Annulation of Tetrathiafulvalene to the Bay Region of Perylenediimide: Fast Electron-Transfer Processes in Polar and Nonpolar Solvents

A tetrathiafulvalene donor has been annulated to the bay region of perylenediimide through a 1H-benzo-[d]pyrrolo[1,2-a]imidazol-1-one spacer affording an extended pi-conjugated molecular dyad (TTF-PDI). To gain insight into its ground- and excited-state electronic properties, the reference compound Ph-PDI has been prepared via a direct Schiff-base condensation of N,N'-bis(1-octylnonyl) benzoperylene-1',2':3,4:9,10-hexacarboxylic-1',2'-anhydride-3,4:9,10-bis (imide) with benzene-1,2-diamine. Both the experimental and the computational (DFT) results indicate that TTF-PDI exhibits significant intramolecular electronic interactions giving rise to an efficient photoinduced charge-separation process. Free-energy calculations verify that the process from TTF to the singlet-excited state of PDI is exothermic in both polar and nonpolar solvents. Fast adiabatic electron-transfer processes of a compactly fused, pi-conjugated TTF-PDI dyad in benzonitrile, 2-methyltetrahydrofuran, anisole and toluene were observed by femtosecond transient absorption spectral measurements. The lifetimes of radical-ion pairs slightly increase with decreasing the solvent polarities, suggesting that the charge-recombination occurs in the Marcus inverted region. By utilizing the nanosecond transient absorption technique, the intermolecular electron-transfer process in a mixture of has been observed via the triplet excited PDI for the first time.

A tetrathiafulvalene-functionalized naphthalene diimide: synthesis, electrochemical and photophysical properties

A tetrathiafulvalene donor has been attached to the naphthalene diimide core via a rigid bridge affording a new planar molecular dyad. Its electronic properties have been studied experimentally by the combination of electrochemistry and UV-vis-NIR spectroscopy. Various electronic excited charge-transfer states are generated in different oxidation states, leading to almost full absorption in the visible to near-IR region with high extinction coefficients. The observed electronic properties are explained on the basis of density-functional-theory. In particular, the oxidized radical species show a strong tendency to undergo aggregation, in which the long-distance attractive interactions overcome the electrostatic repulsions. (C) 2011 Elsevier Ltd. All rights reserved.

Inflammasome-dependent IFN-γ drives pathogenesis in Streptococcus pneumoniae meningitis

The pathology associated with Streptococcus pneumoniae meningitis results largely from activation of immune-associated pathways. We systematically investigated the production of IFN subtypes, as well as their influence on pathology, in a mouse model of S. pneumoniae meningitis. Despite the occurrence of a mixed IFN type I/II gene signature, no evidence for production or involvement of type I IFNs in disease progression was found. In contrast, type II IFN (IFN-γ) was strongly induced, and IFN-γ(-/-) mice were significantly protected from severe disease. Using intracellular cytokine staining and targeted cell-depletion approaches, NK cells were found to be the dominant source of IFN-γ. Furthermore, production of IFN-γ was found to be dependent upon ASC and IL-18, indicating that an ASC-dependent inflammasome pathway was responsible for mediating IFN-γ induction. The influence of IFN-γ gene deletion on a range of processes known to be involved in bacterial meningitis pathogenesis was examined. Although neutrophil numbers in the brain were similar in infected wild-type and IFN-γ(-/-) mice, both monocyte recruitment and CCL2 production were less in infected IFN-γ(-/-) mice compared with infected wild-type controls. Additionally, gene expression of NO synthase was strongly diminished in infected IFN-γ(-/-) mice compared with infected controls. Finally, bacterial clearance was enhanced in IFN-γ(-/-) mice, although the underlying mechanism remains unclear. Together, these data suggest that inflammasome-dependent IFN-γ contributes via multiple pathways to pathology during S. pneumoniae meningitis.

Transmission dynamics of extended-spectrum β-lactamase-producing Enterobacteriaceae in the tertiary care hospital and the household setting

Studies about transmission rates of extended-spectrum β-lactamase (ESBL)-producing Enterobacteriaceae in hospitals and households are scarce.

Gender Stereotypes and Gendered Vocational Aspirations among Secondary School Students

Research Topic/Aim: Horizontal gender inequalities appear to be rather stable, with girls more often choosing ‘female' service professions, and boys choosing career paths related to science, technology, engineering or mathematics, since measures to bring more women into typical ‘male' jobs and more men into typical ‘female' jobs did not turn out to be sustainable. This paper focuses on gender stereotypes, namely non-egalitarian patriarchal gender-role orientations and gender associations of the school subjects German and mathematics. Dealing with and abolishing such gender stereotypes may be key strategy to reach sustainability regarding more equal vocational choices. Thus, gender stereotypes will be theorised and empirically analysed as a major predictor of gender-typical vocational perspectives considering interest in these school subjects as a mediating factor. Furthermore, we focus on structural patriarchy as a root of gender-role orientations, and teacher gender regarding its impact on gendered images of subjects. Theoretical and methodology framework: Our analyses of gender segregation in vocational aspirations and vocational choice center on Gottfredson's (2002; Gottfredson and Becker, 1981) Theory of Circumscription, Compromise and Self-Creation. One of the main assumptions of this theory is that people associate jobs with particular sexes and those jobs that do not fit particular gender roles are not considered. Empirical analyses are based on survey data of eighth-graders in the Swiss canton of Bern (N = 672). Structural Equation Models (SEM) for male and female students are estimated. Conclusions/Findings: Results reveal different patterns for boys and girls; for boys, gender-typical (male) vocational perspective could be explained via gender role orientations, interest in mathematics and gender associations of the school subjects, for girls, the factors under consideration could be empirically linked to ‘atypical vocational perspective'. Relevance to Nordic educational research: The study focuses on gender relations in society and how they are reproduced. Gender segregation in vocational choice and at the labour market is a universal issue - affecting both egalitarian and non-egalitarian gender regimes in similar ways. Although in general Northern countries appear to be more equal regarding gender inequality, gender segregation is rather persistent (Jarman, Blackburn and Brooks, 2012) and therefore remains a relevant topic.

Acculturation and cultural identity of immigrant youth: The impact of courses in the language and culture of origin

Career choices in the fields of science, technology, engineering, and mathematics (STEM) are favoured by men and often avoided by women; on the other hand, women tend to choose fields such as the social sciences. This not only leads to a shortage of employees with STEM degrees, but also reinforces the prejudice that certain (personality) characteristics are ‘typically female’ or ‘typically male’. Career orientation motives of young women and men can have important implications for gender (a-)typical career choices. However, there is little empirical research on the correlates of career orientation motives in young women in the field of STEM. This study seeks to address this gap by outlining the components of career orientation motives and showing relationships among them. Therefore, our results provide insight into the circumstances and conditions that are associated with academic and career choices.

Frauen in MINT-Berufen: Retrospektive Wahrnehmung des mathematisch-naturwissenschaftlichen Unterrichts auf der Sekundarstufe I

Der Beitrag fokussiert die Bedeutung des mathematisch-naturwissenschaftlichen Unterrichts für die Überwindung der geschlechtsbezogenen Disparitäten bei der Berufswahl im Bereich von Mathematik, Informatik, Naturwissenschaft und Technik (MINT). Basierend auf der Annahme, dass in der motivationsförderlichen Gestaltung des Unterrichts ein wirksamer Ansatz zur Reduktion der beharrenden Unterrepräsentation von Frauen in MINT-Berufen liegt, wird der Frage nachgegangen, wie junge Frauen mit einer für ihr Geschlecht untypischen Berufswahl den mathematisch-naturwissenschaftlichen Unterricht, den sie auf der Sekundarstufe I erlebt haben, retrospektiv beurteilen. Der methodische Zugang er- folgt über eine standardisierte Befragung (N = 185) und qualitative Einzelinterviews (N = 71) von Frauen, die eine duale Ausbildung zu einem MINT-Beruf auf der Sekundarstufe II absolvieren. Die Triangulation der quantitativen und qualitativen Ergebnisse zeigt, dass der mathematisch-naturwissenschaftliche Unterricht von den jungen Frauen dann als förderlich und unterstützend wahrgenommen wird, wenn er auf den vier Dimensionen der Vermittlungskompetenz der Lehrperson, der individuellen Förderung durch die Lehrperson, der Orientierung über MINT-Berufe sowie des Alltags- und Phänomenbezugs hohe Ausprägungen aufweist.