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Ectoparasites of bats in Mongolia : Part 2 (Ischnopsyllidae, Nycteribiidae, Cimicidae and Acari)
(2012)
This study analyses ectoparasites found on Mongolian bats between 2008 and 2011. We examined 12 different bat species, with a total of 23 ectoparasite species present. Apart from reporting distributions, we also discuss specific host-parasite relationships. Owing to recent taxonomic changes splitting the Myotis mystacinus-group into several new taxa, their corresponding ectoparasite fauna could also be addressed in detail. Introducing ectoparasitic insects at length elsewhere (SCHEFFLER et al., 2010), this paper focuses on the analysis of parasitic Acari. Additional findings for Spinturnicidae (wing mites) and Macronyssidae broadened the spectrum of known parasites. Altogether, the knowledge of bat ectoparasites from Mongolia remains very sketchy. Based on different examples, we discuss current taxonomic problems regarding the species status of parasites, and suggest avenues for future research.
4,4-Dimethyl-1-(trifluoromethylsulfonyl)-1,4-azasilinane 1 and 2,2,6,6-tetramethyl-4-(trifluoromethylsulfonyl)- 1,4,2,6-oxazadisilinane 2 were studied by variable temperature dynamic 1H, 13C, 19F NMR spectroscopy and theoretical calculations at the DFT (density functional theory) and MP2 (Moller-Plesset 2) levels of theory. Both kinetic (barriers to ring inversion) and thermodynamic data (frozen conformational equilibria) could be obtained for the two compounds. The computations revealed two minima on the potential energy surface for molecules 1 and 2 corresponding to the rotamers with the CF3SO2 group directed inward and outward the ring, the latter being 0.20.4 kcal/mol (for 1) and 1.1 kcal/mol (for 2) more stable than the former. The vibrational calculations at the DFT and MP2 levels of theory give the values of the free energy difference Delta G degrees for the 'inward' reversible arrow 'outward' equilibrium consistent with those determined from the experimentally measured ratio of the rotamers. The structure of crystalline compound 2 was ascertained by X-ray diffraction analysis.
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.
Parameters of a formal working-memory model were estimated for verbal and spatial memory updating of children. The model proposes interference though feature overwriting and through confusion of whole elements as the primary cause of working-memory capacity limits. We tested 2 age groups each containing 1 group of normal intelligence and 1 deficit group. For young children the deficit was developmental dyslexia; for older children it was a general learning difficulty. The interference model predicts less interference through overwriting but more through confusion of whole elements for the dyslexic children than for their age-matched controls. Older children exhibited less interference through confusion of whole elements and a higher processing rate than young children, but general learning difficulty was associated with slower processing than in the age-matched control group. Furthermore, the difference between verbal and spatial updating mapped onto several meaningful dissociations of model parameters.
The conformational equilibria of 1-phenyl-1-silacyclohexane 1, 3-phenyl-1,3-thiasilacyclohexane 2, 1-methyl-1- phenyl-1-silacyclohexane 3, and 3-methyl-3-phenyl-1,3-thiasilacyclohexane 4 have been studied for the first time by low temperature C-13 NMR spectroscopy at 103 K. Predominance of the equatorial conformer of compound 1 (Ph-eq/Ph-ax=78%:22%) is much less than in its carbon analog, phenylcyclohexane (nearly 100% of Ph-eq). And in contrast to 1-methyl-1- phenylcyclohexane, the conformers with the equatorial Ph group are predominant for compounds 3 and 4: at 103 K, Ph-eq/Ph- ax ratios are 63%:37% (3) and 68%:32% (4). As the Si-C bonds are elongated with respect to C-C bonds, the barriers to ring inversion are only between 5.2-6.0 (ax -> eq) and 5.4-6.0 (eq -> ax) kcal mol(-1). Parallel calculations at the DFT and MP2 level of theory (as well as the G2 calculations for compound 1) show qualitative agreement with the experiment. The additivity/nonadditivity of conformational energies of substituents on cyclohexane and silacyclohexane derivatives is analyzed. The geminally disubstituted cyclohexanes containing a phenyl group show large deviations from additivity, whereas in 1-methyl-1-phenyl-1-silacyclohexane and 3-methyl-3-phenyl-1,3-thiasilacyclohexane the effects of the methyl and phenyl groups are almost additive. The reasons for the different conformational preferences in carbocyclic and heterocyclic compounds are analyzed using the homodesmotic reactions approach.
The cognitive sociolinguistic approach to the lexicon of Cameroon English and other world englishes
(2012)
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.
Introduction
(2012)
The spatial magnetic properties, through-space NMR shieldings (TSNMRS), of benzenoid and quinoid tautomeric structures such as benzodifurantrione and phenazine-type molecules have been calculated using the GIAO perturbation method employing the nucleus independent chemical shift (NICS) concept of Paul von Rague Schleyer and visualized as iso- chemical-shielding surfaces (ICSS) of various size and direction. The TSNMRS values were employed to quantify and visualize the partial aromaticity of the studied compounds. In the case of the surprisingly more stable quinoid tautomers, the aromaticity-synonymous with stability due to the conjugation of p electrons and lone pairs-was not found to be particularly reduced.
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.
Based on the nucleus-independent chemical shift (NICS) concept, isotropic magnetic shielding values have been computed along the three Cartesian axes for ethene, cyclobutadiene, benzene, naphthalene, and benzocyclobutadiene, starting from the molecular/ring center up to 10;Å away. These through-space NMR spectroscopic shielding (TSNMRS) values, which reflect the anisotropic effects, have been broken down into contributions from localized- and canonical molecular orbitals (LMOs and CMOs); these contributions revealed that the proton NMR spectroscopic chemical shifts of nuclei that are spatially close to the C=C double bond or the aromatic ring should not be explained in terms of the conventionally accepted ;-electron shielding/deshielding effects. In fact, these effects followed the predictions only for the antiaromatic cyclobutadiene ring.
The minima on the potential energy surface of 1,2-bis(o-carboxyphenoxy) ethane (CPE) molecule in its electronic ground state were searched by a molecular dynamics simulation performed with MM2 force field. For each of the found minimum-energy conformers, the corresponding equilibrium geometry, charge distribution, HOMO-LUMO energy gap, force field, vibrational normal modes and associated IR and Raman spectral data were determined by means of the density functional theory (DFT) based electronic structure calculations carried out by using B3LYP method and various Pople- style basis sets. The obtained theoretical data confirmed the significant effects of the intra- and inter-molecular hydrogen bonding interactions on the conformational structure, force field, and group vibrations of the molecule. The same data have also revealed that two of the determined stable conformers, both of which exhibit pseudo-crown structure, are considerably more favorable in energy to the others and accordingly provide the major c ntribution to the experimental spectra of CPE. In the light of the improved vibrational spectral data obtained within the "SQM FF" methodology and "Dual Scale Factors" approach for the monomer and dimer forms of these two conformers, a reliable assignment of the fundamental bands observed in the experimental room-temperature IR and Raman spectra of the molecule was given, and the sensitivities of its group vibratb20s to conformation, substitution and dimerization were discussed.
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.
Ellenberg indicator values are widely used ecological tools to elucidate relationships between vegetation and environment in ecological research and environmental planning. However, they are mainly deduced from expert knowledge on plant species and are thus subject of ongoing discussion. We researched if Ellenberg indicator values can be directly extracted from the vegetation biomass itself. Mean Ellenberg "moisture" (mF) and "nitrogen" (mN) values of 141 grassland plots were related to nutrient concentrations, fibre fractions and spectral information of the aboveground biomass. We developed calibration models for the prediction of mF and mN using spectral characteristics of biomass samples with near-infrared reflectance spectroscopy (NIRS). Prediction goodness was evaluated with internal cross-validations and with an external validation data set. NIRS could accurately predict Ellenberg mN, and with less accuracy Ellenberg mF. Predictions were not more precise for cover-weighted Ellenberg values compared with un-weighted values. Both Ellenberg mN and mF showed significant and strong correlations with some of the nutrient and fibre concentrations in the biomass. Against expectations, Ellenberg mN was more closely related to phosphorus than to nitrogen concentrations, suggesting that this value rather indicates productivity than solely nitrogen. To our knowledge we showed for the first time that mean Ellenberg indicator values could be directly predicted from the aboveground biomass, which underlines the usefulness of the NIRS technology for ecological studies, especially in grasslands ecosystems.
Ostracods from water bodies in hyperarid Israel and Jordan as habitat and water chemistry indicators
(2012)
The hyperarid region of Israel and Jordan covers a large area where numerous sites of Pleistocene lake sediments suggest that climate conditions were significantly wetter during the Pleistocene. This region experienced a significant increase in aridity in recent decades and the number of existing surface waters is diminishing rapidly. We studied ostracod shells from 49 pond and stream sites to determine the species distribution and to infer ecological preferences especially with respect to general differences in water movement, conductivity and ion composition. Twenty-two ostracod species were identified in total of which 12 taxa occur at three or more sites. Among the rarer species. Cyprinotus scholiosus was identified for the first time after two records from Plio- and Pleistocene sites in Yemen and Saudi Arabia. Further, Paracypretta amati was recorded and its ecological preferences discussed for the first time following the description of the species from its type locality in Sudan. Cypridopsis elongata is the only typical inhabitant of lotic habitats, strictly preferring freshwater conditions and waters with an alkalinity/Ca ratio around 1 and cations dominated by Ca(2+) and anions by HCO(3)(-). In contrast, Cyprideis torosa, Limnocythere inopinata and Heterocypris incongruens apparently prefer waters dominated by Na(+) associated with cations and Cl(-) associated with anions. Heterocypris salina and C. torosa occur over a wide conductivity (or salinity) range and in waters with alkalinity/Ca ratios around 1 and with significant alkalinity depletion. Humphcypris subterranea, Ilyocypris spp. and H. sauna are the only taxa which do not show any preference with respect to both the cation and anion dominance of the waters. The ecological preferences of the ostracod species from water bodies in the study area are discussed in detail and can be used for a qualitative assessment of the hydrodynamical and hydrochemical conditions of former water bodies in the presently hyperarid environment based on ostracod species composition analysis of Pleistocene aquatic sediments.
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.
We excite an epitaxial SrRuO3 thin film transducer by a pulse train of ultrashort laser pulses, launching coherent sound waves into the underlying SrTiO3 substrate. Synchrotron-based x-ray diffraction (XRD) data exhibiting separated sidebands to the substrate peak evidence the excitation of a quasi-monochromatic phonon wavepacket with sub-THz central frequency. The frequency and bandwidth of this sound pulse can be controlled by the optical pulse train. We compare the experimental data to combined lattice dynamics and dynamical XRD simulations to verify the coherent phonon dynamics. In addition, we observe a lifetime of 130 ps of such sub-THz phonons in accordance with the theory.
Single-particle tracking has become a standard tool for the investigation of diffusive properties, especially in small systems such as biological cells. Usually the resulting time series are analyzed in terms of time averages over individual trajectories. Here we study confined normal as well as anomalous diffusion, modeled by fractional Brownian motion and the fractional Langevin equation, and show that even for such ergodic systems time-averaged quantities behave differently from their ensemble-averaged counterparts, irrespective of how long the measurement time becomes. Knowledge of the exact behavior of time averages is therefore fundamental for the proper physical interpretation of measured time series, in particular, for extraction of the relaxation time scale from data.
In this work, we show how Gibbs or thermal states appear dynamically in closed quantum many-body systems, building on the program of dynamical typicality. We introduce a novel perturbation theorem for physically relevant weak system-bath couplings that is applicable even in the thermodynamic limit. We identify conditions under which thermalization happens and discuss the underlying physics. Based on these results, we also present a fully general quantum algorithm for preparing Gibbs states on a quantum computer with a certified runtime and error bound. This complements quantum Metropolis algorithms, which are expected to be efficient but have no known runtime estimates and only work for local Hamiltonians.
A Bose-Hubbard model on a dynamical lattice was introduced in previous work as a spin system analogue of emergent geometry and gravity. Graphs with regions of high connectivity in the lattice were identified as candidate analogues of spacetime geometries that contain trapped surfaces. We carry out a detailed study of these systems and show explicitly that the highly connected subgraphs trap matter. We do this by solving the model in the limit of no back-reaction of the matter on the lattice, and for states with certain symmetries that are natural for our problem. We find that in this case the problem reduces to a one-dimensional Hubbard model on a lattice with variable vertex degree and multiple edges between the same two vertices. In addition, we obtain a (discrete) differential equation for the evolution of the probability density of particles which is closed in the classical regime. This is a wave equation in which the vertex degree is related to the local speed of propagation of probability. This allows an interpretation of the probability density of particles similar to that in analogue gravity systems: matter inside this analogue system sees a curved spacetime. We verify our analytic results by numerical simulations. Finally, we analyze the dependence of localization on a gradual, rather than abrupt, falloff of the vertex degree on the boundary of the highly connected region and find that matter is localized in and around that region.
Predicting the actions of other individuals is crucial for our daily interactions. Recent evidence suggests that the prediction of object-directed arm and full-body actions employs the dorsal premotor cortex (PMd). Thus, the neural substrate involved in action control may also be essential for action prediction. Here, we aimed to address this issue and hypothesized that disrupting the PMd impairs action prediction. Using fMRI-guided coil navigation, rTMS (five pulses, 10Hz) was applied over the left PMd and over the vertex (control region) while participants observed everyday actions in video clips that were transiently occluded for 1s. The participants detected manipulations in the time course of occluded actions, which required them to internally predict the actions during occlusion. To differentiate between functional roles that the PMd could play in prediction, rTMS was either delivered at occluder-onset (TMS-early), affecting the initiation of action prediction, or 300 ms later during occlusion(TMS-late), affecting the maintenance of anongoing prediction. TMS-early over the left PMd produced more prediction errors than TMS-early over the vertex. TMS-late had no effect on prediction performance, suggesting that the left PMd might be involved particularly during the initiation of internally guided action prediction but may play a subordinate role in maintaining ongoing prediction. These findings open a new perspective on the role of the left PMd in action prediction which is in line with its functions in action control and in cognitive tasks. In the discussion, there levance of the left PMd for integrating external action parameters with the observer's motor repertoire is emphasized. Overall, the results are in line with the notion that premotor functions are employed in both action control and action observation.