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The title compound, C30H16N4O4, reveals \overline1 crystallographic and molecular symmetry and accordingly the asymmetric unit comprises one half-molecule. The dihedral angle between the planes of the two geminal benzoxazole rings is 74.39 (5)°. The packing features weak C-H...N and [pi]-[pi] interactions [centroid-centroid distance = 3.652 (1) Å].
To examine their luminescence behavior, two air-stable BN addition compounds were synthesized by the reaction of 5-fluoro-2-(2′-pyridyl)indole with 1,4- and 1,3-bis(bromo(methyl)boryl)benzene, respectively. Both BN adducts are luminescent. Their emission maxima (1,3-substituted BN adduct: 495 nm; 1,4-substituted BN adduct: 497 nm) are comparable with the value (490 nm) of the related mono-borylated benzene species, which is composed of a BPh2 fragment and a 5-fluoro-2-(2′-pyridyl) indole unit. The starting materials 1,4- and 1,3-bis(bromo(methyl)boryl)benzene were accessible by treatment of 1,4- or 1,3-bis(dibromoboryl)benzene with two equivalents of SnMe4. In addition, the results of the X-ray structure analyses of the B,B′-bis-5-fluoro-2-(2′-pyridyl)indolyl-complexed meta-bismethylborylbenzene fragment (9, triclinic, P1̅) as well as of 5-chloro-2-(2′-pyridyl)indole (2, monoclinic, P21/c) and 5-fluoro-2-(2′-pyridyl)indole (1, orthorhombic, Pca21) are reported. The pyridylindole derivatives of this approach were synthesized by an optimized two-step procedure from 2-acetylpyridine and 4-fluoro- or 4-chlorophenylhydrazine hydrochloride.
Single crystals suitable for X-ray diffraction of (tBu2P)3Ga (monoclinic, space group Cc) were obtained from GaCl3 and two equivalents of Li[PtBu2] at room temperature in benzene. The phosphanylgallane (tBu2P)3Ga was also produced via a one-pot approach by reaction of GaCl3 with three or more than three equivalents of Li[PtBu2]. However, treatment of one equivalent of GaCl3 with one equivalent of Li[PtBu2] and subsequent protolysis yielded [tBu2PH2][tBu2P(GaCl3)2 - Li(Cl3Ga)2PtBu2]. Single crystals of this phosphonium salt (monoclinic, space group Cc) were obtained from benzene at room temperature.
The avian magnetic compass was analyzed by testing migratory birds, using their orientation as an indicator. These tests revealed some remarkable properties of the avian magnetic compass: (1) It is an inclination compass’, (2) it is light-dependent, with (3) receptors located in the right eye. These characteristics are in agreement with the Radical Pair model proposed by Ritz et al. (2000). Using the same experimental set-up, we tested the model by behavioral spectroscopy’, exposing migratory birds to radiofrequency fields of different frequencies and intensities. Such fields affected the orientation only when applied at an angle to the field lines. Tests with different frequencies led to an estimate of the life time of the crucial radical pair between 2-10 μs. We also could identify an extremely sensitive resonance at the Larmor frequency, which implies specific properties of the radical pair. Cryptochromes, a blue-light absorbing photopigment, has been proposed to be the receptor-molecule; it has been found to be present in the retina of birds.
ATP-binding cassette (ABC) systems translocate a wide range of solutes across cellular membranes. The thermophilic Gram-negative eubacterium Thermus thermophilus, a model organism for structural genomics and systems biology, discloses ∼46 ABC proteins, which are largely uncharacterized. Here, we functionally analyzed the first two and only ABC half-transporters of the hyperthermophilic bacterium, TmrA and TmrB. The ABC system mediates uptake of the drug Hoechst 33342 in inside-out oriented vesicles that is inhibited by verapamil. TmrA and TmrB form a stable heterodimeric complex hydrolyzing ATP with a Km of 0.9 mm and kcat of 9 s−1 at 68 °C. Two nucleotides can be trapped in the heterodimeric ABC complex either by vanadate or by mutation inhibiting ATP hydrolysis. Nucleotide trapping requires permissive temperatures, at which a conformational ATP switch is possible. We further demonstrate that the canonic glutamate 523 of TmrA is essential for rapid conversion of the ATP/ATP-bound complex into its ADP/ATP state, whereas the corresponding aspartate in TmrB (Asp-500) has only a regulatory role. Notably, exchange of this single noncanonic residue into a catalytic glutamate cannot rescue the function of the E523Q/D500E complex, implicating a built-in asymmetry of the complex. However, slow ATP hydrolysis in the newly generated canonic site (D500E) strictly depends on the formation of a posthydrolysis state in the consensus site, indicating an allosteric coupling of both active sites.
The anaerobic acetogenic bacterium Acetobacterium woodii employs a novel type of Na+-motive anaerobic respiration, caffeate respiration. However, this respiration is at the thermodynamic limit of energy conservation, and even worse, in the first step, caffeate is activated by caffeyl-CoA synthetase, which hydrolyzes ATP to AMP and pyrophosphate. Here, we have addressed whether or not the energy stored in the anhydride bond of pyrophosphate is conserved by A. woodii. Inverted membrane vesicles of A. woodii have a membrane-bound pyrophosphatase that catalyzes pyrophosphate hydrolysis at a rate of 70–120 milliunits/mg of protein. Pyrophosphatase activity was dependent on the divalent cation Mg2+. In addition, activity was strictly dependent on Na+ with a Km of 1.1 mm. Hydrolysis of pyrophosphate was accompanied by 22Na+ transport into the lumen of the inverted membrane vesicles. Inhibitor studies revealed that 22Na+ transport was primary and electrogenic. Next to the Na+-motive ferredoxin:NAD+ oxidoreductase (Fno or Rnf), the Na+-pyrophosphatase is the second primary Na+-translocating enzyme in A. woodii.
Pattern recognition approaches, such as the Support Vector Machine (SVM), have been successfully used to classify groups of individuals based on their patterns of brain activity or structure. However these approaches focus on finding group differences and are not applicable to situations where one is interested in accessing deviations from a specific class or population. In the present work we propose an application of the one-class SVM (OC-SVM) to investigate if patterns of fMRI response to sad facial expressions in depressed patients would be classified as outliers in relation to patterns of healthy control subjects. We defined features based on whole brain voxels and anatomical regions. In both cases we found a significant correlation between the OC-SVM predictions and the patients' Hamilton Rating Scale for Depression (HRSD), i.e. the more depressed the patients were the more of an outlier they were. In addition the OC-SVM split the patient groups into two subgroups whose membership was associated with future response to treatment. When applied to region-based features the OC-SVM classified 52% of patients as outliers. However among the patients classified as outliers 70% did not respond to treatment and among those classified as non-outliers 89% responded to treatment. In addition 89% of the healthy controls were classified as non-outliers.
Event-related potentials (ERPs) are widely used in basic neuroscience and in clinical diagnostic procedures. In contrast, neurophysiological insights from ERPs have been limited, as several different mechanisms lead to ERPs. Apart from stereotypically repeated responses (additive evoked responses), these mechanisms are asymmetric amplitude modulations and phase-resetting of ongoing oscillatory activity. Therefore, a method is needed that differentiates between these mechanisms and moreover quantifies the stability of a response. We propose a constrained subspace independent component analysis that exploits the multivariate information present in the all-to-all relationship of recordings over trials. Our method identifies additive evoked activity and quantifies its stability over trials. We evaluate identification performance for biologically plausible simulation data and two neurophysiological test cases: Local field potential (LFP) recordings from a visuo-motor-integration task in the awake behaving macaque and magnetoencephalography (MEG) recordings of steady-state visual evoked fields (SSVEFs). In the LFPs we find additive evoked response contributions in visual areas V2/4 but not in primary motor cortex A4, although visually triggered ERPs were also observed in area A4. MEG-SSVEFs were mainly created by additive evoked response contributions. Our results demonstrate that the identification of additive evoked response contributions is possible both in invasive and in non-invasive electrophysiological recordings.
IL-22 is an immunoregulatory cytokine displaying pathological functions in models of autoimmunity like experimental psoriasis. Understanding molecular mechanisms driving IL-22, together with knowledge on the capacity of current immunosuppressive drugs to target this process, may open an avenue to novel therapeutic options. Here, we sought to characterize regulation of human IL22 gene expression with focus on the established model of Jurkat T cells. Moreover, effects of the prototypic immunosuppressant cyclosporin A (CsA) were investigated. We report that IL-22 induction by TPA/A23187 (T/A) or αCD3 is inhibited by CsA or related FK506. Similar data were obtained with peripheral blood mononuclear cells or purified CD3(+) T cells. IL22 promoter analysis (-1074 to +156 bp) revealed a role of an NF-AT (-95/-91 nt) and a CREB (-194/-190 nt) binding site for gene induction. Indeed, binding of CREB and NF-ATc2, but not c-Rel, under the influence of T/A to those elements could be proven by ChIP. Because CsA has the capability to impair IκB kinase (IKK) complex activation, the IKKα/β inhibitor IKKVII was evaluated. IKKVII likewise reduced IL-22 induction in Jurkat cells and peripheral blood mononuclear cells. Interestingly, transfection of Jurkat cells with siRNA directed against IKKα impaired IL22 gene expression. Data presented suggest that NF-AT, CREB, and IKKα contribute to rapid IL22 gene induction. In particular the crucial role of NF-AT detected herein may form the basis of direct action of CsA on IL-22 expression by T cells, which may contribute to therapeutic efficacy of the drug in autoimmunity.
Recent genome-wide association studies (GWAS) have identified genetic variations near the IL28B gene which are strongly associated with spontaneous and treatment-induced clearance of hepatitis C virus (HCV) infection. Protective IL28B variations are strongly associated with on-treatment viral kinetics and approximately 2-fold increased sustained virologic response (SVR) rates in HCV genotype 1 and 4 patients. In HCV genotype 1 patients, IL28B variations were shown to be the strongest pre-treatment predictor of virologic response. In the treatment of HCV genotype 2 and 3 infected patients, IL28B variations play only a minor role. Preliminary data indicate that IL28B variations are also associated with treatment outcome of regimens, including directly acting antiviral (DAA) agents, though their impact seems to be attenuated compared to standard treatment. Here, we review these important findings and discuss possible implications for clinical decision making in the treatment of HCV infection.
Herb induced liver injury (HILI) is a particular challenge that also applies to purported cases presumably caused by black cohosh (BC), an herb commonly used to treat menopausal symptoms. We analyzed and reviewed all published case reports and spontaneous reports of initially alleged BC hepatotoxicity regarding quality of case details and causality assessments. Shortcomings of data quality were more evident in spontaneous reports of regulatory agencies compared to published case reports, but assessments with the scale of CIOMS (Council for the International Organizations of Sciences) or its updated version revealed lack of causality for BC in all cases. The applied causality methods are structured, quantitative, and liver specific with clear preference over an ad hoc causality method or the liver unspecific Naranjo scale. Reviewing the case data and the reports dealing with quality specifications of herbal BC products, there is general lack of analysis with respect to authentication of BC in the BC products used by the patients. However, in one single regulatory study, there was a problem of BC authentication in the analysed BC products, and other reports addressed the question of impurities and adulterants in a few BC products. It is concluded that the use of BC may not exert an overt hepatotoxicity risk, but quality problems in a few BC products were evident that require additional regulatory quality specifications.
Rapidity and transverse momentum dependence of inclusive J/ψ production in pp collisions at √s=7 TeV
(2011)
The ALICE experiment at the LHC has studied inclusive J/ψ production at central and forward rapidities in pp collisions at √s=7 TeV. In this Letter, we report on the first results obtained detecting the J/ψ through the dilepton decay into e+e− and μ+μ− pairs in the rapidity ranges |y|<0.9 and 2.5<y<4, respectively, and with acceptance down to zero pT. In the dielectron channel the analysis was carried out on a data sample corresponding to an integrated luminosity Lint=5.6 nb−1 and the number of signal events is NJ/ψ=352±32(stat.)±28(syst.); the corresponding figures in the dimuon channel are Lint=15.6 nb−1 and NJ/ψ=1924±77(stat.)±144(syst.). The measured production cross sections are σJ/ψ(|y|<0.9)=10.7±1.0(stat.)±1.6(syst.)−2.3+1.6(syst.pol.)μb and σJ/ψ(2.5<y<4)=6.31±0.25(stat.)±0.76(syst.)−1.96+0.95(syst.pol.)μb. The differential cross sections, in transverse momentum and rapidity, of the J/ψ were also measured.
Fragment mass distributions for fission after full momentum transfer were measured in the reactions of 30Si,34,36 S,31P,40Ar + 238U at bombarding energies around the Coulomb barrier. Mass distributions change significantly as a function of incident beam energy. The asymmetric fission probability increases at sub-barrier energy. The phenomenon is interpreted as an enhanced quasifission probability owing to orientation effects on fusion and/or quasifission. The evaporation residue (ER) cross sections were measured in the reactions of 30Si + 238U and 34S + 238U to obtain information on fusion. In the latter reaction, significant suppression of fusion was implied. This suggests that fission events different from compound nucleus are included in the masssymmetric fragments. The results are supported by a model calculation based on a dynamical calculation using Langevin equation, in which the mass distribution for fusion-fission and quasifission fragments are separately determined.
We give a brief overview of recent work examining the presence of α-clusters in light nuclei within the Skyrme-force Hartree-Fock model. Of special signif cance are investigations into α-chain structures in carbon isotopes and 16O. Their stability and possible role in fusion reactions are examined in static and time-dependent Hartree-Fock calculations. We f nd a new type of shape transition in collisions and a centrifugal stabilization of the 4α chain state in a limited range of angular momenta. No stabilization is found for the 3α chain.
The present limits of the upper part of the nuclear map are rather close to the beta stability line while the unexplored area of heavy neutron rich nuclides (also those located along the neutron closed shell N = 126 to the right hand side of the stability line) is extremely important for nuclear astrophysics investigations and, in particular, for the understanding of the r-process of astrophysical nucleogenesis. For elements with Z > 100 only neutron deficient isotopes (located to the left of the stability line) have been synthesized so far. The “north-east” area of the nuclear map can be reached neither in fusion–fission reactions nor in fragmentation processes widely used nowadays for the production of new nuclei. Multi-nucleon transfer processes in near barrier collisions of heavy ions seem to be the only reaction mechanism allowing us to produce and explore neutron rich heavy nuclei including those located at the superheavy island of stability. Neutron capture process can be also considered as an alternative method for the production of long-lived neutron rich superheavy nuclei. Strong neutron fluxes might be provided by nuclear reactors and nuclear explosions in laboratory frame and by supernova explosions in nature.
We found that a true ternary fission with formation of a heavy third fragment (a new kind of radioactivity) is quite possible for superheavy nuclei due to the strong shell effects leading to a three-body clusterization with the two doubly magic tin-like cores. The three-body quasifission process could be even more pronounced for giant nuclear systems formed in collisions of heavy actinide nuclei. In this case a three-body clusterization might be proved experimentally by detection of two coincident lead-like fragments in low-energy U+U collisions.
Wilhelm Raabe gehört zu den literarischen Experten, die dem durch beschleunigte Temporalisierungsprozesse bedingten neuen Stellenwert von Kuriositäten schreibend ihre Aufmerksamkeit widmen und dem Plunder bzw. Abfall eine bislang wenig bekannte poetische Seite abgewinnen. Raabe ist ein historistisch geschulter Virtuose in der Adaption und Transformation vorgegebener literarischer Dingdarstellungen. Er weiß die im Rokoko geschulte Koketterie mit dem Minutiösen und Seltenen, mit der Enthüllung und Verhüllung der Dinge zu nutzen, er greift auf die in der Empfindsamkeit betriebene emotionale Aufladung der Dinge zurück, er bedient sich der Traditionen exotischer Amulette und Fetische und er reizt das Erinnerungspotential der Dinge aus. Rezeptionspsychologisch kennt er die poetischen Möglichkeiten des Spiels und Widerspiels von Projektion auf die Dinge und Resonanz der Dinge, das heißt er weiß den Appell- und Signalcharakter der Dinge einzusetzen. Insbesondere vermag er die Dinge als narrative Kerne zu inszenieren, das
heißt sie so erzählerisch zu arrangieren, dass das noch nicht Erzählte oder nicht Erzählbare vom Leser substituiert wird. Zusammenfassend kann man sagen, Wilhelm Raabe ist ein virtuoser erzählerischer Choreograph, der die gesamte Breite an poetischen Dingsuggestionen vom Gebrauchsding zum Fetisch und von der Kuriosität bis zum Abfall, von der traditionellen Locke und dem empfindsamen Taschentuch bis zur modischen Vase aufzurufen weiß.
After the events of 1989 pupils exit German language schools with a degree of German language proficiency which is much lower than research suggests it should be, given the amount of exposure to the language they had throughout their years of schooling. Generally, the only reason put forward for this relative lack of success in acquiring the language is the loss of the ethnic German population, which would have, on the one hand, provided the bulk of learners, and on the other hand, offered a rich linguistic environment to the few pupils of other ethnicities who are not native German speakers. In the present work I intend to challenge this mono-causal explanation by presenting the complexity of variables discussed in SLA research.
Über Treue und Untreue in der Übersetzung : von den Belles Infidèles zum feministischen Paradigma
(2011)
The following paper tries to offer a short outlook on certain aspects of the feminist paradigm in translation theory such as it has emerged from the gender studies and to point out some of the limitations of this paradigm. After outlining the anti-feminist characteristics of the general discourse in translation studies in western culture, the paper discusses the contribution of the so called belles infidèles in the 18th century to the consolidation of a gender discriminating attitude towards translation. The feminist paradigm has been trying to offer an alternative approach, viewing the translation not as a mere copy of the original, but as a creation in itself and the translator as a creator equally important to the author of the source text. It leaves open the question wether it would be acceptable from an ethical point of view to replace the male dominated theoretical discourse in translation studies with an equally ideologically framed one.
Starting from the generally acknowledged fact that exact translation is not possible, this article presents the difficulties of translation between legal systems in general, which appear on different levels and are of such extent, that it has often been spoken about the untranslatability of law. The idea of untranslatability is a controversed one in the specialized literature, as some authors show that it is no case of absolute untranslatability, but one of relative untranslatability, since the translator – who has to bridge the gap between the source and the target legal system – must find a surrogate solution for the missing legal term.