A nearly zero temperature gradient furnace system for high pressure multi-anvil experiments

A new furnace system with an almost zero temperature gradient throughout the sample area was designed for multi-anvil high pressure experiments. Test experiments of the new design were performed using 18/11 and 25/15 cell assemblies at 4?GPa, 1400°C and 1500°C, respectively. The temperature field within the sample capsules appeared to be very homogenous as indicated by Mg₂Si₂O₆–MgCaSi₂O₆ two-pyroxene thermometry, by direct temperature measurements using two thermocouples within the same assembly, and by distribution of solid and liquid phases in the sample capsule. The temperature gradient is estimated to be <2.4°C/mm over an area of 4?×?5?mm² within the furnace. It is significantly lower than standard multi-anvil experiments with straight or stepped furnace systems, which are at the levels of 20–200°C/mm.     

Pyrophosphate Selective Recognition in Aqueous Solution Based on Fluorescence Enhancement of a New Aluminium Complex

A novel and simple fluorescence enhancement method for selective pyrophosphate(PPi) sensing was proposed based on a 1:1 metal complex formation between bis(8-hydroxy quinoline-5-solphonat) chloride aluminum(III) (Al(QS)₂Cl), (L) and PPi in aqueous solution. The linear response range covers a concentration range of 1.6 × 10⁻⁷ to 1.0 × 10⁻⁵ mol/L of PPi and the detection limit of 2.3 × 10⁻⁸ mol/L. The association constant of L-PPi complex was calculated 2.6 × 10⁵ L/mol. L was found to show selectively and sensitively fluorescence enhancement toward PPi over than I₃^-, NO₃^-, CN⁻, CO₃²⁻, Br⁻, Cl⁻, F⁻, H₂PO4⁻ and SO₄²⁻, which was attributed to higher stability of inorganic complex between pyrophosphate and L.     

Three-Component Reaction of Triphenylphosphine,Acetylenic Esters,and Arylsulfonyl Hydrazides or Aryl Hydrazines: An Efficient One-Pot Synthesis of Stable β-Nitrogen-Substituted Phosphorus Ylides

The three-component reaction between dialkyl acetylenedicarboxylates and triphenylphosphine in the presence of arylsulfonyl hydrazides or aryl hydrazines produces highly functionalized, salt-free phosphorus ylides in excellent yields.     

A non-adapted sparse approximation of PDEs with stochastic inputs

We propose a method for the approximation of solutions of PDEs with stochastic coefficients based on the direct, i.e., non-adapted, sampling of solutions. This sampling can be done by using any legacy code for the deterministic problem as a black box. The method converges in probability (with probabilistic error bounds) as a consequence of sparsity and a concentration of measure phenomenon on the empirical correlation between samples. We show that the method is well suited for truly high-dimensional problems.     

Characterization of a peptide family from the skin secretion of the Middle East Tree Frog Hyla savignyi by composition‐based de novo sequencing

A new tryptophyllin‐like peptide family was found in the skin secretion of the tree frog Hyla savignyi. Peptides were characterized by database‐independent sequencing strategies and specific ion fragmentation features were investigated. Skin secretions from specimens of Hyla savignyi were collected by mild electrical stimulation. Peptides were separated by reversed‐phase nano‐high‐performance liquid chromatography (nanoHPLC) and mass spectra were acquired online by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FTICR‐MS). Peptides were characterized by manual de novo sequencing and by composition‐based sequencing (CBS), appearing mostly as C‐terminal free acids and as their acid amide analogs. Amide peptides yielded lower intensities of y‐type ions after collision‐induced dissociation (CID) than their acid analogs. A mechanism of internal b‐ion formation (positive ion mode) and of CO₂ elimination (negative ion mode) is proposed. We also exemplified phenomena such as the proline effect and formation of non‐direct sequence ions after sequence rearrangements. The occurrence of rearrangement products, of internal ions and of the proline effect made the CID spectra highly complex. CBS analysis nevertheless resulted in successful and highly reliable sequence analysis. Copyright © 2010 John Wiley & Sons, Ltd.     

Three-Component Reaction of Triphenylphosphine,Dimethyl Acetylenedicarboxylate,and Aldehyde Benzoylhydrazones: An Efficient One-Pot Synthesis of Stable Phosphorus Ylides

Protonation of the reactive 1:1 intermediate produced in the reaction between dimethyl acetylenedicarboxylate and triphenylphosphine by benzoylhydrazones leads to vinylphosphonium salts, which undergo Michael addition with the conjugate base of the NH acid to produce highly fanctionalized, salt-free phosphorus ylides in excellent yields.     

Localization of elastic waves in heterogeneous media with off-diagonal disorder and long-range correlations

Using the Martin-Siggia-Rose method, we study propagation of acoustic waves in strongly heterogeneous media which are characterized by a broad distribution of the elastic constants. Gaussian-white distributed elastic constants, as well as those with long-range correlations with nondecaying power-law correlation functions, are considered. The study is motivated in part by a recent discovery that the elastic moduli of rock at large length scales may be characterized by long-range power-law correlation functions. Depending on the disorder, the renormalization group (RG) flows exhibit a transition to localized regime in any dimension. We have numerically checked the RG results using the transfer-matrix method and direct numerical simulations for one- and two-dimensional systems, respectively.     

Silica aerogel–iron oxide nanocomposites: recoverable catalysts for the oxidation of alcohols with hydrogen peroxide

Various aerogels of silica gel doped with Fe₂O₃ were prepared by sol–gel method. They were calcined to produce nanoparticle solids. The nanosized mixed oxides were active in the oxidation of alcohols and produced carbonyl compounds in very good to excellent yields using hydrogen peroxide.     

Synthesis,characterization, and molecular structures of Ni(II) and Cd(II) complexes derived from dithiophosphonate

Two novel dithiophosphonate ligands, HS₂P(p‐C₆H₄OMe)(OCH₂CH₂CH(CH₃)₂) ( 1 ) and HS₂P(p‐C₆H₄OMe)(OCH(CH₃)₂) ( 2 ), were synthesized and characterized by multinuclear (¹H, ³¹P, and ¹³C) NMR, infrared spectroscopy as well as elemental analysis. The reactions of 1 and 2 with NiCl₂·6H₂O and Cd(NO₃)₂·4H₂O in methanol led to novel complexes 3 and 4 . The single crystal X‐ray structures of 3 and 4 showed tetracoordinated structure with square planar geometry for the nickel complex, while it showed pentacoordinated structure with distorted square‐pyramid environment for the cadmium complex.