Enantioselective synthesis of cyclic, quaternary oxonitriles

Quaternary oxonitriles are stereoselectively generated from the union of five-, six-, and seven-membered 2-chloroalkenecarbonitriles with chiral alcohols via a Claisen rearrangement. The strategy rests on a new conjugate addition-elimination of allylic alkoxides to 2-chlorocycloalkenecarbonitriles to afford substituted 2-alkoxyalkenenitriles. Subsequent thermolysis unmasks a cyclic oxonitrile while selectively forming a new quaternary center with enantiomeric ratios typically greater than 9:1. The overall alkylation strategy addresses the challenge of enantioselectively generating hindered, quaternary centers while simultaneously installing ketone, nitrile, and olefin functionalities.     

Preparation of quaternized dimethylaminoethylmethacrylate grafted nonwoven fabric for the removal of phosphate

Dimethylaminoethylmethacrylate (DMAEMA) grafted polyethylene/polypropylene (PE/PP) nonwoven fabric was prepared by radiation-induced graft polymerization. Grafting conditions were optimized and about 150% DMAEMA grafted samples were used for further experiments. DMAEMA graft chains were later quaternized with dimethyl sulphate for the removal of phosphate ions. Adsorption experiments were conducted with quaternized DMAEMA grafted fabric for phosphate removal at low (0.5–25 ppm) and high phosphate concentrations (50–1000 ppm). Adsorbed phosphate amounts at pH 7 were found to be 63 mg phosphate/g polymer and 512 mg phosphate/g polymer for low (25 ppm) and high phosphate concentrations (1000 ppm) respectively showing the efficiency of the adsorbent material in removing phosphate. The pH effect on phosphate adsorption showed that the quaternized DMAEMA grafted nonwoven fabric can adsorb phosphate over a wide pH range (5.00–9.00) indicating that adsorbent material can effectively remove different forms of phosphate ions, namely H₂PO₄^?, HPO₄^2? and PO₄^3? in aqueous solution at this pH range where the species exist. Competitive adsorption experiments were also carried out with two concentration levels at pH 7 to investigate the effect of competing ions. Phosphate adsorption on quaternized DMAEMA grafted nonwoven fabric was found to be higher than the other competing ions at two concentration levels. At high concentration level, the adsorption order was phosphate>nitrite>bromide>sulphate>nitrate whereas at low concentration level, the order was phosphate?sulphate>bromide>nitrite>nitrate.     

Thermal desorption/gas chromatography/mass spectrometry approach for characterization of the volatile fraction from amber specimens: A possibility of tracking geological origins

Research on the chemical composition of fossil resins has evolved during the last decades as a multidisciplinary field and is strongly oriented toward the correlation with their geological and botanical origin. Various extraction procedures and chromatographic techniques have been used together for identifying the volatile compounds contained in the fossil resin matrix. Hyphenation between thermal desorption (TD), gas chromatography (GC) and mass spectrometry detection (MS) has been chosen to investigate the volatile compounds fraction from ambers with a focus on Romanite (Romanian amber) and Baltic amber species. A data analysis procedure was developed for the main purpose of fingerprinting ambers based on the MS identity of the peaks generated by the volatile fraction, together with their relative percentual area within the chromatogram. Chromatographic data analysis was based entirely on Automated Mass Spectral Deconvolution & Identification System (AMDIS) software to produce deconvoluted mass spectra which were used to build-up a mixed mass spectra and relative retention scale library. Multivariate data analysis was further applied on AMDIS results with successful discrimination between Romanite and Baltic ambers. A special trial was conducted to generate pyrolysis “like” macromolecular structure breakdown to volatile compounds by gamma irradiation with a high absorbed dose of 500 kGy. Contrary to our expectations the volatile fraction fingerprints were not modified after irradiation experiments. A complementary non-destructive new approach by ESR spectroscopy was also proposed for discriminating between Romanite and Baltic ambers.     

Thermal stability of corrugated epitaxial graphene grown on Re(0001)

We report on a novel approach to determine the relationship between the corrugation and the thermal stability of epitaxial graphene grown on a strongly interacting substrate. According to our density functional theory calculations, the C single layer grown on Re(0001) is strongly corrugated, with a buckling of 1.6 ?, yielding a simulated C 1s core level spectrum which is in excellent agreement with the experimental one. We found that corrugation is closely knit with the thermal stability of the C network: C-C bond breaking is favored in the strongly buckled regions of the moiré cell, though it requires the presence of diffusing graphene layer vacancies.     

On the Eigenvalues and Eigenvectors of a Lorentzian Rotation Matrix by Using Split Quaternions

In this paper, we examine eigenvalue problem of a rotation matrix in Minkowski 3 space by using split quaternions. We express the eigenvalues and the eigenvectors of a rotation matrix in term of the coefficients of the corresponding unit timelike split quaternion. We give the characterizations of eigenvalues (complex or real) of a rotation matrix in Minkowski 3 space according to only first component of the corresponding quaternion. Moreover, we find that the casual characters of rotation axis depend only on first component of the corresponding quaternion. Finally, we give the way to generate an orthogonal basis for ${\mathbb{E}^{3}_{1}}$ by using eigenvectors of a rotation matrix.     

On the best constant in Hyers–Ulam stability of some positive linear operators

We obtain the infimum of the Hyers–Ulam stability constants for Stancu, Bernstein and Kantorovich operators and prove that in a class of certain positive linear operators this infimum for Bernstein operator has a minimality property.     

Strong and Weak Solutions to Second Order Differential Inclusions Governed by Monotone Operators

In this paper we introduce the concept of a weak solution for second order differential inclusions of the form u″(t) ∈ Au(t) + f(t), where A is a maximal monotone operator in a Hilbert space H. We prove existence and uniqueness of weak solutions to two point boundary value problems associated with such kind of equations. Furthermore, existence of (strong and weak) solutions to the equation above which are bounded on the positive half axis is proved under the optimal condition tf(t) ∈ L ¹(0, ∞; H), thus solving a long-standing open problem (for details, see our comments in Section 3 of the paper). Our treatment regarding weak solutions is similar to the corresponding theory related to the first order differential inclusions of the form f(t) ∈ u′(t) + Au(t) which has already been well developed.     

On the Dynamics of Space Debris: 1:1 and 2:1 Resonances

We study the dynamics of the space debris in the 1:1 and 2:1 resonances, where geosynchronous and GPS satellites are located. By using Hamiltonian formalism, we consider a model including the geopotential contribution for which we compute the secular and resonant expansions of the Hamiltonian. Within such model we are able to detect the equilibria and to study the main features of the resonances in a very effective way. In particular, we analyze the regular and chaotic behavior of the 1:1 and 2:1 resonant regions by analytical methods and by computing the Fast Lyapunov Indicators, which provide a cartography of the resonances. This approach allows us to detect easily the location of the equilibria, the amplitudes of the libration islands and the main dynamical stability features of the resonances, thus providing an overview of the 1:1 and 2:1 resonant domains under the effect of Earth’s oblateness. The results are validated by a comparison with a model developed in Cartesian coordinates, including the geopotential, the gravitational attraction of Sun and Moon and the solar radiation pressure.     

Scale-up synthesis of zinc borate from the reaction of zinc oxide and boric acid in aqueous medium

Synthesis of zinc borate was conducted in a laboratory and a pilot scale batch reactor to see the influence of process variables on the reaction parameters and the final product, 2ZnO·3B₂O₃·3.5H₂O. Effects of stirring speed, presence of baffles, amount of seed, particle size and purity of zinc oxide, and mole ratio of H₃BO₃:ZnO on the zinc borate formation reaction were examined at a constant temperature of 85 °C in a laboratory (4 L) and a pilot scale (85 L) reactor. Products obtained from the reaction in both reactors were characterized by chemical analysis, X-ray diffraction, particle size distribution analysis, thermal gravimetric analysis and scanning electron microscopy. The kinetic data for the zinc borate production reaction was fit by using the logistic model. The results revealed that the specific reaction rate, a model parameter, decreases with increase in particle size of zinc oxide and the presence of baffles, but increases with increase in stirring speed and purity of zinc oxide; however, it is unaffected with the changes in the amount of seed and reactants ratio. The reaction completion time is unaffected by scaling-up.