Fractional Hamiltonian Monodromy

We introduce fractional monodromy in order to characterize certain non-isolated critical values of the energy–momentum map of integrable Hamiltonian dynamical systems represented by nonlinear resonant two-dimensional oscillators. We give the formal mathematical definition of fractional monodromy, which is a generalization of the definition of monodromy used by other authors before. We prove that the 1:( − 2) resonant oscillator system has monodromy matrix with half-integer coefficients and discuss manifestations of this monodromy in quantum systems. Communicated by Eduard Zehnder Submitted: February 25, 2005; Accepted: November 17, 2005     

α-Trifluoroacetyl-δ-valerolactone: synthesis, acyl-lactone rearrangement and unexpected easy decarboxylation of the rearranged product

Claisen condensation of δ-valerolactone and ethyl trifluoroacetate leads to α-trifluoroacetyl-δ-valerolactone, existing completely in CDCl₃ solution as an enol. Upon treatment of this cyclic 1,3-ketoester with aqueous HCl, an acyl-lactone rearrangement takes place. The structure of the resulting pyran was confirmed by an X-ray analysis. The ability of the rearrangement product to lose its carboxylic group under unexpected mild conditions was used for the synthesis of the corresponding 3-unsubstituted cyclic hemi-ketal.     

Perfectly dissolved boron nitride nanotubes due to polymer wrapping

We report for the first time that boron nitride nanotubes (BNNTs) may be dissolved in organic solvents by wrapping them with a polymer. Transmission electron microscopy and cathodoluminescence studies indicate the strong pi-pi interactions between BNNTs and the polymer. A band gap ranging from 5.2 to 5.5 eV was documented for the BNNTs independent of their geometrical characteristics by using ultraviolet-visible absorption experiments on composite films and thin BNNT films prepared from solutions.     

Proton Relaxometry of Long-Lived Spin Order

A study of long-lived spin order in chlorothiophene carboxylates at both high and low magnetic fields is presented. Careful sample preparation (removal of dissolved oxygen in solution, chelating of paramagnetic impurities, reduction of convection) allows one to obtain very long-lived singlet order of the two coupled protons in chlorothiophene derivatives, having lifetimes of about 130 s in D₂O and 240 s in deuterated methanol, which are much longer than the T₁-relaxation times (18 and 30 s, respectively, at a field =9.4 T). In protonated solvents the relaxation times become shorter, but the lifetime is still substantially longer than . In addition, long-lived coherences are shown to have lifetimes as long as 30 s. Thiophene derivatives can be used as molecular tags to study slow transport, slow dynamics and slow chemical processes, as has been shown in recent years.     

The rheological similarity of the physical networks of different origin

It has been established that the Newtonian viscosity of solutions of styrene-acrylic acid (4 mol%) copolymers inionomeric form (0–50 mol%) in DMPh is proportional to exp n (n being the degree of neutralization). The principle of temperature-time-concentration superposition is applicable for the dependence of shear modulus on temperature (20–100°), frequency (10^?3–1.5 Hz), decree of neutralization (0–50 mol%) and concentration (15–45 g/dl). These facts can be explained in terms of the rheological similarity of physical networks connected with macromolecular chain entanglements and with salt group interactions. Some details of the model for concentrated polymer solutions are discussed.     

CdSe and CdSe/CdS nanorod solids

We demonstrate the self-organization of CdSe nanorods into nematic, smectic, and crystalline solids. Layered colloidal crystals of CdSe nanorods grow by slow destabilization of a nanocrystal solution upon allowing the diffusion of a nonsolvent into the colloidal solution of nanocrystals. The colloidal crystals of nanorods show characteristic birefringence, which we assign to specific spherulite-like texture of each nanorod assembly. To demonstrate the general character of nanorod self-assembly technique, CdSe/CdS heterostructure nanorods were organized into highly luminescent superlattices.     

Solution Stoichiometry Control for Pure LiLaMo2O8Phases in Sol-Gel Preparation

The hydrolysis of solutions, containing either LiMo₂O₄(OPr ⁱ )₅( ⁱ PrOH) and “La(OPr ⁱ )₃” or LiOPr ⁱ and La₂Mo₄O₈(OPr ⁱ )₁₄ in 1∶1 ratio, in toluene or ⁱ PrOH, by water solutions in isopropanol, leads to formation of monolythic gels. The latter can be converted by drying and heat treatment at 600°C into a fine powder of pure α-LiLaMo₂O₈ phase, which is transformed into β-LiLaMo₂O₈ powder by annealing at 800°C. The sintering of the pellets pressed under 4 bar pressure of α-LiLaMo₂O₈ powder at 800°C for 2 h converts them into pieces of β-LiLaMo₂O₈ transparent ceramics, thus providing a route to LiLnMo₂O₈ laser waveguide materials.     

Chemical composition and structure of the surface layers-products of interaction between steel 3 and hostile aqueous environment: The effect of the environment

The composition and structure of layers formed by corrosion products at the open-circuit and passive potentials on the surface of steel 3 in aqueous media containing sulfate ions, borate ions, or their mixtures are studied by X-ray photoelectron spectroscopy and secondary ion mass spectrometry. The composition and structure of both the phase surface layers and the adsorption surface layers are found to depend on the solution nature. The composition and structure of a corrosion product layer; the composition of the double layer, in particular, the surface charge and potential; and the anion role as a corrosion inhibitor or activator depend on the way the anion coordinates with the corroding-metal surface. The coordination may be strong, in an inner coordination sphere (borate ions), or less strong, in an outer coordination sphere (sulfate ions) of a cation on the surface.     

Isotope exchange of molecular nitrogen on barium nitride

The activity of barium nitride in the isotope exchange of nitrogen is 2–3 orders of magnitude higher than that of Fe and Ru. In the temperature range from 373 to 673 K the activation energy of exchange is 40 kJ/mol.

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2–3 Fe Ru. 373–673 40 /.

     

Impact of reaction products on the Grignard reaction with silanes and ketones

Grignard reactions with alkoxysilanes or carbonyl compounds produce alkoxymagnesium halides as by-products. Kinetic measurements for reactions of silanes and of a ketone were performed with Grignard reagents, enriched in alkoxymagnesium halides and taken in a great excess.The alkoxide-type reaction products complex tightly with Grignard reagents and enhance in this way their nucleophilicity, thus accelerating the reaction. However, alkoxides branched at α-C atom exert an unfavorable steric hindrance to reaction resulting in a decrease in the reaction rate.