Regioselective 1,4-trifluoromethylation of α,β-enones using ‘protect-in-situ’ methodology

In a convenient and efficient procedure, the nucleophilic 1,4-trifluoromethylation of several α,β-enones using (trifluoromethyl)trimethylsilane was achieved. The high regioselectivity of the reaction has been reached by blocking the carbonyl moiety of the electrophile with a bulky aluminum-centered Lewis acid.     

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     

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.     

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.     

Insulating tubular BN sheathing on semiconducting nanowires

An effective method was developed for generation of insulating tubular boron nitride (BN)-sheathed nanostructures. ZnS nanowires and multilayered Si-SiO2 nanowires were successfully sheathed with insulating tubular BN-forming nanocables. Both the semiconductor nanowire cores and the BN sheaths are crystalline with well-uniform morphologies.     

Synthesis of 2,3,9,10,16,17,23,24-Octaalkynylphthalocyanines and the Effects of Concentration and Temperature on Their (1)H NMR Spectra

The syntheses of 3,4- and 4,5-diiodophthalonitriles are described. Coupling of the latter compound with Pd(PPh(3))(2)Cl(2) and 1-octyne, 1-heptyne, 1-hexyne, 1-pentyne, and 3,3-dimethyl-1-butyne gave a series of 4,5-dialkynylphthalonitriles. Hydrogenation of 4,5-bis(1-pentynyl)phthalonitrile and 4,5-bis(3,3-dimethyl-1-butynyl)phthalonitrile gave 4,5-dipentylphthalonitrile and 4,5-bis(3,3-dimethylbutyl)phthalonitriles. Condensation of the dialkynylphthalonitriles with lithium 1-pentoxide in 1-pentanol gave 2,3,9,10,16,17,23,24-octaalkynylphthalocyanines, while intervention of the intermediate dilithium phthalocyanines with zinc acetate gave the related zinc(II) phthalocyanines. (1)H NMR spectroscopy of these octaalkynylphthalocyanines exhibited large chemical shifts (1-2 ppm) of the internal and aromatic protons at concentrations ranging from 10(-)(2) to 10(-)(5) M and at temperatures from 27 to 147 degrees C. The effects of aggregation phenomena are discussed. The importance of reporting concentration and temperature values for NMR spectra of phthalocyanines is stressed.     

Catalyzed collapse and enhanced hydrogen storage of BN nanotubes

The novel morphology of BN nanotubes with a collapsed structure has been discovered by a metal-catalyzed treatment. The collapse causes the dramatic enlargement of a specific surface area of BN nanotubes and remarkably enhances the hydrogen storage capacity of BN nanotubes.     

Probing the kinetic landscape of transient peptide-protein interactions by use of peptide (15)n NMR relaxation dispersion spectroscopy: binding of an antithrombin peptide to human prothrombin

Protein-ligand interactions may lead to the formation of multiple molecular complexes in dynamic exchange, affecting the kinetic and thermodynamic characteristics of the binding equilibrium. We followed the dissociation kinetics of the transient and specific complex of an antithrombotic peptide N-acetyl-Asp(55)-Phe-Glu-Glu-Ile-Pro(60)-Glu-Glu-Tyr-Leu-Gln(65) with human prothrombin by use of (15)N NMR relaxation dispersion spectroscopy of the peptide. Every one of the five (15)N-labeled adjacent residues of the peptide exhibited apparently different kinetic exchange and relaxation behaviors, which were especially evident at different concentrations of prothrombin. Binding-induced (15)N relaxation dispersion of residues Phe(56), Glu(57), Glu(58), and Ile(59) can be fitted phenomenologically to a two-site on-and-off exchange mechanism with physically feasible relaxation and kinetic parameters obtained for residues Phe(56), Glu(58), and Ile(59), independent of the prothrombin concentration. The apparent kinetic parameters of Glu(57) show some dependence on the concentration of prothrombin and the extracted transverse relaxation rate for Glu(57) in the bound state was severalfold higher than that expected for a protein-peptide complex with a size of approximately 72 kDa. In addition, the equilibrium population of the bound peptide obtained for Glu(57) was inconsistent with those for Phe(56), Glu(58), and Ile(59) and with the prothrombin/peptide ratios used in the experiments. These discrepancies can be explained by the presence of two conformations for the peptide-protein complex exchanging at a rate of approximately 100 s(-)(1). In all, our study shows that fast dissociation of protein-peptide complexes can be studied quantitatively using peptide (15)N NMR relaxation dispersion measurements without a precise knowledge of the peptide and protein concentrations. In addition, protein titration was found to improve the accuracy of quantitative analysis and may make it possible to determine the rate of conformational changes within the protein-peptide complex.     

Pyridine Carboxamides Based on Sulfobetaines: Design,Reactivity, and Biological Activity

The synthesis of the products of the 1,3-propanesultone ring opening during its interaction with amides of pyridinecarboxylic acids has been carried out. The dependence of the yield of the reaction products on the position (ortho-, meta-, para-) of the substituent in the heteroaromatic fragment and temperature condition was revealed. In contrast to the meta- and para-substituted substrates, the reaction involving ortho-derivatives at the boiling point of methanol unexpectedly led to the formation of a salt. On the basis of spectroscopic, X-Ray, and quantum-chemical calculation data, a model of the transition-state, as well as a mechanism for this alkylation reaction of pyridine carboxamides with sultone were proposed in order to explain the higher yields obtained with the nicotinamide and its N-methyl analog compared to ortho or meta parents. Based on the analysis of ESP maps, the positions of the binding sites of reagents with a potential complexing agent in space were determined. The in silico evaluation of possible biological activity showed that the synthetized compounds revealed some promising pharmacological effects and low acute toxicity.     

Hybrid Silsesquioxane/Benzoate Cu7-Complexes: Synthesis,Unique Cage Structure,and Catalytic Activity

A series of phenylsilsesquioxane-benzoate heptacopper complexes 1–3 were synthesized and characterized by X-ray crystallography. Two parallel routes of toluene spontaneous oxidation (into benzyl alcohol and benzoate) assisted the formation of the cagelike structure 1. A unique multi-ligation of copper ions (from (i) silsesquioxane, (ii) benzoate, (iii) benzyl alcohol, (iv) pyridine, (v) dimethyl-formamide and (vi) water ligands) was found in 1. Directed self-assembly using benzoic acid as a reactant afforded complexes 2–3 with the same main structural features as for 1, namely heptanuclear core coordinated by (i) two distorted pentameric cyclic silsesquioxane and (ii) four benzoate ligands, but featuring other solvate surroundings. Complex 3 was evaluated as a catalyst for the oxidation of alkanes to alkyl hydroperoxides and alcohols to ketones with hydrogen peroxide and tert-butyl hydroperoxide, respectively, at 50 °C in acetonitrile. The maximum yield of cyclohexane oxidation products as high as 32% was attained. The oxidation reaction results in a mixture of cyclohexyl hydroperoxide, cyclohexanol, and cyclohexanone. Upon the addition of triphenylphosphine, the cyclohexyl hydroperoxide is completely converted to cyclohexanol. The specific regio- and chemoselectivity in the oxidation of n-heptane and methylcyclohexane, respectively, indicate the involvement of of hydroxyl radicals. Complex 3 exhibits a high activity in the oxidation of alcohols.