Can a synthetic thread act as an electrochemically switchable molecular device?

Here we report that at room temperature in acetonitrile after the reduction of the naphthalimide-site, a synthetic molecular thread undergoes a complete conformational change which makes possible an efficient conversion of chemical energy into mechanical work; such results point out the ability of the thread to act as a molecular device under electrochemical control.     

A macroporous polymer-supported cyclic anhydride for efficient sequestration of amines

The efficient removal of primary and secondary amines from organic solutions using a macroporous polymer-supported anhydride is described. The sequestering of primary amines by the anhydride via polymer-bound amide formation is completed within 2-4 h at room temperature. Secondary amines require typically 4 h for complete sequestration.     

Improved parameterization of the quantum harmonic oscillator model based on localized wannier functions to describe Van der Waals interactions in density functional theory

Recently, the quantum harmonic oscillator model has been combined with maximally localized Wannier functions to account for long‐range dispersion interactions in density functional theory calculations (Silvestrelli, J. Chem. Phys. 2013, 139, 054106). Here, we present a new, improved set of values for the three parameters involved in this scheme. To test the new parameter set we have computed the potential energy curves for various systems, including an isolated Ar2 dimer, two N2 dimers interacting within different configurations, and a water molecule physisorbed on pristine graphene. While the original set of parameters generally overestimates the interaction energies and underestimates the equilibrium distances, the new parameterization substantially improves the agreement with experimental and theoretical reference values. © 2016 Wiley Periodicals, Inc.     

High temperature superconductivity in sulfur and selenium hydrides at high pressure

Due to its low atomic mass, hydrogen is the most promising element to search forhigh-temperature phononic superconductors. However, metallic phases of hydrogen are onlyexpected at extreme pressures (400 GPa or higher). The measurement of the recordsuperconducting critical temperature of 203 K in a hydrogen-sulfur compound at 160 GPa ofpressure [A.P. Drozdov, M.I. Eremets, I.A. Troyan, arXiv:1412.0460[cond-mat.supr-con] (2014); A.P. Drozdov, M.I. Eremets, I.A. Troyan, V.Ksenofontov, S.I. Shylin, Nature 525, 73 (2015)], shows that metallization ofhydrogen can be reached at significantly lower pressure by inserting it in the matrix ofother elements. In this work we investigate the phase diagram and the superconductingproperties of the H-S systems by means of minima hopping method for structure predictionand density functional theory for superconductors. We also show that Se-H has a similarphase diagram as its sulfur counterpart as well as high superconducting criticaltemperature. We predict H₃Se to exceed 120 K superconductivity at 100 GPa. We showthat both H₃Se andH₃S, due to thecritical temperature and peculiar electronic structure, present rather unusualsuperconducting properties.     

An efficient LDA+U based tight binding approach

The functionals usually applied in DFT calculations have deficiencies in describing systems with strongly localized electrons such as transition metals or rare earth (RE) compounds. In this work, we present the self-consistent charge density based functional tight binding (SCC-DFTB) calculation scheme including LDA+U like potentials and apply it for the simulation of RE-doped GaN. DFTB parameters for the simulation of GaN and a selection of rare earth ions, where the f electrons were explicitly included in the valence, have been created. The results of the simulations were tested against experimental data (where present) and against various more sophisticated but computationally more costly DFT calculations. Our approach is found to correctly reproduce the geometry and the energetic of the studied systems.     

Analysis of the photon–photon resonance influence on the direct modulation bandwidth of dual-longitudinal-mode distributed feedback lasers

The paper explores the possibilities to extend the direct modulation bandwidth in dual-longitudinal-mode distributed feedback lasers by exploiting the photon–photon resonance induced by the interaction of the two modes in the laser cavity. The effects on the direct amplitude modulation and on the direct modulation of the difference frequency between the two modes are analyzed using simulation and experimental results. When the photon–photon resonance, which occurs at the difference frequency between the two modes, is properly placed at a higher frequency than the carrier-photon resonance, the small-signal amplitude modulation (AM) bandwidth of the laser can be significantly increased. However, both simulations and experiments point out that a high small-signal AM bandwidth does not lead to a high large-signal AM bandwidth if the small-signal modulation response has significant variations across the modulation bandwidth. The paper shows that a high large-signal AM bandwidth is obtained when the two modes are significantly unbalanced, whereas a high-bandwidth difference frequency modulation can be best detected when the two modes are balanced and the DC bias is properly chosen.     

Improved rapid assay of plasma uric acid by short-end injection capillary zone electrophoresis

A rapid and simple short-end injection capillary zone electrophoresis method was developed for the quantification of plasma uric acid. The separation was performed in an uncoated fused-silica capillary (50 μm ID, 60 cm total length, 10.2 cm effective length) by using as a background electrolyte a 75 mmol/L glycylglycine solution titrated with NaOH 5 mol/L to pH 9.0, a voltage of 28 kV, a cartridge temperature of 15 °C, and direct UV detection at 292 nm. Under optimized conditions, uric acid was determinate in little more than 1 min (1.076 minutes). In order to verify the accuracy of the analysis, urate levels were measured in 543 apparently healthy volunteers by the new assay and our previous method, and the obtained data were compared by Passing–Bablock regression, Bland–Altman test, and a new regression-based approach, which showed a good agreement between two methods.     

Temperature and solvent structure dependence of VO2+ complexes of pyridine-N-oxide derivatives and their interaction with human serum transferrin

The behaviour of the systems formed by VO(2+), 2-hydroxypyridine-N-oxide (Hhpo) and 2-mercaptopyridine-N-oxide (Hmpo) was studied both in solution and in the solid state through the combined application of spectroscopic (EPR and UV-Vis spectroscopy) and DFT methods. The geometry of solid bis-chelated complexes [VOL(2)], with L = hpo and mpo, is square pyramidal, but it can change to cis-[VOL(2)S], where S is a solvent molecule, when these are dissolved in a coordinating solvent. The equilibrium between the square pyramidal and cis-octahedral forms is strongly affected by solvent and temperature. At room temperature, the predominant species is [VOL(2)], which gives a pink colour to the solutions; at lower temperatures, the equilibrium is shifted--partially or completely--toward the formation of cis-[VOL(2)S], which is green. In an acidic environment and in the presence of an excess of ligand, [VOL(2)] can transform into the tris-chelated complex [VL(3)](+), in which vanadium loses the oxido ligand and adopts a hexa-coordinated geometry intermediate between octahedral and trigonal prismatic. 1-Methylimidazole (1-MeIm), which represents a model for His-N coordination, forms mixed complexes with stoichiometry cis-[VOL(2)(1-MeIm)], occupying an equatorial position. In the ternary systems VO(2+)-Hhpo-hTf and VO(2+)-Hmpo-hTf at room temperature and pH 7.4, besides (VO)hTf and (VO)(2)hTf, the mixed species cis-VO(hpo)(2)(hTf) and VO(mpo)(hTf) are observed, with the equatorial binding of an accessible histidine residue. Finally, the contribution of the N-oxide group to (51)V A(z) and A(iso) hyperfine coupling constants, which can be important in the characterisation of similar species, is discussed.