Synthesis and Reactivity of Mg(II)–Fe(II)–Fe(III) Hydroxycarbonates

Green rust-like compounds (GRs) were discovered as natural minerals in various hydromorphic soils, where anoxic conditions allow their stability. They may control some redox processes in aquifers and participate to the transformation of various pollutants. Since Mg(II) cations are present in the fields where GRs were discovered, a partial substitution of Mg(II) to Fe(II) leading to intermediate compounds between GRs and usual Mg(II)–Fe(III) hydroxysalts is suspected. Mg(II)–Fe(II)–Fe(II) hydroxycarbonates can be obtained as intermediate oxidation products of (Mg, Fe)(OH)₂ in carbonate-containing aqueous media obeying to [Fe^II _4(1–x)Mg^II _4x Fe^III ₂(OH)₁₂]²⁺ [CO₃ ^2– nH₂O]^–2. TMS spectra at 12 K are similar to those of GRs, i.e., two quadrupole doublets, one due to Fe(II) with a large isomer shift =1.29 mms^–1 (with respect to -iron at room temperature) and quadrupole splitting E _Q=2.76 mms^–1, the other one due to Fe(III) with smaller hyperfine parameters =0.49 mms^–1 and E _Q=0.44 mms^–1. Fe(II) ions oxidise rapidly into Fe(III) with dissolved O₂. The reactivity is similar to that of Fe(II)–Fe(III) hydroxysalts GR, and thus the potential of Mg(II)–Fe(II)–Fe(III) compounds for reducing pollutants.     

Non-uniform Fulde–Ferrell–Larkin–Ovchinnikov (FFLO) state

We provide a general review of the properties of the non-uniform superconducting Fulde–Ferrell–Larkin–Ovchinnikov (FFLO) phase. Special emphasis is made on the orbital and crystal structure effects which may result in the quantum transitions between the higher Landau level states and should be responsible for the strong modification of the anisotropy of the critical field. The FFLO-type instability may be also expected in ultracold Fermi gases. In these systems it is caused not by the Zeeman interaction but by the tuning of the population imbalance between two lowest hyperfine states of the atoms. We also briefly discuss their properties.     

Effects of Poly(Propylene Oxide)–Poly(Ethylene Oxide)–Poly(Propylene Oxide) Triblock Copolymer on the Gelation of Poly(Ethylene Oxide)–Poly(Propylene Oxide)–Poly(Ethylene Oxide) Aqueous Solutions

Poly(ethylene oxide)-poly(propylene oxide)–poly(ethylene oxide) ((EO)_n–(PO)_m–(EO)_n) block copolymers, commercially available as Pluronics (BASF Corp.) and Poloxamers (ICI Corp.), have been widely applied in medicine, biochemistry, and other fields because of their ability to form reversible micelles and physical gels in aqueous solution. Generally, for PEO–PPO–PEO block copolymers with higher ethylene oxide concentration, the micellization and gelation in aqueous solution are easier. However, if we introduce the reverse block copolymer PPO–PEO–PPO into PEO–PPO–PEO aqueous solutions, the micellization and gelation of the system will be more complex. In this work, the reverse block copolymer PO₁₄–EO₂₄–PO₁₄ (17R4) was added to the Pluronics EO₂₀–PO₇₀–EO₂₀ (P123), EO₁₀₀–PO₆₅–EO₁₀₀ (F127), and EO₁₃₃–PO₅₀–EO₁₃₃ (F108) aqueous solutions with different molar ratios. The rheological properties of different mixtures were measured to study the additive effect on the gelation behavior. The sol–gel transition temperature of the P123, F127, and F108 solutions shifted to a higher temperature when 17R4 was added to the solutions. In addition, the existence of 17R4 greatly affected the stability of gels. These results help to better understand the gelation of Pluronic aqueous solutions.     

Microstructural evolution in Al–Mn–Cu–(Be) alloys

This study investigates the effects of alloying elements on the microstructural evolution of Al-rich Al–Mn–Cu–(Be) alloys during solidification, and subsequent heating and annealing. The samples were characterised using scanning electron microscopy, energy dispersive X-ray spectroscopy, synchrotron X-ray diffraction, time-of-flight secondary-ion mass spectroscopy, and differential scanning calorimetry. In the ternary Al₉₄Mn₃Cu₃ (at%) alloy, the phases formed during slower cooling (≈1?K?s^?1) can be predicted by the known Al–Mn–Cu phase diagram. The addition of Be prevented the formation of Al₆Mn, decreased the fraction of τ₁-Al₂₉Mn₆Cu₄, and increased the fraction of Al₄Mn. During faster cooling (≈1000?K?s^?1), Al₄Mn predominantly formed in the ternary alloy, whereas, in the quaternary alloys, the icosahedral quasicrystalline phase dominated. Further heating and annealing of the alloys caused an increase in the volume fractions of τ₁ in all alloys and Be₄Al (Mn,Cu) in quaternary alloys, while fractions of all other intermetallic phases decreased. Solidification with a moderate cooling rate (≈1000?K?s^?1) caused considerable strengthening, which was reduced by annealing for up to 25% in the quaternary alloys, while hardness remained almost the same in the ternary alloy.     

Artem Isaak Alikhanian (1908–1978) (Biographic Sketch)

A.I. Alikhanian is one of founders of experimental nuclear physics in USSR. Starting and development of the atomic nuclei, cosmic ray, and elementary particle physics in Armenia relates to the name Alikhanian. He created the Aragats and Nor-Amberd high-altitude cosmic stations and the Yerevan Physics Institute. He made an essential contribution into the development of high-energy physics and played a significant role in creation of methods of recording high-energy particles.     

Is the (hfac)Cu(I)–(tmvs) bond intrinsically weak?

Density functional theory studies were performed to study the structure and bonding of (hexafluoroacetylacetonate)-copper(I)-(trimethylvinylsilane) [Cu(hfac)(tmvs)], an ideal and important Cu(I)-CVD compound. A popular three-parameter hybrid density functional (B3LYP) with 6-311+G(d,p) and an effective core potential included LanL2DZ basis set was utilized for this purpose. The (hfac)Cu–(tmvs) bond energy of approximately 30?kcal?mol^?1 obtained at the B3LYP/6-311+G(d,p) level of theory reveals that the Cu–olefin bond in Cu(hfac)(tmvs) is not as weak as previously estimated/assumed and, hence, that the substrate plays a vital role in copper film formation from Cu(hfac)(tmvs). Bonding analysis reveals that fairly strong (hfac)Cu–(tmvs) bonding is the result of DCD-model σ-donation and π-back-bonding between the copper and tmvs in Cu(hfac)(tmvs).     

Nikolai Fedorovich Zakhariya (1910–1989)

Obituary

Nikolai Fedorovich Zakhariya (1910–1989)     

Total asymmetric synthesis of (–)-Phenylhistine, (–)-Aurantiamine and related compounds. Part I

A new general, short, and efficient strategy for the construction of dehydro-diketopiperazines was developed. Horner–Emmons type coupling between a phosphinyl glycine ester and a formyl heterocycle is the key coupling reaction, which proceeds in good-to-excellent yields on several sterically-hindered substrates. Moreover, racemization of the parent L-amino acids is avoided as a result of the mild basic conditions used. The selection of the NH protective group of the formyl heterocycle was crucial. N-tosylated heterocycles proved ideal for this reaction sequence. Thus, the title compounds, (–)-Phenylhistine and (–)-Aurantiamine, were prepared in high yield (four steps, 47% overall) and optical purity. Furthermore, the synthesis of unnatural derivatives including an indole analogue was successfully completed.     

Leonid Ivanovich Kiselevskii (1927–1991)

Obituary

Leonid Ivanovich Kiselevskii (1927–1991)     

Magnetic Resonance of Chromium (V) with 2–Hydroxy–2–Ethylbutyrates

A complex of Cr (V) with 2–hydroxy–2–ethylbutyric acid (EHBA) has been studied experimentally by the method of electron spin resonance (ESR). The tensor components of the g–factor, the dependences of the ESR line widths on the concentration of paramagnetic centers, and the SHF power of saturation are determined. It is shown that the main mechanism of dynamic polarization of nuclei in the EHBACr^V complex in a propanediol solution is the mechanism of dynamic cooling with a burnt hole. It has been established that the ESR spectra of the EHBACr^V solutions in deuterated and ordinary propanediol display practically the same behavior, which is indicative of the good solubility of the complex in deuterated alcohols.     

The electronic structures of commensurate Ru(0001)–(3 × 3)–4Kr and Ru(0001)–(5 × 5)–Kr using density functional theory

We have calculated the minimum energies for each of three positionings of the adatom unit cells for Ru(0001)–(3 × 3)–4Kr (high Kr coverage) and for Ru(0001)–(5 × 5)–Kr (low Kr coverage). The differences between the results for the low and high-coverage cases may clarify puzzles posed by the experimental results of Narloch and Menzel. The low-coverage solution converges to a structure having Kr in the top site at a height of 3.09 Å above the substrate with the adsorption energy 185 meV. In the high-coverage case, adatom unit cells with a corner Kr at top, fcc hollow, and hcp hollow locations are found to have nearly the same adsorption energy of 175 meV. The height of the corner atom above the substrate is found to be 3.35, 3.54, and 3.50 Å for the top, fcc hollow and hcp hollow sites, respectively. These results are explained by demonstrating that there is an enhancement of the substrate electronic density of states at krypton orbital energies in the low-coverage case.     

Temperature-Dependent Current–Voltage (I–V) and Capacitance–Voltage (C–V) Characteristics of Ni/Cu/n-InP Schottky Barrier Diodes

The current-voltage (I–V) and capacitance-voltage (C–V) characteristics of Ni/Cu/n-InP Schottky barrier diodes are studied over a wide temperature range, from 210 K to 420 K. The I–V characteristics display anomalous thermal behavior. The apparent barrier height decays, and the ideality factor grows at low temperatures, and the series resistances resulting from Cheung’s and Norde’s procedures are markedly temperature dependent. The nonlinearity of the Richardson plot and the strong temperature dependence of the Schottky-barrier parameters indicate that the interface is spatially inhomogeneous. Plots of the zero-bias barrier height as a function of 1/(2kT) points to a Gaussian distribution of barrier heights with 0.90 eV mean height and 0.014 eV standard deviation. When this distribution is accounted for, a Richardson of 6.5 A/(cm K)² results, relatively close to the 9.4/(cm K)² predicted by theory. We conclude that, combined with a Gaussian distribution of barrier heights, the thermionic-emission mechanism explains the temperature-dependent I–V and C–V characteristics of the studied Schottky-barrier diodes.     

Maleic Acid–alt–Styrene Copolymer as Compatibilizer for Poly(Ethylene Oxide)-Poly(Styrene)Blends

Maleic acid-alt-styrene (MAaS) copolymer with number-average molecular weight [Mbar] _n = 2500 was used as a compatibilizer in blends of poly(ethylene oxide) (PEO) and poly(styrene) (PS). PEO with weight-average molecular weight [Mbar] _w = 10⁵ (PEO₁₀₀) and two PS samples with [Mbar] _w = 9 × 10⁴ and 4 × 10⁵, respectively (PS₉₀ and PS₄₀₀, respectively) were used. A depression of the melting temperature T _m of PEO in blends containing MAaS relative to pure PEO and PEO/PS blends was observed. The melting enthalpy ΔH _m for the PEO/PS blends containing MAaS was lower than those of pure PEO and PEO/PS blends without compatibilizer. The crystallization kinetics of PEO and the blends were studied by differential scanning calorimetry (DSC) at different crystallization temperatures T _c. Flory-Huggins interaction parameters χ₁₂ for the blends were estimated. Their values are in good agreement with those obtained for similar systems and suggest that the free energy of mixing ΔG _mix should be negative. Polarized optical microscopy shows differences in the macroscopic homogeneity of the blends containing compatibilizer that could be attributed to a compatibilization process.     

Cardy–Verlinde formula in Taub–NUT/Bolt–(A)dS space

We consider a finite action for a higher dimensional Taub–NUT/Bolt–(A)dS space via the so-called counter term subtraction method. In the limit of high temperature, we show that the Cardy–Verlinde formula holds for the Taub–Bolt–AdS metric and for the specific dimensional Taub–NUT–(A)dS metric, except for the Taub–Bolt–dS metric.     

Properties of the Ce–Pd–Pt(111) overlayer system

The Pd–Pt(111) and the Ce–Pd–Pt(111) overlayer systems were studied by X-ray photoelectron spectroscopy and low-energy electron diffraction (LEED). Variations in the work function were measured by ultraviolet photoelectron spectroscopy. The Pd overlayer thicknesses were in the range of 1 to 4 monolayers (MLs). The Ce overlayer thicknesses were in the range is of 0.5 to 1.5 MLs. The interfaces were studied for annealing temperatures up to 700°C. Surface alloying or intermixing of Ce, Pd and Pt was observed. Upon deposition at ambient temperatures, Ce forms an overlayer. During annealing, both Pd and Ce were found to dissolve into the Pt substrate. For a Pd coverage of about 1 ML, the Ce–Pd–Pt(111) system was found to be Pt, terminated after annealing to 700°C. For Pd coverage above 1 ML, both Pd and Pt were found to be present at the surface. Cerium was found to be absent from the top surface layer in both cases.     

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