regulatory role in lung inflammation. Therefore, we established a pneumococcal infection model on human lung tissue demonstrating mitogen-activated protein kinase (MAPK)-dependent induction of cyclooxygenase-2 and its related metabolites.
In addition to alveolar macrophages and the vascular endothelium, cyclooxygenase-2 was upregulated in alveolar type II but not type I epithelial cells, which was confirmed in lungs of patients suffering from acute pneumonia. Moreover, we demonstrated the expression profile of all four E prostanoid receptors at the mRNA level and showed functionality of the E prostanoid(4) receptor by cyclic adenosine monophosphate production. Additionally, in comparison to previous studies, cyclooxygenase-2/prostaglandin E-2 related pro- and anti-inflammatory mediator regulation was partly confirmed in human lung tissue after pneumococcal infection.
Overall, cell type-specific and MAPK-dependent cyclooxygenase-2 expression and prostaglandin E-2 formation in human lung tissue may play an important role in the early phase of pneumococcal infections.
Here we present orbitally-resolved records of terrestrial higher plant leaf wax input to the North Atlantic over the last 3.5 Ma, based on the accumulation of long-chain n-alkanes and n-alkanl-1-ols at IODP Site U1313. These lipids are a major component of dust, even in remote ocean areas, and have a predominantly aeolian origin in distal marine sediments. Our results demonstrate that around 2.7 million years ago (Ma), coinciding with the intensification of the Northern Hemisphere glaciation (NHG), the aeolian input of terrestrial material to the North Atlantic increased drastically. Since then, during every glacial the aeolian input of higher plant material was up to 30 times higher than during interglacials. The close correspondence between aeolian input to the North Atlantic and other dust records indicates a globally uniform response of dust sources to Quaternary climate variability, although the amplitude of variation differs among areas. We argue that the increased aeolian input at Site U1313 during glacials is predominantly related to the episodic appearance of continental ice sheets in North America and the associated strengthening of glaciogenic dust sources. Evolutional spectral analyses of the n-alkane records were therefore used to determine the dominant astronomical forcing in North American ice sheet advances. These results demonstrate that during the early Pleistocene North American ice sheet dynamics responded predominantly to variations in obliquity (41 ka), which argues against previous suggestions of precession-related variations in Northern Hemisphere ice sheets during the early Pleistocene.
Hydrological response to earthquakes has long been observed, yet the mechanisms responsible still remain unclear and likely vary in space and time. This study explores the base flow response in small upland catchments of the Coastal Range of south-central Chile after the M-W 8.8 Maule earthquake of 27 February 2010. An initial decline in streamflow followed by an increase of up to 400% of the discharge measured immediately before the earthquake occurred, and diurnal streamflow oscillations intensified after the earthquake. Neither response time, nor time to maximum streamflow discharge showed any relationship with catchment topography or size, suggesting non-uniform release of water across the catchments. The fast response, unaffected stream water temperatures and a simple diffusion model point to the sandy saprolite as the source of the excess water. Base flow recession analysis reveals no evidence for substantial enhancement of lateral hydraulic conductivity in the saprolite after the earthquake. Seismic energy density reached similar to 170 J/m(3) for the main shock and similar to 0.9 J/m(3) for the aftershock, exceeding the threshold for liquefaction by undrained consolidation only during the main shock. Although increased hydraulic gradient due to ground acceleration-triggered, undrained consolidation is consistent with empirical magnitude-distance relationships for liquefaction, the lack of independent evidence for liquefaction means that enhanced vertical permeability (probably in combination with co-seismic near-surface dilatancy) cannot be excluded as a potential mechanism. Undrained consolidation may have released additional water from the saturated saprolite into the overlying soil, temporarily reducing water transfer to the creeks but enlarging the cross-section of the saturated zone, which in turn enhanced streamflow after establishment of a new hydraulic equilibrium. The enlarged saturated zone facilitated water uptake by roots and intensified evapotranspiration.
To ensure long-term competitiveness, companies need to develop the ability to explore, plan, and develop new business fields. A suitable approach faces multiple challenges because it needs to (1) integrate multiple perspectives, (2) ensure a high level of participation of the major stakeholders and decision-makers, (3) function despite a high level of uncertainty, and (4) take into account interdependencies between the influencing factors. In this paper, we present an integrated approach that combines multiple strategic-foresight methods in a synergetic way. It was applied in an inter-organizational business field exploration project in the telecommunications industry.
Motivation: Metabolic engineering aims at modulating the capabilities of metabolic networks by changing the activity of biochemical reactions. The existing constraint-based approaches for metabolic engineering have proven useful, but are limited only to reactions catalogued in various pathway databases.
Results: We consider the alternative of designing synthetic strategies which can be used not only to characterize the maximum theoretically possible product yield but also to engineer networks with optimal conversion capability by using a suitable biochemically feasible reaction called 'stoichiometric capacitance'. In addition, we provide a theoretical solution for decomposing a given stoichiometric capacitance over a set of known enzymatic reactions. We determine the stoichiometric capacitance for genome-scale metabolic networks of 10 organisms from different kingdoms of life and examine its implications for the alterations in flux variability patterns. Our empirical findings suggest that the theoretical capacity of metabolic networks comes at a cost of dramatic system's changes.
The scanning tunnelling microscope (STM)-induced switching of a single cyclooctadiene molecule between two stable conformations chemisorbed on a Si(100) surface is investigated using an above threshold model including a neutral ground state and an ionic excited state potential. Switching was recently achieved experimentally with an STM operated at cryogenic temperatures (Nacci et al 2008 Phys. Rev. B 77 121405(R)) and rationalized by a below threshold model using just a single potential energy surface (Nacci et al 2009 Nano Lett. 9 2997).
In the present paper, we show that experimental key findings on the inelastic electron tunnelling (IET) switching can also be rationalized using an above threshold density matrix model, which includes, in addition to the neutral ground state potential, an anionic or cationic excited potential. We use one and two-dimensional potential energy surfaces. Furthermore, the influence of two key parameters of the density matrix description, namely the electronic lifetime of the ionic resonance and the vibrational lifetimes, on the ground state potential are discussed.
Three ERP experiments examined the effect of word presentation rate (i.e., stimulus onset asynchrony, SOA) on the time course of word frequency and predictability effects in sentence reading. In Experiments 1 and 2, sentences were presented word-by-word in the screen center at an SOA of 700 and 490 ms, respectively. While these rates are typical for psycholinguistic ERP research, natural reading happens at a considerably faster pace. Accordingly. Experiment 3 employed a near-normal SOA of 280 ms, which approximated the rate of normal reading. Main results can be summarized as follows: (1) The onset latency of early frequency effects decreases gradually with increasing presentation rates. (2) An early interaction between top-down and bottom-up processing is observed only under a near-normal SOA. (3) N400 predictability effects occur later and are smaller at a near-normal (i.e., high) presentation rate than at the lower rates commonly used in ERP experiments. (4) ERP morphology is different at the shortest compared to longer SOAs. Together, the results point to a special role of a near-normal presentation rate for visual word recognition and therefore suggest that SOA should be taken into account in research of natural reading.
Hepatic steatosis is recognized as hepatic presentation of the metabolic syndrome. Hyperinsulinaemia, which shifts fatty acid oxidation to de novo lipogenesis and lipid storage in the liver, appears to be a principal elicitor particularly in the early stages of disease development. The impact of PGE(2), which has previously been shown to attenuate insulin signaling and hence might reduce insulin-dependent lipid accumulation, on insulin-induced steatosis of hepatocytes was studied. The PGE(2)-generating capacity was enhanced in various obese mouse models by the induction of cyclooxygenase 2 and microsomal prostaglandin E-synthases (mPGES1, mPGES2). PGE(2) attenuated the insulin-dependent induction of SREBP-1c and its target genes glucokinase and fatty acid synthase. Nevertheless, PGE(2) enhanced incorporation of glucose into hepatic triglycerides synergistically with insulin. This was most likely due to a combination of a PGE(2)-dependent repression of (1) the key lipolytic enzyme adipose triglyceride lipase, (2) carnitine-palmitoyltransferase 1, a key regulator of mitochondrial beta-oxidation, and (3) microsomal transfer protein, as well as (4) apolipoprotein B, key components of the VLDL synthesis. Repression of PGC1 alpha, a common upstream regulator of these genes, was identified as a possible cause. In support of this hypothesis, overexpression of PGC1 alpha completely blunted the PGE(2)-dependent fat accumulation. PGE(2) enhanced lipid accumulation synergistically with insulin, despite attenuating insulin signaling and might thus contribute to the development of hepatic steatosis. Induction of enzymes involved in PGE(2) synthesis in in vivo models of obesity imply a potential role of prostanoids in the development of NAFLD and NASH. Laboratory Investigation (2012) 92, 1597-1606; doi:10.1038/labinvest.2012.128; published online 10 September 2012
A comparison of deformation rates in active rifts over different temporal scales may help to decipher variations in their structural evolution, controlling mechanisms, and evolution of sedimentary environments through time. Here we use deformed lake shorelines in the Suguta and Turkana basins in northern Kenya as strain markers to estimate deformation rates at the 10(3)-10(4) yr time scale and compare them with rates spanning 10(1)-10(7) yr. Both basins are internally drained today, but until 7 to 5 kyr lake levels were 300 and 100 m higher, respectively, maintained by the elevation of overflow sills connecting them with the Nile drainage. Protracted high lake levels resulted in formation of a maximum highstand shoreline - a distinct geomorphic feature virtually continuous for several tens of kilometers. We surveyed the elevation of this geomorphic marker at 45 sites along >100 km of the rift, and use the overflow sills as vertical datum. Thin-shell elastic and thermomechanical models for this region predict up to similar to 10 m of rapid isostatic rebound associated with lake-level falls lasting until similar to 2 kyr ago. Holocene cumulative throw rates along four rift-normal profiles are 6.8-8.5 mm/yr, or 7.5-9.6 mm/yr if isostatic rebound is considered. Assuming fault dips of 55-65, inferred from seismic reflection profiles, we obtained extension rates of 3.2-6 mm/yr (including uncertainties in field measurements, fault dips, and ages), or 3.5-6.7 mm/yr considering rebound. Our estimates are consistent, within uncertainties, with extension rates of 4-5.1 mm/yr predicted by a modern plate-kinematic model and plate reconstructions since 3.2 Myr. The Holocene strain rate of 10(-15) s(-1) is similar to estimates on the similar to 10(6) yr scale, but over an order of magnitude higher than on the similar to 10(7) yr scale. This is coherent with continuous localization and narrowing of the plate boundary, implying that the lithospheric blocks limiting the Kenya Rift are relatively rigid. Increasing strain rate under steady extension rate suggests that, as the magnitude of extension and crustal thinning increases, the role of regional processes such as weakening by volcanism becomes dominant over far-field plate tectonics controlling the breakup process and the transition from continental rifting to oceanic spreading.
The standard assumption of identically distributed training and test data is violated when the test data are generated in response to the presence of a predictive model. This becomes apparent, for example, in the context of email spam filtering. Here, email service providers employ spam filters, and spam senders engineer campaign templates to achieve a high rate of successful deliveries despite the filters. We model the interaction between the learner and the data generator as a static game in which the cost functions of the learner and the data generator are not necessarily antagonistic. We identify conditions under which this prediction game has a unique Nash equilibrium and derive algorithms that find the equilibrial prediction model. We derive two instances, the Nash logistic regression and the Nash support vector machine, and empirically explore their properties in a case study on email spam filtering.
In the course of this thesis gold nanoparticle/polyelectrolyte multilayer structures were prepared, characterized, and investigated according to their static and ultrafast optical properties. Using the dip-coating or spin-coating layer-by-layer deposition method, gold-nanoparticle layers were embedded in a polyelectrolyte environment with high structural perfection. Typical structures exhibit four repetition units, each consisting of one gold-particle layer and ten double layers of polyelectrolyte (cationic+anionic polyelectrolyte). The structures were characterized by X-ray reflectivity measurements, which reveal Bragg peaks up to the seventh order, evidencing the high stratication of the particle layers. In the same measurements pronounced Kiessig fringes were observed, which indicate a low global roughness of the samples. Atomic force microscopy (AFM) images veried this low roughness, which results from the high smoothing capabilities of polyelectrolyte layers. This smoothing effect facilitates the fabrication of stratified nanoparticle/polyelectrolyte multilayer structures, which were nicely illustrated in a transmission electron microscopy image. The samples' optical properties were investigated by static spectroscopic measurements in the visible and UV range. The measurements revealed a frequency shift of the reflectance and of the plasmon absorption band, depending on the thickness of the polyelectrolyte layers that cover a nanoparticle layer. When the covering layer becomes thicker than the particle interaction range, the absorption spectrum becomes independent of the polymer thickness. However, the reflectance spectrum continues shifting to lower frequencies (even for large thicknesses). The range of plasmon interaction was determined to be in the order of the particle diameter for 10 nm, 20 nm, and 150 nm particles. The transient broadband complex dielectric function of a multilayer structure was determined experimentally by ultrafast pump-probe spectroscopy. This was achieved by simultaneous measurements of the changes in the reflectance and transmittance of the excited sample over a broad spectral range. The changes in the real and imaginary parts of the dielectric function were directly deduced from the measured data by using a recursive formalism based on the Fresnel equations. This method can be applied to a broad range of nanoparticle systems where experimental data on the transient dielectric response are rare. This complete experimental approach serves as a test ground for modeling the dielectric function of a nanoparticle compound structure upon laser excitation.
The aim of this study was to acquire static and dynamic foot geometry and loading in childhood, and to establish data for age groups of a population of 1-13 year old infants and children.
A total of 10,382 children were recruited and 7788 children (48% males and 52% females) were finally included into the data analysis. For static foot geometry foot length and foot width were quantified in a standing position. Dynamic foot geometry and loading were assessed during walking on a walkway with self selected speed (Novel Emed X, 100 Hz, 4 sensors/cm(2)). Contact area (CA), peak pressure (PP), force time integral (FTI) and the arch index were calculated for the total, fore-, mid- and hindfoot.
Results show that most static and dynamic foot characteristics change continuously during growth and maturation. Static foot length and width increased with age from 13.1 +/- 0.8 cm (length) and 5.7 +/- 0.4 cm (width) in the youngest to 24.4 +/- 1.5 cm (length) and 8.9 +/- 0.6 cm (width) in the oldest. A mean walking velocity of 0.94 +/- 0.25 m/s was observed. Arch-index ranged from 0.32 +/- 0.04 [a.u.] in the one-year old to 0.21 +/- 0.13 [a.u.] in the 5-year olds and remains constant afterwards.
This study provides data for static and dynamic foot characteristics in children based on a cohort of 7788 subjects. Static and dynamic foot measures change differently during growth and maturation. Dynamic foot measurements provide additional information about the children's foot compared to static measures.
State sucession in treaties
(2012)
Tagetes spp. belongs to the Asteraceae family. It is recognized as a major source of lutein ester (lutein esterified with fatty acids such as lauric, myristic and palmitic acids), a natural colorant belonging to the xanthophylls or oxygenated carotenoids. Four species of Tagetes flower (Tagetes tenuifolia, Tagetes erecta, Tagetes patula, and Tagetes lucida) were used to extract lutein and lutein esters with three different methods. The results showed that T. erecta, type "orangeprinz", is the richest source of lutein esters (14.4 +/- 0.234 mg/g) in comparison to other Tagetes spp. No significant differences between extractions of lutein esters with medium-chain triacylglycerols (MCT) oil, orange oil or solvent (hexane/isopropanol) could be observed. MCT oil also improved stability of lutein esters at 100 degrees C for 40 min. Emulsification of MCT oil improved the stability of lutein ester extract against UV light at 365 nm for 72 h. Finally, an emulsion was prepared under food processing conditions, spray dried and its bioavailability investigated in a preliminary human intervention study. The results show a lower resorption, but further data suggest improvements in implementation of such supplements. (c) 2012 Elsevier Ltd. All rights reserved.
The development of infrared observational facilities has revealed a number of massive stars in obscured environments throughout the Milky Way and beyond. The determination of their stellar and wind properties from infrared diagnostics is thus required to take full advantage of the wealth of observations available in the near and mid infrared. However, the task is challenging. This session addressed some of the problems encountered and showed the limitations and successes of infrared studies of massive stars.
We study the properties of energy spreading in a lattice of elastically colliding harmonic oscillators (Ding-Dong model). We demonstrate that in the regular lattice the spreading from a localized initial state is mediated by compactons and chaotic breathers. In a disordered lattice, the compactons do not exist, and the spreading eventually stops, resulting in a finite configuration with a few chaotic spots.
Splay faults are thrusts that emerge from the plate boundaries of subduction zones. Such structures have been mapped at several convergent margins and their activity commonly ascribed to large megathrust earthquakes. However, the behavior of splay faults during the earthquake cycle is poorly constrained because typically these structures are located offshore and are difficult to access. Here we use geologic mapping combined with space and land geodesy, as well as offshore sonar data, to document surface-fault ruptures and coastal uplift at Isla Santa Maria in south-central Chile (37 degrees S) caused by the 27 February 2010 Maule earthquake (M-w 8.8). During the earthquake, the island was tilted parallel to the margin, and normal faults ruptured the surface and adjacent ocean bottom. We associate tilt and crestal normal faulting with growth of an anticline above a blind reverse fault rooted in the Nazca-South America plate boundary, which slipped during the Maule earthquake. The splay fault system has formed in an area of reduced coseismic plate-boundary slip, suggesting that anelastic deformation in the upper plate may have restrained the 2010 megathrust rupture. Surface fault breaks were accompanied by prominent discharge of fluids. Our field observations support the notion that splay faulting may frequently complement and influence the rupture of subduction-zone earthquakes.
This thesis is focussed on the electronic properties of the new material class named topological insulators. Spin and angle resolved photoelectron spectroscopy have been applied to reveal several unique properties of the surface state of these materials. The first part of this thesis introduces the methodical background of these quite established experimental techniques.
In the following chapter, the theoretical concept of topological insulators is introduced. Starting from the prominent example of the quantum Hall effect, the application of topological invariants to classify material systems is illuminated. It is explained how, in presence of time reversal symmetry, which is broken in the quantum Hall phase, strong spin orbit coupling can drive a system into a topologically non trivial phase. The prediction of the spin quantum Hall effect in two dimensional insulators an the generalization to the three dimensional case of topological insulators is reviewed together with the first experimental realization of a three dimensional topological insulator in the Bi1-xSbx alloys given in the literature.
The experimental part starts with the introduction of the Bi2X3 (X=Se, Te) family of materials. Recent theoretical predictions and experimental findings on the bulk and surface electronic structure of these materials are introduced in close discussion to our own experimental results. Furthermore, it is revealed, that the topological surface state of Bi2Te3 shares its orbital symmetry with the bulk valence band and the observation of a temperature induced shift of the chemical potential is to a high probability unmasked as a doping effect due to residual gas adsorption.
The surface state of Bi2Te3 is found to be highly spin polarized with a polarization value of about 70% in a macroscopic area, while in Bi2Se3 the polarization appears reduced, not exceeding 50%. We, however, argue that the polarization is most likely only extrinsically limited in terms of the finite angular resolution and the lacking detectability of the out of plane component of the electron spin. A further argument is based on the reduced surface quality of the single crystals after cleavage and, for Bi2Se3 a sensitivity of the electronic structure to photon exposure.
We probe the robustness of the topological surface state in Bi2X3 against surface impurities in Chapter 5. This robustness is provided through the protection by the time reversal symmetry. Silver, deposited on the (111) surface of Bi2Se3 leads to a strong electron doping but the surface state is observed up to a deposited Ag mass equivalent to one atomic monolayer. The opposite sign of doping, i.e., hole-like, is observed by exposing oxygen to Bi2Te3. But while the n-type shift of Ag on Bi2Se3 appears to be more or less rigid, O2 is lifting the Dirac point of the topological surface state in Bi2Te3 out of the valence band minimum at $\Gamma$. After increasing the oxygen dose further, it is possible to shift the Dirac point to the Fermi level, while the valence band stays well beyond. The effect is found reversible, by warming up the samples which is interpreted in terms of physisorption of O2.
For magnetic impurities, i.e., Fe, we find a similar behavior as for the case of Ag in both Bi2Se3 and Bi2Te3. However, in that case the robustness is unexpected, since magnetic impurities are capable to break time reversal symmetry which should introduce a gap in the surface state at the Dirac point which in turn removes the protection. We argue, that the fact that the surface state shows no gap must be attributed to a missing magnetization of the Fe overlayer. In Bi2Te3 we are able to observe the surface state for deposited iron mass equivalents in the monolayer regime. Furthermore, we gain control over the sign of doping through the sample temperature during deposition.
Chapter6 is devoted to the lifetime broadening of the photoemission signal from the topological surface states of Bi2Se3 and Bi2Te3. It is revealed that the hexagonal warping of the surface state in Bi2Te3 introduces an anisotropy for electrons traveling along the two distinct high symmetry directions of the surface Brillouin zone, i.e., $\Gamma$K and $\Gamma$M. We show that the phonon coupling strength to the surface electrons in Bi2Te3 is in nice agreement with the theoretical prediction but, nevertheless, higher than one may expect. We argue that the electron-phonon coupling is one of the main contributions to the decay of photoholes but the relatively small size of the Fermi surface limits the number of phonon modes that may scatter off electrons. This effect is manifested in the energy dependence of the imaginary part of the electron self energy of the surface state which shows a decay to higher binding energies in contrast to the monotonic increase proportional to E$^2$ in the Fermi liquid theory due to electron-electron interaction.
Furthermore, the effect of the surface impurities of Chapter 5 on the quasiparticle life- times is investigated. We find that Fe impurities have a much stronger influence on the lifetimes as compared to Ag. Moreover, we find that the influence is stronger independently of the sign of the doping. We argue that this observation suggests a minor contribution of the warping on increased scattering rates in contrast to current belief. This is additionally confirmed by the observation that the scattering rates increase further with increasing silver amount while the doping stays constant and by the fact that clean Bi2Se3 and Bi2Te3 show very similar scattering rates regardless of the much stronger warping in Bi2Te3.
In the last chapter we report on a strong circular dichroism in the angle distribution of the photoemission signal of the surface state of Bi2Te3. We show that the color pattern obtained by calculating the difference between photoemission intensities measured with opposite photon helicity reflects the pattern expected for the spin polarization. However, we find a strong influence on strength and even sign of the effect when varying the photon energy. The sign change is qualitatively confirmed by means of one-step photoemission calculations conducted by our collaborators from the LMU München, while the calculated spin polarization is found to be independent of the excitation energy. Experiment and theory together unambiguously uncover the dichroism in these systems as a final state effect and the question in the title of the chapter has to be negated: Circular dichroism in the angle distribution is not a new spin sensitive technique.
Although the lipid mediator sphingosine 1-phosphate (S1P) has been identified to induce cell growth arrest of human keratinocytes, the sphingolipid effectively protects these epidermal cells from apoptosis. The molecular mechanism of the anti-apoptotic action induced by S1P is less characterized. Apart from S1P, endogenously produced nitric oxide (NOaEuro cent) has been recognized as a potent modulator of apoptosis in keratinocytes. Therefore, it was of great interest to elucidate whether S1P protects human keratinocytes via a NOaEuro cent-dependent signalling pathway. Indeed, S1P induced an activation of endothelial nitric oxide synthase (eNOS) in human keratinocytes leading to an enhanced formation of NOaEuro cent. Most interestingly, the cell protective effect of S1P was almost completely abolished in the presence of the eNOS inhibitor L-NAME as well as in eNOS-deficient keratinocytes indicating that the sphingolipid metabolite S1P protects human keratinocytes from apoptosis via eNOS activation and subsequent production of protective amounts of NOaEuro cent. It is well established that most of the known actions of S1P are mediated by a family of five specific G protein-coupled receptors. Therefore, the involvement of S1P-receptor subtypes in S1P-mediated eNOS activation has been examined. Indeed, this study clearly shows that the S1P(3) is the exclusive receptor subtype in human keratinocytes which mediates eNOS activation and NOaEuro cent formation in response to S1P. In congruence, when the S1P(3) receptor subtype is abrogated, S1P almost completely lost its ability to protect human keratinocytes from apoptosis.
Dendritic cells (DCs) play a pivotal role in the development of cutaneous contact hypersensitivity (CHS) and atopic dermatitis as they capture and process antigen and present it to T lymphocytes in the lymphoid organs. Recently, it has been indicated that a topical application of the sphingolipid sphingosine 1-phosphate (S1P) prevents the inflammatory response in CHS, but the molecular mechanism is not fully elucidated. Here we indicate that treatment of mice with S1P is connected with an impaired antigen uptake by Langerhans cells (LCs), the initial step of CHS. Most of the known actions of S1P are mediated by a family of five specific G protein-coupled receptors. Our results indicate that S1P inhibits macropinocytosis of the murine LC line XS52 via S1P(2) receptor stimulation followed by a reduced phosphatidylinositol 3-kinase (PI3K) activity. As down-regulation of S1P(2) not only diminished S1P-mediated action but also enhanced the basal activity of LCs on antigen capture, an autocrine action of S1P has been assumed. Actually, S1P is continuously produced by LCs and secreted via the ATP binding cassette transporter ABCC1 to the extracellular environment. Consequently, inhibition of ABCC1, which decreased extracellular S1P levels, markedly increased the antigen uptake by LCs. Moreover, stimulation of sphingosine kinase activity, the crucial enzyme for S1P formation, is connected not only with enhanced S1P levels but also with diminished antigen capture. These results indicate that S1P is essential in LC homeostasis and influences skin immunity. This is of importance as previous reports suggested an alteration of S1P levels in atopic skin lesions. Citation: Japtok L, Schaper K, Baumer W, Radeke HH, Jeong SK, et al. (2012) Sphingosine 1-Phosphate Modulates Antigen Capture by Murine Langerhans Cells via the S1P(2) Receptor Subtype. PLoS ONE 7(11): e49427. doi:10.1371/journal.pone.0049427
Background: Female sperm storage has evolved independently multiple times among vertebrates to control reproduction in response to the environment. In internally fertilising amphibians, female salamanders store sperm in cloacal spermathecae, whereas among anurans sperm storage in oviducts is known only in tailed frogs. Facilitated through extensive field sampling following historical observations we tested for sperm storing structures in the female urogenital tract of fossorial, tropical caecilian amphibians.
Findings: In the oviparous Ichthyophis cf. kohtaoensis, aggregated sperm were present in a distinct region of the posterior oviduct but not in the cloaca in six out of seven vitellogenic females prior to oviposition. Spermatozoa were found most abundantly between the mucosal folds. In relation to the reproductive status decreased amounts of sperm were present in gravid females compared to pre-ovulatory females. Sperm were absent in females past oviposition.
Conclusions: Our findings indicate short-term oviductal sperm storage in the oviparous Ichthyophis cf. kohtaoensis. We assume that in female caecilians exhibiting high levels of parental investment sperm storage has evolved in order to optimally coordinate reproductive events and to increase fitness.
The indirect detection of dark matter requires that dark matter annihilation products be discriminated from conventional astrophysical backgrounds. Here, we re-analyze GeV-band gamma-ray observations of the prominent Milky Way dwarf satellite galaxy Segue 1, for which the expected astrophysical background is minimal. We explicitly account for the angular extent of the conservatively expected gamma-ray signal and keep the uncertainty in the dark-matter profile external to the likelihood analysis of the gamma-ray data.
Friedreich's ataxia is an inherited neurodegenerative disease caused by the reduced expression of the mitochondrially active protein frataxin. We have previously shown that mice with a hepatocyte-specific frataxin knockout (AlbFxn(-/-)) develop multiple hepatic tumors in later life. In the present study, hepatic carbohydrate metabolism in AlbFxn(-/-) mice at an early and late life stage was analyzed. In young (5-week-old) AlbFxn(-/-) mice hepatic ATP, glucose-6-phosphate and glycogen levels were found to be reduced by similar to 74, 80 and 88%, respectively, when compared with control animals. This pronounced ATP, G6P and glycogen depletion in the livers of young mice reverted in older animals: while half of the mice die before 30 weeks of age, the other half reaches 17 months of age and exhibits glycogen, G6P and ATP levels similar to those in age-matched controls. A key event in this respect seems to be the up-regulation of GLUT1, the predominant glucose transporter in fetal liver parenchyma, which became evident in AlbFxn(-/-) mice being 5-12 weeks of age. The most significant histological findings in animals being 17 or 22 months of age were the appearance of multiple clear cell, mixed cell and basophilic foci throughout the liver parenchyma as well as the development of hepatocellular adenomas and carcinomas. The hepatocarcinogenic process in AlbFxn 2/2 mice shows remarkable differences regarding carbohydrate metabolism alterations when compared with all other chemically and virally driven liver cancer models described up to now.
We tested, in the laboratory, the influence of light intensity, temperature, and phosphorus (P) supply on fatty acid (FA) concentrations of four freshwater algae: the green algae Scenedesmus quadricauda (Turpin) Breb. and Chlamydomonas globosa J. Snow, the cryptophyte Cryptomonas ovata Ehrenb., and the diatom Cyclotella meneghiniana Kutz. We investigated the main and interactive effects of two variables on algal FA concentrations (i.e., light intensity and P supply or temperature and P supply). Interactive effects of light intensity and P supply were most pronounced in C. meneghiniana, but were also found in S. quadricauda and C. ovata. Changes in several saturated and unsaturated FA concentrations with light were more distinct in the low-P treatments than in the high-P treatments. Interactive effects of temperature and P supply on various FA concentrations were observed in all four species, but there was no consistent pattern. In lake ecosystems, P limitation often coincides with high light intensities and temperatures in summer. Therefore, it is important to examine how combinations of these environmental conditions affect FA concentrations of primary producers that are important sources of FAs for higher trophic levels.
The tectonic and climatic boundary conditions of the broken foreland and the orogen interior of the southern Central Andes of northwestern Argentina cause strong contrasts in elevation, rainfall, and surface-process regimes. The climatic gradient in this region ranges from the wet, windward eastern flanks (similar to 2 m/yr rainfall) to progressively drier western basins and ranges (similar to 0.1 m/yr) bordering the arid Altiplano-Puna Plateau. In this study, we analyze the impact of spatiotemporal climatic gradients on surface erosion: First, we present 41 new catchment-mean erosion rates derived from cosmogenic nuclide inventories to document spatial erosion patterns. Second, we re-evaluate paleoclimatic records from the Calchaquies basin (66 W, 26 S), a large intermontane basin bordered by high (> 4.5 km) mountain ranges, to demonstrate temporal variations in erosion rates associated with changing climatic boundary conditions during the late Pleistocene and Holocene. Three key observations in this region emphasize the importance of climatic parameters on the efficiency of surface processes in space and time: (1) First-order spatial patterns of erosion rates can be explained by a simple specific stream power (SSP) approach. We explicitly account for discharge by routing high-resolution, satellite derived rainfall. This is important as the steep climatic gradient results in a highly non-linear relation between drainage area and discharge. This relation indicates that erosion rates (ER) scale with ER similar to SSP1.4 on cosmogenic-nuclide time scales. (2) We identify an intrinsic channel-slope behavior in different climatic compartments. Channel slopes in dry areas (< 0.25 m/yr rainfall) are slightly steeper than in wet areas (> 0.75 m/yr) with equal drainage areas, thus compensating lower amounts of discharge with steeper slopes. (3) Erosion rates can vary by an order of magnitude between presently dry (similar to 0.05 mm/yr) and well-defined late Pleistocene humid (similar to 0.5 mm/yr) conditions within an intemontane basin. Overall, we document a strong climatic impact on erosion rates and channel slopes. We suggest that rainfall reaching areas with steeper channel slopes in the orogen interior during wetter climate periods results in intensified sediment mass transport, which is primarily responsible for maintaining the balance between surface uplift, erosion, sediment routing and transient storage in the orogen.
Spatiotemporal chaos arising from standing waves in a reaction-diffusion system with cross-diffusion
(2012)
We show that quasi-standing wave patterns appear in the two-variable Oregonator model of the Belousov-Zhabotinsky reaction when a cross-diffusion term is added, no wave instability is required in this case. These standing waves have a frequency that is half the frequency of bulk oscillations displayed in the absence of diffusive coupling. The standing wave patterns show a dependence on the systems size. Regular standing waves can be observed for small systems, when the system size is an integer multiple of half the wavelength. For intermediate sizes, irregular patterns are observed. For large sizes, the system shows an irregular state of spatiotemporal chaos, where standing waves drift, merge, and split, and also phase slips may occur.