A [4 + 4] annulation strategy for the synthesis of eight-membered carbocycles based on intramolecular cycloadditions of conjugated enynes

A [4+4] annulation strategy for the synthesis of eight-membered carbocycles is reported that proceeds via a cascade involving two pericyclic processes. In the first step, the [4+2] cycloaddition of a conjugated enyne with an electron-deficient cyclobutene generates a strained six-membered cyclic allene that isomerizes to the corresponding 1,3-cyclohexadiene. In the second step, this bicyclo[4.2.0]octa-2,4-diene intermediate undergoes thermal or acid-promoted 6-electron electrocyclic ring opening to furnish a 2,4,6-cyclooctatrienone. The latter transformation represents the first example of the promotion of 6-electron electrocyclic ring opening reactions by acid.     

Counterion effects in iminium-activated electrophilic aromatic substitutions of pyrroles

Electrophilic substitution of pyrroles by α,β-unsaturated iminium ions is slow in acetonitrile when only weakly basic counterions are present. When the reactions are carried out in the presence of KCF(3)CO(2), fast deprotonation of the intermediate σ-adducts occurs, and the rate constant for the rate-determining CC bond-forming step can be predicted from the electrophilicity parameter E of the iminium ion and the N and s parameters of the pyrroles.     

Preparation of polyester-based metal-cross linked polymeric composites as novel materials resistant to bacterial adhesion and biofilm formation

Bacterial biofilms constitute an extremely resistant form of bacterial colonization with dire health and economical implications. Towards achieving polymeric composites capable of resisting bacterial adhesion and biofilm formation, we prepared five 2,6-pyridinedicarboxylate-based polyesters employing five different diol monomers. The resulting polyesters were complexed with copper (II) or silver (I). The new polymers were characterized by proton and carbon nuclear magnetic resonance spectroscopy, inherent viscosity, infrared spectroscopy, differential scanning calorimetry and thermogravimetric analysis. The corresponding metal complexes were characterized by differential scanning calorimetry and infrared spectroscopy. The amounts of complexed copper and silver were determined by atomic absorption spectrophotometry. Finally, the resulting composites were tested for their antibacterial potential and were found to effectively resist bacterial attachment and growth.     

Transport behavior and mechanism of conduction of simultaneously substituted Y and Fe in La0.7Ba0.3MnO3 perovskite

The electrical properties and the mechanism of conduction of the simultaneously substituted La_0.7−xY_xBa_0.3Mn_1−xFe_xO₃ perovskite (0≤x≤0.30) have been studied. The insertion of Y³⁺ and Fe³⁺ ions in the parent compound La_0.7Ba_0.3MnO₃ leads to an increase of the resistivity. The undoped sample (x=0) shows a metallic behavior, which can be fitted by the relation ρ(T)=ρ₀+ρ₂T²+ρ_4.5T^4.5, indicating the importance of electron-magnon scattering effects in this material. All the other samples (x≥0.10) are semiconductors throughout the studied temperature range (80-290 K). Several models have been used to fit their temperature-dependent resistivity: thermal activation, adiabatic nearest-neighbor hopping of small polarons (Holstein theory) and variable range hopping (VRH) models. The fits show that the electronic transport in semiconducting La_0.7−xY_xBa_0.3Mn_1−xFe_xO₃ is well described and dominated by the VRH mechanism, for which the hopping distance (a) grows with increasing Fe³⁺ doping, thus increasing the average hopping energy W.     

A class of asymptotically self-similar stable processes with stationary increments

We generalize the BM-local time fractional symmetric α$\alpha$-stable motion introduced in Cohen and Samorodnitsky (2006) by replacing the local time with a general continuous additive functional (CAF). We show that the resulting process is again symmetric α$\alpha$-stable with stationary increments. Depending on the CAF, the process is either self-similar or lies in the domain of attraction of the BM-local time fractional symmetric α$\alpha$-stable motion. We also show that the process arises as a weak limit of a discrete “random rewards scheme” similar to the one described by Cohen and Samorodnitsky.     

Electrical and magnetic properties of La0.67Ba0.33Mn1−x (Me) x O3 perovskite manganites: case of manganese substituted by trivalent (Me = Cr) and tetravalent (Me = Ti) elements

The effects of non-magnetic Ti⁴⁺ substitution on the structural, electrical and magnetic properties of La_0.67Ba_0.33Mn_1?x Ti _x O₃ (0≤x≤0.1) are investigated and compared to those existing in La_0.67Ba_0.33Mn_1?x Cr _x O₃ (magnetic Cr³⁺). The structural refinement by the Rietveld method revealed that Ti-doped samples crystallize in the cubic lattice with space group $\mathrm{Pm}\bar{3}\mathrm{m}$ , while samples with Cr crystallize in the hexagonal setting of the rhombohedral $\mathrm{R}\bar{3}\mathrm{C}$ space group for identical contents of dopant. The most relevant structural features are an increase of the lattice parameters, of the cell volume and of the inter-ionic distances with increasing Ti doping level. Both series of samples show a decrease of the paramagnetic–ferromagnetic transition temperature when the amount of chromium or titanium increases. Transport measurements show that when increasing the metal doping, the resistivity increases whereas the metallic behavior of the parent compound La_0.67Ba_0.33MnO₃ is destroyed. For a substitution higher than 5 at.% of Ti and 10 at.% of Cr, the samples exhibit a semiconducting behavior in the whole range of temperature, for which the electronic transport can be explained by variable range hopping and/or small polaron hopping models.     

Localisation in granular media: Particle approach,homogenisation and continuum modelling

The individual motion of grains in granular material has a strong influence on the macroscopic material behaviour, which is in particular the case for the phenomena of strain localisation in shear zones and justifies the need for techniques that incorporate a micro-macro transition. In this contribution, granular media are investigated in three steps. Firstly, a microscopic particle-based modelling is set up, where individual grains are considered as rigid uncrushable particles while their motion is obtained through Newton's equations of state. The inter-particle contact forces are thereby determined via constitutive contact-force formulations, which have to account for the envisaged material behaviour. The second step is the homogenisation of the obtained particle's displacements and contact forces through a particle-centre-based strategy towards continuum quantities. Therefore, Representative Elementary Volumes (REV) are introduced on the mesoscale and the specific construction of the REV boundary leads to the understanding of granular media as a micropolar continuum. Finally, in order to verify the homogenisation strategy, a continuum based micropolar model is applied to model localisation phenomena and a comparative study of the results is carried out in a qualitative way. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Nanofibrillated cellulose: surface modification and potential applications

Interest in nanofibrillated cellulose has been increasing exponentially because of its relatively ease of preparation in high yield, high specific surface area, high strength and stiffness, low weight and biodegradability etc. This bio-based nanomaterial has been used mainly in nanocomposites due to its outstanding reinforcing potential. Solvent casting, melt mixing, in situ polymerization and electrospinning are important techniques for the fabrication of nanofibrillated cellulose-based nanocomposites. Due to hydrophilic character along with inherent tendency to form strong network held through hydrogen-bonding, nanofibrillated cellulose cannot uniformly be dispersed in most non-polar polymer matrices. Therefore, surface modification based on polymer grafting, coupling agents, acetylation and cationic modification was used in order to improve compatibility and homogeneous dispersion within polymer matrices. Nanofibrillated cellulose opens the way towards intense and promising research with expanding area of potential applications, including nanocomposite materials, paper and paperboard additive, biomedical applications and as adsorbent.     

Direct Assembly of 2‐Oxazolidinones by Chemical Fixation of Carbon Dioxide

The reaction of β‐ and γ‐haloamines with carbon dioxide to give pharmaceutically relevant 2‐oxazolidinones and 1,3‐dioxazin‐2‐ones, was found to proceed efficiently in the presence of a base and in the absence of catalyst. After optimization of reaction conditions, the system was successfully expanded to a variety of haloamines, even at multigram scale. The reaction was further studied in silico by DFT calculations.