Periodic points in the intersection of attracting immediate basins boundaries

We give conditions under which the intersection between two attracting immediate basins boundaries of a rational map contains at least one periodic point.     

Programmed Multiple C-H Bond Functionalization of the Privileged 4-hydroxyquinoline Template

The introduction of substituents on bare heterocyclic scaffolds can selectively be achieved by directed C−H functionalization. However, such methods have only occasionally been used, in an iterative manner, to decorate various positions of a medicinal scaffold to build chemical libraries. We herein report the multiple, site selective, metal-catalyzed C−H functionalization of a “programmed” 4-hydroxyquinoline. This medicinally privileged template indeed possesses multiple reactive sites for diversity-oriented functionalization, of which four were targeted. The C-2 and C-8 decorations were directed by an N-oxide, before taking benefit of an O-carbamoyl protection at C-4 to perform a Fries rearrangement and install a carboxamide at C-3. This also released the carbonyl group of 4-quinolones, the ultimate directing group to functionalize position 5. Our study highlights the power of multiple C−H functionalization to generate diversity in a biologically relevant library, after showing its strong antimalarial potential.     

Optimization of flow diverters for cerebral aneurysms

A modern technique to treat cerebral aneurysms is to insert a flow diverter in the parent artery. In order to produce an optimal design of such devices, we consider a methodology combining simulated annealing optimization and lattice Boltzmann simulations. Our results surpass, in terms of stent efficiency, those obtained in the recent literature with an other optimization method. Although our approach is still in 2D, it demonstrates the potential of the method. We give some hint on how the 3D cases can be investigated.     

Insights into the Complexity of Weak Intermolecular Interactions Interfering in Host–Guest Systems

The recognition properties of heteroditopic hemicryptophane hosts towards anions, cations, and neutral pairs, combining both cation–π and anion–π interaction sites, were investigated to probe the complexity of interfering weak intermolecular interactions. It is suggested from NMR experiments, and supported by CASSCF/CASPT2 calculations, that the binding constants of anions can be modulated by a factor of up to 100 by varying the fluorination sites on the electron‐poor aromatic rings. Interestingly, this subtle chemical modification can also reverse the sign of cooperativity in ion‐pair recognition. Wavefunction calculations highlight how short‐ and long‐range interactions interfere in this recognition process, suggesting that a disruption of anion–π interactions can occur in the presence of a co‐bound cation. Such molecules can be viewed as prototypes for examining complex processes controlled by the competition of weak interactions.     

Non smooth dynamics of mechanical systems with history term

Models involving maximal monotone term and history (delay) term are considered in a mathematical and numerical point of view.     

Orchestrating the Biosynthesis of an Unnatural Pyrrolysine Amino Acid for Its Direct Incorporation into Proteins Inside Living Cells

We here report the construction of an E. coli expression system able to manufacture an unnatural amino acid by artificial biosynthesis. This can be orchestrated with incorporation into protein by amber stop codon suppression inside a living cell. In our case an alkyne‐bearing pyrrolysine amino acid was biosynthesized and incorporated site‐specifically allowing orthogonal double protein labeling.     

Suberitane sesterterpenoids from the Antarctic sponge Phorbas areolatus (Thiele, 1905)

Following ecological and chemical screenings, the Antarctic sponge Phorbas areolatus was chemically investigated for the first time. Three new suberitane derivatives named isosuberitenone B, 19-episuberitenone B, and isoxaspirosuberitenone were identified together with the known compounds suberitenones A and B, and oxaspirosuberitenone after a thorough inspection of their NMR data. These compounds were found to exhibit moderate cytotoxic activity and their presence in this sponge rules out their use as a chemotaxonomic marker for Suberites sponges.     

Influence of nanotopography on phospholipid bilayer formation on silicon dioxide

We have investigated the effect of well-defined nanoscale topography on the 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) lipid vesicle adsorption and supported phospholipid bilayer (SPB) formation on SiO2 surfaces using a quartz crystal microbalance with dissipation monitoring (QCM-D) and atomic force microscopy (AFM). Unilamellar lipid vesicles with two different sizes, 30 and 100 nm, were adsorbed on pitted surfaces with two different pit diameters, 110 and 190 nm, as produced by colloidal lithography, and the behavior was compared to results obtained on flat surfaces. In all cases, complete bilayer formation was observed after a critical coverage of adsorbed vesicles had been reached. However, the kinetics of the vesicle-to-bilayer transformation, including the critical coverage, was significantly altered by surface topography for both vesicle sizes. Surface topography hampered the overall bilayer formation kinetics for the smaller vesicles, but promoted SPB formation for the larger vesicles. Depending on vesicle size, we propose two modifications of the precursor-mediated vesicle-to-bilayer transformation mechanism used to describe supported lipid bilayer formation on the corresponding flat surface. Our results may have important implications for various lipid-membrane-based applications using rough or topographically structured surfaces.     

Nano-Architecture of Facetted NiFe<Subscript>2</Subscript>O<Subscript>4</Subscript>/(Ni,Fe)O Particles Produced by Induction Plasma

Facetted nickel ferrite (NiFe₂O₄) and bunsenite [(Ni,Fe)O] nanocrystals were grown from the decomposition of iron and nickel nitrate precursors using an inductively coupled plasma reactor. The full range of the two-phase region of the Fe₂O₃–NiO pseudo-equilibrium phase diagram was investigated by producing nanopowders with bulk Ni/(Ni + Fe) ratios of 0.33, 0.4, 0.5, 0.75 and 1.0. A Ni-poor [Ni/(Ni + Fe) ≤ 0.5] precursor solution produced truncated octahedron nanocrystals, whereas nanocubes were obtained at higher ratios [Ni/(Ni + Fe) ≈ 1]. In both cases, it is shown that the nanocrystals adopt a morphology close to the Wulff shape of the crystalline system (spinel and NaCl, respectively). As the bulk Ni/(Ni + Fe) ratio increases from 0.33 (the stoechiometric composition of nickel ferrite), bunsenite is epitaxially segregated on the {110} and {111} facets of nickel ferrite, while leaving the NiFe₂O₄ {100} facets exposed. A precursor solution at a Ni/(Ni + Fe) ratio of 0.75 gave an (Ni,Fe)O-rich nanopowder with a random and irregular interconnected morphology. The structure of these nanocrystals can be understood in terms of their thermal history in the plasma reactor. These results highlights the possibility of producing organized multi-phased nanomaterials of binary systems having two phases stable at high temperatures, using a method known to be easily scalable.