Electrically Switchable Magnetic Molecules: Inducing a Magnetic Coupling by Means of an External Electric Field in a Mixed‐Valence Polyoxovanadate Cluster

Herein we evaluate the influence of an electric field on the coupling of two delocalized electrons in the mixed‐valence polyoxometalate (POM) [GeV₁₄O₄₀]^8? (in short V₁₄) by using both a t‐J model Hamiltonian and DFT calculations. In absence of an electric field the compound is paramagnetic, because the two electrons are localized on different parts of the POM. When an electric field is applied, an abrupt change of the magnetic coupling between the two delocalized electrons can be induced. Indeed, the field forces the two electrons to localize on nearest‐neighbors metal centers, leading to a very strong antiferromagnetic coupling. Both theoretical approaches have led to similar results, emphasizing that the sharp spin transition induced by the electric field in the V₁₄ system is a robust phenomenon, intramolecular in nature, and barely influenced by small changes on the external structure.     

Mechanistic Elucidations of Highly Dispersed Metalloporphyrin Metal-Organic Framework Catalysts for CO2 Electroreduction

Immobilization of porphyrin complexes into crystalline metal–organic frameworks (MOFs) enables high exposure of porphyrin active sites for CO₂ electroreduction. Herein, well-dispersed iron-porphyrin-based MOF (PCN-222(Fe)) on carbon-based electrodes revealed optimal turnover frequencies for CO₂ electroreduction to CO at 1 wt.% catalyst loading, beyond which the intrinsic catalyst activity declined due to CO₂ mass transport limitations. In situ Raman suggested that PCN-222(Fe) maintained its structure under electrochemical bias, permitting mechanistic investigations. These revealed a stepwise electron transfer-proton transfer mechanism for CO₂ electroreduction on PCN-222(Fe) electrodes, which followed a shift from a rate-limiting electron transfer to CO₂ mass transfer as the potential increased from −0.6 V to −1.0 V vs. RHE. Our results demonstrate how intrinsic catalytic investigations and in situ spectroscopy are needed to elucidate CO₂ electroreduction mechanisms on PCN-222(Fe) MOFs.     

A Mononuclear Uranium(IV) Single‐Molecule Magnet with an Azobenzene Radical Ligand

A tetravalent uranium compound with a radical azobenzene ligand, namely, [{(SiMe₂NPh)₃‐tacn}U^IV(η²‐N₂Ph₂^.)] ( 2 ), was obtained by one‐electron reduction of azobenzene by the trivalent uranium compound [U^III{(SiMe₂NPh)₃‐tacn}] ( 1 ). Compound 2 was characterized by single‐crystal X‐ray diffraction and ¹H NMR, IR, and UV/Vis/NIR spectroscopy. The magnetic properties of 2 and precursor 1 were studied by static magnetization and ac susceptibility measurements, which for the former revealed single‐molecule magnet behaviour for the first time in a mononuclear U^IV compound, whereas trivalent uranium compound 1 does not exhibit slow relaxation of the magnetization at low temperatures. A first approximation to the magnetic behaviour of these compounds was attempted by combining an effective electrostatic model with a phenomenological approach using the full single‐ion Hamiltonian.     

Discrimination of Beers by Cyclic Voltammetry Using a Single Carbon Screen-printed Electrode

A fast, simple and costless methodology without sample pre-treatment is proposed for the discrimination of beers. It is based on cyclic voltammetry (CV) using commercial carbon screen-printed electrodes (SPCE) and includes a correction of the signals measured with different SPCE units. Data are submitted to partial least squares discriminant analysis (PLS−DA) and support vector machine discriminant analysis (SVM−DA), which allow a reasonable classification of the beers. Also, CV data from beers can be used to predict their alcoholic degree by partial least squares (PLS) and artificial neural networks (ANN). In general, non-linear methods provide better results than linear ones.     

Life and health insurance behaviour of individuals having undergone a predictive genetic testing programme for hereditary non-polyposis colorectal cancer

Objective and Methods: We describe the insurance behaviour of subjects (n=271) who had previously taken a predictive genetic test for hereditary non-polyposis colorectal cancer (HNPCC); 31% of them were mutation positive, indicating a high risk of cancer. One year after testing, subjects were sent a questionnaire including questions about their present life and health insurance before participation in the study, and their actual and planned purchase of the insurance policies during the testing programme which compromised a pre-test counseling session, a period for reflection, the testing, and a test disclosure session. Results: Thirty percent reported that they already had a life insurance and 14% a health insurance before participating in the study. The mutation-positive subjects possessed a health insurance significantly more often than the mutation-negative individuals (21 vs. 11%, p=0.02) and similar trend was observed for life insurance (36 vs. 28%, p=0.12). Life and health insurance policies purchased just before testing was reported by 3 and 2% of the subjects, respectively. Life and health insurance policies purchased after testing were reported by 3 and <1% respectively, and planned purchase by 3 and 2%, respectively. No statistically significant differences were found between the groups defined by mutation status in reports of life or health insurance behaviour during or after the programme. Conclusion: According to self-reported data, the mutation-positive subjects did not differ from the others in the purchase of life or health insurance policies. However, the mutation-positive individuals reported that they possessed health insurance policies before entering the study more often than their counterparts.     

Structural and transport properties of Sn–Mg alloys

In this work, the structural and transport properties of Mg-doped Sn-based alloys have been investigated. The temperature-dependent transport and structural properties of Sn–Mg alloys were investigated for five different samples (Pure Sn, Sn-1.0 wt% Mg, Sn-2.0 wt% Mg, Sn-6.0 wt% Mg and Pure Mg). Scanning electron microscopy (SEM), X-ray diffraction and energy dispersive X-ray analysis measurements were carried out in order to clarify the structural properties of the samples. It was found that the samples had tetragonal crystal symmetry, except for pure Mg which had hexagonal crystal symmetry. We also found that the cell parameters changed slightly with the addition of Mg element. The SEM micrographs of the samples showed that they had smooth surfaces with a clear grain boundary. The electrical and thermal conductivity of the samples were measured by four-point probe and the radial heat flow method, respectively. The electrical resistivity of the samples increased almost linearly with the increasing temperature. The thermal conductivity values ranged between 0.60 and 1.00 W/Km, while they decreased slightly with temperature and increased with Mg composition. The thermal conductivity values of the alloys were in between the values of pure Sn and Mg. The thermal conductivity results of the alloys were compared with other available results, and a good agreement was seen between the results. In addition, the temperature coefficients of electrical resistivity and thermal conductivity were determined; these were independent of the composition of the alloying elements.     

Synthesis of polyester from renewable feedstock: a comparison between microwave and conventional heating

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