Asymmetric synthesis of 6-(2′,3′,4′,5′,6′-pentafluorophenyl)-δ-lactones via “allyl”boranes: application for the synthesis of fluorinated analog of key pharmacophore of statin drugs

Asymmetric “allyl”boration of pentafluorobenzaldehyde with various α-pinene based “allyl”boranes provides homoallylic alcohols in high de and ee; the alcohols have been converted into δ-lactones via acryloylation, ring-closing metathesis and hydrogenation. Pentafluorophenyl analog of key pharmacophore of statin drugs has been synthesized using diastereoselective epoxidation and regioselective reduction as key steps.     

Iridodials: enantiospecific synthesis and stereochemical assignment of the pheromone for the golden-eyed lacewing, Chrysopa oculata

1R,2S,5R,8R; 1R,2S,5R,8S; 1S,2S,5R,8R; and 1S,2S,5R,8S-Iridodials have been prepared in five steps from 4aS,7S,7aR and 4aS,7S,7aS-nepetalactones, major components of catnip oil. 1R,2S,5R,8R-Iridodial has been identified as a male-produced male-aggregation pheromone for Chrysopa oculata, the first pheromone of any kind identified for lacewings.     

Electronic structure and spectra of fused n/m ring systems with one or two bridgehead nitrogen atoms

The semiempirical ASMO-SCF-CI method has been applied to study the electronic structures and ultraviolet absorption spectra of the 4-azapentalenyl anion, 4,8-diazapentalene and related azaderivatives. The agreement between observed and calculated transition energies is, in general, satisfactory. Chemical reactivity and assignment of the observed bands are discussed.

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Zusammenfassung Mit Hilfe einer semi-empirischen ASMO-SCF-CI Methode wurden Elektronenstruktur und UV Absorptionsspektren des 4-Azapentalenylanions, des 4,8-Diazapentalens und der entsprechenden Azaderivate studiert. Im allgemeinen ist die Übereinstimmung zwischen experimentellen und theoretischen Übergangsenergien zufriedenstellend. Die Zuordnung der beobachteten Banden und Reaktivitäten werden diskutiert.

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Résumé La méthode semi-empirique ASMO-SCF-CI a été appliquée à l'étude de la structure électronique et des spectres d'absorption U.V. de l'anion 4-azapentalenil, du 4,8-diazapentalene et de composés aza-derivés apparentés. L'accord entre les énergies de transition observées et calculées est, dans l'ensemble, satisfaisant. La reactivité chimique et l'attribution des bandes observées ont été discutées.

     

Beaded reactive polymers 3 effect of triacrylates as crosslinkers on the physical properties of glycidyl methacrylate copolymers and immobilization of penicillin G acylase

Various glycidyl methacrylate (GMA) copolymers were synthesized by suspension polymerization, using pentaerythritol triacrylate (PETA), trimethylolpropane triacrylate (TMPTA), and trimethylolpropane trimethacrylate (TRIM) as crosslinking comonomers. These copolymers were evaluated for the immobilization of penicillin G acylase. Broad pore-size distribution that was observed was in the range 5-300 nm. Both surface area and pore volume increased with increase in the mole fraction of crosslinking comonomer (increasing crosslink density). The pore volume of the copolymers was more than doubled by including lauryl alcohol as porogen. Binding of penicillin G acylase (PGA) was quantitative on highly crosslinked copolymers. The expression of bound PGA was better on the relatively more hydrophilic GMA-TMPTA and GMA-PETA copolymer supports compared to the GMA-TRIM copolymers. Among the different copolymers studied, GMA-TMPTA copolymer 7411 exhibited highest activity of immobilized penicillin G acylase (167.4 IU/g) with 35.1% expression.     

Synthesis of indenoquinolinone through aryne-mediated Pd(II)-catalysed remote C–H activation

Research on Chemical Intermediates - Indenoquinolinones have been synthesized from 2-haloquinoline-3-carbaldehyde through Pd-mediated simultaneous C–H (aldehyde) and C–X bond...     

Stereopositional Outcome in the Packing of Dissimilar Aromatics in Designed β‐Hairpins

A popular strategy in the de novo design of stable β‐sheet structures for various biomedical applications is the incorporation of aromatic pairs at the non‐hydrogen‐bonding (NHB) position. However, it is important to explicitly understand how aryl pair packing at the NHB region is coordinated with backbone structural rearrangements, and to delineate the benefits and drawbacks associated with stereopositional choice of dissimilar aromatic pairs. Here, we probe the consequences of flipped Trp/Tyr pairs by using engineered permutants at the NHB position of dodecapeptide β‐hairpins, proximal and distal to the turn. Extensive conformational analysis of these peptides using NMR and CD spectroscopy reveal that a classic Edge‐to‐Face and Face‐to‐Edge geometry at the proximal and distal aromatic pairs, respectively, in YW‐WY, is the most stabilizing. Such a preferred packing geometry in YW‐WY results in a highly twisted β‐sheet backbone, with Trp always providing a ‘Face’ orientation to its dissimilar aromatic partner Tyr. Flipping the proximal and/or distal aromatic pair distorts the ideal T‐shaped geometry, and results in alternate aryl arrangements that can adversely affect strand twist and β‐sheet stability. Our study reveals the existence of a strong stereopositional influence on the packing of dissimilar aromatic pairs. Our findings highlight the importance of modeling physical interaction forces while designing protein and peptide structures for functional applications.     

MULTIPLE EMULSIONS STABILIZED BY COLLOIDAL MICROGRYSTALLINE CELLULOSE

Multiple emulsions stabilized by colloidal microcrystalline cellulose (CMCC, Avicel RC591) at the w/o and o/w interfaces, and by the addition of Span 80 or Span 85 at the w/o interface, were studied by means of brightfield microscopy, freeze-etch electron microscopy, droplet size distribution analysis and rheologic measurements. Stable multiple emulsions were prepared by incorporation of sodium chloride in the innermost aqueous phase, thereby creating an osmotic gradient preventing loss of the inner aqueous phase to the external aqueous phase. Freeze-etch electron microscopy of the multiple emulsions indicated the presence of a network of microcrystalline cellulose at the outer o/w interface. It may be assumed that the surfactant directly stabilized the w/o interface by adsorption at the interface, as well as indirectly by facilitating wetting of the microcrystalline cellulose by the oil. From rheologic measurements, the existence of a three-dimensional network in the external aqueous phase was indicated by the considerable degrees of thlxotropy and significant static yield values of these multiple emulsions.     

Bioinspired Synthesis of Well‐Ordered Layered Organic–Inorganic Nanohybrids: Mimicking the Natural Processing of Nacre by Mineralization of Block Copolymer Templates

The unique mechanical performance of nacre, the pearly internal layer of shells, is highly dependent on its complex morphology. Inspired by the structure of nacre, the fabrication of well‐ordered layered inorganic–organic nanohybrids is presented herein. This biomimetic approach includes the use of a block copolymer template, consisting of hydrophobic poly(vinylidene fluoride) (PVDF) lamellae covered with hydrophilic poly(methacrylic acid) (PMAA), to direct silica (SiO₂) mineralization. The resulting PVDF/PMAA/SiO₂ nanohybrid material resembles biogenic nacre with respect to its well‐ordered and layered nanostructure, alternating organic–inorganic phases, macromolecular template, and mild processing conditions.

     

Strip-electromechanical model solution for piezoelectric plate cut along two semi-permeable collinear cracks

A strip electric saturation and mechanical yielding model solution is proposed for a piezoelectric plate cut along two equal collinear semi-permeable mode-I cracks with electrical polarization reaching a saturation limit and normal stress reaching a yield stress along a line segment in front of the cracks. By using Stroh formalism and complex variable technique, we derived the analytical solution for the field quantities. Three different situations are investigated when developed electrical saturation zone is bigger/smaller or equal to the developed mechanical yield zone. Numerical results show that the effect of different electric boundary conditions on the crack opening displacement and crack opening potential drop is significant and should not be ignored. The influence of electric load displacement on the energy release rate is also investigated for PZT-4, PZT-5H and BaTiO₃ ceramics, and it may assists for the correct choosing of ceramic for specific job.