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In its practical outlook, the interdisciplinary-driven colonial discourse theory is often criticized for its totalizing tendencies regarding the structure of the exam-ined discourse and the power relations prevailing in this framework. As a result of this structural totalization, the concerned subjects got disempowered and de-graded to mere passive objects incapable of raising their voices within the dis-course. Based on this justified criticism, this thesis investigates the role colonial subjects played in the emergence, the distribution, as well as in questioning and critiquing of the colonial discourse during the initial phase of British colonialism in West Africa. The focal point lies on three themes relevant to the period be-tween 1874 and 1914: The Ashanti-Wars, the creation of an educational system, and the issue of the so-called "Europeanized Africans." Newspapers published by the colonial elite serve as the central source material in order to reconstruct Afri-can perspectives on these subjects. First, the discursive trajectory of the first two themes will be reconstructed and then shown why the initial support of the elite gradually declined towards the end of the century. Eventually, the analyzed tendencies culminated in the emergence of the "African Regeneration" discourse, which was able to reverse the colonial discourse's basic assumptions, at least on a theoretical level. Consequently, the Africans were displayed as the "civilizer" of Europe. On the structural level, however, this discourse likewise employed a to-talizing picture of African and European societies, respectively.
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.
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.
"Unavoidably side by side"
(2011)
Als die SED-Diktatur zusammenbrach, übte der Glanz der ostdeutschen Medaillen nach wie vor eine große Anziehungskraft aus, vor allem auf westdeutsche Sportpolitiker. Der Sport war ein Spezialfall der deutschen Vereinigung, da hier der Westen vom Osten zu lernen hoffte. Bald jedoch wurden die dunklen Seiten des DDR-Sports offensichtlich: die Verstrickung mit dem Ministerium für Staatsicherheit ebenso wie das staatlich forcierte Zwangsdoping. Bis heute gehen die Meinungen über den DDR-Sport weit auseinander: während die Einen ihn als repressiv und unmenschlich verurteilen, wird er von den Anderen gleichzeitig als Organisationsvorbild für die Zukunft gehandelt.
Empirical evidence of the relationship between social support and post-disaster mental health provides support for a general beneficial effect of social support (main-effect model; Wheaton, 1985). From a theoretical perspective, a buffering effect of social support on the negative relationship between disaster-related stress and mental health also seems plausible (stress-buffering model; Wheaton, 1985). Previous studies, however, (a) have paid less attention to the buffering effect of social support and (b) have mainly relied on interpersonal support (but not collective-level support such as community resilience) when investigating this issue. This previous work might have underestimated the effect of support on post-disaster mental health. Building on a sample of residents in Germany recently affected by flooding (N = 118), we show that community resilience to flooding (but not general interpersonal social support) buffered against the negative effects of flooding on post-disaster mental health. The results support the stress-buffering model and call for a more detailed look at the relationship between support and resilience and post-disaster adjustment, including collective-level variables.
Cross-dressing took on new political meanings in Germany's Weimar Republic, with the emergence of organizations and periodicals aimed at promoting the interests of self-identified "transvestites." This new sexological category, developed by Magnus Hirschfeld in 1910, formed the basis for a shared sense of identity and belonging among individuals who identified as members of the "opposite" sex. Drawing on the experiences of the homosexual emancipation movement and discourses of bourgeois respectability, middle-class transvestites came together to demand legal and social recognition, including acknowledgement of "transsexual" desires. Their efforts represent a critical but forgotten moment in the history of transgender political activism.
Participation has become an orthodoxy in the field of development, an essential element of projects and programmes. This book analyses participation in development interventions as an institutionalised expectation – a rationalized myth – and examines how organisations on different levels of government process it. At least two different objectives of participation are appropriate and legitimate for international organisations in the field: the empowerment of local beneficiaries and the achievement of programme goals. Both integrate participatory forums into the organisational logic of development interventions. Local administrations react to the institutionalised expectation with means-ends decoupling, where participatory forums are implemented superficially but de facto remain marginalised in local administrative processes and activities. The book furthermore provides a thick description of the organisationality of participation in development interventions. Participatory forums are shown to be a form of partial organisation. They establish an order in the relationship between administrations and citizens through the introduction of rules and the creation of a defined membership. At the same time, this order is found to be fragile and subject to criticism and negotiation.
Two decades ago, Tarana Burke started using the phrase ‘me too’ to release victims of sexual abuse and rape from their shame and to empower girls from minority communities. In 2017, actress Alyssa Milano made the hashtag #MeToo go viral. This article’s concern is with the role of testimonial practices in the context of sexual violence. While many feminists have claimed that the word of those who claim to being sexually violated by others (should) have political and/or epistemic priority, others have failed to recognize the harm and injury of instances of sexual violence that are not yet acknowledged as such and failed to listen to victims from marginalized social groups. In fact, some feminists have attacked #MeToo for mingling accounts of ‘proper’ sexual violence and accounts that are not ‘proper’ experiences of sexual violence. My aim in this article is to show why this critique is problematic and find a philosophically fruitful way to understand the #MeToo-movement as a movement that strives for moral and conceptual progress.
'...just as it would have been in 1861' : stuttering colonial beginnings in ABC's outback house
(2010)
This MA thesis examines novels by Native American authors of the 20th century in regard to their representation of conflicts between the indigenous population of North America and the dominant Christian religion of the mainstream society. Several major points can be followed throughout the century, which have been presented repeatedly and discussed in various perspectives. Historical conflicts of colonization and Christianization, as well as the perpetual question of Native American Christians -- 'How can you go to a church that killed so many Indians?' [Alexie, Reservation Blues] -- are debated in these novels and analyzed in this paper. Furthermore, I have tried to position and classify the works according to their representation of these problems within literary history. Following Charles Larson's chronologic and thematic examination of American Indian Fiction, the categories rejection, (syncretic) adaptation, and postmodern-ironic revision are introduced to describe the various forms of representation. On the basis of five main examples, we can observe an evolution of contemporary Native American literature, which has liberated itself from the narrow definition of the 1960s and 1970s, in favor of a broader and more varied approach. In so doing, and by means of intercultural and intertextual referencing, postmodern irony, and a new Indian self-confidence, it has also taken a new position towards the religion of the former colonizer.
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.
'Tools' in public management
(2022)
Tools are methods or procedures, and thus operational patterns of action, applied in public administrations to solve standard problems. It is also possible to consider them as structured communication according to professional standards aiming at complexity reduction. Regularly, tools in management stem on a deductive-synoptic rationale offering a seemingly ‘objective’ decision basis. They have a strong formative influence on the organization, regularly also beyond the intended effects. The prominence of tools is sometimes confused with management as such, e.g. introducing tools is mistaken as equivalent to managing for a particular purpose. However, tools have to be closely and carefully managed regarding the objectives and purposes they should serve.
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).
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.
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 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.
The paper investigates Tolkien’s narratives of decline through the lens of their classical ancestry. Narratives of decline are widespread in ancient culture, in both philosophical and literary discourses. They normally posit a gradual degradation (moral and ontological) from an idealized Golden Age, which went hand-in-hand with increasing detachment of gods from mortal affairs. Narratives of decline are also at the core of Tolkien’s mythology, constituting yet another underresearched aspect of classical influence on Tolkien. Such Classical narratives reverberate e.g. in Tolkien’s division of Arda’s history into ages, from an idealized First Age filled with Joy and Light to a Third Age, described as “Twilight Age (…) the first of the broken and changed world” (Letters 131). More generally, these narratives are related to Tolkien’s notorious perception of history as a “long defeat” (Letters 195) and to that “heart-racking sense of the vanished past” which pervades Tolkien’s works – the emotion which, in his words, moved him “supremely” and which he found “small difficulty in evoking” (Letters 91). The paper analyses the reception of narratives of decline in Tolkien’s legendarium, pointing out similarities but also contrasts and differences, with the aim to discuss some key patterns of (classical) reception in Tolkien’s theory and practice (‘renewal’, ‘accommodation’, ‘focalization’).
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
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.
The ability to reflect is considered an essential element of Education for Sustainable Development (ESD) and a key competence for learners and educators in ESD (UNECE Strategy for ESD, 2012). In contrast to its high importance, little is known about how reflective thinking can be identified, influenced or increased in the classroom. Therefore, the objective of this study is to address this need by developing an empirical multi-stage model designed to help educators diagnose different levels of reflective thinking and to identify factors that influence students’ reflective thinking about sustainability. Based on a 4–8-week project with grade 10 and 11 students studying sustainability, reflective thinking performance using weblogs as reflective journals was analysed. In addition, qualitative semi-structured interviews were conducted with the teachers to comprehend the learning environment and the personal value they assigned to ESD in their geography class. To determine the levels of reflective thinking achieved by the students, the study built on the work of Dewey (1933) and pre-existing multi-stage models of reflective thinking (Bain, Ballantyne, & Packer, 1999; Chen, Wei, Wu, & Uden, 2009). Using a qualitative, iterative data analysis, the study adapted the stage models to be applicable in ESD and found great differences in the students’ reflection levels. Furthermore, the study identified eight factors that influence students’ reflective thinking about sustainability. The outcomes of this study may be valuable for educators in high school and higher education, who seek to diagnose their students’ reflective thinking performance and facilitate reflection about sustainability.
(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
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.
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.
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.
.NET Gadgeteer Workshop
(2013)
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.
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.
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.
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.
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.
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.
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.