A Happy Get-Together – Probing Electrochemical Interfaces by Non-Linear Vibrational Spectroscopy

Electrochemical interfaces are key structures in energy storage and catalysis. Hence, a molecular understanding of the active sites at these interfaces, their solvation, the structure of adsorbates, and the formation of solid-electrolyte interfaces are crucial for an in-depth mechanistic understanding of their function. Vibrational sum-frequency generation (VSFG) spectroscopy has emerged as an operando spectroscopic technique to monitor complex electrochemical interfaces due to its intrinsic interface sensitivity and chemical specificity. Thus, this review discusses the happy get-together between VSFG spectroscopy and electrochemical interfaces. Methodological approaches for answering core issues associated with the behavior of adsorbates on electrodes, the structure of solvent adlayers, the transient formation of reaction intermediates, and the emergence of solid electrolyte interphase in battery research are assessed to provide a critical inventory of highly promising avenues to bring optical spectroscopy to use in modern material research in energy conversion and storage.     

Tuning the Structure and Properties of N-doped Positively Charged Polycyclic Aromatic Hydrocarbons

A detailed study of the geometry, aromatic character, electronic and magnetic properties for a series of positively charged N-doped polycyclic aromatic hydrocarbons (PAHs) was performed. Magnetic properties of the examined molecules were analyzed by means of the magnetically induced current density calculated using the diamagnetic-zero version of the continuous transformation of origin of current density (CTOCD-DZ) method. The comparative study of the local aromaticity of the studied molecules was performed using several different indices: energy effect (ef), harmonic oscillator model of aromaticity (HOMA) index, six centre delocalization index (SCI) and nucleus independent chemical shifts (NICS). The presence of N-atoms in the inner rings was found to cause a planarity distortion in the studied N-doped systems. The geometric changes and charged nature of the studied N-doped systems do not significantly influence the current density and the local aromaticity distribution in comparison with the corresponding parent benzenoid hydrocarbons. The present study demonstrates how quantum chemical calculations can be used for rational design of novel PAHs and for fine tuning of their properties.     

Competing symmetries and broken bonds in superconducting vortex-antivortex molecular crystals

Hall probe microscopy has been used to image vortex-antivortex molecules induced in superconducting Pb films by the stray fields from square arrays of magnetic dots. We have directly observed spontaneous vortex-antivortex pairs and studied how they interact with added free (anti)fluxons in an applied magnetic field. We observe a variety of phenomena arising from competing symmetries which either drive added antivortices to join antivortex shells around dots or stabilize the translationally symmetric antivortex lattice between the dots. Added vortices annihilate antivortex shells, leading first to a stable "nulling state" with no free fluxons and then, at high densities, to vortex shells around the dots stabilized by the asymmetric antipinning potential. Our experimental findings are in good agreement with Ginzburg-Landau calculations.     

Inhibition of copper corrosion in acidic sulphate media by eco-friendly amino acid compound

This investigation aimed to study a “green” non-toxic biodegradable copper corrosion inhibitor in an acidic sodium sulphate solution. The methods used in the investigation of cysteine as a copper corrosion inhibitor in an acidic sodium sulphate solution were: potentiodynamic measurements, open circuit potential measurements, and chronoamperometric measurements. Optical microscopy was used in addition to electrochemical methods. Potentiodynamic measurements show that cysteine has good inhibitory properties in an acidic medium. Polarisation curves indicate that the presence of cysteine in a sulphate solution decreases the current density and that using various cysteine concentrations results in the formation of a protective film on the surface of the electrode due to the formation of the Cu(I)-cys complex. These results are confirmed by chronoamperometric measurements. Furthermore, it is clear from microphotographs that a protective film does form on copper electrode in the presence of cysteine. The Langmuir adsorption isotherm indicates that cysteine is chemisorbed on the surface of the electrode.     

Determining elemental strontium distribution in rat bones treated with strontium ranelate and strontium citrate using 2D micro-XRF and 3D dual energy K-edge subtraction synchrotron imaging

Strontium-based medications, such as strontium ranelate, have been suggested to have therapeutic effects in patients with osteoporosis. Strontium salts available off-shelf in stores across North America are assumed to provide similar effects as strontium ranelate and thus should lead to similar distributions of elemental strontium incorporated in bone. The objective of this study was to compare the spatial distribution of strontium in animal bones following the administration of strontium ranelate and strontium citrate. Seventeen-week-old Sprague–Dawley rats were split into three groups over 10 weeks and given 625 mg/kg/day of strontium ranelate and 676 mg/kg/day of strontium citrate; the control group received no additional supplementary strontium. The humeri were collected from all animals, and strontium distribution was mapped using 2D micro-XRF and 3D dual energy K-edge subtraction (KES) imaging. 2D and 3D elemental mapping methods demonstrated that strontium delivered during treatment by both salts had the same spatial distribution. 3D elemental strontium maps of treated animal bones showed that strontium was largely observed in the trabecular regions under the epiphyseal (growth) plate. The thickness of the strontium layers in both the strontium ranelate and strontium citrate sample was not significantly different (p = .9201). 2D micro-XRF and 3D dual-energy KES images effectively elucidated the spatial distribution of elemental strontium in calcified tissue. These methods provide a novel approach to evaluating the potential efficacy of strontium supplements in the treatment of osteoporosis.     

Structural diversity of isothiocyanato Cd(II) and Zn(II) Girard’s T hydrazone complexes in solution and solid state: effect of H-bonding on coordination number and supramolecular assembly of Cd(II) complex in solid state

The isothiocyanato Zn(II) complex (1) and mixed isothiocyanato/thiocyanato Cd(II) complex (2) with the condensation product of 2-acetylpyridine and trimethylammoniumacetohydrazide chloride (Girard’s T reagent) (HLCl) were investigated both experimentally and theoretically. The crystal structures of both complexes showed tridentate N₂O coordination of hydrazine ligand. In complex 1 square-pyramidal coordination surrounding of Zn(II) consists of deprotonated hydrazone ligand and two isothiocyanato ligands, while in octahedral Cd(II) complex ligand is coordinated without deprotonation as a positively charged species and coordination geometry is completed with two N-coordinated and one S-coordinated NCS^? anions. NMR spectroscopy and molar conductivity results for Cd(II) and Zn(II) complexes indicated their instability in solution. DFT calculations were performed to explain coordination preference and stability of complexes 1 and 2 in solid state and in solution. The obtained Cd(II) complex is the first reported mononuclear pseudohalide/halide Cd(II) complex with quinoline-/pyridine-based hydrazone ligands possessing octahedral geometry in solid state. In this complex, H-bonding has significant impact on coordination number and supramolecular assembly in solid state.     

Regge oscillations in integral cross sections for proton impact on atomic hydrogen

The integral cross sections for elastic scattering and spin exchange for proton impact on atomic hydrogen show several oscillations in the energy range 0.01-1.0 eV that cannot be associated with resonances or the glory effect. A complex angular momentum analysis using computed Regge trajectories shows that each peak of the oscillatory structure is predominantly associated with at most three trajectories. In this way, the peaks are related to the L=0 bound states of H+ 2. The complex angular momentum theory for integral cross sections that we introduce shows that such oscillations are a general feature of potential scattering.