Iron-Cobalt-Silica Aerogel Nanocomposite Materials

Iron-Cobalt-Silica nanocomposites were prepared in form of aerogels. X-ray diffraction, transmission electron microscopy and N₂ physisorption at 77 K were used to investigate the structure, size and dispersion of the nanocrystals and the porous structure in the aerogels and in the final composites. The variation of the supercritical drying conditions gives rise to differences in the morphological features of the aerogels. These differences influence the size of the cobalt oxide nanoparticles in the aerogels. On the other hand, after the reduction treatment the average size of the alloy nanoparticles is the same in all the aerogel nanocomposites. The effect of reduction temperature on alloy formation and particle size is also discussed.     

A DFT investigation of the addition reaction of monomeric lithium enolate derived from propiophenone to propene oxide: examination of the possible transition structures

The addition reaction of monomeric lithium enolate (Z)-1, derived from propiophenone, to propene oxide 2, was examined to clarify the exact geometry of the transition state (TS) involved in this type of reaction. The eight possible TSs and the corresponding pathways, four leading to syn gamma-hydroxy ketone (gamma-HK) 3 and four leading to anti gamma-HK 4, were compared, using the B3LYP/6-31+G(d)//B3LYP/6-31+G(d) theory level in vacuo and in the presence of the reaction solvent (toluene/hexane). In every case, the favored pathway involves a TS where the enolate C=C and the epoxide C-C are in a gauche relationship and where the Li(+) is stabilized by some C-C and C-H sigma bonds of epoxide 2.     

Iron–cobalt nanocrystalline alloy supported on a cubic mesostructured silica matrix: FeCo/SBA-16 porous nanocomposites

A series of novel nanocomposites constituted of FeCo nanoparticles dispersed in an ordered cubic Im3m mesoporous silica matrix (SBA-16) have been successfully synthesized using the wet impregnation method. SBA-16, prepared using the non-ionic Pluronic 127 triblock copolymer as a structure-directing agent, is an excellent support for catalytic nanoparticles because of its peculiar three-dimensional cage-like structure, high surface area, thick walls, and high thermal stability. Low-angle X-ray diffraction, N₂ physisorption, and transmission electron microscopy analyses show that after metal loading, calcination at 500 °C, and reduction in H₂ flux at 800 °C, the nanocomposites retain the well-ordered structure of the matrix with cubic symmetry of pores. FeCo alloy nanoparticles with spherical shape and narrow size distribution (4–8 nm) are homogeneoulsy distributed throughout the matrix and they seem in a large extent to be allocated inside the pores.     

Structural evolution in mechanical alloying of Co and B powders

X-ray diffraction and scanning electron microscopy were used to monitor the mechanical alloying of four different mixtures of cobalt and boron with atomic compositions Co₅₀B₅₀, Co₆₇B₃₃, Co₇₅B₂₅ and Co₈₀B₂₀, respectively. The process induces amorphization reactions depending on the boron content; an almost complete amorphization was reached for the Co₆₇B₃₃ and Co₈₀B₂₀ samples, where only minor traces of unreacted cobalt are present. Extended X-ray absorption fine structure data collected on the most amorphous sample confirmed the diffraction results. In all the samples, the formation of t-Co₂B was detected.     

Design of water-based ferrofluids as contrast agents for magnetic resonance imaging

We report the synthesis, characterization and relaxometric study of ferrofluids based on iron oxide, with potential for use as magnetic resonance imaging (MRI) contrast agents (CAs). The effect of different cost-effective, water-based surface modification approaches which can be easily scaled-up for the large scale synthesis of the ferrofluids has been investigated. Surface modification was achieved by silanization, and/or coating with non-toxic commercial dispersants (a lauric polysorbate and a block copolymer with pigment affinic groups, namely Tween 20 and Disperbyk 190) which were added after or during iron oxide nanoparticle synthesis. It was observed that all the materials synthesized functioned as negative contrast agents at physiological temperature and at frequencies covered by clinical imagers. The relaxometric properties of the magnetic nanoparticles were significantly improved after surface coating with stabilizers compared to the original iron oxide nanoparticles, with particular reference to the silica-coated magnetic nanoparticles. The results indicate that the optimization of the preparation of colloidal magnetic ferrofluids by surface modification is effective in the design of novel contrast agents for MRI by enabling better or more effective interaction between the coated iron oxide nanoparticles and protons present in their aqueous environment.     

Critical space for the parabolic-parabolic Keller–Segel model in Rd

We study the Keller–Segel system in ${\mathbb{R}}^d$ when the chemoattractant concentration is described by a parabolic equation. We prove that the critical space, with some similarity to the elliptic case, is that the initial bacteria density satisfies $n_0\in L^a({\mathbb{R}}^d)$, $a>d/2$, and that the chemoattractant concentration satisfies $\mathrm{?}{c}_0\in L^d({\mathbb{R}}^d)$. In these spaces, we prove that small initial data give rise to global solutions that vanish as the heat equation for large times and that exhibit a regularizing effect of hypercontractivity type. To cite this article: L. Corrias, B. Perthame, C. R. Acad. Sci. Paris, Ser. I 342 (2006).     

Stereoselective synthesis of 2,3-unsaturated-aza-O-glycosides via new diastereoisomeric N-Cbz-imino glycal-derived allyl epoxides

Diastereoisomeric D,L-N-Cbz-imino glycal-derived allyl epoxides 5 and 6 have been synthesized, and their addition reactions with alcohols examined. The reactions lead to the corresponding 2,3-unsaturated-aza-O-glycosides through a new, completely regioselective 1,4-addition process which proceeds with complete substrate-dependent stereoselectivity.     

Theoretical conformational study of six-membered cyclic allyl epoxides

Accurate “ab initio” calculations (MP2 method) were performed to outline the conformational profile of a number of six-membered cyclic allyl epoxides differing either in the nature of the cycle fragment (Y) bound to the unsaturation, or in the substitution at the endocyclic carbon bound to the epoxy ring and bridging the epoxy ring with the Y fragment. In particular, we calculated structures 4 (Y=CH₂), 5 (Y=O), 6 (Y=NH), 7 (Y=S), 8 (Y=CF₂), 9 (Y=NH₂ ⁺), 10 (Y=CO), 11 (Y=BH) and 12 (Y=NCOOH), where the fragment of the endocyclic carbon bridging “Y” and the epoxy fragment is either non-substituted (4a – 12a) or bears a methyl side chain trans (4b–12b) or cis (4c–12c) to the epoxidic oxygen. Saturated analogs (Y=O and Y=CH₂) were also computed to test the method and to evaluate the conformational profile in the absence of the unsaturation. Minimum energy conformations were found which differ in the relative position of the Y group and the epoxy oxygen, with respect to a plane containing the epoxy ring carbons and the adjacent saturated endocyclic carbon: they may be on the same side (conformer A) or on opposite sides (conformer B). Conformers A are generally more stable. The conjugation effect of Y with the double bond lowers the barrier between the two conformers to the extent that in a few cases only conformer A is associated with a minimum of energy. On the basis of the elongation of the allylic oxirane C–O bond, we postulated the order of reactivity of epoxides 4–12 in the oxirane ring-opening process, and a mechanism based on the more reactive conformer A. A comparison was also made between MP2 and DFT calculation methods.     

Nonlinear multi-frequency generation for underwater application

This study examines the feasibility of designing a multi-frequency acoustic surveying tool based on the saturation effect. The transmitter is driven by a high-power single tone-burst: nonlinear propagation creates the beams at harmonic frequencies. A simple pseudo one-dimensional model is used to estimate the expected on-axis harmonic levels generated with a rectangular aperture. First measurements are reported and compared with the estimations.