@article{KolocourisKochKleinpeteretal.2015, author = {Kolocouris, Antonios and Koch, Andreas and Kleinpeter, Erich and Stylianakis, Ioannis}, title = {2-Substituted and 2,2-disubstituted adamantane derivatives as models for studying substituent chemical shifts and C-H-ax center dot center dot center dot Y-ax cyclohexane contacts-results from experimental and theoretical NMR spectroscopic chemical shifts and DFT structures}, series = {Tetrahedron}, volume = {71}, journal = {Tetrahedron}, number = {16}, publisher = {Elsevier}, address = {Oxford}, issn = {0040-4020}, doi = {10.1016/j.tet.2015.01.044}, pages = {2463 -- 2481}, year = {2015}, abstract = {The complete H-1 and C-13 NMR chemical shifts assignment for various 2-substituted and 2,2-disubstituted adamantane derivatives 1-38 in CDCl3 solution was realized on the basis of NMR experiments combined with chemical structure information and DFT-GIAO (B3LYP/6-31+G(d,p)-GIAO) calculations of chemical shifts in solution. Substituent-induced C-13 NMR chemical shifts (SCS) are discussed. C-H-ax center dot center dot center dot Y-ax contacts are a textbook prototype of steric hindrance in organic chemistry. The nature of these contacts will be further investigated in this work on basis of new adamantane derivatives, which are substituted at C-2 to provide models for 1,4-C-H-ax center dot center dot center dot Y-ax and 1,5-C-H-ax center dot center dot center dot Y-ax contacts. The B3LYP/6-31+G(d,p) calculations predicted the presence of NBO hyperconjugative attractive interactions between C-H-ax and Y-ax groups along C-H-ax center dot center dot center dot Y-ax contacts. The H-1 NMR signal separation, Delta delta(gamma-CH2), reflects the strength of the H-bonded C-H-ax center dot center dot center dot Y-ax contact. (C) 2015 Elsevier Ltd. All rights reserved.}, language = {en} } @article{ShakiSeryFischer2015, author = {Shaki, Samuel and Sery, Noa and Fischer, Martin H.}, title = {1 + 2 is more than 2 + 1: Violations of commutativity and identity axioms in mental arithmetic}, series = {Journal of cognitive psychology}, volume = {27}, journal = {Journal of cognitive psychology}, number = {4}, publisher = {Routledge, Taylor \& Francis Group}, address = {Abingdon}, issn = {2044-5911}, doi = {10.1080/20445911.2014.973414}, pages = {471 -- 477}, year = {2015}, abstract = {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.}, language = {en} } @article{PazBecerraSilvaetal.2015, author = {Paz, Cristian and Becerra, Jose and Silva, Mario and Burgos, Viviana and Heydenreich, Matthias and Schmidt, Bernd and Thu Tran, and Vetter, Irina}, title = {(-)-Pentylsedinine, a New Alkaloid from the Leaves of Lobelia tupa with Agonist Activity at Nicotinic Acetylcholine Receptor}, series = {Natural product communications : an international journal for communications and reviews}, volume = {10}, journal = {Natural product communications : an international journal for communications and reviews}, number = {8}, publisher = {NPC}, address = {Westerville}, issn = {1934-578X}, pages = {1355 -- 1357}, year = {2015}, abstract = {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}, language = {en} } @article{SchrapersHartmannKositzkietal.2015, author = {Schrapers, Peer and Hartmann, Tobias and Kositzki, Ramona and Dau, Holger and Reschke, Stefan and Schulzke, Carola and Leimk{\"u}hler, Silke and Haumann, Michael}, title = {'Sulfido and Cysteine Ligation Changes at the Molybdenum Cofactor during Substrate Conversion by Formate Dehydrogenase (FDH) from Rhodobacter capsulatus}, series = {Inorganic chemistry}, volume = {54}, journal = {Inorganic chemistry}, number = {7}, publisher = {American Chemical Society}, address = {Washington}, issn = {0020-1669}, doi = {10.1021/ic502880y}, pages = {3260 -- 3271}, year = {2015}, abstract = {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.}, language = {en} } @article{Wiese2015, author = {Wiese, Heike}, title = {"This migrants' babble is not a German dialect!": The interaction of standard language ideology and 'us'/'them' dichotomies in the public discourse on a multiethnolect}, series = {Language in society}, volume = {44}, journal = {Language in society}, number = {3}, publisher = {Cambridge Univ. Press}, address = {New York}, issn = {0047-4045}, doi = {10.1017/S0047404515000226}, pages = {341 -- 368}, year = {2015}, abstract = {This article investigates a public debate in Germany that put a special spotlight on the interaction of standard language ideologies with social dichotomies, centering on the question of whether Kiezdeutsch, a new way of speaking in multilingual urban neighbourhoods, is a legitimate German dialect. Based on a corpus of emails and postings to media websites, I analyse central topoi in this debate and an underlying narrative on language and identity. Central elements of this narrative are claims of cultural elevation and cultural unity for an idealised standard language High German', a view of German dialects as part of a national folk culture, and the construction of an exclusive in-group of German' speakers who own this language and its dialects. The narrative provides a potent conceptual frame for the Othering of Kiezdeutsch and its speakers, and for the projection of social and sometimes racist deliminations onto the linguistic plane.}, language = {en} } @article{HurleySchwarz2015, author = {Hurley, Andrew Wright and Schwarz, Anja}, title = {"The greatest son of our Heimat": reading German Leichhardts across the National Socialist era}, series = {Journal of Australian studies}, volume = {39}, journal = {Journal of Australian studies}, number = {4}, publisher = {Routledge, Taylor \& Francis Group}, address = {Abingdon}, issn = {1444-3058}, doi = {10.1080/14443058.2015.1076025}, pages = {529 -- 545}, year = {2015}, abstract = {The article discusses German commemorations of Ludwig Leichhardt (1813-1848) in the National Socialist era when officials, journalists, educators and writers, spurred by the double anniversary of the explorer's 125th birthday and the 90th anniversary of his disappearance, began to re-imagine the explorer's life and fate in the light of the ideological imperatives of the day. Our analysis of this period pays particular attention to how these reimagined Leichhardts emphasise or neglect some of the key elements that make up his story to this day, among them: Leichhardt's ethnicity; his sense of attachment to place and home; his homosocial relationships; his evasion of Prussian military service; his role in the British colonial project; and finally, his engagements with Aborigines. On the one hand, our analysis reveals, how Leichhardt was portrayed first on the local and, later, the national level in ways that increasingly sought to elide ambiguous aspects of his life and deeds. However, it also uncovers some of the ideological labour required to render him useful to the National Socialist cause. Often enough, these re-imagined Leichhardts escaped party politics, and cast up some of the logical inconsistencies and limits to key terms in National Socialist thinking.}, language = {en} } @article{JordanFechlerXuetal.2015, author = {Jordan, Thomas and Fechler, Nina and Xu, Jingsan and Brenner, Thomas J. K. and Antonietti, Markus and Shalom, Menny}, title = {"Caffeine Doping" of Carbon/Nitrogen-Based Organic Catalysts: Caffeine as a Supramolecular Edge Modifier for the Synthesis of Photoactive Carbon Nitride Tubes}, series = {ChemCatChem : heterogeneous \& homogeneous \& bio- \& nano-catalysis ; a journal of ChemPubSoc Europe}, volume = {7}, journal = {ChemCatChem : heterogeneous \& homogeneous \& bio- \& nano-catalysis ; a journal of ChemPubSoc Europe}, number = {18}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1867-3880}, doi = {10.1002/cctc.201500343}, pages = {2826 -- 2830}, year = {2015}, abstract = {An alternative method for the structure tuning of carbon nitride materials by using a supramolecular approach in combination with caffeine as lining-agent is described. The self-assembly of the precursor complex consisting of melamine and cyanuric acid can be controlled by this doping molecule in terms of morphology, electronic, and photophysical properties. Caffeine is proposed to insert as an edge-molecule eventually leading to hollow tube-like carbon nitride structures with improved efficiency of charge formation. Compared to the bulk carbon nitride, the caffeine-doped analogue possesses a higher photocatalytic activity for the degradation of rhodamineB dye. Furthermore, this approach is also shown to be suitable for the modification of carbon nitride electrodes.}, language = {en} }