Refine
Year of publication
Document Type
- Article (32856) (remove)
Language
Is part of the Bibliography
- yes (32856) (remove)
Keywords
- climate change (95)
- Germany (76)
- stars: massive (58)
- diffusion (47)
- stars: early-type (47)
- German (46)
- gamma rays: general (46)
- stars: winds, outflows (45)
- Arabidopsis thaliana (43)
- Climate change (43)
Institute
- Institut für Physik und Astronomie (4146)
- Institut für Biochemie und Biologie (3788)
- Institut für Geowissenschaften (2823)
- Institut für Chemie (2415)
- Department Psychologie (1761)
- Institut für Romanistik (1130)
- Wirtschaftswissenschaften (1108)
- Institut für Mathematik (1064)
- Historisches Institut (1050)
- Department Sport- und Gesundheitswissenschaften (1042)
100 Jahre Roter Oktober
(2017)
100 Jahre Roter Oktober
(2017)
1-Oxo-1,3-dithiolane (4) and its cis- andtrans-2-methyl (5,6), -4-methyl (7,8) and -5-methyl (9,10) derivatives were prepared by oxidizing the corresponding 1,3-dithiolanes (1-3) with NaIO4 in water. The oxides were purified and their isomers separated using thin layer chromatography. The structural characterization was carried out with 1H and 13C NMR spectroscopy and molecular modelling. The sulfoxides 4-6 and 8-10 attain two S(1) type envelopes (sometimes slightly distorted) the S=Oax envelope greatly dominating. Cis-4-methyl-1-oxo-1,3-dithiolane is a special case exhibiting both two closely related S=Oax (30 and 27%) as well as S=Oeq (21 and 22%) forms [S(1) and C(4) envelopes, respectively]. The relative energies of these conformations, the values of 1H-1H coupling constants and 1H and 13C chemical shifts were estimated by computational methods and they support well the conclusions based on the experimental data.
1-Oxo-1,3-dithiolane (4) and its cis- and trans-2-methyl (5,6), -4-methyl (7,8) and -5-methyl (9,10) derivatives were prepared by oxidizing the corresponding 1,3-dithiolanes (1-3) with NaIO(4) in water. The oxides were purified and their isomers separated using thin layer chromatography. The structural characterization was carried out with (1)H and (13)C NMR spectroscopy and molecular modelling. The sulfoxides 4-6 and 8-10 attain two S(1) type envelopes (sometimes slightly distorted) the S=O(ax) envelope greatly dominating. Cis-4-methyl-1-oxo-1,3-dithiolane is a special case exhibiting both two closely related S=O(ax) (30 and 27%) as well as S=O(eq) (21 and 22%) forms [S(1) and C(4) envelopes, respectively]. The relative energies of these conformations, the values of (1)H-(1)H coupling constants and (1)H and (13)C chemical shifts were estimated by computational methods and they support well the conclusions based on the experimental data.
1-Methylthio-1-phenyl-1-silacyclohexane 1, the first silacyclohexane with the sulfur atom at silicon, was synthesized and its molecular structure and conformational preferences studied by gas-phase electron diffraction (GED) and low temperature C-13 and Si-29 NMR spectroscopy (LT NMR). Quantum-chemical calculations were carried out both for the isolated species and solvate complexes in gas and in polar medium. The predominance of the 1-MeSaxPheq conformer in gas phase (1-Ph-eq :1-Ph-ax = 55:45, Delta G degrees = 0.13 kcal/mol) determined from GED is consistent with that measured in the freon solution by LT NMR (1-Ph-eq:1-Ph-ax = 65:35, Delta G degrees = 0.12 kcal/mol), the experimentally measured ratios being close to that estimated by quantum chemical calculations at both the DFT and MP2 levels of theory. (C) 2019 Elsevier Ltd. All rights reserved.
We previously showed that purified 1-methoxy-3-indolylmethyl (1-MIM) glucosinolate, a secondary plant metabolite in Brassica species, is mutagenic in various in vitro systems and forms DNA and protein adducts in mouse models. In the present study, we administered 1-MIM glucosinolate in a natural matrix to mice, by feeding a diet containing pak choi powder and extract. Groups of animals were killed after 1, 2, 4 and 8 days of pak choi diet, directly or, in the case of the 8-day treatment, after 0, 8 and 16 days of recovery with pak choi-free diet. DNA adducts [N-2-(1-MIM)-dG, N-6-(1-MIM)-dA] in six tissues, as well as protein adducts [tau N-(1-MIM)-His] in serum albumin (SA) and hemoglobin (Hb) were determined using UPLC-MS/MS with isotopically labeled internal standards. None of the samples from the 12 control animals under standard diet contained any 1-MIM adducts. All groups receiving pak choi diet showed DNA adducts in all six tissues (exception: lung of mice treated for a single day) as well as SA and Hb adducts. During the feeding period, all adduct levels continuously increased until day 8 (in the jejunum until day 4). During the 14-day recovery period, N-2-(1-MIM)-dG in liver, kidney, lung, jejunum, cecum and colon decreased to 52, 41, 59, 11, 7 and 2%, respectively, of the peak level. The time course of N-6-(1-MIM)-dA was similar. Immunohistochemical analyses indicated that cell turnover is a major mechanism of DNA adduct elimination in the intestine. In the same recovery period, protein adducts decreased more rapidly in SA than in Hb, to 0.7 and 37%, respectively, of the peak level, consistent with the differential turnover of these proteins. In conclusion, the pak choi diet lead to the formation of high levels of adducts in mice. Cell and protein turnover was a major mechanism of adduct elimination, at least in gut and blood.
The first Si-H-containing azasilaheterocycle, 1,3-dimethyl-3-silapiperidine 1, was synthesized, and its molecular structure and conformational properties were studied by gas-phase electron diffraction (GED), low temperature NMR, IR and Raman spectroscopy and quantum chemical calculations. The compound exists as a mixture of two conformers possessing the chair conformation with the equatorial NMe group and differing by axial or equatorial position of the SiMe group. In the gas phase, the SiMeax conformer predominates (GED: ax/eq = 65(7):35(7)%,Delta G = 0.36(18) kcal/mol; IR: ax/eq = 62(5):38(5)%,Delta G = 0.16(7) kcal/mol). In solution, at 143 k the SiMeeq conformer predominates' in the frozen equilibrium (NMR: ax/eq = 31.5(1.5):68.5(1.5)%, Delta G = -0.22(2) kcal/mol). Thermodynamic parameters of the ring inversion are determined (Delta G(double dagger) = 8.9-9.0 kcal/mol, Delta H-double dagger = 9.6 kcal/mol, Delta S-double dagger = 2.1 eu). High-level quantum chemical calculations :(MP2, G2, CCSD(T)) nicely reproduce the experimental geometry and the predominance of the axial conformer in the gas phase.
Background and objective Whether treatment with vitamin D receptor activators contributes to cardiovascular disease in patients with chronic kidney disease is a matter of debate. We studied mechanisms involved in vitamin D-related vascular calcifications in vivo and in vitro.
Methods Aortic calcifications were induced in subtotally nephrectomized (SNX) rats by treatment with a high dose (0.25 mu g/kg per day) of 1,25-dihydroxyvitamin D-3 (calcitriol) given for 6 weeks. Likewise, primary rat vascular smooth muscle cells (VSMCs) were incubated with calcitriol at concentrations ranging from 10(-11) to 10(-7) mol/l. Immunohistochemistry revealed that the aortic expression of osteopontin, osteocalcin and bone sialoprotein was significantly increased in calcitriol-treated SNX rats compared to untreated SNX controls. In addition, aortic expression of the transient receptor potential vanilloid calcium channel 6 (TRPV6) and calbindin D9k was significantly up-regulated by treatment with calcitriol. Furthermore, calcitriol significantly increased expression of the osteogenic transcription factor osterix. In-vitro studies showed similar results, confirming that these effects could be attributed to treatment with calcitriol.
Conclusions High-dose calcitriol treatment induces an osteoblastic phenotype in VSMC both in SNX rats and in vitro, associated with up-regulation of proteins regulating mineralization and calcium transport, and of the osteogenic transcription factor osterix.
Indium(III) chloride forms in water with potassium 1,2-dithiooxalate (dto) and potassium 1,2-dithiosquarate (dtsq) stable coordination compounds. Due to the higher bridging ability of the 1,2-dithiooxalate ligand in all cases only thiooxalate bridged binuclear complexes were found. From 1,2-dithioquadratate with an identical donor atom set mononuclear trischelates could be isolated. Five crystalline complexes, (BzlMe(3)N)(4)[(dto)(2)In(dto)In(dto)(2)] (1), (BzlPh(3)P)(4)[(dto)(2)In(dto)In(dto)(2)] (2), (BzlMe(3)N)(3)[In(dtsq)(3)] (3), (Bu4N)(3)[In(dtsq)(3)] (4) and (Ph4P)[In(dtsq)(2)(DMF)(2)] (5), have been isolated and characterized by X-ray analyses. Due to the type of the complex and the cations involved these compounds crystallize in different space groups with the following parameters: 1, monoclinic in P2(1)/c with a = 14.4035(5) Angstrom, b = 10.8141(5) Angstrom, c = 23.3698(9) Angstrom, beta = 124.664(2)degrees, and Z = 2; 2, triclinic in P (1) over bar with a = 11.3872(7) Angstrom, b = 13.6669(9) Angstrom, c = 17.4296(10) Angstrom, alpha = 88.883(5)degrees, beta = 96.763(1)degrees, gamma = 74.587(5)degrees, and Z = 1; 3, hexagonal in R3 with a = 20.6501(16) Angstrom, b = 20.6501(16) Angstrom, c = 19.0706(13) Angstrom and Z = 6; 4, monoclinic in P21/c with a = 22.7650(15) Angstrom, b = 20.4656(10) Angstrom, c = 14.4770(9) Angstrom, P
Herein, we represent cation-responsive fluorescent probes for the divalent cations Zn2+, Mg2+ and Ca2+, which show cation-induced fluorescence enhancements (FE) in water. The Zn2+-responsive probes Zn1, Zn2, Zn3 and Zn4 are based on o-aminoanisole-N,N-diacetic acid (AADA) derivatives and show in the presence of Zn2+ FE factors of 11.4, 13.9, 6.1 and 8.2, respectively. Most of all, Zn1 and Zn2 show higher Zn2+ induced FE than the regioisomeric triazole linked fluorescent probes Zn3 and Zn4, respectively. In this set, ZN2 is the most suitable probe to detect extracellular Zn2+ levels. For the Mg2+-responsive fluorescent probes Mg1, Mg2 and Mg3 based on o-aminophenol-N,N,O-triacetic acid (APTRA) derivatives, we also found that the regioisomeric linkage influences the fluorescence responds towards Mg2+ (Mg1+100 mM Mg2+ (FEF=13.2) and Mg3+100 mM Mg2+ (FEF=2.1)). Mg2 shows the highest Mg2+-induced FE by a factor of 25.7 and an appropriate K-d value of 3 mM to measure intracellular Mg2+ levels. Further, the Ca2+-responsive fluorescent probes Ca1 and Ca2 equipped with a 1,2-bis(o-aminophenoxy)ethane-N,N,N',N'-tetraacetic acid (BAPTA) derivative show high Ca2+-induced FEs (Ca1 (FEF=22.1) and Ca2 (FEF=23.0)). Herein, only Ca1 (K-d=313 nM) is a suitable Ca2+ fluorescent indicator to determine intracellular Ca2+ levels.
A series of new monocationic iridium(III) complexes [Ir((CN)-N-boolean AND)(2)((NN)-N-boolean AND)]PF6 with "large-surface" alpha,alpha'-diimin ligands (NN)-N-boolean AND (dap = 1,12-diazaperylene, dmedap = 2,11-dimethyl-1,12-diazaperylene, dipdap = 2,11-diisopropyl-1,12-diazaperylene) and different cyclometalating ligands (CN)-N-boolean AND (piq = 1-phenylisoquinoline, bzq = benzo[h]quinoline, ppz = 1-phenylpyrazole, thpy = 2-(2-thienyl)pyridine, ppy = 2-phenylpyridine, meppy = 2-(4-methylphenyl)pyridine, dfppy = 2-(2,4-difluorophenyl)pyridine) were synthesized. The solid structures of the complexes [Ir(piq)(2)(dap)]PF6, [Ir(bzq)(2)(dap)]PF6, [Ir(ppy)(2)(dipdap)]PF6, [Ir(piq)(2)(dmedap)]PF6, [Ir(ppy)(2)(dap)]PF6 and [Ir(ppz)(2)(dap)]PF6 are reported. In [Ir(piq)(2)(dap)]PF6, the dap ligand and one of the piq ligands of each cationic complex are involved in pi-pi stacking interactions forming supramolecular channels running along the crystallographic c axis. In the crystalline [Ir(bzq)(2)(dap)]PF6 pi-pi stacking interactions between the metal complexes lead to the formation of a 2D layer structure. In addition, CH-pi interactions were found in all compounds, which are what stabilizes the solid structure. In particular, a significant number of them were found in [Ir(piq)(2)(dap)]PF6 and [Ir(bzq)(2)(dap)]PF6. The crystal structures of [Ir(ppy)(2)(dipdap)]PF6 and [Ir(ppy)(2)(dmedap)]PF6 are also presented, being the first examples of bis-cyclometalated iridium(III) complexes with phenanthroline-type alpha,alpha'-diimin ligands bearing bulky alkyl groups in the neighbourhood of the N-donor atoms. These ligands implicate a distorted octahedral coordination geometry that in turn destabilized the Ir-N-N boolean AND N bonds. The new iridium (III) complexes are not luminescent. All compounds show an electrochemically irreversible anodic peak between 1.15 and 1.58 V, which is influenced by the different cyclometalated ligands. All of the new complexes show two reversible successive one-electron "large-surface" ligand-centred reductions around -0.70 V and -1.30 V. Electrospray ionisation mass spectrometry (ESI-MS) and collision induced decomposition (CID) measurements were used to investigate the stability of the new complexes. Thereby, the stability agreed well with the order of the Ir-N-N boolean AND N bond lengths.
A series of new N2S2 mixed ligand transition metal complexes, where N-2 is phenanthroline and S-2 is 1,2- dithiooxalate (dto) or 1,2-dithiosquarate (dtsq), has been synthesized and characterized. IR spectra reveal that the 1,2- dithiolate ligands are coordinated via the sulfur atoms forming a N2S2 coordination sphere. The copper(II) complex [Cu(phen)(dto)] was studied by EPR spectroscopy as a diamagnetically diluted powder. The diamagnetic dilution resulted from doping of the copper complex into the isostructural host lattice of the nickel complex [Ni(phen)(dto)]. The electronic situation in the frontier orbitals of the copper complex calculated from the experimental data is compared to the results of EHT and DFT calculations. Furthermore, one side product, chlorobis(1,10-phenanthroline)copper(I) ethanol solvate hydrate [(phen)(2)CuCl]center dot C2H5OH center dot H2O, was formed by a reduction process and characterized by X-ray diffraction. In the crystal packing one-dimensional columns of dimers are formed, stabilized by significant pi-pi interactions.
Mit Urteil vom 28.3.2006 hat das BVerfG ein staatliches Monopol für Sportwetten nur dann mit der Berufsfreiheitsgarantie des Art. 12 I GG für vereinbar erklärt, wenn es konsequent am Ziel der Bekämpfung von Suchtgefahren ausgerichtet ist. Aktuelle Rechtslage und Staatspraxis werden hingegen als verfassungswidrig benannt. Der Beitrag stellt die Entscheidung in ihren Grundzügen dar und unterzieht sie einer kritischen Würdigung.
1 + 2 is more than 2 + 1: Violations of commutativity and identity axioms in mental arithmetic
(2015)
Over the past decade or so, a large number of studies have revealed that conceptual meaning is sensitive to situational context. More recently, similar contextual influences have been documented in the domain of number knowledge. Here we show such context dependency in a length production task. Adult participants saw single digit addition problems of the form n1 + n2 and produced the sum by changing bi-directionally the length of a horizontally extended line, using radially arranged buttons. We found that longer lines were produced when n1 < n2 compared to n1 > n2 and that unit size increased with result size. Thus, the mathematical axioms of commutativity and identity do not seem to hold in mental addition. We discuss implications of these observations for our understanding of cognitive mechanisms involved in mental arithmetic and for situated cognition generally.
We dissect the sources of error leading to inaccuracies in the description of the geometry and optical excitation energies of pi-conjugated polymers. While the ground-state bond length alternation is shown to be badly reproduced by standard functionals, the recently adapted functionals PBEh* and omega PBE* as well as the double hybrid functional XYGJ-OS manage to replicate results obtained at the CCSD(T) level. By analysis of the bond length alternation in the excited state, a sensitive dependence of the exciton localization on the long-range behavior of the functional and the amount of Hartree-Fock exchange present is shown. Introducing thermal disorder through molecular dynamics simulations allows the consideration of a range of thermally accessible configurations of each oligomer, including trans to cis rotations, which break the conjugation of the backbone. Thermal disorder has a considerable effect when combined with functionals that overestimate the delocalization of the excitation, such as B3LYP. For functionals with a larger amount of exact exchange such as our PBEh* and omega PBE*, however, the effect is small, as excitations are often localized enough to fit between twists in the chain.
Der Artikel praesentiert eine empirische Untersuchung der von kindlichen DaZ-Lernern gebildeten Pluralformen zu deutschen Substantiven. Die Frage, auf welche Weise der Erwerb dieses komplexen morphologischen Teilsystems erfolgt und wie er erklaert werden kann, reiht sich ein in die Diskussion zweier entgegen gesetzter Konzepte zum Erwerb und mentalen Repraesentation morphologisch komplexer (ir)regulaerer Formen, naemlich des Duale Routen Modells und des Netzwerkmodells. Aufgrund der Komplexitaet des deutschen Plurals sind die hier praesentierten Daten hervorragend geeignet, einen Beitrag zu leisten zu der seit ca. 20 Jahren in der Psycholinguistik und Spracherwerbsforschung gefuehrten Diskussion darueber, nach welchem Modell morphologische Systeme im natuerlichen Spracherwerb gelernt und verarbeitet werden. Die Untersuchung zeigt, dass Umlaut-konforme Formen unter den uebergeneralisierungen deutlich ueberwiegen. Dies ist Evidenz fuer das Vorliegen von Musterextraktion und deren assoziativer Verknuepfung zu Netzwerken. Denn diese mehrheitlich Umlaut-konformen Bildungen deuten darauf hin, dass die Lerner eine ungefaehre Vorstellung vom richtigen Muster entwickelt haben, die Verknuepfung aber nur unvollkommen herstellen. Offenbar haben sie eine Vorstellung hinsichtlich des Vokals der Pluralform. Sie folgen also keiner Regel, sondern einem Muster, das sie aus den im Input vorgefundenen Formen extrahiert und durch Verknuepfung mit aehnlichen Formen zu einem Schema aufgebaut haben. Musterextraktion und Analogiebildung besteht in der Konnektion zwischen Singular- und Pluralform einerseits und der zwischen verschiedenen Pluralformen eines Musters andererseits. Dafuer spielt der betonte Stammvokal eine zentrale Rolle. Unter- und uebergeneralisierung des Umlauts kann konnektionistisch erklaert werden: Fehlende Umlautung beruht auf zu enger Bindung des Lerners an den Singular bzw. zu enger Verknuepfung der Pluralform mit dem Singularstamm - von Fuchs gelangt man leichter zu *Fuchse als zu Fuechse. Hyperkorrekte Umlautung beruht dagegen auf zu enger Verknuepfung der Pluralformen einer Umlaut-Klasse untereinander: von Fuechse gelangt man leichter zu *Huende als zu Hunde.
The Social War (91-88 BCE) is one of the most significant episodes in Roman history: from this war, in which Rome fought against her Italic allies, emerged the elite that would lead the Republic in the last decades of its existence and that would provide the senatorial aristocracy of the early imperial age. The Italic rebels were defeated militarily, yet they achieved their political aims. As such, this war – and its elaboration and memorialization in Roman cultural memory – provides a very interesting case study about how "victory" and "defeat" are constructed discursively after a disruptive war, and how its narration is "functionalized" for a re-foundation of the civic body.
We present novel experimental evidence on the availability and the status of exhaustivity inferences with focus partitioning in German, English, and Hungarian. Results suggest that German and English focus-background clefts and Hungarian focus share important properties, (É. Kiss 1998, 1999; Szabolcsi 1994; Percus 1997; Onea & Beaver 2009). Those constructions are anaphoric devices triggering an existence presupposition. EXH-inferences are not obligatory in such constructions in English, German, or Hungarian, against some previous literature (Percus 1997; Büring & Križ 2013; É. Kiss 1998), but in line with pragmatic analyses of EXH-inferences in clefts (Horn 1981, 2016; Pollard & Yasavul 2016). The cross-linguistic differences in the distribution of EXH-inferences are attributed to properties of the Hungarian number marking system.
(Near-)inverses of sequences
(2006)
We introduce the notion of a near-inverse of a non-decreasing sequence of positive integers; near-inverses are intended to assume the role of inverses in cases when the latter cannot exist. We prove that the near-inverse of such a sequence is unique; moreover, the relation of being near-inverses of each other is symmetric, i.e. if sequence g is the near-inverse of sequence f, then f is the near-inverse of g. There is a connection, by approximations, between near- inverses of sequences and inverses of continuous strictly increasing real-valued functions which can be exploited to derive simple expressions for near-inverses
(Moralisch) guter Sex
(2023)
In einem kürzlich erschienenen Artikel argumentiert Almut v. Wedelstaedt überzeugend, warum Zustimmung zwar „die Bedingung für die Legitimation von Sex“ ist (2020, 127), dass die moralische Güte von Sex aber nur dann einzuschätzen ist, wenn wir darauf achten, ob die Beteiligten der Handlung sich auf Augenhöhe begegnen. Die Idee ist: Es gibt legitime sexuelle Handlungen, die moralisch gut sind, und es gibt legitime sexuelle Handlungen, die moralisch besser sind. Hier möchte ich die Idee des besseren Sexes genauer ausloten. Während v. Wedelstaedt von moralisch gelungenem Sex spricht und somit auf der Ebene der moralischen Bewertung von Sex bleibt, möchte ich die Frage danach stellen, was Sex qualitativ gut macht. Tatsächlich wird in der Zustimmungsdebatte meist davon ausgegangen, dass diese zwei Fragen wenig gemeinsam haben; ob eine sexuelle Handlung legitim ist, hat zunächst nichts damit zu tun, ob diese auch gut ist. Ich werde drei Argumente liefern, warum wir legitimen Sex und qualitativ guten Sex zusammen betrachten sollten – und es wird sich zeigen, dass die gegenwärtige philosophische und rechtstheoretische Debatte Zustimmung verkürzt diskutiert und daher alleingenommen wenig hilfreich ist, stattdessen benötigt die Zustimmungsdebatte auch eine Untersuchung von qualitativ gutem Sex.
Molecular excitons play a central role in processes of solar energy conversion, both natural and artificial. It is therefore no wonder that numerous experimental and theoretical investigations in the last decade, employing state-of-the-art spectroscopic techniques and computational methods, have been driven by the common aim to unravel exciton dynamics in multichromophoric systems. Theoretically, exciton (de)localization and transfer dynamics are most often modelled using either mixed quantum-classical approaches (e.g., trajectory surface hopping) or fully quantum mechanical treatments (either using model diabatic Hamiltonians or direct dynamics). Yet, the terms such as "exciton localization" or "exciton transfer" may bear different meanings in different works depending on the method in use (quantum-classical vs. fully quantum). Here, we relate different views on exciton (de)localization. For this purpose, we perform molecular surface hopping simulations on several tetracene dimers differing by a magnitude of exciton coupling and carry out quantum dynamical as well as surface hopping calculations on a relevant model system. The molecular surface hopping simulations are done using efficient long-range corrected time-dependent density functional tight binding electronic structure method, allowing us to gain insight into different regimes of exciton dynamics in the studied systems.
We discuss the dynamics of a condensate in a miniaturized electromagnetic trap formed above a microstructured substrate. Recent experiments have found that trap lifetimes get reduced when approaching the substrate because atoms couple to thermally excited near fields. The data agree quantitatively with our theory [Appl. Phys. B 69, 379 (1999)]. We focus on the decoherence of a quantum degenerate gas in a quasi-one-dimensional trap. Monte Carlo simulations indicate that atom interactions reduce the condensate decoherence rate. This is explained by a simple theory in terms of the suppression of long-wavelength excitations. We present preliminary simulation results for the adiabatic generation of dark solitons
Homeoffice und mobiles Arbeiten haben sich infolge der Covid-19-Pandemie bei vielen Unternehmen bekanntlich etabliert. Die Anweisung bzw. „Duldung“ des Homeoffice beruhte allerdings meist mehr auf tatsächlicher als auf rechtlicher Grundlage. Letztere könnte aber aus betrieblicher Übung erwachsen. Dieser Beitrag geht dem rechtlichen Rahmen dafür nach.
The spatial magnetic properties (Through-Space NMR Shieldings-TSNMRS) of already synthesized dehydro[n]annulenes of various ring size (from C-12 to C-20) have been computed, visualized as Isochemical Shielding Surfaces (ICSS) of various size and direction, and were examined subject to present (anti)aromaticity. For this purpose the thus quantified ring current effect of the macro cycles on proximate protons in proton NMR spectra was employed.
Lobelia tupa, also called devil's tobacco, is a native plant from the center-south of Chile which has been used by the native people of Chile as a hallucinogenic and anesthetic plant. A new piperidine alkaloid, called pentylsedinine, which comprises five carbons in the side chain, was isolated from the aerial part of L. tupa, along with lobeline and lobelanidine. The structure was established on the basis of 1D and 2D NMR spectroscopy. While lobeline is a neutral antagonist at alpha 3 beta 2/alpha 3 beta 4 nAChR and alpha 7 nAChR, both lobelanidine and pentylsedinine act as partial agonists at nAChR
The fruit of Aristotelia chilensis is considered a "super fruit" due to its high concentration of polyphenols displaying exceptional antioxidant capacities ORAC. From maqui berries have been reported several anthocyanins and glycosylated flavonoids, those benefits increase the attention to restudy the plant. From the leaves of A. chilensis several indole alkaloids have been reported, we in addition to aristoteline, aristone, aristoquinoline and 3-fromylindole report the spectroscopic elucidation of 8-oxo-9-dehydromakomakine (1), hobartine (2) and a new alkaloid named 8-oxohobartine (3). Compound 1 to 3 did not show bactericidal activity against E. coli and S. aureus till 200 mu g.
Both the seat of the German government and the capitol of queer German culture, Berlin has been that spatial nexus of politics, sexuality and gender, work and leisure that has enabled the development of multifarious sexual and gender identities. This has caused celebration and consternation among Germans and foreigners alike. Contemporary studies of urban homosexual space cite an erosion of its 'authenticity' when cities market homosexual space in order to attract tourists. My literary analysis shows that Berlin's homosexual male culture and space had already been subject to commoditisation in the Weimar period (1918-1933), when Berliners discovered marketing potential in the French slight la vice allemand [the German vice] - male homosexuality. This article's examination of Weimar Berlin's spatial binary as 'sexy space' and 'sexualised place' in literature by Klaus Mann and Curt Moreck engages with current debates in leisure studies on the gendering and sexing of geography and leisure. Central to this re-evaluation of leisure and tourism in Weimar Berlin is my discussion of flanerie: the figure of the flaneuse indicates that flanerie was not the lone dominion of heterosexual men. In the context of urban leisure and male homosexuality, I argue that Weimar Berlin consistently and successfully negotiated its dual function of sexy space (allowing self-fashioning for homosexual men in Berlin) and sexualised place (voyeurism and sexual exploration for Berlin's newcomers and tourists).
Formate dehydrogenase (FDH) enzymes are attractive catalysts for potential carbon dioxide conversion applications. The FDH from Rhodobacter capsulatus (RcFDH) binds a bis-molybdopterin-guanine-dinucleotide (bis-MGD) cofactor, facilitating reversible formate (HCOO-) to CO2 oxidation. We characterized the molecular structure of the active site of wildtype RcFDH and protein variants using X-ray absorption spectroscopy (XAS) at the Mo K-edge. This approach has revealed concomitant binding of a sulfido ligand (Mo=S) and a conserved cysteine residue (S(Cys386)) to Mo(VI) in the active oxidized molybdenum cofactor (Moco), retention of such a coordination motif at Mo(V) in a chemically reduced enzyme, and replacement of only the S(Cys386) ligand by an oxygen of formate upon Mo(IV) formation. The lack of a Mo=S bond in RcFDH expressed in the absence of FdsC implies specific metal sulfuration by this bis-MGD binding chaperone. This process still functioned in the Cys386Ser variant, showing no Mo-S(Cys386) ligand, but retaining a Mo=S bond. The C386S variant and the protein expressed without FdsC were inactive in formate oxidation, supporting that both Moligands are essential for catalysis. Low-pH inhibition of RcFDH was attributed to protonation at the conserved His387, supported by the enhanced activity of the His387Met variant at low pH, whereas inactive cofactor species showed sulfido-to-oxo group exchange at the Mo ion. Our results support that the sulfido and S(Cys386) ligands at Mo and a hydrogen-bonded network including His387 are crucial for positioning, deprotonation, and oxidation of formate during the reaction cycle of RcFDH.
'Mitfühlend sprechen'
(2014)
Im Zentrum dieser interaktional-linguistischen Untersuchung steht die Frage, welchen Beitrag die prosodisch-phonetische Gestaltung einer Äußerung zu ihrer Interpretation als Darstellung von Empathie leistet. Dem liegt eine interaktionale Auffassung von Empathie zu Grunde: Empathie wird nicht als psychoemotionaler Zustand konzeptualisiert, sondern als Darstellung von Verstehen/ Verständnis/ Mitgefühl/ Mitleid in sozialer Interaktion. Gegenstand der Untersuchung ist die interaktive Bearbeitung persönlicher Erlebnisse in deutschen Alltagsgesprächen. Es wird gezeigt, dass – an spezifischen sequentiellen Positionen – Kombinationen folgender prosodisch-phonetischer Ressourcen potenziell relevant sind, um Äußerungen als empathisch, hier i.S.v. 'mitfühlend', interpretierbar zu machen: geringere und/ oder abnehmende Lautstärke/ Diminuendo, tiefes Tonhöhenregister, flach auslaufende Kontur, Behauchung, Knarrstimme, geringe Sprechspannung/ weiche Artikulation, Silbendehnung, Lippenrundung, rhythmische Integration/ Legato-Rhythmus.
'Gelegenheitsdichtung'
(2010)