Liquid AP-UV-MALDI enables stable ion yields of multiply charged peptide and protein ions for sensitive analysis by mass spectrometry

In biological mass spectrometry (MS), two ionization techniques are predominantly employed for the analysis of larger biomolecules, such as polypeptides. These are nano-electrospray ionization [1, 2] (nanoESI) and matrix-assisted laser desorption/ionization [3, 4] (MALDI). Both techniques are considered to be “soft”, allowing the desorption and ionization of intact molecular analyte species and thus their successful mass-spectrometric analysis. One of the main differences between these two ionization techniques lies in their ability to produce multiply charged ions. MALDI typically generates singly charged peptide ions whereas nanoESI easily provides multiply charged ions, even for peptides as low as 1000 Da in mass. The production of highly charged ions is desirable as this allows the use of mass analyzers, such as ion traps (including orbitraps) and hybrid quadrupole instruments, which typically offer only a limited m/z range (< 2000–4000). It also enables more informative fragmentation spectra using techniques such as collisioninduced dissociation (CID) and electron capture/transfer dissociation (ECD/ETD) in combination with tandem MS (MS/MS). [5, 6] Thus, there is a clear advantage of using ESI in research areas where peptide sequencing, or in general, the structural elucidation of biomolecules by MS/MS is required. Nonetheless, MALDI with its higher tolerance to contaminants and additives, ease-of-operation, potential for highspeed and automated sample preparation and analysis as well as its MS imaging capabilities makes it an ionization technique that can cover bioanalytical areas for which ESI is less suitable. [7, 8] If these strengths could be combined with the analytical power of multiply charged ions, new instrumental configurations and large-scale proteomic analyses based on MALDI MS(/MS) would become feasible.

Radical Conservatism

In 1938, Yugoslav sculptor Oscar Nemon arrived in Britain, having fled the Nazi invasion of Brussels, where he was living with Magritte. He was part of the European avant-garde that came to the UK as a refugee. Shortly thereafter, Nemon proposed a bold architectural plan to construct a temple of universal ethics in London and was in correspondence over this with central figures in Britain. After the war, he became know for his portrayal of figures like Churchil, culminating in a bust of Margaret Thatcher that is currently at the Tory HQ. Shown at Castlefield Gallery in 2013-2014, Radical Conservatism was an exhibition that explored the space between these two moments and asked whether these two terms are really antithetical. In the British context in particular, where the European avant-garde never really took hold, a kind of reactionary modernism has always defined a culture wary of revolution. But today more than ever, with the left increasingly holding on to the past of the welfare state as an ideal, and the right quietly revolutionising our world through neoliberal reforms, the paradigms of radicalism and conservatism need to be redefined. Can conservatism be seen as a radical position in itself? If art is defined by a movement towards the new - could 'holding on to the past' stubbornly be seen as a critical position, now that neo-liberalism has forced a far more radical shift in politics than the left has managed in a long time? Curated by Pil and Galia Kollectiv, featuring work by Chris Evans, IRWIN, Pil and Galia Kollectiv, Joseph Lewis, Patrick Moran, Oscar Nemon and Public Movement and a symposium with contributions from Professor Alun Rowlands and Robert Garnett.

The kinetics of the gas-phase reactions of selected monoterpenes and cyclo-alkenes with ozone and the NO3 radical

The relative rate method has been used to measure the room-temperature rate constants for the gasphase reactions of ozone and NO3 with selected monoterpenes and cyclo-alkenes with structural similarities to monoterpenes. Measurements were carried out at 298 ! 2 K and 760 ! 10 Torr. The following rate constants (in units of 10"18 cm3 molecule"1 s"1) were obtained for the reaction with ozone: methyl cyclohexene (132 ! 17), terpinolene (1290 ! 360), ethylidene cyclohexane (223 ! 57), norbornene (860 ! 240), t-butyl isopropylidene cyclohexane (1500 ! 460), cyclopentene (543 ! 94), cyclohexene (81 ! 18), cyclooctene (451 ! 66), dicyclopentadiene (1460 ! 170) and a-pinene (107 ! 13). For the reaction with NO3 the rate constants obtained (in units of 10"12 cm3 molecule"1 s"1) were: methyl cyclohexene (7.92 ! 0.95), terpinolene (47.9 ! 4.0), ethylidene cyclohexane (4.30 ! 0.24), norbornene (0.266 ! 0.029), cyclohexene (0.540 ! 0.017), cyclooctene (0.513 ! 0.029), dicyclopentadiene (1.20 ! 0.10) and a-pinene (5.17 ! 0.62). Errors are quoted as the root mean square of the statistical error (95% con!dence) and the quoted error in the rate constant for the reference compound. Combining these results with previous studies, new recommendations for the rate constants are presented. Molecular orbital energies were calculated for each alkene and the kinetic data are discussed in terms of the deviation from the structureeactivity relationship obtained from the rate constants for a series of simple alkenes. Lifetimes with respect to key initiators of atmospheric oxidation have been calculated suggesting that the studied reactions play dominant roles in the night-time removal of these compounds from the atmosphere.

Implications of climate change for diseases, crop yields and food security

Accelerated climate change affects components of complex biological interactions differentially, often causing changes that are difficult to predict. Crop yield and quality are affected by climate change directly, and indirectly, through diseases that themselves will change but remain important. These effects are difficult to dissect and model as their mechanistic bases are generally poorly understood. Nevertheless, a combination of integrated modelling from different disciplines and multi-factorial experimentation will advance our understanding and prioritisation of the challenges. Food security brings in additional socio-economic, geographical and political factors. Enhancing resilience to the effects of climate change is important for all these systems and functional diversity is one of the most effective targets for improved sustainability.

Uncertainty in simulating wheat yields under climate change

Projections of climate change impacts on crop yields are inherently uncertain1. Uncertainty is often quantified when projecting future greenhouse gas emissions and their influence on climate2. However, multi-model uncertainty analysis of crop responses to climate change is rare because systematic and objective comparisons among process-based crop simulation models1, 3 are difficult4. Here we present the largest standardized model intercomparison for climate change impacts so far. We found that individual crop models are able to simulate measured wheat grain yields accurately under a range of environments, particularly if the input information is sufficient. However, simulated climate change impacts vary across models owing to differences in model structures and parameter values. A greater proportion of the uncertainty in climate change impact projections was due to variations among crop models than to variations among downscaled general circulation models. Uncertainties in simulated impacts increased with CO2 concentrations and associated warming. These impact uncertainties can be reduced by improving temperature and CO2 relationships in models and better quantified through use of multi-model ensembles. Less uncertainty in describing how climate change may affect agricultural productivity will aid adaptation strategy development andpolicymaking.

Radical cations of end-capped tetrathienoacenes and their p-dimerization controlled by the nature of a-substituents and counterion concentration

Radical cations of a soluble rigid tetrathienoacene are capable of forming stable p-dimer dications at ambient temperature when the short backbone becomes extended with conjugated thiophene-2-yl substituents in the a-positions. On the other hand, simple attachment of methyl groups on the a-carbon of the external thiophen-2-yl rings proved sufficient to inhibit the dimerization. Stable radical cationswere also exclusively formed for tetrathienoacene derivatives end-capped with bulky TIPS and phenyl substituents.

RuII(α-diimine) or RuIII(α-diimine·–)? Structural, spectroscopic, and theoretical evidence for the stabilization of a prominent metal-to-Ligand charge- transfer excited-state configuration in the ground state

The new compounds [Ru(R-DAB)(acac)2] (R-DAB = 1,4-diorganyl- 1,4-diazabuta-1,3-diene; R = tert-butyl, 4-methoxyphenyl, 2,6-dimethylphenyl; acac– = 2,4-pentanedionate) exhibit intrachelate ring bond lengths 1.297radical ligand to produce UV/Vis/NIR and electron paramagnetic resonance (EPR) spectroelectrochemically detectable RuIII species, whereas the reduction proceeds less reversibly and yields predominantly (R-DAB)-ligand-based spin for the 4-methoxyphenyl derivative, measured at low temperature. The results are discussed with respect to metal-to-ligand chargetransfer (MLCT) excited states of conventional (α-diimine)- ruthenium(II) complexes and in view of other (α-diimine)- metal complexes with ambiguous oxidation-state assignments.

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∞.

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.

High pressure intensification of cassava resistant starch (RS3) yields

Cassava starch, typically, has resistant starch type 3 (RS3) content of 2.4%. This paper shows that the RS3 yields can be substantially enhanced by debranching cassava starch using pullulanase followed by high pressure or cyclic high-pressure annealing. RS3 yield of 41.3% was obtained when annealing was carried out at 400 MPa/60°C for 15 min, whereas it took nearly 8 h to obtain the same yield under conventional atmospheric annealing at 60°C. The yield of RS3 could be further significantly increased by annealing under 400MPa/60°C pressure for 15 min followed by resting at atmospheric pressure for 3 h 45 min, and repeating this cycle for up to six times. Microstructural surface analysis of the product under a scanning electron microscope showed an increasingly rigid density of the crystalline structure formed, confirming higher RS3 content.

Production of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) P(3HB-co-3HV) with a broad range of 3HV content at high yields by Burkholderia sacchari IPT 189

The biosynthesis of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) from sucrose and propionic acid by Burkholderia sacchari IPT 189 was studied using a two-stage bioreactor process. In the first stage, this bacterium was cultivated in a balanced culture medium until sucrose exhaustion. In the second stage, a solution containing sucrose and propionic acid as carbon source was fed to the bioreactor at various sucrose/propionic acid (s/p) ratios at a constant specific flow rate. Copolymers with 3HV content ranging from 40 down to 6.5 (mol%) were obtained with 3HV yield from propionic acid (Y-3HV/prop) increasing from 1.10 to 1.34 g g(-1). Copolymer productivity of 1 g l(-1) h(-1) was obtained with polymer biomass content rising up to 60% by increasing a specific flow rate at a constant s/p ratio. Increasing values of 3HV content were obtained by varying the s/p ratios. A simulation of production costs considering Y-3HV/prop obtained in the present work indicated that a reduction of up to 73% can be reached, approximating US$ 1.00 per kg which is closer to the value to produce P3HB from sucrose (US$ 0.75 per kg).