Magnetic phase diagram of Fe1.1Te1-xSex: A comparative study with the stoichiometric superconducting FeTe1-xSex system

We report a comparative study of the series Fe1.1Te1-xSex and the stoichiometric FeTe1-xSex to bring out the difference in their magnetic, superconducting and electronic properties. The Fe1.1Te1-xSex series is found to be magnetic and its microscopic properties are elucidated through Moessbauer spectroscopy. The magnetic phase diagram of Fe1.1Te1-xSex is traced out and it shows the emergence of spin-glass state when the antiferromagnetic state is destabilized by the Se substitution. The isomer shift and quadrupolar splitting obtained from the Moessbauer spectroscopy clearly brings out the electronic differences in these two series.Comment: 6 pages, 9 figure

On the group theoretic structure of a class of quantum dialogue protocols

Intrinsic symmetry of the existing protocols of quantum dialogue are explored. It is shown that if we have a set of mutually orthogonal $n$-qubit states {\normalsize $\{|\phi_{0}>,|\phi_{1}>,....,|\phi_{i}\}$ and a set of $m-qubit$ ($m\leq n$) unitary operators $\{U_{0},U_{2},...,U_{2^{n}-1}\}:U_{i}|\phi_{0}>=|\phi_{i}>$ and $\{U_{0},U_{2},...,U_{2^{n}-1}\}$ forms a group under multiplication then it would be sufficient to construct a quantum dialogue protocol using this set of quantum states and this group of unitary operators}. The sufficiency condition is used to provide a generalized protocol of quantum dialogue. Further the basic concepts of group theory and quantum mechanics are used here to systematically generate several examples of possible groups of unitary operators that may be used for implementation of quantum dialogue. A large number of examples of quantum states that may be used to implement the generalized quantum dialogue protocol using these groups of unitary operators are also obtained. For example, it is shown that GHZ state, GHZ-like state, W state, 4 and 5 qubit Cluster states, Omega state, Brown state, $Q_{4}$ state and $Q_{5}$ state can be used for implementation of quantum dialogue protocol. The security and efficiency of the proposed protocol is appropriately analyzed. It is also shown that if a group of unitary operators and a set of mutually orthogonal states are found to be suitable for quantum dialogue then they can be used to provide solutions of socialist millionaire problem.Comment: 15 page

Ecotoxicological impacts of landfill sites: Towards risk assessment, mitigation policies and the role of artificial intelligence.

Waste disposal in landfills remains a global concern. Despite technological developments, landfill leachate poses a hazard to ecosystems and human health since it acts as a secondary reservoir for legacy and emerging pollutants. This study provides a systematic and scientometric review of the nature and toxicity of pollutants generated by landfills and means of assessing their potential risks. Regarding human health, unregulated waste disposal and pathogens in leachate are the leading causes of diseases reported in local populations. Both in vitro and in vivo approaches have been employed in the ecotoxicological risk assessment of landfill leachate, with model organisms ranging from bacteria to birds. These studies demonstrate a wide range of toxic effects that reflect the complex composition of leachate and geographical variations in climate, resource availability and management practices. Based on bioassay (and other) evidence, categories of persistent chemicals of most concern include brominated flame retardants, per- and polyfluorinated chemicals, pharmaceuticals and alkyl phenol ethoxylates. However, the emerging and more general literature on microplastic toxicity suggests that these particles might also be problematic in leachate. Various mitigation strategies have been identified, with most focussing on improving landfill design or leachate treatment, developing alternative disposal methods and reducing waste volume through recycling or using more sustainable materials. The success of these efforts will rely on policies and practices and their enforcement, which is seen as a particular challenge in developing nations and at the international (and transboundary) level. Artificial intelligence and machine learning afford a wide range of options for evaluating and reducing the risks associated with leachates and gaseous emissions from landfills, and various approaches tested or having potential are discussed. However, addressing the limitations in data collection, model accuracy, real-time monitoring and our understanding of environmental impacts will be critical for realising this potential

Structural and Mechanistic Insights into Hemoglobincatalyzed Hydrogen Sulfide Oxidation and the Fate of Polysulfide Products

Hydrogen sulfide is a cardioprotective signaling molecule but is toxic at elevated concentrations. Red blood cells can synthesize H2S but, lacking organelles, cannot dispose of H2S via the mitochondrial sulfide oxidation pathway. We have recently shown that at high sulfide concentrations, ferric hemoglobin oxidizes H2S to a mixture of thiosulfate and iron-bound polysulfides in which the latter species predominates. Here, we report the crystal structure of human hemoglobin containing low spin ferric sulfide, the first intermediate in heme-catalyzed sulfide oxidation. The structure provides molecular insights into why sulfide is susceptible to oxidation in human hemoglobin but is stabilized against it in HbI, a specialized sulfide-carrying hemoglobin from a mollusk adapted to life in a sulfide-rich environment. We have also captured a second sulfide bound at a postulated ligand entry/exit site in the α-subunit of hemoglobin, which, to the best of our knowledge, represents the first direct evidence for this site being used to access the heme iron. Hydrodisulfide, a postulated intermediate at the junction between thiosulfate and polysulfide formation, coordinates ferric hemoglobin and, in the presence of air, generated thiosulfate. At low sulfide/heme iron ratios, the product distribution between thiosulfate and iron-bound polysulfides was approximately equal. The iron-bound polysulfides were unstable at physiological glutathione concentrations and were reduced with concomitant formation of glutathione persulfide, glutathione disulfide, and H2S. Hence, although polysulfides are unlikely to be stable in the reducing intracellular milieu, glutathione persulfide could serve as a persulfide donor for protein persulfidation, a posttranslational modification by which H2S is postulated to signal

Structural and Mechanistic Insights into Hemoglobincatalyzed Hydrogen Sulfide Oxidation and the Fate of Polysulfide Products

Hydrogen sulfide is a cardioprotective signaling molecule but is toxic at elevated concentrations. Red blood cells can synthesize H2S but, lacking organelles, cannot dispose of H2S via the mitochondrial sulfide oxidation pathway. We have recently shown that at high sulfide concentrations, ferric hemoglobin oxidizes H2S to a mixture of thiosulfate and iron-bound polysulfides in which the latter species predominates. Here, we report the crystal structure of human hemoglobin containing low spin ferric sulfide, the first intermediate in heme-catalyzed sulfide oxidation. The structure provides molecular insights into why sulfide is susceptible to oxidation in human hemoglobin but is stabilized against it in HbI, a specialized sulfide-carrying hemoglobin from a mollusk adapted to life in a sulfide-rich environment. We have also captured a second sulfide bound at a postulated ligand entry/exit site in the α-subunit of hemoglobin, which, to the best of our knowledge, represents the first direct evidence for this site being used to access the heme iron. Hydrodisulfide, a postulated intermediate at the junction between thiosulfate and polysulfide formation, coordinates ferric hemoglobin and, in the presence of air, generated thiosulfate. At low sulfide/heme iron ratios, the product distribution between thiosulfate and iron-bound polysulfides was approximately equal. The iron-bound polysulfides were unstable at physiological glutathione concentrations and were reduced with concomitant formation of glutathione persulfide, glutathione disulfide, and H2S. Hence, although polysulfides are unlikely to be stable in the reducing intracellular milieu, glutathione persulfide could serve as a persulfide donor for protein persulfidation, a posttranslational modification by which H2S is postulated to signal

Structural and Mechanistic Insights into Hemoglobincatalyzed Hydrogen Sulfide Oxidation and the Fate of Polysulfide Products

Hydrogen sulfide is a cardioprotective signaling molecule but is toxic at elevated concentrations. Red blood cells can synthesize H2S but, lacking organelles, cannot dispose of H2S via the mitochondrial sulfide oxidation pathway. We have recently shown that at high sulfide concentrations, ferric hemoglobin oxidizes H2S to a mixture of thiosulfate and iron-bound polysulfides in which the latter species predominates. Here, we report the crystal structure of human hemoglobin containing low spin ferric sulfide, the first intermediate in heme-catalyzed sulfide oxidation. The structure provides molecular insights into why sulfide is susceptible to oxidation in human hemoglobin but is stabilized against it in HbI, a specialized sulfide-carrying hemoglobin from a mollusk adapted to life in a sulfide-rich environment. We have also captured a second sulfide bound at a postulated ligand entry/exit site in the α-subunit of hemoglobin, which, to the best of our knowledge, represents the first direct evidence for this site being used to access the heme iron. Hydrodisulfide, a postulated intermediate at the junction between thiosulfate and polysulfide formation, coordinates ferric hemoglobin and, in the presence of air, generated thiosulfate. At low sulfide/heme iron ratios, the product distribution between thiosulfate and iron-bound polysulfides was approximately equal. The iron-bound polysulfides were unstable at physiological glutathione concentrations and were reduced with concomitant formation of glutathione persulfide, glutathione disulfide, and H2S. Hence, although polysulfides are unlikely to be stable in the reducing intracellular milieu, glutathione persulfide could serve as a persulfide donor for protein persulfidation, a posttranslational modification by which H2S is postulated to signal

Solar twins in M67

The discovery of true solar analogues is fundamental for a better understanding of the Sun and of the solar system. The open cluster M67 offers a unique opportunity to search for solar analogues because its chemical composition and age are very similar to those of the Sun. We analyze FLAMES spectra of a large number of M67 main sequence stars to identify solar analogues in this cluster.We first determine cluster members which are likely not binaries, by combining proper motions and radial velocity measurements. We concentrate our analysis on the determination of stellar effective temperature, using analyses of line-depth ratios and H$\alpha$ wings, making a direct comparison with the solar spectrum obtained with the same instrument. We also compute the lithium abundance for all the stars.Ten stars have both the temperature derived by line-depth ratios and H$\alpha$ wings within 100 K from the Sun. From these stars we derive, assuming a cluster reddening $E(B-V)=0.041$, the solar colour $(B-V)_\odot=0.649\pm0.016$ and a cluster distance modulus of 9.63. Five stars are most similar (within 60 K) to the Sun and candidates to be true solar twins. These stars have also a low Li content, comparable to the photospheric abundance of the Sun, likely indicating a similar mixing evolution. We find several candidates for the best solar analogues ever. These stars are amenable to further spectroscopic investigations and planet search. The solar colours are determined with rather high accuracy with an independent method, as well as the cluster distance modulus.Comment: 13pages and 8 figures, accepted for publication in A&

Sn nanoparticles on gas diffusion electrodes: Synthesis, characterization and use for continuous CO2 electroreduction to formate

Electrochemical reduction of CO2 has been pointed out as an interesting strategy to convert CO2 into useful chemicals. In addition, coupling CO2 electroreduction with renewable energies would allow storing electricity from intermittent renewable sources such as wind or solar power. In this work, an easy and fast method is adapted for the synthesis of pure and carbon supported Sn nanoparticles. The resulting nanoparticles have been characterized by transmission electron microscopy and their electrocatalytic properties towards CO2 reduction evaluated by cyclic voltammetry. Carbon supported Sn nanoparticles have been subsequently used to prepare Gas Diffusion Electrodes (Sn/C-GDEs). The electrodes have been characterized by scanning electron microscopy and also by cyclic voltammetry. Finally, the electrodes were tested on a continuous and single pass CO2 electroreduction filter-press type cell system in aqueous solution, to obtain formate at ambient pressure and temperature. These Sn/C-GDEs allow working at high current densities with low catholyte flow. Thus, for instance, at 150 mA cm−2, a 70% Faradaic Efficiency (FE) was obtained with a formate concentration of 2.5 g L−1. Interestingly, by increasing the current density to 200 mA cm−2 and decreasing the flow rate, a concentration over 16 g L−1 was reached. Despite the high concentrations obtained, further research is still required to keep high FE operating at high current densities.This work was conducted under the framework of the Spanish Ministry of Economy and Competitiveness projects CTQ2013-48280-C3-1-R and CTQ2013-48280-C3-3-R. Andrés Del Castillo also acknowledges the research grant from University of Cantabria, co-financed by the Regional Government of Cantabria

Synthesis of a Novel Type of 2,3'-BIMs via Platinum-Catalysed Reaction of Indolylallenes with Indoles

Optimisation, scope and mechanism of the platinum-catalysed addition of indoles to indolylallenes is reported here to give 2,3'-BIMs with a novel core structure very relevant for pharmaceutical industry. The reaction is modulated by the electronic properties of the substituents on both indoles, with the 2,3'-BIMs favoured when electron donating groups are present. Although simple at first, a complex mechanism has been uncovered that explains the different behaviour of these systems with platinum when compared with other metals (e.g. gold). Detailed labelling studies have shown Pt-catalysed 6-endo-trig cyclisation of the indollylallene as the first step of the reaction and the involvement of two cyclic vinyl-platinum intermediates in equilibrium through a platinum carbene, as the key intermediates of the catalytic cycle towards the second nucleophilic attack and formation of the BIMs