Bloch wave homogenization of a non-homogeneous Neumann problem

In this paper, we use the Bloch wave method to study the asymptotic behavior of the solution of the Laplace equation in a periodically perforated domain, under a non-homogeneous Neumann condition on the boundary of the holes, as the size of the holes goes to zero more rapidly than the domain period. This method allows to prove that, when the hole size exceeds a given threshold, the non-homogeneous boundary condition generates an additional term in the homogenized problem, commonly referred to as “the strange term” in the literature.     

Screening of dimethoate in food by isotope dilution and electrospray ionization tandem mass spectrometry

Crop control is an important issue in both developed and developing countries. An environmentally friendly approach is represented by the so‐called Integrated Pest Management (IPM), whereby synthetic pesticides are only applied as a last resort, under the strict control of suitable experts. European and US regulatory authorities, such as the US EPA, are constantly assessing the risks of exposure to the organophosphate (OP) class of pesticides and, among these, specifically dimethoate. The use of dimethoate is still allowed in many crops, including olives, which once was based in the Mediterranean area but now is expanding rapidly throughout the world. An important aspect of IPM protocols is represented by the availability of reliable and sensitive methods to detect pesticides residues. This paper describes an isotope dilution dimethoate assay based on the application of electrospray ionization tandem mass spectrometry (ESI‐MS/MS) by means of a deuterium‐labeled internal standard. Copyright © 2009 John Wiley & Sons, Ltd.     

Synthesis of purinobenzodiazepine and purinobenzotriazocine derivatives,two new heterocyclic ring systems

The preparation of two new heterocyclic ring systems, purinobenzodiazepine and purinobenzotriazocine derivatives by the condensation of 8-aminotheophylline or 8-hydrazinotheophylline with o-carboxybenzaldehyde or o-carboxyacetophenone is described.     

Spectroscopic analysis of imidazolidines. Part I: Electron impact mass spectrometry

The electron impact mass spectral fragmentation pathways for a series of 1,3‐di‐ and 1,2,3‐trisubstituted imidazolidines were investigated. The data show remarkable differences depending on the location and identity of substituents. The atypical 1,2,2,3‐tetrasubstituted imidazolidine, 2‐cyano‐1‐methyl‐3‐(p‐nitro‐phenyl)‐2‐phenylimidazolidine, was also investigated.     

Photophysical Properties and Photobiological Activity of the Furanochromones Visnagin and Khellin

The larger photobiological activity of visnagin (VI) versus khellin (KH) toward several living organisms, including fungi, viruses, yeasts and bacteria, induced a detailed investigation of the photophysical properties of these naturally occurring furanochromones, using laser-flash-photolysis, photoacoustic calorimetry and fluorescence (steady-state and time-resolved) techniques in solvents with different polarity and content of water, including micelles and vesicles. The results have shown that the magnitude of all the three rate constants out of S₁ (radiative, k_f; internal conversion, k_ic and intersystem crossing, k_isc) for VI and KH strongly depend on the solvent, namely on its hydrogen bonding ability and polarity. The changes of k_f and k_isc are due to the solvent-assisted mixing and/or inversion of the two first singlet excited states (¹n,π* and ¹π,π*), while k_ic increases with a decrease of the S_o–S₁ energy gap. As a consequence, the quantum yield of triplet formation (φ_T) strongly decreases from values of ?0.8 in dioxane to < 0.05 in water for both compounds. The magnitude of solvent polarity/hydrogen bonding ability required, at which the state order is inverted and φ_T starts to decrease, is greater for VI than for KH and consequently φ_T (VI) > φ_T (KH) over a broad range of water content including that appropriate to the environment of the compounds in a living system. These facts account for the larger photobiological activity of VI with respect to KH, regarding both the fungus Fusarium culmorum L. and the wild strain of Escherichia coli, studied by us.     

Highly efficient and versatile acetylation of alcohols catalyzed by cerium(III) triflate

Cerium(III) triflate is a powerful catalyst for the acetylation of alcohols. The reaction works well for a large variety of simple and functionalized alcohols, without isomerisation of chiral centres. Changes of hydroxyl protective groups are possible in a one-pot procedure. The catalyst can be easily recycled.     

Platinum–polytyramine composite material with improved performances for methanol oxidation

Polytyramine (PTy) is shown to be a possible alternative to other conducting polymers as a support material for fuel cell electrocatalysts such as platinum. In this work, a Pt–PTy composite was prepared via potentiodynamic deposition of polytyramine on graphite substrate, followed by the electrochemical deposition of Pt nanoparticles. The material obtained by this straightforward method exhibited, for platinum loadings as low as ca. 0.12 mg cm⁻², a specific electrochemically active surface area of the electrocatalyst of ca. 54 m² g⁻¹, together with a good electrocatalytic activity for methanol oxidation in acidic media, thus ensuring better efficiency of Pt utilization. The system Pt–PTy appears to be worthy of development for methanol fuel cell applications also because the results suggested that, when deposited as small particles in a PTy matrix, platinum is less sensitive to fouling during CH₃OH oxidation.     

A straightforward synthetic access to symmetrical glycosyl disulfides and biological evaluation thereof

Symmetrical glycosyl disulfides can be prepared within a few hours from per-O-acetylated precursors via a sequential approach entailing short reactions and no purification of any intermediate. The final thiolate-to-disulfide oxidation step is noticeably accelerated by low amounts of phenyl diselenide under air. Applicability of the strategy to non-saccharidic symmetrical alkyl disulfides has also been examined. A preliminary assay of the cytotoxic activity of symmetrical 1,1'- disulfides was performed on two human tumor cell lines, and a noteworthy activity was recorded for a range of these synthetic compounds.     

Carotenoids and lung cancer: biochemical aspects

Carotenoids are part of the human diet and a regular low-dose intake of these compounds from natural sources is normally preferred. Carotenoid supplementation in various diseases, including cancer, was described to be useful, but evidence has been obtained that high-dose supplementation of β-carotene may be unsafe, especially to smokers and asbestos-exposed workers, because of a stastically detected increased cancer risk. The negative effect might be mediated by carotenoid breakdown products having a high reactivity towards biomolecules. It has been suggested that these compounds originate from nonenzymatic cleavage of carotenoids by oxidants liberated in large amounts by neutrophils that accumulate in various inflammatory diseases and, in particular, in pulmonary disorders characterized by profound abnormalities in inflammatory pathways, such as those triggered by tobacco smoking. Carotenoid breakdown products, in turn, may affect neutrophil response in different ways that depend on the concentration that is reached by these products in the medium. In vitro studies show that nanomolar and micromolar concentrations of carotenoid derivatives stimulate superoxide production by neutrophils activated by phorbol myristate acetate (PMA), while a slight inhibition is noticed with cells activated by the chemotactic tripeptide N-formyl-Met-Leu-Phe (f-MLP). At higher concentrations, carotenoid breakdown products inhibit superoxide production in the presence of both PMA and f-MLP.      

A simple and convenient synthesis of substituted furans and pyrroles by CuCl2-catalyzed heterocyclodehydration of 3-yne-1,2-diols and N-Boc- or N-tosyl-1-amino-3-yn-2-ols

A simple and economical synthesis of substituted furans and pyrroles, by ligand-free CuCl₂-catalyzed heterocyclodehydration of readily available 3-yne-1,2-diols and N-Boc- or N-tosyl-1-amino-3-yn-2-ols, respectively, is presented. Reactions are carried out in MeOH at 80-100 °C for 1-24 h and afford the corresponding heterocyclic derivatives in 53-99% isolated yields.