Selective P4 activation by an organometallic nickel(I) radical: formation of a dinuclear nickel(II) tetraphosphide and related di- and trichalcogenides

The reaction of the 17e nickel(I) radical [CpNi(IDipp)] (1, IDipp = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) with P4 results in a nickel tetraphosphide [{CpNi(IDipp)}2(μ-η1:η1-P4)] with a butterfly-P42− ligand; related chalcogenides [{CpNi(IDipp)}2(μ-E2)] (E = S, Se, Te) and [{CpNi(IDipp)}2(μ-E3)] (E = S, Se) are formed with S8, Se∞ and Te∞.

Tagged phosphine reagents to assist reaction work-up by phase-switched scavenging using a modular flow reactor

The use of three orthogonally tagged phosphine reagents to assist chemical work-up via phase-switch scavenging in conjunction with a modular flow reactor is described. These techniques (acidic, basic and Click chemistry) are used to prepare various amides and tri-substituted guanidines from in situ generated iminophosphoranes.

Anti-Slavic imagery in German radical nationalist discourse at the turn of the twentieth century: a prelude to Nazi ideology?

By applying methods of cognitive metaphor theory, Jaworska examines metaphorical scenarios employed in the discourse of anti-Slavism, which featured prominently in radical nationalist propaganda in Germany at the turn of the twentieth century. She does so by analysing metaphorical expressions used to refer to the Polish population living in the eastern provinces of Prussia, in the so-called Ostmark. Her article is based on an analysis of a range of pamphlets and newspaper articles written by some of the leading figures of two nationalist organizations: the Pan-German League (Alldeutscher Verband) and the Eastern Marches Society(Ostmarkenverein). The main research questions it addresses are: What kind of metaphoric scenarios were used to depict the Polish minority, and to what extent were the metaphorical patterns of anti-Slavic imagery similar to those employed in the antisemitic propaganda of the Nazi era? Is there a discursive continuity between the radical nationalism of imperial Germany and the National Socialism of the Third Reich at the level of metaphorical scenarios? Ultimately, Jaworska attempts to contribute to a better understanding of the cognitive mechanisms underlying radical and essentially racist attitudes.

Multistep π dimerization of tetrakis(n-decyl)heptathienoacene radical cations: a combined experimental and theoretical study

Radical cations of a heptathienoacene a,b-substituted with four n-decyl side groups (D4T7C+) form exceptionally stable p-dimer dications already at ambient temperature (Chem. Comm. 2011, 47, 12622). This extraordinary p-dimerization process is investigated here with a focus on the ultimate[D4T7C+]2 p-dimer dication and yet-unreported transitoryspecies formed during and after the oxidation. To this end, we use a joint experimental and theoretical approach that combines cyclic voltammetry, in situ spectrochemistry and spectroelectrochemistry, EPR spectroscopy, and DFT calculations. The impact of temperature, thienoacene concentration, and the nature and concentration of counteranions on the p-dimerization process is also investigated in detail. Two different transitory species were detected in the course of the one-electron oxidation: 1) a different transient conformation of the ultimate [D4T7C+]2 p-dimer dications, the stability of which is strongly affected by the applied experimental conditions, and 2) intermediate [D4T7]2C+ p-dimer radical cations formed prior to the fully oxidized [D4T7]2C+ p-dimer dications. Thus, this comprehensive work demonstrates the formation of peculiar supramolecular species of heptathienoacene radical cations, the stability, nature, and structure of which have been successfully analyzed. We therefore believe that this study leads to a deeper fundamental understanding of the mechanism of dimer formation between conjugated aromatic systems.

Radical left-wing Euroscepticism in the 2014 elections: a cross-European comparison

This article examines the varied performance of radical left-wing Eurosceptic parties during the 2014 EP elections. While the performance of the radical right during this 'earthquake' election has been widely discussed, little attention has been paid to the radical left. The article examines the result comparatively, and identifies that: (1) across Europe, radical left-wing euroscepticism is limited to few countries, including Greece, Cyprus, France and Portugal; (2) the countries that have experienced the worst of the economic crisis did not experience a significant rise in far right-wing party support but did experience the rise of left-wing euroscepticism; (3) from this sample only Greece experienced the rise of both the radical right and radical left.

Key bioactive reaction products of the NO/H2S interaction are S/N-hybrid species, polysulfides, and nitroxyl

Experimental evidence suggests that nitric oxide (NO) and hydrogen sulfide (H2S) signaling pathways are intimately intertwined, with mutual attenuation or potentiation of biological responses in the cardiovascular system and elsewhere. The chemical basis of this interaction is elusive. Moreover, polysulfides recently emerged as potential mediators of H2S/sulfide signaling, but their biosynthesis and relationship to NO remain enigmatic. We sought to characterize the nature, chemical biology, and bioactivity of key reaction products formed in the NO/sulfide system. At physiological pH, we find that NO and sulfide form a network of cascading chemical reactions that generate radical intermediates as well as anionic and uncharged solutes, with accumulation of three major products: nitrosopersulfide (SSNO−), polysulfides, and dinitrososulfite N-nitrosohydroxylamine-N-sulfonate (SULFI/NO), each with a distinct chemical biology and in vitro and in vivo bioactivity. SSNO− is resistant to thiols and cyanolysis, efficiently donates both sulfane sulfur and NO, and potently lowers blood pressure. Polysulfides are both intermediates and products of SSNO− synthesis/decomposition, and they also decrease blood pressure and enhance arterial compliance. SULFI/NO is a weak combined NO/nitroxyl donor that releases mainly N2O on decomposition; although it affects blood pressure only mildly, it markedly increases cardiac contractility, and formation of its precursor sulfite likely contributes to NO scavenging. Our results unveil an unexpectedly rich network of coupled chemical reactions between NO and H2S/sulfide, suggesting that the bioactivity of either transmitter is governed by concomitant formation of polysulfides and anionic S/N-hybrid species. This conceptual framework would seem to offer ample opportunities for the modulation of fundamental biological processes governed by redox switching and sulfur trafficking.