Effects of the dispersion methods in Pluronic F108 on the size and the surface composition of MWCNTs and their implications in toxicology assessment

Multi-walled carbon nanotubes (MWCNTs) were dispersed in water and in a Pluronic F108 solution by four different dispersion methods (stirring, bath sonication, stirring followed by bath sonication, and sonication probe). The effect of the dispersion methods were evaluated in terms of the particle size distribution, the agglomerates size, and the exfoliated fraction produced, as well as in terms of the surface and bulk chemical composition. Energy dispersive X-ray, X-ray photoelectron spectroscopy, and centrifugal liquid sedimentation techniques were used to characterize pristine MWCNTs and their dispersion. It is shown that, irrespective of the dispersion methods used, the MWCNTs are strongly wrapped with the biocompatible surfactant Pluronic F108, thereby modifying the external surface of the MWCNTs. Some shortening of MWCNTs and more wrapping are also observed when sonication methods are used. These observations raise questions as to the validity of results obtained in toxicology tests, in vitro and in vivo, were such methods of dispersion procedures are used.     

Large displacement analysis of shear deformable composite beams with interlayer slips

This paper presents a novel geometric non-linear finite element formulation for the analysis of shear deformable two-layer beams with interlayer slips. We adopt the co-rotational approach where the motion of the element is decomposed into two parts: a rigid body motion which defines a local coordinate system and a small deformational motion of the element relative to this local coordinate system. The main advantage of this approach is that the transformation matrices relating local and global quantities are independent to the choice of the geometrical linear local element. The effect of transverse shear deformation of the layers is taken into account by assuming that each layer behaves as a Timoshenko beam element. The layers are assumed to be continuously connected and partial interaction is considered by considering a continuous relationship between the interface shear flow and the corresponding slip. In order to avoid curvature and shear locking phenomena, the local linear element is formulated using “exact” displacement shape functions derived from the closed-form solution of the governing equations of a two-layer beam element. Finally, three numerical applications are presented in order to assess the performance of the proposed formulation.     

Spin State Tunes Oxygen Atom Transfer towards FeIVO Formation in FeII Complexes

Oxoiron(IV) complexes bearing tetradentate ligands have been extensively studied as models for the active oxidants in non-heme iron-dependent enzymes. These species are commonly generated by oxidation of their ferrous precursors. The mechanisms of these reactions have seldom been investigated. In this work, the reaction kinetics of complexes [Fe^II(CH₃CN)₂L](SbF₆)₂ ( [1](SbF₆)₂ and [2](SbF₆)₂ ) and [Fe^II(CF₃SO₃)₂L] ( [1](OTf)₂ and [2](OTf)₂ ( 1 , L=^Me,HPytacn; 2 , L=^nP,HPytacn; ^R,R′Pytacn=1-[(6-R′-2-pyridyl)methyl]-4,7- di-R-1,4,7-triazacyclononane) with Bu₄NIO₄ to form the corresponding [Fe^IV(O)(CH₃CN)L]²⁺ ( 3 , L=^Me,HPytacn; 4 , L=^nP,HPytacn) species was studied in acetonitrile/acetone at low temperatures. The reactions occur in a single kinetic step with activation parameters independent of the nature of the anion and similar to those obtained for the substitution reaction with Cl⁻ as entering ligand, which indicates that formation of [Fe^IV(O)(CH₃CN)L]²⁺ is kinetically controlled by substitution in the starting complex to form [Fe^II(IO₄)(CH₃CN)L]⁺ intermediates that are converted rapidly to oxo complexes 3 and 4 . The kinetics of the reaction is strongly dependent on the spin state of the starting complex. A detailed analysis of the magnetic susceptibility and kinetic data for the triflate complexes reveals that the experimental values of the activation parameters for both complexes are the result of partial compensation of the contributions from the thermodynamic parameters for the spin-crossover equilibrium and the activation parameters for substitution. The observation of these opposite and compensating effects by modifying the steric hindrance at the ligand illustrates so far unconsidered factors governing the mechanism of oxygen atom transfer leading to high-valent iron oxo species.     

On the probability that n and [n c] are coprime

We prove that for any positive real number which is not an integer, the density of the integers which are coprime to , a result conjectured by Moser, Lambek and Erd Hs. This revised version was published online in June 2006 with corrections to the Cover Date.     

The pyridyl-tag strategy applied to the hydrocarbon/perfluorocarbon phase-switching of a porphyrin and a fullerene

A new hydrocarbon/perfluorocarbon phase-switching strategy based on coordination of pyridyl-tagged molecules to a highly fluorinated dicopper-carboxylate complex possessing two accessible axial coordination sites is described. When a chloroform solution of the tetrapyridyl-substituted porphyrin 3 (0.1 mM, 2 mL) is layered on a perfluorodecalin solution of 2 (3.25 mM, 1.5 mL), complete extraction of the porphyrin into the fluorous phase is observed after 30 min of stirring. Quantitative release of both the porphyrin and 2 is achieved simply by adding excess THF to the biphasic system, the THF acting as a pyridine competing ligand. The recovered perfluorocarbon solution containing 2 can be reused for another complexation with the same efficiency. The scope of this approach is emphasized by the phase-switching of a dipyridyl-substituted fullerene, another example of a molecule for which solubilization in perfluorocarbons is very challenging.     

Milliwatt-peak-power pulse characterization at 1.55 microm by wavelength-conversion frequency-resolved optical gating

A novel wavelength-conversion configuration based on four-wave mixing in an optical fiber has been used to generate a frequency-resolved optical gating (FROG) trace identical to that obtained from second-harmonic generation (SHG). The use of an optical fiber waveguide permits enhanced measurement sensitivity compared with that of conventional SHG-FROG and has been used for complete characterization of 1-mW peak-power picosecond pulses at 1.55 microm from an unamplified semiconductor laser diode gain switched at 10 GHz.     

Clustering for routing in densely populated areas

This paper introduces a new approach for generating school bus routes in a dense urban area. First, a districting algorithm is used to determine clusters including appropriate numbers of students. Then, for each cluster, a route and the stops along this route are determined. Numerical results are reported and compared with those obtained previously. Although the algorithm has been developped and tested in a specific context, it could easily be extended to more general vehicle routing problems.