Surfactant (bi)layers on gold nanorods

Gold nanorods in aqueous solution are generally surrounded by surfactants or capping agents. This is crucial for anisotropic growth during synthesis and for their final stability in solution. When CTAB is used, a bilayer has been evidenced from analytical methods even though no direct morphological characterization of the precise thickness and compactness has been reported. The type of surfactant layer is also relevant to understand the marked difference in further self-assembling properties of gold nanorods as experienced using 16-EO(1)-16 gemini surfactant instead of CTAB. To obtain a direct measure of the thickness of the surfactant layer on gold nanorods synthesized by the seeded growth method, we coupled TEM, SAXS, and SANS experiments for the two different cases, CTAB and gemini 16-EO(1)-16. Despite the strong residual signal from micelles in excess, it can be concluded that the thickness is imposed by the chain length of the surfactant and corresponds to a bilayer with partial interdigitation.     

Computation of the invariant measure for a Lévy driven SDE: Rate of convergence

We study the rate of convergence of some recursive procedures based on some “exact” or “approximate” Euler schemes which converge to the invariant measure of an ergodic SDE driven by a Lévy process. The main interest of this work is to compare the rates induced by “exact” and “approximate” Euler schemes. In our main result, we show that replacing the small jumps by a Brownian component in the approximate case preserves the rate induced by the exact Euler scheme for a large class of Lévy processes.     

Measurement of Total and Unbound Mycophenolic Acid and Its Glucuronide by LC Coupled with MS. Application to a Pharmacokinetic Study of Mycophenolate Mofetil in Patients with Autoimmune Diseases

Liquid chromatography coupled with mass spectrometry for the determination of total and unbound mycophenolic acid and its major metabolite in human plasma has been developed. Sample preparations were based on a fully automated solid-phase extraction process and ultrafiltration. Mass spectrometric data were acquired in a single-ion monitoring method. The analytes and nevirapine (internal standard) were well separated in an isocratic mode over 8 min. Validation study exhibited excellent linearity, with intra- and inter-day precision and accuracy of less than 12%. The assay was successfully applied to the pharmacokinetic study of mycophenolic acid in patients with autoimmune diseases.     

A vibrational study of the nature of hydroxyl groups chemical bonding in two aluminium hydroxides

Lengths, strengths and valences of OH bonds in the two aluminium hydroxides gibbsite and bayerite were determined on the basis of vibrational spectral data. The uncoupled OD stretching modes in the range 2400–2800 cm⁻¹ were recorded by means of infrared diffuse reflectance, thereby avoiding effects of surface, vibrational coupling or particle shape. The assignment of the corresponding Raman spectra resulted in the determination of harmonic wavenumbers, force constants and anharmonicity coefficients of bulk OH groups in the two minerals. OH bond lengths deduced from these data varied from 0.964 Å to 0.975 Å in gibbsite and 0.962 Å to 0.973 Å in bayerite. These lengths appear to correspond to weak H-bonds contrary to previously recognized data from X-ray diffraction and neutron diffraction studies. Finally, bond valences were calculated on the basis of these new bond lengths and discussed as a function of crystallographic structures and the nature of hydrogen bonding in these two structures.     

A heuristic for the multi-period petrol station replenishment problem

In the multi-period petrol station replenishment problem (MPSRP) the aim is to optimize the delivery of several petroleum products to a set of petrol stations over a given planning horizon. One must determine, for each day of the planning horizon, how much of each product should be delivered to each station, how to load these products into vehicle compartments, and how to plan vehicle routes. The objective is to maximize the total profit equal to the revenue, minus the sum of routing costs and of regular and overtime costs. This article describes a heuristic for the MPSRP. It contains a route construction and truck loading procedures, a route packing procedure, and two procedures enabling the anticipation or the postponement of deliveries. The heuristic was extensively tested on randomly generated data and compared to a previously published algorithm. Computational results confirm the efficiency of the proposed methodology.     

Turbulent Energy Scale-Budget Equations for nearly Homogeneous Sheared Turbulence

For moderate Reynolds numbers, the isotropic relation between second-order and third-order moments for velocity increments (Kolmogorov's equation) is not respected, reflecting a non-negligible correlation between the scales responsible for the injection, transfer and dissipation of the turbulent energy. For (shearless) grid turbulence, there is only one dominant large-scale phenomenon, which is the non-stationarity of statistical moments resulting from the decay of energy downstream of the grid. In this case, the extension of Kolmogorov's analysis, as carried out by Danaila, Anselmet, Zhou and Antonia, J. Fluid Mech. 391, 1999 359-369) is quite straightforward. For shear flows, several large-scale phenomena generally coexist with similar amplitudes. This is particularly the case for wall-bounded flows, where turbulent diffusion and shear effects can present comparable amplitudes. The objective of this work is to quantify, in a fully developed turbulent channel flow and far from the wall, the influence of these two effects on the scale-by-scale energy budget equation. A generalized Kolmogorov equation is derived. Relatively good agreement between the new equation and hot-wire measurements is obtained in the outer region (40 < x ⁺ ₃ < 150) of the channel flow, for which the turbulent Reynolds number is R _λ≈ 36.     

The magic effect of endocyclic but non-sterically hindering biisoquinoline chelates: From fast-moving molecular shuttles to [3]rotaxanes

The use of 8,8′-diaryl-substituted 3,3′-biisoquinolines allows the construction of new multi-component assemblies that are inaccessible with the 2,9-diaryl-substituted 1,10-phenanthroline ligands previously developed by the Sauvage group. This is due to the sterically non-hindering nature of the new chelates, which makes three-component entanglements around octahedral metal centres such as iron(II), cobalt(II) and ruthenium(II) readily possible. Among the newly synthesized molecular assemblies are [3]rotaxanes and [3]pseudorotaxanes in which two molecular strings pass through a single macrocycle, as well as molecular shuttles that exhibit greatly improved shuttling kinetics when compared to previously investigated molecular machines that are based on copper(I)/copper(II) redox chemistry.     

Synthesis and characterization of high surface area TiO2/SiO2 mesostructured nanocomposite

Recently titania synthesis was reported using various structuration procedures, leading to the production of solid presenting high surface area but exhibiting moderate thermal stability. The study presents the synthesis of TiO₂/SiO₂ nanocomposites, a solid that can advantageously replace bulk titania samples as catalyst support. The silica host support used for the synthesis of the nanocomposite is a SBA-15 type silica, having a well-defined 2D hexagonal pore structure and a large pore size. The control of the impregnation media is important to obtain dispersed titania crystals into the porosity, the best results have been obtained using an impregnation in an excess of solvent. After calcination at low temperature (400 °C), nanocomposites having titania nanodomains (～2–3 nm) located inside the pores and no external aggregates visible are obtained. This nanocomposite exhibits high specific surface area (close to that of the silica host support, even with a titania loading of 55 wt.%) and a narrow pore size distribution. Surprisingly, the increase in calcination temperature up to 800 °C does not allow to detect the anatase to rutile transition. Even at 800 °C, the hexagonal mesoporous structure of the silica support is maintained, and the anatase crystal domain size is evaluated at ～10 nm, a size close to that of the silica host support porosity (8.4 nm). Comparison of their physical properties with the results presented in literature for bulk samples evidenced that these TiO₂/SiO₂ solids are promising in term of thermal stability.