Gas phase isopropylation of aromatic hydrocarbons. Fluorine and methyl substituent effects on reactivity and orientation.

The isopropylation of substituted benzenes by $\text{s}$C₃H⁺₇ cations is studied to evaluate the directive effects of fluorine, methyl group and their combinations as ring substituents in the gas-phase aromatic substitution.     

Morphology and surface heterogeneities in synthetic goethites

In the framework on a study of the acido-basic and sorption properties of iron oxides, a thorough characterization of two types of goethite powders was performed in several laboratories joined in a common project. Chemical analysis by ICPAES; high-resolution SEM, TEM, and AFM observations; XRD with line width analysis; and argon and nitrogen sorption isotherms were used for that purpose. The main crystallographic faces of goethite particles could be identified as {001}, {101}, and {121}, and their abundance correlated with the distribution of low-pressure argon adsorption local isotherms. These results will be very useful for further studies on the relationship between surface reactivity in aqueous solution and orientation of solid surfaces.     

Acid catalyzed rearrangements in the arylimino indoline series. Part IV . Reactions of 1,2-dihydro-2-phenyl-2-(indol-3-yl-derivatives)-3-phenylimino-3H-indole with trichloroacetic and hydrochloric acids. Crystal structure of 1,2-dihydro-2-phenyl-2-(indol-3-yl)-3-phenylimino-3H-indole

2-Phenyl-3-phenylimino-3H-indole reacts with indole, 2-methylindole and 1,2-dimethylindole in the presence of stoichiometric trichloroacetic acid to form 1,2-dihydro-2-phenyl-2-(indol-3-yl-derivatives)-3-phenylimino-3H-indole, which during a longer period of time (16 hours) undergoes indolyl transposition to carbon-3 and elimination of aniline affording the 3,3′-bis-indolyls. In the case of 1,2-dimethylindole the intermediate coming from the indolyl migration may undergo a nucleophilic addition to carbon-2 of another molecule of indole; the new intermediate leads to the formation of 2-phenyl-3,3′-di-(1,2-dimethylindol-3-yl)-3H-indole by elimination of aniline and migration to carbon-3 of the second molecule of indole. By treatment with hydrochloric acid in refluxing ethanol, 1,2-dihydro-2-phenyl-2-(indol-3-yl-derivatives)-3-phenylimino-3H-indole afford to 3,3′-bis-indolyls and 1,2-dihydro-2-phenyl-2-(indol-3-yl-derivatives)-3H-indol-3-one (indoxyls). The crystal structure of 1,2-dihydro-2-phenyl-2-(indol-3-yl)-3-phenylimino-3H-indole is also reported. The latter compound does not give rearrangement products by acid treatment, only untreatable tarry material.     

A convenient method for the assignment of the absolute configuration to cyclic amines

We have assigned the absolute configuration to trans-2,5-dimethylpyrrolidine and trans-2,6-dimethyl-piperidine through radical chlorination in ω-1 position of optically active amines, 2 and 5, of known absolute configuration, followed by cyclization. CD curves of 1f and 4g derivatives indicate that the reaction is stereospecific. The absolute configuration of trans-2,5-dimethyl-Δ³-pyrròline has also been determined.     

Efficient cleavage of carboxylic tert-butyl and 1-adamantyl esters, and N-Boc-amines using H2SO4 in CH2Cl2

A new procedure for the deprotection of carboxylic tert-butyl and 1-adamantyl esters, and N-Boc-amines using H₂SO₄ in CH₂Cl₂ is described. The proposed method is simple, cheap, eco-friendly and represents a valid alternative to existing ones, with special significance in large scale applications.     

Rumor spreading in random evolving graphs

We analyze randomized broadcast in dynamic networks modeled as edge‐Markovian evolving graphs. The most realistic range of edge‐Markovian parameters yields sparse and disconnected graphs. We prove that, in this setting, the “push” protocol completes with high probability in optimal logarithmic time. © 2015 Wiley Periodicals, Inc. Random Struct. Alg., 48, 290–312, 2016     

Natural almost contact structures and their 3D homogeneous models

We consider a natural condition determining a large class of almost contact metric structures. We study their geometry, emphasizing that this class shares several properties with contact metric manifolds. We then give a complete classification of left‐invariant examples on three‐dimensional Lie groups, and show that any simply connected homogeneous Riemannian three‐manifold admits a natural almost contact structure having g as a compatible metric. Moreover, we investigate left‐invariant CR structures corresponding to natural almost contact metric structures.     

LC–MS–MS Determination of Rotenone, Deguelin, and Rotenolone in Human Serum

For the first time we report a rapid and sensitive LC–MS–MS method for quantification of rotenone, deguelin, and rotenolone in human serum. The analytical procedure involves extraction with ethyl acetate without further clean-up. The active ingredients were separated on a C₈ reversed-phase column by isocratic elution. Eleven simultaneous transitions of precursor ions were monitored. Excellent selectivity and sensitivity enables quantification and identification of low levels of rotenoids (LOD 2 ng mL^?1, LOQ 5 ng mL^?1) in human serum.     

Structure and morphology of HDPE-g-MA/organoclay nanocomposites: Effects of the preparation procedures

Nanocomposites comprising high density polyethylene (HDPE) or maleic anhydride-grafted HDPE (HDMA) as the host polymers and Cloisite^® 20A (20A) as the organoclay filler were prepared by melt-compounding, solution-blending and static annealing of polymer/clay powder mixtures. The dependence of their structure and morphology on the preparation conditions was studied by X-ray diffraction (XRD and SAXS), polarized optical microscopy (POM), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). It was shown that intercalated nanocomposites based on HDPE or HDMA cannot be obtained by solution-blending, as long as solvent removal is made at room temperature. In fact, wide angle XRD patterns of solution blended composites are similar to those of mechanical blends of clay and polymer. However, as demonstrated by XRD and SAXS, fast intercalation or even complete delamination was obtained when the HDMA composites prepared from solution were annealed statically at temperatures higher than the polymer melting point. This implies that solution-blending causes efficient fragmentation of the clay agglomerates into thin tactoids (though unintercalated) homogeneously dispersed in the polymer matrix. This conclusion, supported by the finding that annealing mechanical blends of polymer and clay powders only leads to intercalated structures, was confirmed by TEM and SEM analyses. Morphology investigation revealed that, in contrast to melt-compounding, solution-blending followed by static annealing fails to produce significant orientation of clay platelets and polymer crystallites. However, repeated compression molding cycles were shown by XRD and SAXS to cause increasing levels of orientation of the platelets and the polymer matrix parallel to the sample flat surface.