N-propargylic beta-enaminones: common intermediates for the synthesis of polysubstituted pyrroles and pyridines.

N-Propargylic beta-enaminones have been used as common intermediates for the synthesis of polysubstituted pyrroles and pyridines. Best results have been obtained using DMSO as solvent. In the presence of Cs(2)CO(3) N-propargylic beta-enaminones are cyclized to pyrroles in good to high yields, whereas omitting bases and using CuBr leads to the selective formation of pyridines.     

ATRP synthesis and association properties of thermoresponsive anionic block copolymers

Thermosensitive anionic block copolymers of sodium 2‐acrylamido‐2‐methylpropanesulfonate (AMPS) and N‐isopropylacrylamide (NIPAAM) with different block lengths were prepared by atom transfer radical polymerization (ATRP). Controlled polymerization was achieved by using ethyl 2‐chloropropionate (ECP) as initiator and CuCl/CuCl₂/tris(2‐dimethylaminoethyl)amine (Me₆TREN) catalytic system in DMF:water 50:50 (v/v) mixtures at 20 °C. Blocks lengths ranging from 36 to 98 repeating units were obtained. The association properties in aqueous solutions at different NaCl ionic strengths were studied as a function of temperature and polymer concentration by dynamic light scattering, fluorescence spectroscopy, and energy‐filtered transmission electron microscopy. The block copolymers with a higher pNIPAAM/pAMPS ratio formed spherical core‐shell type micelles independently of the ionic strength. The block copolymers with lower pNIPAAM/pAMPS ratio formed core‐shell type micelles at high ionic strength. Larger particles were observed at low ionic strength, which could be due to the formation of vesicles or compound micelles/micellar clusters. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4830–4842, 2008     

Analysis of underivatized oligosaccharides by liquid chromatography/electrospray ionization tandem mass spectrometry with post‐column addition of formic acid

Underivatized oligosaccharides were analyzed by electrospray ionization (ESI) using a linear ion trap mass spectrometer in the negative ion mode with post‐column addition of an aqueous solution of formic acid. Under these conditions all oligosaccharides showed the presence of the corresponding formate adduct [M + HCOO]^? with high intensity and easy subsequent low‐energy collision‐induced dissociation (CID) fragmentation using successive MSⁿ experiments. A careful examination of the mass spectra obtained from these MSⁿ experiments pointed out some significant differences useful to identify and quantify the single components in mixtures of coeluted disaccharides. This new sensitive and rapid method was successfully applied to the quantification of oligosaccharides in some juices minimizing sample handling. Copyright © 2009 John Wiley & Sons, Ltd.     

Novel strategy for tailoring of SiO2 and TiO2 nanoparticle surfaces with poly(ε-caprolactone)

A novel strategy was developed for tailoring of SiO₂ and TiO₂ nanoparticle surfaces with poly(ε-caprolactone) (PCL). Thus, a self-curable polyester, poly(2-hydroxypropylene maleate) was adsorbed on the nanoparticle surfaces and heated to 180 °C to give a cross-linked polyester layer with residual hydroxyalkyl groups on their surfaces. Surface-initiated polymerization of ε-caprolactone from hydroxyalkyl groups on the surfaces yielded core-shell nanoparticles with cross-linked core and PCL shells (22.2–71.4%). The organic shell layers around the nanoparticle cores were evidenced by transmission electron microscopy, dynamic light scattering, and thermogravimetric analyses techniques. The core-shell nanoparticles were then employed in preparing the stable and the homogenous dispersions with poly(methyl methacrylate-stat-butyl acrylate) solutions. An application of the solutions onto glass substrates yielded uniform and nearly transparent free standing films (40–60 μm) with good homogeneity as inferred from scanning electron microscopy pictures.     

Analytical characterization of cell–asbestos fiber interactions in lung pathogenesis

Asbestos is a fiber causing lung diseases such as asbestosis and mesothelioma. Although the process involving these diseases remains to be elucidated for developing drugs and treatments, direct consequences of fiber exposure in humans have been clearly demonstrated. These diseases are first characterized by histological heterogeneity and combine chronic inflammation with fibrosis and cellular alterations. As a consequence, asbestosis is usually diagnosed at advanced stages of the disease and treatments are usually inefficient to cure the patients. Here, we review the links established between asbestos fiber chemistry and morphology with the occurrence of associated lung diseases. Cytological and histological aspects of diseases are described with respect to current analytical capabilities, notably for microscopy techniques.     

Principal differential analysis of the Aneurisk65 data set

We explore the use of principal differential analysis as a tool for performing dimensional reduction of functional data sets. In particular, we compare the results provided by principal differential analysis and by functional principal component analysis in the dimensional reduction of three synthetic data sets, and of a real data set concerning 65 three-dimensional cerebral geometries, the AneuRisk65 data set. The analyses show that principal differential analysis can provide an alternative and effective representation of functional data, easily interpretable in terms of exponential, sinusoidal, or damped-sinusoidal functions and providing a different insight to the functional data set under investigation. Moreover, in the analysis of the AneuRisk65 data set, principal differential analysis is able to detect interesting features of the data, such as the rippling effect of the vessel surface, that functional principal component analysis is not able to detect.