A DFT/PCM Study on the Affinity of Salinomycin to Bind Monovalent Metal Cations

The affinity of the polyether ionophore salinomycin to bind IA/IB metal ions was accessed using the Gibbs free energy of the competition reaction between SalNa (taken as a reference) and its rival ions: [M+-solution] + [SalNa] → [SalM] + [Na+-solution] (M = Li, K, Rb, Cs, Cu, Ag, Au). The DFT/PCM computations revealed that the ionic radius, charge density and accepting ability of the competing metal cations, as well as the dielectric properties of the solvent, have an influence upon the selectivity of salinomycin. The optimized structures of the monovalent metal complexes demonstrate the flexibility of the ionophore, allowing the coordination of one or two water ligands in SalM-W1 and SalM-W2, respectively. The metal cations are responsible for the inner coordination sphere geometry, with coordination numbers spread between 2 (Au+), 4 (Li+ and Cu+), 5/6 (Na+, K+, Ag+), 6/7 (Rb+) and 7/8 (Cs+). The metals’ affinity to salinomycin in low-polarity media follows the order of Li+ > Cu+ > Na+ > K+ > Au+ > Ag+ > Rb+ > Cs+, whereas some derangement takes place in high-dielectric environment: Li+ ≥ Na+ > K+ > Cu+ > Au+ > Ag+ > Rb+ > Cs+.

Phase Stability and Mechanical Properties of the Monoclinic, Monoclinic-Prime and Tetragonal REMO4 (M = Ta, Nb) from First-Principles Calculations

YTaO4 and the relevant modification are considered to be a promising new thermal barrier coating. In this article, phase stability and mechanical properties of the monoclinic (M), monoclinic-prime (M′), and tetragonal (T) REMO4 (M = Ta, Nb) are systematically investigated from first-principles calculations method based on density functional theory (DFT). Our calculations show that M′-RETaO4 is the thermodynamically stable phase at low temperatures, but the stable phase is a monoclinic structure for RENbO4. Moreover, the calculated relative energies between M (or M′) and T phases are inversely proportional to the ionic radius of rare earth elements. It means that the phase transformation temperature of M′→T or M→T could decrease along with the increasing ionic radius of RE3+, which is consistent with the experimental results. Besides, our calculations exhibit that adding Nb into the M′-RETaO4 phase could induce phase transformation temperature of M′→M. Elastic coefficient is attained by means of the strain-energy method. According to the Voigt–Reuss–Hill approximation method, bulk modulus, shear modulus, Young’s modulus, and Poisson’s ratio of T, M, and M’ phases are obtained. The B/G criterion proposed by Pugh theory exhibits that T, M, and M’ phases are all ductile. The hardness of REMO4 (M = Ta, Nb) phases are predicted based on semi-empirical equations, which is consistent with the experimental data. Finally, the anisotropic mechanical properties of the REMO4 materials have been analyzed. The emerging understanding provides theoretical guidance for the related materials development.

Химическое сжатие, структурная нестабильность и ИК-активные фононы в ряду редкоземельных аналогов францисита Cu-=SUB=-3-=/SUB=-RE(SeO-=SUB=-3-=/SUB=-)-=SUB=-2-=/SUB=-O-=SUB=-2-=/SUB=-Cl

ATR and transmission spectra of a series of rare-earth francisite-like phases Cu3RE(SeO3)2O2Cl (RE is a rare earth element, RE = Nd, Sm, Eu, Gd, Dy, Ho, Tm, Yb) were studied. The frequencies of the IR-active phonons of the crystals under study were determined. In the dependences of phonon frequencies on the ionic radius in a series of isostructural compounds, two tendencies are observed: a hardening of frequencies due to an increase in chemical pressure and a softening of the vibration frequencies, in which rare-earth ions are involved, due to an increase in the mass of a specific rare-earth ion. In the Cu3Dy(SeO3)2O2Cl crystal, an anomalous softening of low-frequency phonons at low temperatures was observed, which was apparently associated with the structural instability of the compound.

Pr- and Sm-Substituted Layered Perovskite Oxide Systems for IT-SOFC Cathodes

In this study, the phase synthesis and electrochemical properties of A/A//A///B2O5+d (A/: Lanthanide, A//: Ba, and A//: Sr) layered perovskites in which Pr and Sm were substituted at the A/-site were investigated for cathode materials of Intermediate Temperature-Operating Solid Oxide Fuel cells (IT-SOFC). In the PrxSm1-xBa0.5Sr0.5Co2O5+d (x = 0.1–0.9) systems, tetragonal (x < 0.4) and orthorhombic (x ≥ 0.5) crystalline structures were confirmed according to the substitution amount of Pr, which has a relatively large ionic radius, and Sm, which has a small ionic radius. All of the layered perovskite oxide systems utilized in this study presented typical metallic conductivity behavior, with decreasing electrical conductivity as temperature increased. In addition, Pr0.5Sm0.5Ba0.5Sr0.5Co2O5+d (PSBSCO55), showing a tetragonal crystalline structure, had the lowest conductivity values. However, the Area-Specific Resistance (ASR) of PSBSCO55 was found to be 0.10 Ωcm2 at 700 °C, which is lower than those of the other compositions.

Crystal Chemistry of Six Grossular Garnet Samples from Different Well-Known Localities

Two isotropic grossular (ideally Ca3Al2Si3O12) samples from (1) Canada and (2) Tanzania, three optically anisotropic grossular samples (3, 4, 5) from Mexico, and one (6) anisotropic sample from Italy were studied. The crystal structure of the six samples was refined in the cubic space group Ia3¯d, using monochromatic synchrotron high-resolution powder X-ray diffraction (HRPXRD) data and the Rietveld method. The compositions of the samples were obtained from electron microprobe analyses (EPMA). The HRPXRD traces show a single cubic phase for two isotropic samples, whereas the four anisotropic samples contain two different cubic phases that were also resolved using X-ray elemental line scans, backscattered electron (BSE) images, and elemental maps. Structural mismatch from two cubic phases intergrown in the birefringent samples gives rise to strain-induced optical anisotropy. Considering the garnet general formula, [8]X3[6]Y2[4]Z3[4]O12, the results of this study show that with increasing unit-cell parameter, the Y-O distance increases linearly and rather steeply, the average <X-O> distance increases just slightly in response to substitution mainly on the Y site, while the Z-O distance remains nearly constant. The X and Z sites in grossular contain Ca and Si atoms, respectively; both sites show insignificant substitutions by other atoms, which is supported by a constant Z-O distance and only a slight increase in the average <X-O> distance. The main cation exchange is realized in the Y site, where Fe3+ (ionic radius = 0.645 Å) replaces Al3+ (ionic radius = 0.545 Å), so the Y-O distance increases the most.

Role of redox-inactive metals in controlling the redox potential of heterometallic manganese–oxido clusters

Photosystem II (PSII) contains Ca2+, which is essential to the oxygen-evolving activity of the catalytic Mn4CaO5 complex. Replacement of Ca2+ with other redox-inactive metals results in a loss/decrease of oxygen-evolving activity. To investigate the role of Ca2+ in this catalytic reaction, we investigate artificial Mn3[M]O2 clusters redox-inactive metals [M] ([M] = Mg2+, Ca2+, Zn2+, Sr2+, and Y3+), which were synthesized by Tsui et al. (Nat Chem 5:293, 2013). The experimentally measured redox potentials (Em) of these clusters are best described by the energy of their highest occupied molecular orbitals. Quantum chemical calculations showed that the valence of metals predominantly affects Em(MnIII/IV), whereas the ionic radius of metals affects Em(MnIII/IV) only slightly.

Site-occupancy scheme in disordered Ca3RE2(BO3)4: a dependence on rare-earth (RE) ionic radius

The structures of polycrystalline Ca3RE2(BO3)4 (RE = La, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Y; space group Pnma) orthoborates were determined using powder X-ray diffraction. Trends in the unit-cell dimensions and yet unreported trends in other structural properties (interatomic distances and the fractional occupation of three Ca/RE sites) for these compounds are demonstrated as a function of RE ionic radius. The unit-cell volume and a unit-cell parameter present a linear dependence, while the b and c unit-cell parameters change in a nonlinear manner. For the whole series, the RE atoms are present at all three cationic sites (labelled as M1, M2 and M3), but the fractional occupancies depend on the RE ionic radius. The small rare-earth atoms tend to enter mainly the M3 site; for the larger rare earths, the occupancy of this site decreases sharply. The occupancy of the M1 site by RE atoms is around 0.5 and tends to increase with increasing RE ionic radius. The M2 site is the least preferentially occupied by RE ions, but the occupancy discernibly increases with rising radius as well. These findings are assembled with properties of isostructural strontium and barium borates, allowing prediction of occupancy schemes for not yet investigated compounds from the A 3RE2(BO3)4 (A = Ca, Ba, Sr).