Organocatalytic,Asymmetric Eliminative [4+2] Cycloaddition of Allylidene Malononitriles with Enals: Rapid Entry to Cyclohexadiene‐Embedding Linear and Angular Polycycles

A direct aminocatalytic synthesis has been developed for the chemo‐, regio‐, diastereo‐, and enantioselective construction of densely substituted polycyclic carbaldehydes containing fused cyclohexadiene rings. The chemistry utilizes, for the first time, remotely enolizable π‐extended allylidenemalononitriles as electron‐rich 1,3‐diene precursors in a direct eliminative [4+2] cycloaddition with both aromatic and aliphatic α,β‐unsaturated aldehydes. The generality of the process is demonstrated by approaching 6,6‐, 5,6‐, 7,6‐, 6,6,6‐, and 6,5,6‐fused ring systems, as well as biorelevant steroid‐like 6,6,6,6,5‐ and 6,6,6,5,6‐rings. A stepwise reaction mechanism for the key [4+2] addition is proposed as a domino bis‐vinylogous Michael/Michael/retro‐Michael reaction cascade. The utility of the malononitrile moiety as traceless activating group of the dicyano nucleophilic substrates is demonstrated.     

Opening the Pandora's jar of molecule‐to‐material conversion in chemical vapor deposition: Insights from theory

First‐principles modeling can be a powerful tool for the understanding and optimization of bottom‐up processes for nanomaterials fabrication, such as chemical vapor deposition (CVD), a key technology for the development of advanced systems and devices. Molecule‐to‐material conversion by CVD involves complex chemical phenomena, which are often obscure and still largely unexplored. A proper modeling would require high level of accuracy, large sized models and should include both temperature effects and statistical sampling of reactive events. By presenting a few selected examples, this perspective surveys such problems and discusses currently available approaches for their solution. Possible strategies for future advances in the field are also highlighted. © 2013 Wiley Periodicals, Inc.     

Blue fluorescent dye-protein complexes based on fluorogenic cyanine dyes and single chain antibody fragments

Fluoromodules are complexes formed upon the noncovalent binding of a fluorogenic dye to its cognate biomolecular partner, which significantly enhances the fluorescence quantum yield of the dye. Previously, several single-chain, variable fragment (scFv) antibodies were selected from a yeast cell surface-displayed library that activated fluorescence from a family of unsymmetrical cyanine dyes covering much of the visible and near-IR spectrum. The current work expands our repertoire of genetically encodable scFv-dye pairs by selecting and characterizing a group of scFvs that activate fluorogenic violet-absorbing, blue-fluorescing cyanine dyes, based on oxazole and thiazole heterocycles. The dye binds to both yeast cell surface-displayed and soluble scFvs with low nanomolar K(d) values. These dye-protein fluoromodules exhibit high quantum yields, approaching unity for the brightest system. The promiscuity of these scFvs with other fluorogenic cyanine dyes was also examined. Fluorescence microscopy demonstrates that the yeast cell surface-displayed scFvs can be used for multicolor imaging. The prevalence of 405 nm lasers on confocal imaging and flow cytometry systems make these new reagents potentially valuable for cell biological studies.     

A new azorellane diterpenoid from Azorella madreporica

A new azorellane diterpenoid has been isolated and identified from the aerial parts of Azorella madreporica Clos. The structure of 1 was established by one- and two-dimensional NMR techniques.     

Commutability of homogenization and linearization at identity in finite elasticity and applications

We prove under some general assumptions on elastic energy densities (namely, frame indifference, minimality at identity, non-degeneracy and existence of a quadratic expansion at identity) that homogenization and linearization commute at identity. This generalizes a recent result by S. Müller and the second author by dropping their assumption of periodicity. As a first application, we extend their Γ-convergence commutation diagram for linearization and homogenization to the stochastic setting under standard growth conditions. As a second application, we prove that the Γ-closure is local at identity for this class of energy densities.     

Highly efficient hydrogen-bonding catalysis of the Diels-Alder reaction of 3-vinylindoles and methyleneindolinones provides carbazolespirooxindole skeletons

Carbazolespirooxindole derivatives were synthesized in a high-yielding, atypically rapid, stereocontrolled Diels-Alder reaction catalyzed by a C(2)-symmetric bisthiourea organocatalyst. Simple precursors and mild conditions were used to construct carbazolespirooxindole derivatives with high enantiopurity and structural diversity under H-bonding catalysis. The practical approach recycles the organocatalyst and solvent. This simple and efficient operational procedure will allow diversity-oriented syntheses of this intriguing class of compounds.     

Elucidating the nature and reactivity of Ti ions incorporated in the framework of AlPO-5 molecular sieves. New evidence from 31P HYSCORE spectroscopy

The incorporation of Ti ions within the framework of aluminophosphate zeotype AlPO-5 and their chemical reactivity is studied by means of CW-EPR, HYSCORE, and UV-vis spectroscopies. Upon reduction, Ti(3+) ions are formed, which exhibit large (31)P hyperfine couplings, providing direct evidence for framework substitution of reducible Ti ions at Al sites.     

Structural and spectroscopic investigation of ZnS nanoparticles grown in quaternary reverse micelles

ZnS nanoparticles were synthesized in four component "water in oil" microemulsions formed by a cationic surfactant (cetyltrimethylammonium bromide, CTAB), a cosurfactant (pentanol or butanol), n-hexane and water. The effect of various parameters (nature of cosurfactant, water/surfactant W(0), and alcohol/surfactant P(0)) on the formation and stability of ZnS nanoparticles was investigated thoroughly. UV-Vis spectroscopy was employed to directly follow the formation of ZnS systems in the microemulsions. Thus, particle size was estimated from the position of the first excitonic transition by employing an approximate finite-depth equation and an empirical correlation, giving average diameters in the ranges 2.3-2.5 and 3.0-3.5nm, respectively. Stable ZnS nanoparticles were obtained by employing low water and high cosurfactant amounts. This suggests that at high concentration the cosurfactant molecules act as capping agents on the surface of the inverse micelles, while low water amounts are needful to obtain water droplets with a radius close to that of the interfacial film spontaneous curvature. HRTEM analysis showed that the samples are formed by a few crystalline ZnS nanoparticles of spherical shape, embedded in and amorphous organic matrix, with a coherent scattering domain between 2 and 4nm.     

Hetero-Diels-Alder reaction of phosphinyl and phosphonyl nitroso alkenes with conjugated dienes: an aza-Cope rearrangement

Phosphorylated nitroso alkenes react with cyclic dienes such as cyclopentadiene or cyclohexadiene to afford hetero Diels-Alder-type cycloadducts where the nitroso alkene participates as dienophile component and the cyclic olefin acts as the 4π-electron (diene) system. Subsequent aza-Cope rearrangement affords highly functionalized 5,6-dihydro-4H-1,2-oxazines. Conversely, the reaction of TMS-substituted cyclopentadiene (dienophile) with nitroso alkenes as heterodienes leads directly to bicyclic 1,2-oxazines. Theoretical studies are in agreement with the experimental results and with the new aza-Cope rearrangement proposed.