Trifluorosulfonylation Cascade in Allenols: Stereocontrolled Synthesis of Bis(triflyl)enones

Herein, we report investigations embodying the first example of reversal of the native regioselectivity in the reaction of allenols with electrophiles. The effortlessness of C−C bond formation, mild reaction conditions, neither catalysts nor light irradiation, and exquisite selectivity, both in terms of functional-group tolerance and chemo-, site-, and stereo-selectivity, converts this trifluorosulfonylation-rearrangement sequence into an appealing protocol for the preparation of novel functionalized enones. The synthetic utility of this method has been validated by the conversion of the initially prepared bis(triflyl)enones into a variety of bis(triflyl)-functionalized molecules such as 1,3-dienes, allylic alcohols, pyrroles, pyrazoles, and chromenes. Besides, DFT calculations have provided a reliable understanding of observed selectivity.     

Elucidating the Nature of the External Acid Sites of ZSM-5 Zeolites Using NMR Probe Molecules

The identification of acid and nonacid species at the external surface of zeolites remains a major challenge, in contrast to the extensively-studied internal acid sites. Here, it is shown that the synthesis of zeolite ZSM-5 samples with distinct particle sizes, combined with solid-state NMR and computational studies of trimethylphosphine oxide (TMPO) adsorption, provides insight into the chemical species on the external surface of the zeolite crystals. ¹H–³¹P HETCOR NMR spectra of TMPO-loaded zeolites exhibit a broad correlation peak at δ_P ∼35–55 ppm and δ_H ∼5–12 ppm assigned to external SiOH species. Pore-mouth Brønsted acid sites exhibit ³¹P and ¹H NMR resonances and adsorption energies close to those reported for internal acid sites interacting with TMPO. The presence of an external tricoordinate Al-Lewis site interacting strongly with TMPO is suggested, resulting in ³¹P resonances that overlap with the peaks usually ascribed to the interaction of TMPO with Brønsted sites.     

Games with guaranteed scores and waiting moves

Combinatorial scoring games, with the property ‘extra pass moves for a player will do him no harm’, are characterized. The characterization involves an order embedding of Conway’s normal play games, and we call our class the universe of Guaranteed scoring games. Also, we give a theorem for comparing guaranteed games with scores (numbers) which extends Ettinger’s work on Dicot scoring games.     

Reflectance and ultraviolet spectroscopy: predicting the relative growth of Saccharomyces cerevisiae in pine biomass

Ultrasound treatment favors enzymatic attack on vegetal materials and influences biological activity. The objective of this study was to develop substrates for Saccharomyces cerevisiae based on the hydrothermal treatment and ultrasound treatment of pine needle biomass. The samples subjected to ultrasound treatment at 550?°C and 650?°C showed higher reflectance bands at around 200?nm after 80?min of ultrasound treatment and lower band gap energies associated with lower IC₃₀ values. The hydrothermal treatment with 100?min of ultrasound treatment generated more promising materials for the use of the substrates with the eukaryotic model S. cerevisiae.     

Structural and morphological studies on the deformation behavior of polypropylene/multi‐walled carbon nanotubes nanocomposites prepared through ultrasound‐assisted melt extrusion process

Structural and morphological behavior under stress–strain of polypropylene/multi‐walled carbon nanotubes (PP/MWCNTs) nanocomposites prepared through ultrasound‐assisted melt extrusion process was studied by means of optical microscopy, scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, small angle X‐ray scattering (SAXS), and wide angle X‐ray scattering (WAXS). A high ductile behavior was observed in the PP/MWCNT nanocomposites with low concentration of MWCNTs. This was related to an energy‐dissipating mechanism, achieved by the formation of an ordered PP‐CNTs interphase zone and crystal oriented structure in the undeformed samples. Different strain‐induced‐phase transformations were observed by ex situ SAXS/WAXS, characterizing the different stages of structure development during the deformation of PP and PP/MWCNTs nanocomposites. The high concentration of CNTs reduced the strain behavior of PP due to the agglomeration of nanoparticles. A structural pathway relating the deformation‐induced phase transitions and the dissipation energy mechanism in the PP/MWCNTs nanocomposites at low concentration of nanoparticles was proposed. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 475–491     

On Clifford Space Relativity,Black Hole Entropy,Rainbow Metrics,Generalized Dispersion and Uncertainty Relations

An analysis of some of the applications of Clifford space relativity to the physics behind the modified black hole entropy-area relations, rainbow metrics, generalized dispersion and minimal length stringy uncertainty relations is presented.     

Synthesis of Highly Functionalized N,N-Diarylamides by an Anodic C,N-Coupling Reaction

We report an innovative, sustainable and straightforward protocol for the synthesis of N,N-diarylamides equipped with nonprotected hydroxyl groups by using electrosynthesis. The concept allows the application of various substrates furnishing diarylamides with yields up to 57 % within a single and direct electrolytic protocol. The method is thereby easy to conduct in an undivided cell with constant current conditions offering a versatile and short-cut alternative to conventional pathways.     

A simple and efficient approach to the synthesis of β-N-methylamino-l-alanine (BMAA)

A novel, efficient, and straightforward synthesis of β-N-methylamino-l-alanine (BMAA) in two steps starting from l-N,N-dibenzylserine benzyl ester is described. This method, in the light of other syntheses of BMAA, provides benefits such as mild reaction conditions, a simple work-up procedure, good yields, and the retention of the serine stereochemistry.