Ethyl-2-(2-chloroethyl)acrylate: a new very versatile α-cyclopropylester cation synthon. Efficient synthesis of cyclopropane ester derivatives by Michael addition-induced cyclization reaction

We report here the use of the readily accessible ethyl-2-(2-chloroethyl)acrylate as a new very versatile α-cyclopropylester cation synthon, which reacts efficiently and selectively with carbon-, nitrogen-, sulfur- or phosphorus-centered nucleophiles through Michael addition followed by intramolecular capture of the incipient ester enolate to afford funtionalized cyclopropane esters in high yields.     

C5-functionalized DNA, LNA, and α-L-LNA: positional control of polarity-sensitive fluorophores leads to improved SNP-typing

Single nucleotide polymorphisms (SNPs) are important markers in disease genetics and pharmacogenomic studies. Oligodeoxyribonucleotides (ONs) modified with 5-[3-(1-pyrenecarboxamido)propynyl]-2'-deoxyuridine monomer X enable detection of SNPs at non-stringent conditions due to differential fluorescence emission of matched versus mismatched nucleic acid duplexes. Herein, the thermal denaturation and optical spectroscopic characteristics of monomer X are compared to the corresponding locked nucleic acid (LNA) and α-L-LNA monomers Y and Z. ONs modified with monomers Y or Z result in a) larger increases in fluorescence intensity upon hybridization to complementary DNA, b) formation of more brightly fluorescent duplexes due to markedly larger fluorescence emission quantum yields (Φ(F)=0.44-0.80) and pyrene extinction coefficients, and c) improved optical discrimination of SNPs in DNA targets. Optical spectroscopy studies suggest that the nucleobase moieties of monomers X-Z adopt anti and syn conformations upon hybridization with matched and mismatched targets, respectively. The polarity-sensitive 1-pyrenecarboxamido fluorophore is, thereby, either positioned in the polar major groove or in the hydrophobic duplex core close to quenching nucleobases. Calculations suggest that the bicyclic skeletons of LNA and α-L-LNA monomers Y and Z influence the glycosidic torsional angle profile leading to altered positional control and photophysical properties of the C5-fluorophore.     

Geographical dispersal of mobile communication networks

In this paper, we analyze statistical properties of a communication network constructed from the records of a mobile phone company. The network consists of 2.5 million customers that have placed 810 million communications (phone calls and text messages) over a period of 6 months and for whom we have geographical home localization information. It is shown that the degree distribution in this network has a power-law degree distribution k⁻⁵ and that the probability that two customers are connected by a link follows a gravity model, i.e. decreases as d⁻², where d is the distance between the customers. We also consider the geographical extension of communication triangles and we show that communication triangles are not only composed of geographically adjacent nodes but that they may extend over large distances. This last property is not captured by the existing models of geographical networks and in a last section we propose a new model that reproduces the observed property. Our model, which is based on the migration and on the local adaptation of agents, is then studied analytically and the resulting predictions are confirmed by computer simulations.     

Monitoring the buckling threshold of drying colloidal droplets using water-ethanol mixtures

We visualize the drying of droplets of colloids suspended in a mixture of two miscible solvents, namely water and ethanol. After a period of isotropic shrinkage, droplets suddenly buckle like elastic shells. For a fixed colloid solid fraction, the buckling threshold evolves as a function of ethanol content, due to changes of the solvent mixture physical properties, such as viscosity and evaporation rate. A simplified model predicting the qualitative behavior of the buckling threshold as a function of the initial ethanol mass fraction has been developed that fits well experimental results.     

Optimization of Mn-Mg-Al Mixed Oxides Composition on their Activity towards the Total Oxidation of Aromatic and Oxygenated VOCs

A series of mixed oxides (Mn-Mg-Al) is prepared by coprecipitation via a hydrotalcite route with different manganese ratios. Structural, textural, and redox properties are studied by XRD, N₂-sorption, H₂-TPR, and XPS techniques. Mn_xMg_6-xAl₂-O mixed oxides (with 0≤x≤6) are tested in the total oxidation of ethanol and toluene, two probe molecules representing respectively oxygenated and aromatic VOCs. Catalysts with higher manganese contents have shown the best catalytic performance for the oxidation of both ethanol and toluene. The surface activity of the materials is mainly related to the presence of manganese species in three different oxidation states (+II, +III, and +IV) in the bulk and on the material's surface. Since high Mn-content catalysts showed similar physicochemical properties and catalytic activity, Mn₄Mg₂-O is selected as the optimal composition of these materials. Furthermore, its aging test is compared to that of noble metal-based commercial catalysts (Pd/γ-Al₂O₃).