Strong Coupling of Chiral Frenkel Exciton for Intense,Bisignate Circularly Polarized Luminescence

We show that chiral Frenkel excitons yield intense circularly polarized luminescence with an intrinsic dissymmetry factor in emission g_lum as high as 0.08. This outstanding value is measured through thin films of cyanine J-aggregates that form twisted bundles. Our measurements, obtained by a Mueller polarization analysis, are artifact-free and reveal a quasi-perfect correlation between the dissymmetry factors in absorption, g_abs, and in emission g_lum. We interpret the bisignate dissymmetry factors as the signature of a strong coupling between chiral Frenkel excitons longitudinally excited along the bundles. We further resolve by polarimetry analysis the split in energy between the excited states with a Davydov splitting as small as 28 meV. We finally show the anti-Kasha nature of the chiral emission bands with opposite optical chirality. These mirror-imaged emissive chiroptical features emerge from the structural rigidity of the bundles that preserves the ground- and excited-state chirality.     

Palladium-catalyzed coupling of vinyl tosylates with arylsulfinate salts

The first palladium-catalyzed coupling of vinyl tosylates with arylsulfinate salts is described. A variety of cyclic and acyclic vinyl tosylates were coupled with aryl sulfinate salts using 2.5 mol % Pd₂(dba)₃/5.0 mol % XantPhos to give vinyl aryl sulfone products in good yields. The coupling was extended to the preparation of a cyclopropyl vinyl sulfone.     

Protoilludane sesquiterpenes: synthesis of (±)-cerapicol, formal synthesis of (±)-sterpurene, and synthesis and absolute configuration of (+)-cerapicol

New approaches to the protoilludane sesquiterpenes (±)-cerapicol and (±)-sterpurene via rearrangement routes are described. The absolute configuration of (+)-cerapicol has been determined and found in accord with a biosynthesis of the natural product via cyclization of humulene to the so-called protoilludyl cation and a subsequent 1,2-alkyl shift.     

New (PP/EPR)/nano‐CaCO3 based formulations in the perspective of polymer recycling. Effect of nanoparticles properties and compatibilizers

Phase structure of composite polypropylene (PP)/ethylene–propylene–rubber (EPR)/coated nano‐CaCO₃ composites, used in the manufacture of bumpers, with and without compatibilizers has been investigated using scanning electron microscopy (SEM), dynamic mechanical analysis (DMA) mechanical tests, and differential scanning calorimetry (DSC). Blends of various compositions were prepared using a corotating twin‐screw extruder. The experimental results indicated that the dispersion of nanoparticles in (PP/EPR) depends on their surface (stearic acid and fatty acid coatings). In both cases, the final morphology is the core–shell structure in which EPR acts as the shell part encapsulating coated nano‐CaCO₃. In this case, EPR‐g‐MAH copolymer does not improve the interface between (PP/EPR) and nanoparticles but PEP propylene ethylene copolymer should be preferentially localized at the interface of PP and (EPR/nano‐CaCO₃) phases generating an improved adherence, which will ensure a better cohesion of the whole material. According to the nature of the compatibilizers and surface treatment, it is believed that the synergistic effect of both the EPR elastomer and CaCO₃ nanoparticles should account for the balanced performance of the ternary composites. Copyright © 2009 John Wiley & Sons, Ltd.     

Altholactone displays promising antimicrobial activity

The antimicrobial activity of altholactone, a naturally extracted styryllactone isolated from Goniothalamus malayanus, was determined against Gram positive (S. aureus ATTC 25923, S. aureus ATTC 25392, and E. faecalis ATTC 29212) and Gram negative (E. coli ATTC 35218, S. typhi ATTC 14023 and P. aeruginosa ATCC 27853) reference bacteria and against the fungus C. albicans ATTC 10231. Different concentrations of altholactone (0, 12, 25, and 50 μg/mL) were used. Results revealed that altholactone inhibited the growth of all tested microbes except P. aeruginosa ATCC 27853 in a dose-dependent manner, with the highest cytotoxic effects occurring at 50 μg/mL. The average of the inhibition zones of the different concentrations was between 0-30 mm. Furthermore, altholactone-induced antimicrobial activity against the more sensitive microbes was assessed by measuring the minimal inhibitory concentration (MIC). Results indicated that Gram positive (S. aureus ATTC 25923, S. aureus ATTC 25392, and E. faecalis ATTC 29212) cells were more sensitive to altholactone than Gram negative ones (E. coli ATTC 35218, S. typhi ATTC 14023). C. albicans showed moderate sensitivity. These results indicate that altholactone might be a potential antimicrobial agent, particularly in ciprofloxacin-refractory S. aureus and E. faecalis infections. Further investigations are required to illustrate the mechanism(s) by which altholactone produces its antimicrobial effects.     

Substituent effects on the reactions of aromatic triflones with para‐X‐anilines in methanol: Low intrinsic reactivity and transition state imbalances

A kinetic study is reported for S_NA_r reactions of 2,4,6‐tris(trifluoromethanesulfonyl) anisole 1a with a series of para‐X‐substituted anilines 2a–e in a methanol solution at various temperatures. The substituent effects on free energy (Δ^≠G), enthalpy (Δ^≠H), and entropy (Δ^≠S) of activation are examined. Aniline addition to triflone 1a is characterized by a β_X=0.57, α_Z=0.31, and an imbalance of I = α_Z–β_X=?0.26. The imbalance shows that resonance development lags behind C? N bond formation at the transition state. Interestingly, analysis of the results in terms of Marcus theory reveals that these S_NAr are associated with some extremely low intrinsic reactivity (log k_o=?1.25& © 2011 Wiley Peiodicals, Inc. Int J Chem Kinet 43: 255–262, 2011     

A conservative stabilized finite element method for the magneto‐hydrodynamic equations

This work presents a finite element solution of the 3D magneto‐hydrodynamics equations. The formulation takes explicitly into account the local conservation of the magnetic field, giving rise to a conservative formulation and introducing a new scalar variable. A stabilization technique is used in order to allow equal linear interpolation on tetrahedral elements of all the variables. Numerical tests are performed in order to assess the stability and the accuracy of the resulting methods. The convergence rates are calculated for different stabilization parameters. Well‐known MHD benchmark tests are calculated. Results show good agreement with analytical solutions. Copyright © 1999 John Wiley & Sons, Ltd.     

1,2,3-Triazolyl-tetrahydropyrimidine Conjugates as Potential Sterol Carrier Protein-2 Inhibitors: Larvicidal Activity against the Malaria Vector Anopheles arabiensis and In Silico Molecular Docking Study

Alteration of insect growth regulators by the action of inhibitors is becoming an attractive strategy to combat disease-transmitting insects. In the present study, we investigated the larvicidal effect of 1,2,3-triazolyl-pyrimidinone derivatives against the larvae of the mosquito Anopheles arabiensis, a vector of malaria. All compounds demonstrated insecticidal activity against mosquito larvae in a dose-dependent fashion. A preliminary study of the structure–activity relationship indicated that the electron-withdrawing substituent in the para position of the 4-phenyl-pyrimidinone moiety enhanced the molecules’ potency. A docking study of these derivatives revealed favorable binding affinity for the sterol carrier protein-2 receptor, a protein present in the intestine of the mosquito larvae. Being effective insecticides against the malaria-transmitting Anopheles arabiensis, 1,2,3-triazole-based pyrimidinones represent a starting point to develop novel inhibitors of insect growth regulators.     

Deacetylation of Thioacetate using Acetyl Chloride in Methanol

A highly efficient method for the deacetylation of thioacetate is reported under mild acidic conditions employing acetyl chloride in methanol. Some of the major advantages are mild conditions, high efficiency, high yields, and easy operations.     

Application of the palladium-catalyzed N-arylation of hydrazones to deactivated heteroaryl halides in the synthesis of pyrazoles

A versatile synthesis of heteroaryl pyrazoles from deactivated heteroaryl halides was demonstrated with different 1,3-bifunctional substrates under acidic conditions. Practical conditions for the transhydrazonation/cyclization step were developed.