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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.
The following article aims to show how the Zionist movement defined its loyalty to Zionism, Germany, and German culture, as well as its reaction to the First World War. Central to the Zionist movement was the "creation of a home for Jewish people secured by public law." This is why superficial examinations assume that for Zionists the conflicts of the European powers were important only as they affected the pursuit of their own political agendas, an impression intensified by their posture of reserve towards military service. Crucial for Zionist positions on the First World War are the discourses revolving around the relationship between German culture, patriotism, and loyalty within the movement. This project is conducted with the help of the Judische Rundschau (JR; Jewish Review), which functions as the official organ of the "Zionistische Vereinigung fur Deutschland" (ZVfD; Zionist Association of Germany).
"The greatest son of our Heimat": reading German Leichhardts across the National Socialist era
(2015)
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.
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.
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.
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
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.
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.
We present spectral classifications from optical spectroscopy of 263 massive stars in the north-eastern region of the Large Magellanic Cloud. The observed two-degree field includes the massive 30 Doradus star-forming region, the environs of SN1987A, and a number of star-forming complexes to the south of 30 Dor. These are the first classifications for the majority (203) of the stars and include eleven double-lined spectroscopic binaries. The sample also includes the first examples of early OC-type spectra (AA Omega 30 Dor 248 and 280), distinguished by the weakness of their nitrogen spectra and by C IV lambda 4658 emission. We propose that these stars have relatively unprocessed CNO abundances compared to morphologically normal O-type stars, indicative of an earlier evolutionary phase. From analysis of observations obtained on two consecutive nights, we present radial-velocity estimates for 233 stars, finding one apparent single-lined binary and nine (>3 sigma) outliers compared to the systemic velocity; the latter objects could be runaway stars or large-amplitude binary systems and further spectroscopy is required to investigate their nature.
Flow phenomena in the unsaturated zone are highly variable in time and space. Thus, it is challenging to measure and monitor such processes under field conditions. Here, we present a new setup and interpretation approach for combining a dye tracer experiment with a 4D ground-penetrating radar (GPR) survey. Therefore, we designed a rainfall experiment during which we measured three surface-based 3D GPR surveys using a pair of 500 MHz antennas. Such a survey setup requires accurate acquisition and processing techniquesto extract time-lapse information supporting the interpretation of selected cross-sections photographed after excavating the site. Our results reveal patterns of traveltime changes in the measured GPR data, which are associated with soil moisture changes. As distinct horizons are present at our site, such changes can be quantified and transferred into changes in total soil moisture content. Our soil moisture estimates are similar to the amount of infiltrated water, which confirms our experimental approach and makes us confident for further developing this strategy, especially, with respect to improving the temporal and spatial resolution. (C) 2015 Elsevier B.V. All rights reserved.
Timing and magnitude of surface uplift are key to understanding the impact of crustal deformation and topographic growth on atmospheric circulation, environmental conditions, and surface processes. Uplift of the East African Plateau is linked to mantle processes, but paleoaltimetry data are too scarce to constrain plateau evolution and subsequent vertical motions associated with rifting. Here, we assess the paleotopographic implications of a beaked whale fossil (Ziphiidae) from the Turkana region of Kenya found 740 km inland from the present-day coastline of the Indian Ocean at an elevation of 620 m. The specimen is similar to 17 My old and represents the oldest derived beaked whale known, consistent with molecular estimates of the emergence of modern straptoothed whales (Mesoplodon). The whale traveled from the Indian Ocean inland along an eastward-directed drainage system controlled by the Cretaceous Anza Graben and was stranded slightly above sea level. Surface uplift from near sea level coincides with paleoclimatic change from a humid environment to highly variable and much drier conditions, which altered biotic communities and drove evolution in east Africa, including that of primates.
One of the fundamental challenges in anti-doping is identifying athletes who use, or are at risk of using, prohibited performance enhancing substances. The growing trend to employ a forensic approach to doping control aims to integrate information from social sciences (e.g., psychology of doping) into organised intelligence to protect clean sport. Beyond the foreseeable consequences of a positive identification as a doping user, this task is further complicated by the discrepancy between what constitutes a doping offence in the World Anti-Doping Code and operationalized in doping research. Whilst psychology plays an important role in developing our understanding of doping behaviour in order to inform intervention and prevention, its contribution to the array of doping diagnostic tools is still in its infancy. In both research and forensic settings, we must acknowledge that (1) socially desirable responding confounds self-reported psychometric test results and (2) that the cognitive complexity surrounding test performance means that the response-time based measures and the lie detector tests for revealing concealed life-events (e.g., doping use) are prone to produce false or non-interpretable outcomes in field settings. Differences in social-cognitive characteristics of doping behaviour that are tested at group level (doping users vs. non-users) cannot be extrapolated to individuals; nor these psychometric measures used for individual diagnostics. In this paper, we present a position statement calling for policy guidance on appropriate use of psychometric assessments in the pursuit of clean sport. We argue that, to date, both self-reported and response-time based psychometric tests for doping have been designed, tested and validated to explore how athletes feel and think about doping in order to develop a better understanding of doping behaviour, not to establish evidence for doping. A false 'positive' psychological profile for doping affects not only the individual 'clean' athlete but also their entourage, their organisation and sport itself. The proposed policy guidance aims to protect the global athletic community against social, ethical and legal consequences from potential misuse of psychological tests, including erroneous or incompetent applications as forensic diagnostic tools in both practice and research. (C) 2015 Elsevier B.V. All rights reserved.
Oxidative stress causes dramatic changes in the expression levels of many genes. The formation of a functional protein through successful mRNA translation is central to a coordinated cellular response. To what extent the response towards reactive oxygen species (ROS) is regulated at the translational level is poorly understood. Here we analysed leaf- and tissue-specific translatomes using a set of transgenic Arabidopsis thaliana lines expressing a FLAG-tagged ribosomal protein to immunopurify polysome-bound mRNAs before and after oxidative stress. We determined transcript levels of 171 ROS-responsive genes upon paraquat treatment, which causes formation of superoxide radicals, at the whole-organ level. Furthermore, the translation of mRNAs was determined for five cell types: mesophyll, bundle sheath, phloem companion, epidermal and guard cells. Mesophyll and bundle sheath cells showed the strongest response to paraquat treatment. Interestingly, several ROS-responsive transcription factors displayed cell type-specific translation patterns, while others were translated in all cell types. In part, cell type-specific translation could be explained by the length of the 5-untranslated region (5-UTR) and the presence of upstream open reading frames (uORFs). Our analysis reveals insights into the translational regulation of ROS-responsive genes, which is important to understanding cell-specific responses and functions during oxidative stress.
The study illustrates the response of different Arabidopsis thaliana leaf cells and tissues to oxidative stress at the translational level, an aspect of reactive oxygen species (ROS) biology that has been little studied in the past. Our data reveal insights into how translational regulation of ROS-responsive genes is fine-tuned at the cellular level, a phenomenon contributing to the integrated physiological response of leaves to stresses involving changes in ROS levels.
X-ray photoelectron spectroscopy (XPS) is a powerful tool for probing the local chemical environment of atoms near surfaces. When applied to soft matter, such as polymers, XPS spectra are frequently shifted and broadened due to thermal atom motion and by interchain interactions. We present a combined quantum mechanical QM/molecular dynamics (MD) simulation of X-ray photoelectron spectra of polyvinyl alcohol (PVA) using oligomer models in order to account for and quantify these effects on the XPS (C1s) signal. In our study, molecular dynamics at finite temperature were performed with a classical forcefield and by ab initio MD (AIMD) using the Car-Parrinello method. Snapshots along, the trajectories represent possible conformers and/or neighbouring environments, with different C1s ionization potentials for individual C atoms leading to broadened XPS peaks. The latter are determined by Delta-Kohn Sham calculations. We also examine the experimental practice of gauging XPS (C1s) signals of alkylic C-atoms in C-containing polymers to the C1s signal of polyethylene.
We find that (i) the experimental XPS (C1s) spectra of PVA (position and width) can be roughly represented by single-strand models, (ii) interchain interactions lead to red-shifts of the XPS peaks by about 0.6 eV, and (iii) AIMD simulations match the findings from classical MD semi-quantitatively. Further, (iv) the gauging procedure of XPS (C1s) signals to the values of PE, introduces errors of about 0.5 eV. (C) 2014 Elsevier B.V. All rights reserved.
Land-use concepts provide decision support for the most efficient usage options according to sustainable development and multifunctionality requirements. However, developments in landscape-related, agricultural production schemes are primarily driven by economic benefits. Therefore, most agricultural land-use concepts tackle particular problems or interests and lack a systemic perspective. As a result, we discuss a conceptual model for future site-specific agricultural land-use with an inbuilt requirement for adequate experimental sites to enable monitoring systems for a new generation of ecosystem models and for new approaches to address science-stakeholder interactions.
The Net Reclassification Improvement (NRI) has become a popular metric for evaluating improvement in disease prediction models through the past years. The concept is relatively straightforward but usage and interpretation has been different across studies. While no thresholds exist for evaluating the degree of improvement, many studies have relied solely on the significance of the NRI estimate. However, recent studies recommend that statistical testing with the NRI should be avoided. We propose using confidence ellipses around the estimated values of event and non-event NRIs which might provide the best measure of variability around the point estimates. Our developments are illustrated using practical examples from EPIC-Potsdam study.