The system Na2CO3–CaCO3–MgCO3 at 6 GPa and 900–1250°C and its relation to the partial melting of carbonated mantle

In order to constrain the Na₂CO₃–CaCO₃–MgCO₃ T–X diagram at 6?GPa in addition to the binary and pseudo-binary systems we conducted experiments along the Na₂CO₃–Ca_0.5Mg_0.5CO₃ join. At 900–1000°C, melting does not occur and isothermal sections are presented by one-, two- and three-phase regions containing Ca-bearing magnesite, aragonite, Na₂CO₃ (Na₂) and Na₂(Ca_1–0.9Mg_0-0.1)_3-4(CO₃)_4-5 (Na₂Ca_3-4), Na₄(Ca_1–0.6Mg_0–0.4)(CO₃)₃ (Na₄Ca), Na₂(Ca_0-0.08Mg_1–0.92)(CO₃)₂ (Na₂Mg) phases with intermediate compositions. The minimum melting point locates between 1000°C and 1100°C. This point would resemble that of three eutectics: Mgs–Na₂Ca₃–Na₂Mg, Na₂Mg–Na₂Ca₃–Na₄Ca or Na₂Mg–Na₄Ca–Na₂, in the compositional interval of [45Na₂CO₃·55(Ca_0.6Mg_0.4)CO₃]–[60Na₂CO₃·40Ca_0.6Mg_0.4CO₃]. The liquidus projection has seven primary solidification phase regions for Mgs, Dol, Arg, Na₂Ca₃, Na₄Ca, Na₂ and Na₂Mg. The results suggest that extraction of Na and Ca from silicate to carbonate components has to decrease minimum melting temperature of carbonated mantle rocks to 1000–1100°C at 6?GPa and yields Na-rich dolomitic melt with a Na# (Na₂O/(Na₂O?+?CaO?+?MgO))?≥?28?mol%.     

Synthesis of Tetrazino‐tetrazine 1,3,6,8‐Tetraoxide (TTTO)

This study presents the first synthesis and characterization of a new high energy compound [1,2,3,4]tetrazino[5,6‐e][1,2,3,4]tetrazine 1,3,6,8‐tetraoxide (TTTO). It was synthesized in ten steps from 2,2‐bis(tert‐butyl‐NNO‐azoxy)acetonitrile. The synthetic strategy was based on the sequential closure of two 1,2,3,4‐tetrazine 1,3‐dioxide rings by the generation of oxodiazonium ions and their intramolecular coupling with tert‐butyl‐NNO‐azoxy groups. The TTTO structure was confirmed by single‐crystal X‐ray.     

UV Raman spatially resolved melting dynamics of isotopically labeled polyalanyl peptide: slow alpha-helix melting follows 3(10)-helices and pi-bulges premelting

We used UV resonance Raman (UVRR) to examine the spatial dependence of the T-jump secondary structure relaxation of an isotopically labeled 21-residue mainly Ala peptide, AdP. The AdP penultimate Ala residues were perdeuterated, leaving the central residues hydrogenated, to allow separate monitoring of melting of the middle versus the end peptide bonds. For 5 to 30 degrees C T-jumps, the central peptide bonds show a approximately 2-fold slower relaxation time (189 +/- 31 ns) than do the exterior peptide bonds (97 +/- 15 ns). In contrast, for a 20 to 40 degrees C T-jump, the central peptide bond relaxation appears to be faster (56 +/- 6 ns) than that of the penultimate peptide bonds (131 +/- 46 ns). We show that, if the data are modeled as a two-state transition, we find that only exterior peptide bonds show anti-Arrhenius folding behavior; the middle peptide bonds show both normal Arrhenius-like folding and unfolding. This anti-Arrhenius behavior results from the involvement of pi-bulges/helices and 3(10)-helix states in the melting. The unusual temperature dependence of the (un)folding rates of the interior and exterior peptide bonds is due to the different relative (un)folding rates of 3(10)-helices, alpha-helices, and pi-bulges/helices. Pure alpha-helix unfolding rates are approximately 12-fold slower (approximately 1 micros) than that of pi-bulges and 3(10)-helices. In addition, we also find that the alpha-helix is most stable at the AdP N-terminus where eight consecutive Ala occur, whereas the three hydrophilic Arg located in the middle and at the C-terminus destabilize the alpha-helix in these regions and induce defects such as pi-bulges and 3(10)-helices.     

C‐phosphorylation of 5,10‐dimethyl‐5,10‐dihydrophenazine and its carbo‐ and heteroanalogs

This study covers phosphorylation of heterocyclic analogues of N‐methyldiphenylamine with phosphorus tribromide in pyridine solution. The reaction is found to proceed regioselectively in accordance with the orienting effect of the amino group. Mono and bis‐phosphorylated derivatives of the heterocycles have been isolated and characterized. It is pointed out that the heterocyclic systems under study exhibit reduced reactivity in electrophilic phosphorylation as compared to N‐methyldiphenylamine. The results of calculations by the PM3 method are reported for the starting molecules and their σ‐complexes. © 2001 John Wiley & Sons, Inc. Heteroatom Chem 12:652–657, 2001     

Potassium 3‐cyano‐4‐(dicyanomethylene)‐5‐oxo‐4,5‐dihydro‐1H‐pyrrol‐2‐olate

The crystal structure of the title potassium salt, K⁺·C₈HN₄O₂⁻, of the organic anion 3‐cyano‐4‐(di­cyano­methyl­ene)‐5‐oxo‐4,5‐di­hydro‐1H‐pyrrol‐2‐olate shows that the di­cyano­methyl­ene moiety is able to accept an electron in the same way as does tetra­cyano­ethyl­ene, to yield the novel product. The organic anion is nearly planar, with deviations caused by steric crowding among the exocyclic cyano groups. The K⁺ cations lie within tricapped trigonal prisms that stack to form channels. The three‐dimensional structure is completed by the formation of hydrogen‐bonded chains by the anions.     

Structural and Spectroscopic Effects of Li+ Substitution for Na+ in LixNa1-xCaGd0.5Ho0.05Yb0.45(MoO4)3 Scheelite-Type Upconversion Phosphors

A set of new triple molybdates, Li_xNa_1-xCaGd_0.5(MoO₄)₃:Ho³⁺_0.05/Yb³⁺_0.45, was successfully manufactured by the microwave-accompanied sol–gel-based process (MAS). Yellow molybdate phosphors Li_xNa_1-xCaGd_0.5(MoO₄)₃:Ho³⁺_0.05/Yb³⁺_0.45 with variation of the Li_xNa_1-x (x = 0, 0.05, 0.1, 0.2, 0.3) ratio under constant doping amounts of Ho³⁺ = 0.05 and Yb³⁺ = 0.45 were obtained, and the effect of Li⁺ on their spectroscopic features was investigated. The crystal structures of Li_xNa_1-xCaGd_0.5(MoO₄)₃:Ho³⁺_0.05/Yb³⁺_0.45 (x = 0, 0.05, 0.1, 0.2, 0.3) at room temperature were determined in space group I4₁/a by Rietveld analysis. Pure NaCaGd_0.5Ho_0.05Yb_0.45(MoO₄)₃ has a scheelite-type structure with cell parameters a = 5.2077 (2) and c = 11.3657 (5) Å, V = 308.24 (3) ų, Z = 4. In Li-doped samples, big cation sites are occupied by a mixture of (Li,Na,Gd,Ho,Yb) ions, and this provides a linear cell volume decrease with increasing Li doping level. The evaluated upconversion (UC) behavior and Raman spectroscopic results of the phosphors are discussed in detail. Under excitation at 980 nm, the phosphors provide yellow color emission based on the ⁵S₂/⁵F₄ → ⁵I₈ green emission and the ⁵F₅ → ⁵I₈ red emission. The incorporated Li⁺ ions gave rise to local symmetry distortion (LSD) around the cations in the substituted crystalline structure by the Ho³⁺ and Yb³⁺ ions, and they further affected the UC transition probabilities in triple molybdates Li_xNa_1-xCaGd_0.5(MoO₄)₃:Ho³⁺_0.05/Yb³⁺_0.45. The complex UC intensity dependence on the Li content is explained by the specificity of unit cell distortion in a disordered large ion system within the scheelite crystal structure. The Raman spectra of Li_xNa_1-xCaGd_0.5(MoO₄)₃ doped with Ho³⁺ and Yb³⁺ ions were totally superimposed with the luminescence signal of Ho³⁺ ions in the range of Mo–O stretching vibrations, and increasing the Li⁺ content resulted in a change in the Ho³⁺ multiplet intensity. The individual chromaticity points (ICP) for the LiNaCaGd(MoO₄)₃:Ho³⁺,Yb³⁺ phosphors correspond to the equal-energy point in the standard CIE (Commission Internationale de L’Eclairage) coordinates.     

BKP and projective Hurwitz numbers

We consider d-fold branched coverings of the projective plane \(\mathbb {RP}^2\) and show that the hypergeometric tau function of the BKP hierarchy of Kac and van de Leur is the generating function for weighted sums of the related Hurwitz numbers. In particular, we get the \(\mathbb {RP}^2\) analogues of the \(\mathbb {CP}^1\) generating functions proposed by Okounkov and by Goulden and Jackson. Other examples are Hurwitz numbers weighted by the Hall–Littlewood and by the Macdonald polynomials. We also consider integrals of tau functions which generate Hurwitz numbers related to base surfaces with arbitrary Euler characteristics \(\textsc {e}\), in particular projective Hurwitz numbers \(\textsc {e}=1\).     

Synthesis and properties of As<Subscript>x</Subscript>Te<Subscript>100−x</Subscript> films prepared by plasma deposition via elemental As and Te

As_xTe_100?x chalcogenide films (where x = 30–80 at.%) were synthesized via direct interaction of arsenic and tellurium vapors into low-temperature non-equilibrium RF (40 MHz) plasma discharge at reduced pressure. Phase and structural evolution of As_xTe_100?x films were implemented by gradual changing of the ratio of the initial substances in the gas phase. The dependence of the films structure, surface morphology and optical properties on phase and chemical content has been studied.