Easy and effective method to produce functionalized particles for cellular uptake

In this contribution, a versatile approach for the synthesis of functionalized particles for drug delivery is presented, using two nonaggressive standardized procedures. The first procedure considered is the functionalization of an azido‐terminated α‐norbornenyl poly(ethylene oxide) (PEO) macromonomer with an alkyne‐containing active molecule via the copper catalyzed azide alkyne cycloaddition, click type reaction. The functionalized macromonomer is then polymerized by Ring‐Opening Metathesis Polymerization (ROMP) in dispersion to form functionalized particles. The second procedure consists in synthesizing particles by ROMP in dispersed media of norbornene with azido‐terminated α‐norbornenyl PEO macromonomer. The ROMP was initiated by the first generation Grubbs catalyst. Such functionalized core‐shell particles have stealthy properties due to their PEO shell and can be viewed as universal nanocarriers on which any alkyne‐modified active molecule can be grafted by click chemistry. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Pyridylmagnesiates: generation by bromine–metal exchange and enantioselective addition to aldehydes

Butyl and dibutylmagnesiates incorporating chiral ligands have been prepared and their reactivity studied. The reagents were efficient to promote the clean bromine–magnesium exchange of azinyl bromides at room temperature and subsequent reaction with aldehydes affording pyridylcarbinols. (R,R)-TADDOL-based dibutylmagnesiate was the best reagent leading to acceptable to good enantioselectivities, depending on the substrate and on the aldehyde substitution. This is the first example of enantioselective addition of in situ generated pyridylmagnesiate to carbonyl electrophiles.     

Preparation of Chiral Amino Esters by Asymmetric Phase‐Transfer Catalyzed Alkylations of Schiff Bases in a Ball Mill

The asymmetric alkylation of Schiff bases under basic conditions in a ball mill was performed. The starting Schiff bases of glycine were prepared beforehand by milling protected glycine hydrochloride and benzophenone imine, in the absence of solvent. The Schiff base was then reacted with a halogenated derivative in a ball mill in the presence of KOH. By adding a chiral ammonium salt derived from cinchonidine, the reaction proceeded asymmetrically under phase‐transfer catalysis conditions, giving excellent yields and enantiomeric excesses up to 75 %. Because an equimolar amount of starting material was used, purification was greatly simplified.     

A vectorial algorithm with finite element method for prediction of powder segregation in metal injection molding

The design of the mold and the choice of the injection parameters for metal injection molding (MIM) is required to maintain homogeneity of the filled mixture. However, powder segregation is unavoidable in MIM because of the significant difference in densities of the metallic powder and the polymer binder. To achieve an effective prediction of segregation effect, a biphasic model based on mixture theory is employed. The viscous behaviors of each phase and the interaction coefficient between the flows of the two phases should be determined. The solution of two coupled Navier–Stokes equations results in a tremendous computation effort. The previous development of an explicit algorithm makes the biphasic simulation much faster than that of the classic methods. However, it is strongly desired to reduce or even eliminate the numerous global solutions for pressure fields at each time step. Hence, a new vectorial algorithm is proposed and developed to perform the simulation only by vectorial operations. It provides the anticipated efficiency in the simulation of biphasic modeling, and the advantage to use the classic elements of equal‐order interpolations. Some results produced by the two algorithms are compared with the experimental values to validate the new vectorial algorithm. Copyright © 2012 John Wiley & Sons, Ltd.     

Aerodynamic optimization of the flat-plate leading edge for experimental studies of laminar and transitional boundary layers

This work is concerned with the design of a leading edge for a flat-plate model used to study laminar and transitional boundary layers. For this study, the flow over the complete boundary-layer model, including leading edge, flat section, and trailing-edge flap, is modeled. The effect of important geometrical features of the leading edge on the resulting pressure distribution, starting from the well-known symmetric modified super ellipse, is investigated. A minimal pressure gradient on the measurement side of the plate is achieved using an asymmetrical configuration of modified super ellipses, with a thickness ratio of 7/24. An aerodynamic shape optimization is performed to obtain a novel leading edge shape that greatly reduces the length of the non-zero pressure gradient region and the adverse pressure gradient region compared to geometries defined by ellipses. Wind tunnel testing is used to validate the numerical solutions.     

Distinctive field dependence of the longitudinal muon polarization for Mu* in polycrystalline silicon

A distinctive longitudinal magnetic field dependence of the muon polarization for anomalous muonium in polycrystalline semiconductor targets has been predicted. The polarization exhibits a cusp,i.e., a discontinuous jump in the slope from negative to positive. Measurements of the longitudinal polarization for polycrystalline silicon in fields up to 0.5 T, and temperatures 53 and 200 K have been made at LAMPF. A cusp in the field dependence indeed occurs at 0.345 T, in excellent agreement with the prediction. No cusp is observed at 200 K because Mu^* has been thermally ionized.     

A Hybrid Approach to Scheduling with Earliness and Tardiness Costs

A hybrid technique using constraint programming and linear programming is applied to the problem of scheduling with earliness and tardiness costs. The linear model maintains a set of relaxed optimal start times which are used to guide the constraint programming search heuristic. In addition, the constraint programming problem model employs the strong constraint propagation techniques responsible for many of the advances in constraint programming for scheduling in the past few years. Empirical results validate our approach and show, in particular, that creating and solving a subproblem containing only the activities with direct impact on the cost function and then using this solution in the main search, significantly increases the number of problems that can be solved to optimality while significantly decreasing the search time.     

Pointwise gradient estimates of solutions to onedimensional nonlinear parabolic equations

We present here an improved version of the method introduced by the first author to derive pointwise gradient estimates for the solutions of one-dimensional parabolic problems. After considering a general qualinear equation in divergence form we apply the method to the case of a nonlinear diffusion-convection equation. The conclusions are stated first for classical solutions and then for generalized and mild solutions. In the case of unbounded initial datum we obtain several regularizing effects for t > 0. Some unilateral pointwise gradient estimates are also obtained. The case of the Dirichlet problem is also considered. Finally, we collect, in the last section, several comments showing the connections among these estimates and the study of the free boundaries associated to the solutions of the diffusion-convection equation.     

Étude d'un modèle de fragmentation secondaire pour les brouillards de gouttelettes

In this Note, we first present a model for droplet secondary breakup, in liquid sprays. This model is based on the kinetic theory formalism and uses experimental correlations found in the literature (L.-P. Hsiang, G.M. Faeth, Int. J. Multiphase Flow 19 (5) (1993) 721–735; R. Maxey, J. Riley, Phys. Fluids 26 (4) (1983) 883–889; M. Pilch, C.A. Erdman, Int. J. Multiphase Flow 13 (6) (1987) 741–757) to determine the fragmentation rate and its outcome. We then conduct a mathematical study of the resulting kinetic equation. We prove, under some physically reasonable assumptions, an existence and uniqueness theorem and characterize the long-time behaviour of the solution. To cite this article: G. Dufour et al., C. R. Acad. Sci. Paris, Ser. I 336 (2003).