Competitive Gold‐Promoted Meyer–Schuster and oxy‐Cope Rearrangements of 3‐Acyloxy‐1,5‐enynes: Selective Catalysis for the Synthesis of (+)‐(S)‐γ‐Ionone and (−)‐(2S,6 R)‐cis‐γ‐Irone

We report a simple, highly stereoselective synthesis of (+)‐(S)‐γ‐ionone and (‐)‐(2S,6R)‐cis‐γ‐irone, two characteristic and precious odorants; the latter compound is a constituent of the essential oil obtained from iris rhizomes. Of general interest in this approach are the photoisomerization of an endo trisubstituted cyclohexene double bond to an exo vinyl group and the installation of the enone side chain through a [(NHC)Au^I]‐catalyzed Meyer–Schuster‐like rearrangement. This required a careful investigation of the mechanism of the gold‐catalyzed reaction and a judicious selection of reaction conditions. In fact, it was found that the Meyer–Schuster reaction may compete with the oxy‐Cope rearrangement. Gold‐based catalytic systems can promote either reaction selectively. In the present system, the mononuclear gold complex [Au(IPr)Cl], in combination with the silver salt AgSbF₆ in 100:1 butan‐2‐one/H₂O, proved to efficiently promote the Meyer–Schuster rearrangement of propargylic benzoates, whereas the digold catalyst [{Au(IPr)}₂(μ‐OH)][BF₄] in anhydrous dichloromethane selectively promoted the oxy‐Cope rearrangement of propargylic alcohols.     

Gilch Synthesis of Poly(ortho‐Phenylene Vinylenes): A Powerful Access to High‐Molecular‐Weight Blue‐Emitting Polymers

For the first time, the successful Gilch synthesis of poly(ortho‐phenylene vinylenes) (ortho‐PPVs) is reported. The molar mass of the constitutionally homogeneous ortho‐PPVs reaches values as high as M_w ≈ 300 000 Da. The ortho‐connectivity of the repeating units forces the chains to assume closely packed conformations even in good solvents. Significant perturbation of the π–electron systems and considerable shortening of the conjugation lengths are the consequences. UV–vis absorption and photoluminescence maxima consequently are shifted clearly toward shorter wavelengths compared to, e.g., classic para‐PPVs.

     

Biomimetic anchors for antifouling and antibacterial polymer brushes on stainless steel

Barnacle cement (BC) was beneficially applied on stainless steel (SS) to serve as the initiator anchor for surface-initiated polymerization. The amine and hydroxyl moieties of barnacle cement reacted with 2-bromoisobutyryl bromide to provide the alkyl halide initiator for the surface-initiated atom transfer radical polymerization (ATRP) of 2-hydroxyethyl methacrylate (HEMA). The hydroxyl groups of HEMA polymer (PHEMA) were then converted to carboxyl groups for coupling of chitosan (CS) to impart the SS surface with both antifouling and antibacterial properties. The surface-functionalized SS reduced bovine serum albumin adsorption, bacterial adhesion, and exhibited antibacterial efficacy against Escherichia coli (E. coli). The effectiveness of barnacle cement as an initiator anchor was compared to that of dopamine, a marine mussel inspired biomimetic anchor previously used in surface-initiated polymerization. The results indicate that the barnacle cement is a stable and effective anchor for functional surface coatings and polymer brushes.     

Synthesis of cobalt doped silica thin film for low temperature optical gas sensor

A modified sol–gel method was used to prepare cobalt doped silica thin film with a cobalt content of 10, 20 and 30 mol% (10Co, 20Co and 30Co). The prepared films were annealed at different temperatures in the range 400–1,000 °C, and their structural evolution examined. The mixed valence cobalt oxide, Co₃O₄, crystallizes only in the sample with the higher cobalt content, while cobalt silicate is the only crystalline phase detected in the sample 10Co and 20Co. Both the cobalt content and the temperature of heat treatment resulted to affect the nature of cobalt species dispersed in the silica matrix. The 30Co was selected for further investigations by FTIR spectroscopy to follow the structural evolution of 30Co film as function of the temperature and UV–Vis to get information on the cobalt valence state. The optical gas-sensing properties of 30Co films, containing Co₃O₄ as the major cobalt phase, were studied through the measuring of the film transmittance in dry air and in presence of dry air containing variable concentrations of polluting gases, CO and NO₂. The 30Co samples resulted to be highly sensitive to CO at room temperature. An explanation for the CO sensing characteristics, at low temperature, was proposed by referring to the physisorption-related mechanics of CO.     

Evaluation of the separation mechanism of electrokinetic chromatography with a microemulsion and cyclodextrins using NMR and molecular modeling

Electrokinetic chromatography (EKC) allows the separation of closely related substances by the detection of fine effects in analyte-separation system interactions. With the goal of understanding the fine effects involved in separation using a dual cyclodextrin-microemulsion EKC system, an integrated study of NMR and molecular modeling was carried out. The above dual cyclodextrin-microemulsion system was previously used in the separation of clemastine and its related substances and was prepared by the addition of methyl-β-cyclodextrin (MβCD) and heptakis(2,6-di-O-methyl)-β-cyclodextrin (DMβCD) to an oil-in-water microemulsion. The use of DMβCD was shown to be essential in the separation of clemastine from one of its related substance (I(B) ). A molecular modeling study allowed the different affinities of clemastine and I(B) for the two cyclodextrins to be explained. Furthermore, rotating-frame Overhauser effect spectroscopy NMR experiments clearly indicated that besides the primary pseudostationary phase, namely the ionic microemulsion, cyclodextrins acted as a secondary pseudostationary phase. In addition, it was shown that inclusion complexation of sodium dodecyl sulfate (SDS) monomers into the cyclodextrins cavity occurs; differently, the oil (n-heptane) used in the preparation of microemulsion system resulted to be not included into the macrocycle cavity. These experimental results were supported by molecular modeling, which highlighted the preferential inclusion of SDS into DMβCD. On the basis of these results, it was confirmed that, besides its primary role as the ionic carrier in EKC, SDS is involved in inclusion equilibria toward CDs, which can be effective in increasing the system selectivity.     

Effects of the net charge on abundance and stability of supramolecular surfactant aggregates in gas phase

Self-assembling of amphiphilic molecules under electrospray ionization (ESI) conditions is characterized by quite unexpected phenomenology. The noticeable differences with respect to the condensed phase are attributable to the absence of the surfactant-solvent interactions, the presence of net charge in the aggregates, and the strong deviation from equilibrium conditions. Aiming to investigate the effects of the net charge on abundance and stability of supramolecular surfactant aggregates, positively and negatively charged aggregates of sodium bis(2-ethylhexyl)sulfosuccinate (AOT) and sodium methane sulfonate (MetS), butane sulfonate (ButS) and octane sulfonate (OctS) have been studied by ESI mass spectrometry, energy resolved mass spectrometry and density functional theory calculations. The negatively charged aggregates are found to be less stable than their positive counterparts. The results are consistent with a self-assembling pattern dominated by electrostatic interactions involving the counterions and head groups of the investigated amphiphilic compounds while the alkyl chains point outwards, protecting the aggregates from unlimited growth processes.     

Green microfluidic devices made of corn proteins

An alternative green microfluidic device made of zein, a prolamin of corn, can be utilized as a disposable environmentally friendly microchip especially in agriculture applications. Using standard soft lithography and stereo lithography techniques, we fabricated thin zein films with microfluidic chambers and channels. These were bonded to both a glass slide and another zein film. The zein film with microfluidic features bonds irreversibly with other surfaces by vapor-deposition of ethanol to create an adhesive layer resulting in very little or no trapped air and small shape distortion. Zein-zein and zein-glass microfluidic devices demonstrated sufficient strength to facilitate fluid flow in a complex microfluidic design that showed no leakage under high hydraulic pressure. Zein-glass microfluidic devices with serpentine mixing design showed successful fluid manipulation as a concentration gradient of Rhodamine B solution was generated. The ease of fabrication and bonding and the flexibility and moldability of zein offer attractive possibilities for microfluidic device design and manufacturing. These devices can include several unit operations with mixing being one of the most commonly used. The zein-based microfluidic devices, made entirely from a biopolymer from agricultural origin, offer alternative environmentally friendly material choices that are less dependent on limited petroleum based polymer resources.     

A study on the essential oil of Ferulago campestris: How much does extraction method influence the oil composition?

The essential oil of different parts of Ferulago campestris (Bess.) collected in Sicily has been extracted by microwave-assisted hydrodistillation (MAHD) and by classic hydrodistillation (HD). A comparative qualitative-quantitative study on the composition of the oils was carried out. A total of 100 compounds were identified in the oils obtained by MAHD, whereas 88 compounds characterized the HD oils. The most prominent components were, in all different parts of F. campestris and in both extraction methods, 2,4,5-trimethylbenzaldehyde and 2,4,6-trimethylbenzaldehyde isomers; the latter was not previously found. The attempt to evaluate where the oil components are located in all parts of the plant was carried out by means of a kinetic study. Then, electron microscopy observation on the different parts before and after MAHD and HD was performed.     

Concentration of solutions for a singularly perturbed Neumann problem in non-smooth domains

We consider the equation −?²Δu+u=up in a bounded domain Ω⊂R³ with edges. We impose Neumann boundary conditions, assuming 1<p<5, and prove concentration of solutions at suitable points of ∂Ω on the edges.