Enantioselective Synthesis of exo-4-Nitroprolinates from Nitro­alkenes and Azomethine Ylides Catalyzed by Chiral Phosphor­amidite·Silver(I) or Copper(II) Complexes

Chiral complexes formed by privileged phosphoramidites derived from chiral binol and optically pure Davies’ amines, and copper(II) triflate, silver(I) triflate or silver(I) benzoate are excellent catalysts for the general 1,3-dipolar cycloaddition between nitroalkenes and azomethine ylides generated from α-amino acid derived imino esters. These three methods can be conducted at room temperature to afford the exo-cycloadducts (4,5-trans-2,5-cis-4-nitroprolinates) with high diastereoselectivity and high enantioselectivity. In general, the three procedures are complementary but silver catalysts are more versatile and less sensitive to sterically congested starting materials.

An XMM-Newton view of FeKα in high-mass X-ray binaries

We present a comprehensive analysis of the whole sample of available XMM-Newton observations of high-mass X-ray binaries (HMXBs) until August 2013, focusing on the FeKα emission line. This line is key to better understanding the physical properties of the material surrounding the X-ray source within a few stellar radii (the circumstellar medium). We collected observations from 46 HMXBs and detected FeKα in 21 of them. We used the standard classification of HMXBs to divide the sample into different groups. We find that (1) different classes of HMXBs display different qualitative behaviours in the FeKα spectral region. This is visible especially in SGXBs (showing ubiquitous Fe fluorescence but not recombination Fe lines) and in γ Cass analogues (showing both fluorescent and recombination Fe lines). (2) FeKα is centred at a mean value of 6.42 keV. Considering the instrumental and fits uncertainties, this value is compatible with ionization states that are lower than Fe xviii. (3) The flux of the continuum is well correlated with the flux of the line, as expected. Eclipse observations show that the Fe fluorescence emission comes from an extended region surrounding the X-ray source. (4) We observe an inverse correlation between the X-ray luminosity and the equivalent width of FeKα (EW). This phenomenon is known as the X-ray Baldwin effect. (5) FeKα is narrow (σline< 0.15 keV), reflecting that the reprocessing material does not move at high speeds. We attempt to explain the broadness of the line in terms of three possible broadening phenomena: line blending, Compton scattering, and Doppler shifts (with velocities of the reprocessing material V ~ 1000 km s-1). (6) The equivalent hydrogen column (NH) directly correlates to the EW of FeKα, displaying clear similarities to numerical simulations. It highlights the strong link between the absorbing and the fluorescent matter. (7) The observed NH in supergiant X-ray binaries (SGXBs) is in general higher than in supergiant fast X-ray transients (SFXTs). We suggest two possible explanations: different orbital configurations or a different interaction compact object – wind. (8) Finally, we analysed the sources IGR J16320-4751 and 4U 1700-37 in more detail, covering several orbital phases. The observed variation in NH between phases is compatible with the absorption produced by the wind of their optical companions. The results clearly point to a very important contribution of the donor’s wind in the FeKα emission and the absorption when the donor is a supergiant massive star.

Cobalt-Impregnated Magnetite as General Heterogeneous Catalyst for the Hydroacylation Reaction of Azodicarboxylates

Catalysts consisting of cobalt and nickel impregnated on magnetite have been prepared, characterized and used for the hydroacylation reaction of different azodicarboxylate compounds with aldehydes, using nearly stoichiometric amounts of both reagents in only 3 h. Furthermore, this reaction has been conducted with the smallest amount of catalyst. The cobalt catalyst is stable enough to be removed by magnetic decantation and recycled ten-fold without any detrimental effect on the results.

Osmium impregnated on magnetite as a heterogeneous catalyst for the syn-dihydroxylation of alkenes

A new catalyst derived from osmium has been prepared, fully characterized and tested in the dihydroxylation of alkenes. The catalyst was prepared by wet impregnation methodology of OsCl3·3H2O on a commercial micro-magnetite surface. The catalyst allowed the reaction with one of the lowest osmium loadings for a heterogeneous catalyst and was selective for the monodihydroxylation of 1,5-dienes. Moreover, the catalyst was easily removed from the reaction medium by the simple use of a magnet. The selectivity of catalyst is very high with conversions up to 99%. Preliminary kinetics studies showed a first-order reaction rate with respect to the catalyst.

Modulation of the Silica Sol–Gel Composition for the Promotion of Direct Electron Transfer to Encapsulated Cytochrome c

The direct electron transfer between indium–tin oxide electrodes (ITO) and cytochrome c encapsulated in different sol–gel silica networks was studied. Cyt c@silica modified electrodes were synthesized by a two-step encapsulation method mixing a phosphate buffer solution with dissolved cytochrome c and a silica sol prepared by the alcohol-free sol–gel route. These modified electrodes were characterized by cyclic voltammetry, UV–vis spectroscopy, and in situ UV–vis spectroelectrochemistry. The electrochemical response of encapsulated protein is influenced by the terminal groups of the silica pores. Cyt c does not present electrochemical response in conventional silica (hydroxyl terminated) or phenyl terminated silica. Direct electron transfer to encapsulated cytochrome c and ITO electrodes only takes place when the protein is encapsulated in methyl modified silica networks.

Enhancement of the Electrochemical Performance of SWCNT dispersed in a Silica Sol-gel Matrix by Reactive Insertion of a Conducting Polymer

The electroassisted encapsulation of Single-Walled Carbon Nanotubes was performed into silica matrices (SWCNT@SiO2). This material was used as the host for the potentiostatic growth of polyaniline (PANI) to yield a hybrid nanocomposite electrode, which was then characterized by both electrochemical and imaging techniques. The electrochemical properties of the SWCNT@SiO2-PANI composite material were tested against inorganic (Fe3+/Fe2+) and organic (dopamine) redox probes. It was observed that the electron transfer constants for the electrochemical reactions increased significantly when a dispersion of either SWCNT or PANI was carried out inside of the SiO2 matrix. However, the best results were obtained when polyaniline was grown through the pores of the SWCNT@SiO2 material. The enhanced reversibility of the redox reactions was ascribed to the synergy between the two electrocatalytic components (SWCNTs and PANI) of the composite material.

From the boom to the crisis: changes in employment conditions of immigrants in Spain and their effects on mental health

Background: Migrant workers have been one of the groups most affected by the economic crisis. This study evaluates the influence of changes in employment conditions on the incidence of poor mental health of immigrant workers in Spain, after a period of 3 years, in context of economic crisis. Methods: Follow-up survey was conducted at two time points, 2008 and 2011, with a reference population of 318 workers from Colombia, Ecuador, Morocco and Romania residing in Spain. Individuals from this population who reported good mental health in the 2008 survey (n = 214) were interviewed again in 2011 to evaluate their mental health status and the effects of their different employment situations since 2008 by calculating crude and adjusted odds ratios (aORs) for sociodemographic and employment characteristics. Findings: There was an increased risk of poor mental health in workers who lost their jobs (aOR = 3.62, 95%CI: 1.64–7.96), whose number of working hours increased (aOR = 2.35, 95%CI: 1.02–5.44), whose monthly income decreased (aOR = 2.75, 95%CI: 1.08–7.00) or who remained within the low-income bracket. This was also the case for people whose legal status (permission for working and residing in Spain) was temporary or permanent compared with those with Spanish nationality (aOR = 3.32, 95%CI: 1.15–9.58) or illegal (aOR = 17.34, 95%CI: 1.96–153.23). In contrast, a decreased risk was observed among those who attained their registration under Spanish Social Security system (aOR = 0.10, 95%CI: 0.02–0.48). Conclusion: There was an increase in poor mental health among immigrant workers who experienced deterioration in their employment conditions, probably influenced by the economic crisis.

The “dehesa”, a key ecosystem in maintaining the diversity of Mediterranean saproxylic insects (Coleoptera and Diptera: Syrphidae)

The “dehesa” is a traditional Iberian agrosilvopastoral ecosystem characterized by the presence of old scattered trees that are considered as “keystone-structures”, which favor the presence of a wide range of biodiversity. We show the high diversity of saproxylic beetles and syrphids (Diptera) in this ecosystem, including red-listed species. We analyzed whether saproxylic species distribution in the “dehesa” was affected by tree density per hectare, dominant tree species or vegetation coverage. Species diversity did not correlate with tree density; however, it was affected by tree species and shrub coverage but in a different way for each taxon. The highest beetle diversity was linked to Quercus pyrenaica, the most managed tree species, with eight indicator species. In contrast, Q. rotundifolia hosted more species of saproxylic syrphids. Regarding vegetation coverage, shrub coverage was the only variable that affected insect richness, again in a different way for both taxa. In contrast, beetle species composition was only affected by dominant tree species whereas syrphid species composition was not affected by tree species or shrub coverage. We concluded that the high diversity of saproxylic insects in the “dehesa” is related to its long history of agrosilvopastoral management, which has generated landscape heterogeneity and preserved old mature trees. However, the richness and composition of different taxa of insects respond in different ways to tree species and vegetation coverage. Consequently, conservation strategies should try to maintain traditional management, and different saproxylic taxa should be used to monitor the effect of management on saproxylic diversity.

Microwave-Enhanced Asymmetric Transfer Hydrogenation of N-(tert-Butylsulfinyl)imines

Microwave irradiation has considerably enhanced the efficiency of the asymmetric transfer hydrogenation of N-(tert-butylsulfinyl)imines in isopropyl alcohol catalyzed by a ruthenium complex bearing the achiral ligand 2-amino-2-methylpropan-1-ol. In addition to shortening reaction times for the transfer hydrogenation processes to only 30 min, the amounts of ruthenium catalyst and isopropyl alcohol can be considerably reduced in comparison with our previous procedure assisted by conventional heating, which diminishes the environmental impact of this new protocol. This methodology can be applied to aromatic, heteroaromatic and aliphatic N-(tert-butylsulfinyl)ketimines, leading, after desulfinylation, to the expected primary amines in excellent yields and with enantiomeric excesses of up to 96 %.

The donor star of the X-ray pulsar X1908+075

High-mass X-ray binaries consist of a massive donor star and a compact object. While several of those systems have been well studied in X-rays, little is known for most of the donor stars as they are often heavily obscured in the optical and ultraviolet regime. There is an opportunity to observe them at infrared wavelengths, however. The goal of this study is to obtain the stellar and wind parameters of the donor star in the X1908+075 high-mass X-ray binary system with a stellar atmosphere model to check whether previous studies from X-ray observations and spectral morphology lead to a sufficient description of the donor star. We obtained H- and K-band spectra of X1908+075 and analysed them with the Potsdam Wolf-Rayet (PoWR) model atmosphere code. For the first time, we calculated a stellar atmosphere model for the donor star, whose main parameters are: Mspec = 15 ± 6 M⊙, T∗ = 23-3+6 kK, log geff = 3.0 ± 0.2 and log L/L⊙ = 4.81 ± 0.25. The obtained parameters point towards an early B-type (B0–B3) star, probably in a supergiant phase. Moreover we determined a more accurate distance to the system of 4.85 ± 0.50 kpc than the previously reported value.

Singular Temperatures Connected to Charge Transport Mechanism Transitions in Perylene Bisimides from Steady-State Photocurrent Measurements

Perylene bisimides (PBIs) are n-type semiconducting and photogenerating materials widely used in a variety of optoelectronic devices. Particularly interesting are PBIs that are simultaneously water-soluble and liquid-crystalline (PBI-W+LC) and, thus, attractive for the development of high-performing easily processable applications in biology and “green” organic electronics. In this work, singular temperatures connected to charge transport mechanism transitions in a PBI-W+LC derivative are determined with high accuracy by means of temperature-dependent photocurrent studies. These singular temperatures include not only the ones observed at 60 and 110 °C, corresponding to phase transition temperatures from crystalline to liquid-crystalline (LC) and from LC to the isotropic phase, respectively, as confirmed by differential scanning calorimetry (DSC), but also a transition at 45 °C, not observed by DSC. By analyzing the photocurrent dependence simultaneously on temperature and on light intensity, this transition is interpreted as a change from monomolecular to bimolecular recombination. These results might be useful for other semiconducting photogenerating materials, not necessarily PBIs or even organic semiconductors, which also show transport behavior changes at singular temperatures not connected with structural or phase transitions.

Palladium and Bimetallic Palladium–Nickel Nanoparticles Supported on Multiwalled Carbon Nanotubes: Application to Carbon–Carbon Bond-Forming Reactions in Water

Palladium and bimetallic Pd–Ni nanoparticles (NPs) protected by polyvinylpyrrolidone were prepared by the reduction-by-solvent method and deposited on multiwalled carbon nanotubes (MWCNTs). The catalytic activity of these NPs to carbon–carbon bond-forming reactions was studied by using 0.1 mol % Pd loading, at 120 °C for 1 h and water as a solvent under ligand-free conditions. The Suzuki–Miyaura reaction took place quantitatively for the cross-coupling of 4-bromoanisole with phenylboronic acid, better than those obtained with potassium phenyltrifluoroborate, with Pd50Ni50/MWCNTs as a catalyst and K2CO3 as a base and TBAB as an additive, with good recyclability during 4 cycles with some Ni leaching. The Hiyama reaction of 4-iodoanisole with trimethoxyphenylsilane, under fluoride-free conditions using 50 % aqueous NaOH solution, was performed with Pd/MWCNTs as a catalyst in 83 % yield with low recyclability. For the Mizoroki-Heck reaction 4-iodoanisole and styrene gave the corresponding 4-methoxystilbene quantitatively with Pd50Ni50/MWCNTs using K2CO3 as a base and TBAB as an additive although the recycle failed. In the case of the Sonogashira-Hagihara reaction, Pd/MWCNTs had to be used as a catalyst and pyrrolidine as a base for the coupling of 4-iodoanisole with phenylacetylene under copper-free conditions. The corresponding 4-methoxytolane was quantitatively obtained allowing the recycling of the catalyst during 3 cycles.

Electrochemical behaviour of activated carbons obtained via hydrothermal carbonization

Activated carbons were prepared by chemical activation of hydrochars, obtained by hydrothermal carbonisation (HTC) using low cost and abundant precursors such as rye straw and cellulose, with KOH. Hydrochars derived from rye straw were chemically activated using different KOH/precursor ratios, in order to assess the effect of this parameter on their electrochemical behaviour. In the case of cellulose, the influence of the hydrothermal carbonisation temperature was studied by fixing the activating agent/cellulose ratio. Furthermore, N-doped activated carbons were synthesised by KOH activation of hydrochars prepared by HTC from a mixture of glucose with melamine or glucosamine. In this way, N-doped activated carbons were prepared in order to evaluate the influence of nitrogen groups on their electrochemical behaviour in acidic medium. The results showed that parameters such as chemical activation or carbonisation temperature clearly affect the capacitance, since these parameters play a key role in the textural properties of activated carbons. Finally, symmetric capacitors based on activated carbon and N-doped activated carbon were tested at 1.3 V in a two-electrode cell configuration and the results revealed that N-groups improved the capacitance at high current density.

Enantioselective Solvent-Free Synthesis of 3-Alkyl-3-hydroxy-2-oxoindoles Catalyzed by Binam-Prolinamides

BINAM-prolinamides are very efficient catalyst for the synthesis of non-protected and N-benzyl isatin derivatives by using an aldol reaction between ketones and isatins under solvent-free conditions. The results in terms of diastereo- and enantioselectivities are good, up to 99% de and 97% ee, and higher to those previously reported in the literature under similar reaction conditions. A high variation of the results is observed depending on the structure of the isatin and the ketone used in the process. While 90% of ee and 97% ee, respectively, is obtained by using (Ra)-BINAM-l-(bis)prolinamide as catalyst in the addition of cyclohexanone and α-methoxyacetone to free isatin, 90% ee is achieved for the reaction between N-benzyl isatin and acetone using N-tosyl BINAM-l-prolinamide as catalyst. This reaction is also carried out using a silica BINAM-l-prolinamide supported catalyst under solvent-free conditions, which can be reused up to five times giving similar results.

Orbital phase-resolved spectroscopy of 4U 1538−52 with MAXI

Context. 4U 1538−52, an absorbed high mass X-ray binary with an orbital period of ~3.73 days, shows moderate orbital intensity modulations with a low level of counts during the eclipse. Several models have been proposed to explain the accretion at different orbital phases by a spherically symmetric stellar wind from the companion. Aims. The aim of this work is to study both the light curve and orbital phase spectroscopy of this source in the long term. In particular, we study the folded light curve and the changes in the spectral parameters with orbital phase to analyse the stellar wind of QV Nor, the mass donor of this binary system. Methods. We used all the observations made from the Gas Slit Camera on board MAXI of 4U 1538−52 covering many orbits continuously. We obtained the good interval times for all orbital phase ranges, which were the input for extracting our data. We estimated the orbital period of the system and then folded the light curves, and we fitted the X-ray spectra with the same model for every orbital phase spectrum. We also extracted the averaged spectrum of all the MAXI data available. Results. The MAXI spectra in the 2–20 keV energy range were fitted with an absorbed Comptonisation of cool photons on hot electrons. We found a strong orbital dependence of the absorption column density but neither the fluorescence iron emission line nor low energy excess were needed to fit the MAXI spectra. The variation in the spectral parameters over the binary orbit were used to examine the mode of accretion onto the neutron star in 4U 1538−52. We deduce a best value of Ṁ/v∞ = 0.65 × 10-9M⊙ yr-1/ (km s-1) for QV Nor.