Enantioselective organocatalytic formal allylation of α-branched aldehydes

Heteroarylvinyl sulfone 1 has been successfully used as a new sulfonyl Michael acceptor in aminocatalytic reactions with branched aldehydes. Subsequent one-pot Julia-Kocienski olefination allows the challenging preparation of enantiomerically pure α-allylated aldehydes bearing C-α quaternary carbons.     

Diffusion of moisture in deformable porous media. Anisotropic fibrous materials

This paper presents a study on the deformation of anisotropic fibrous porous media subjected to moistening by water in the liquid phase. The deformation of the medium is studied by applying the concept of effective stress. Given the structure of the medium, the displacement of the solid matrix is not taken into account with respect to the displacement of the liquid phase. The transport equations are derived from the model proposed by Narasimhan. The transport coefficients and the relation between the variation in apparent density and effective stress are obtained by test measurements. A numerical model has been established and applied for studying drip moistening of mineral wool samples capable or incapable of deformation.Nomenclature D mass diffusion coefficient [L²t^–1] - e void fraction - g gravity acceleration [Lt^–2] - J mass transfer density [ML^–2t^–1] - K hydraulic conductivity [Lt^–1] - K _s hydraulic conductivity of the solid phase [Lt^–1] - K ^* hydraulic conductivity of the deformable porous medium [Lt^–1] - P pressure of moistening liquid [ML^–1 t^–2] - S degree of saturation - t time [t] - V speed [Lt^–1] - X horizontal coordinate [L] - Z vertical coordinate measured from the bottom of porous medium [L] - z z-coordinate [L] Greek Letters porosity - ₁ total hydric potential [L] - _g gas density [ML^–3] - ₁ liquid density [ML^–3] - ₀ apparent density [ML^–3] - _s density of the solid phase [ML^–3] - density of the moist porous medium [ML^–3] - external load [ML^–1t^–2] - effective stress [ML^–1t^–2] - bishop's parameter - matrix potential or capillary suction [L] Indices g gas - 1 moistening liquid - p direction perpendicular to fiber planes - s solid matrix - t direction parallel to fiber planes - v pore Exponent * movement of solid particles taken into account     

Enhanced frequency upconversion in Er doped fluoroindate glass due to energy transfer from Tm

Energy transfer processes between Er³⁺ and Tm³⁺ were investigated examining the frequency upconversion emissions in a fluoroindate glass pumped at 790 nm. A 60-fold enhancement in the emission at ≈670 nm originating from Er³⁺ was observed when Tm³⁺ at concentration of 2% was introduced in a sample containing 2% of Er³⁺. The results are explained considering the influence of cross-relaxation processes between the active ions.     

Trivalent boron nucleophile as a new tool in organic synthesis: reactivity and asymmetric induction

Boron compounds have been traditionally regarded as "Lewis acids" preferring to accept electrons rather than donate them in the course of their reactions but current examples of unusual reactivity between tricoordinated boranes and electrophilic sites suggest a new conceptual context for the boryl moieties, based on their nucleophilic character which can be enhanced depending on the substituents on boron.     

The effect of stoichiometry on curing and properties of epoxy–clay nanocomposites

Epoxy–clay nanocomposites have been prepared with an organically modified montmorillonite. The epoxy network was based on diglycidyl ether of bisphenol A (DGEBA) cured with diaminodiphenylmethane (DDM). The stoichiometry DGEBA–DDM was varied, the molar ratio of amine hydrogen/epoxy groups, r, ranged from 0.85 to 1.15. The influence of stoichiometry on curing and properties of the nanocomposites was studied using differential scanning calorimetry, dynamic mechanical thermal analysis and X-ray diffraction. All nanocomposites had intercalated clay structures. The clays accelerated the curing reaction whose rate was also increased when increasing r. The heat of reaction, −ΔH (J/g epoxy), increased as r increased, reaching a constant value for r ≥ 1. In the presence of clays −ΔH was lower than in the neat DGEBA–DDM. The glass transition temperature (T _g) of the neat epoxy thermosets reached a maximum at r = 1; however, the nanocomposites showed the T _g maximum at 0.9 < r < 1. The presence of clay lowered the T _g for r > 0.94 and raised T _g for r ≤ 0.85. The elastic modulus of neat epoxy thermosets reached a maximum in the rubber state and a minimum in the glassy state at r = 1. The nanocomposites showed similar behavior, but the maximum and the minimum values of the elastic modulus were reached at stoichiometry r < 1. The comparison of the properties of neat epoxy with those of the nanocomposites varying the stoichiometry indicates that the clay itself induces stoichiometric changes in the system.     

N-Alkylamines-Based Micelles Aggregation Number Determination by Fluorescence Techniques

Aggregation numbers of micelles based on N-alkylamines and mixed systems CTACl/N-alkylamines have been determined using fluorescence techniques. The values of aggregation number are compared as a function of hydrocarbon chain length and as a function of the molar fraction in the mixed systems.     

Selective α-monoallylation of phenyl ketones and benzocycloalkanones under microwave irradiation

A method for the selective α-monoallylation of phenyl ketones and benzocycloalkanones with allyl alcohol under microwave irradation is described. The corresponding α-allyl ketones are obtained in moderate to good yields with only minor quantities of diallylation by-products.     

Hydrogen effects on the catalytic activity and selectivity of the zeolites H?NaY and PtH?NaY

The decomposition of methylcyclohexane on H–NaY and PtH–NaY zeolites has been studied. It has been found that the presence or abscence of H₂ affects not only the activity of these catalysts but also their selectivity to dehydrogenation and isomerization products.

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H–NaY PtH–NaY. , H₂ , .

     

A Covalent Organic Helical Cage with Remarkable Chiroptical Amplification

Purely organic shape‐persistent chiral cages are designed through the use of rigid chiral axes. Covalent dimerization of a tripodal fragment bearing chiral allenes forms a molecular twisted prism with loop‐like lateral edges presenting 10‐fold chiroptical amplification compared to its isolated building blocks. The expected geometry of covalent organic helical cage (M,M)₃‐ 1 was confirmed by X‐ray crystal structure analysis. Comparison of the chiroptical responses of this shape‐persistent molecular container with more flexible analogues highlights how the control of the conformational freedom of the molecule can be used to obtain molecular cages with strong chiroptical responses. Selective inclusion‐complex formation with ferrocenium ions [(P,P)₃‐ 1 @Fc⁺] was confirmed and quantified with HR‐ESI‐MS and NMR spectroscopy.