Syntheses of alpha- and beta-C-glucopyranosyl serines from a common intermediate

A versatile synthesis leading to either C-linked alpha- or beta-glucopyranosyl serines is presented from a common, advanced synthetic intermediate. Cyclization of the penultimate carbinol onto the alkene and methanolysis of the lactone yields selectively the alpha-linkage. A transposition of these last steps leads to the beta-linked isomer selectively.     

Marine derived polysaccharides for biomedical applications: chemical modification approaches

Polysaccharide-based biomaterials are an emerging class in several biomedical fields such as tissue regeneration, particularly for cartilage, drug delivery devices and gelentrapment systems for the immobilization of cells. Important properties of the polysaccharides include controllable biological activity, biodegradability, and their ability to form hydrogels. Most of the polysaccharides used derive from natural sources; particularly, alginate and chitin, two polysaccharides which have an extensive history of use in medicine, pharmacy and basic sciences, and can be easily extracted from marine plants (algae kelp) and crab shells, respectively. The recent rediscovery of poly-saccharidebased materials is also attributable to new synthetic routes for their chemical modification, with the aim of promoting new biological activities and/or to modify the final properties of the biomaterials for specific purposes. These synthetic strategies also involve the combination of polysaccharides with other polymers. A review of the more recent research in the field of chemical modification of alginate, chitin and its derivative chitosan is presented. Moreover, we report as case studies the results of our recent work concerning various different approaches and applications of polysaccharide-based biomaterials, such as the realization of novel composites based on calcium sulphate blended with alginate and with a chemically modified chitosan, the synthesis of novel alginate-poly(ethylene glycol) copolymers and the development of a family of materials based on alginate and acrylic polymers of potential interest as drug delivery systems.     

Uncatalyzed, anti-Michael addition of amines to β-nitroacrylates: practical, eco-friendly synthesis of β-nitro-α-amino esters

A variety of primary and secondary amines give the conjugate reaction with β-nitroacrylates, via an anti-Michael addition, without any catalyst and/or solvent, allowing good yields of β-nitro-α-amino esters.     

Environment effects on the CO vibrational shifts in erbium complexes: a quantum chemical study

The stability of lanthanide complexes and the efficiency of the energy transfer process, which makes these molecules interesting materials for technological applications, are correlated to the chemical environment surrounding the metal ion. In particular the efficiency depends on the relative position of the antenna (the ligand moiety that acts as photon absorption center) and the lanthanide ion (the emitting center), while the stability of the complex is correlated to the strength of the coordination between the rare earth and the ligands. For these reasons, knowledge of the structural properties of the complex is an interesting task to achieve. Since a large number of ligand structures hold the carboxylate group (COO(-)), which is used as an anchor for binding the antennae to the lanthanide ion, in this work we will show how the vibrational shifts of this group, induced by the interactions between the carboxylate moiety and the metal center of the lanthanide complex, can be used for obtaining in a simple way information on the structure of the chemical environment surrounding the lanthanide ion.     

Global regularity for solutions to Dirichlet problem for discontinuous elliptic systems with nonlinearity q > 1 and with natural growth

In this paper we deal with the Hölder regularity up to the boundary of the solutions to a nonhomogeneous Dirichlet problem for second-order discontinuous elliptic systems with nonlinearity q > 1 and with natural growth. The aim of the paper is to clarify that the solutions of the above problem are always global Hölder continuous in the case of the dimension n = q without any kind of regularity assumptions on the coefficients. As a consequence of this sharp result, the singular sets $\Omega_0 \subset \OmegaIn this paper we deal with the H?lder regularity up to the boundary of the solutions to a nonhomogeneous Dirichlet problem for second-order discontinuous elliptic systems with nonlinearity q > 1 and with natural growth. The aim of the paper is to clarify that the solutions of the above problem are always global H?lder continuous in the case of the dimension n = q without any kind of regularity assumptions on the coefficients. As a consequence of this sharp result, the singular sets , are always empty for n = q. Moreover we show that also for 1 < q < 2, but q close enough to 2, the solutions are global H?lder continuous for n = 2.      

Synthesis and complete assignment of the 1H and 13C NMR signals of some oxopyrancoumarin and oxofuropyrancoumarin derivatives

The synthesis of four pyranocoumarins starting from phloroglucinol and the complete (1)H and (13)C NMR assignment of seven pyranocoumarins has been performed using 1D and 2D NMR techniques including COSY, HMQC and HMBC experiments.     

Water-soluble, electroactive, and photoluminescent quaterthiophene-dinucleotide conjugates

Quaterthiophene-dinucleotide conjugates 5'TA3'-t4-3'AT5', 5'AA3'-t4-3'AA5', and 5'TT3'-t4-3'TT5' (TA: thymidine-adenosine, AA: adenosine-adenosine, TT: thymidine-thymidine) were synthesized and analyzed by a combination of spectroscopy and microscopy, electrical characterization, and theoretical calculations. Circular dichroism (CD) experiments demonstrated a transfer of chirality from the dinucleotides to quaterthiophene at high ionic strength and in cast films. The films were photoluminescent and electroactive. CD and photoluminescence spectra and current density/voltage plots (measured under dynamic vacuum) displayed significant variation on changing the dinucleotide scaffold. Molecular mechanics and molecular dynamics calculations indicated that the conformation and packing modes of the conjugates are the result of a balance between intra- and intermolecular nucleobase-thiophene stacking interactions and intramolecular hydrogen bonding between the nucleobases.     

Concentration as the switch for chiral recognition in biomembrane models

Chiral recognition was observed in a biomembrane model. Micellar aggregates formed by enantiopure N-alkyl-N,N-dimethyl-N-(1-phenyl)ethylammonium bromide were in fact able to convert the racemic mixture of bilirubin-IXalpha into an enantiomerically enriched mixture. The stereochemical preference and the extent of enantiomeric enrichment depend on the length of the hydrophobic portion of the surfactant and on the concentration conditions, and changes in the stereochemical bias are reversible.     

Multifunctional nanostructures based on inorganic nanoparticles and oligothiophenes and their exploitation for cellular studies

The combination of materials that possess different properties (such as, for instance, fluorescence and magnetism) into one single object of nanoscale size represents an attractive challenge for biotechnology, especially for their potential relevance in biomedical applications. We report here the preparation of novel bifunctional conjugates based on the linkage of inorganic nanoparticles to organic oligothiophene fluorophores (OTFs). In comparison to the organic dyes commonly used in bioimaging and more similarly to colloidal quantum dots, OTFs have broad optical absorption spectra, and therefore OTF fluorophores emitting at different colors can be excited with a single excitation source, allowing for easier multiplexing analysis. In this work we show the preparation of OTF-nanoparticle conjugates based on gold and iron oxide nanoparticles and their characterization using different techniques such as gel electrophoresis, photoluminescence spectroscopy, dynamic light scattering, and so on. In addition, by performing an in vitro study on human tumor cells we show that OTF-nanoparticle conjugates emitting at different colors can be used for multiplexing detection. Also, in the case of iron oxide-OTF conjugates, once uptaken by the cells, we show that they preserve both their fluorescent and their magnetic properties.     

Role of the hydrophobic effect in the transfer of chirality from molecules to complex systems: from chiral surfactants to porphyrin/surfactant aggregates

The interaction between the achiral sulfonated porphyrin 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin, H 2TPPS 4 (4-), and two chiral cationic surfactants has been studied by optical absorption, fluorescence, and circular dichroism (CD) spectroscopies. At surfactant concentrations above the critical micellar concentration (cmc) the porphyrin is included in the micellar aggregates, but it is CD silent. Below the cmc at a definite porphyrin/surfactant stoichiometry the formation of heteroaggregates with transfer of chirality to the porphyrin chromophore occurs. The preferred surfactant/porphyrin stoichiometry is 3:1, which suggests a structure driven by electrostatic and hydrophobic interactions between porphyrin and surfactant and dipolar and ionic interactions with the water solution. At surfactant concentrations above the cmc, depending on the protocol of preparation of the samples, the formation of the two kinds of aggregates can be observed, reversible for the simple surfactant micelles incorporating the porphyrin, but irreversible for the heteroaggregates.