Aqueous MADIX/RAFT polymerization of diallyldimethylammonium chloride: Extension to the synthesis of poly(DADMAC)‐based double hydrophilic block copolymers

Macromolecular design by interchange of xanthates/reversible addition fragmentation chain transfer polymerization (MADIX/RAFT) of diallyldimethylammonium chloride (DADMAC) using the hydrophobic O‐ethyl‐S‐(1‐methoxycarbonyl) ethyl dithiocarbonate MADIX/RAFT mediating agent, Rhodixan A1, was investigated. Attempts to obtain an efficient control of DADMAC polymerization in a water/ethanol mixture failed because of significant chain transfer to ethanol. The use of a water‐soluble Rhodixan A1‐terminated acrylamide oligomer as the MADIX/RAFT agent enabled the controlled polymerization of DADMAC in water at 50 °C using the cationic azo initiator V‐50. An excellent agreement was found between experimental and theoretical M_n values throughout polymerization and over a broad range of initial concentration of xanthate. Polydispersity indexes (PDIs) at the end of the polymerization were abnormally high for a process showing a linear increase of M_n with monomer conversion (1.8 < PDI < 2.0). This feature was explained by the measurement of a high transfer constant to xanthate (C_x = 18.8 ± 1.6) but a low interchange transfer constant (C_ex = 1.5). Nevertheless, poly(acrylamide)–poly(DADMAC) double hydrophilic block copolymers (DHBCs) of controlled M_n and composition could be successfully synthesized for the first time. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Accounting for Polydispersion in the Eulerian Large Eddy Simulation of the Two-Phase Flow in an Aeronautical-type Burner

A major issue for the simulation of two-phase flows in engines concerns the modeling of the liquid disperse phase, either in the Lagrangian or the Eulerian approach. In the perspective of massively parallel computing, the Eulerian approach seems to be more suitable, as it uses the same algorithms as the gaseous phase solver. However taking into account the whole physics of a turbulent spray, especially in terms of polydispersity, requires an additional modeling effort. The Mesoscopic Eulerian Formalism (MEF) [13] accounts for the effect of turbulence on the disperse phase, and was extended to the Large Eddy Simulation framework [41], but is limited to monodisperse flows. In [38], the influence of polydispersity on resolved and unresolved turbulent motions of the disperse phase was highlighted, and a first model was proposed, based on size-conditioned statistics. Starting from this idea, a coupling between the MEF and the Multifluid Approach (MA) [30] is proposed. The MA decomposes the Eulerian phase into several fluid classes called sections, and corresponding to size intervals. Each section uses then size-conditioned closures. The original idea of this work is to use the MEF closures independently in each section, taking into account the mean droplet size of this section. This new approach, called Multifluid Mesoscopic Eulerian Formalism (MMEF), is then able to capture polydispersion with associated size-conditioned turbulent dynamics. First, the importance of polydispersity and the ability of MMEF to capture it are highlighted with a 0D evaporation case and a 2D vortex case, showing its impact on dynamics in both size and physical spaces. Then, the MMEF is applied to the MERCATO configuration of ONERA [18]. Results are compared to monodisperse Eulerian, Lagrangian and experimental results.     

Structure and dynamics of electrostatically interacting magnetic nanoparticles in suspension

We investigate the structure and dynamics of charge-stabilized CoFe(2)O(4)-SiO(2) core-shell magnetic nanoparticles in suspensions. Small angle x-ray scattering and x-ray photon correlation spectroscopy allow us to analyze the intraparticle (core-shell) and interparticle structure of the suspension, as well as their dynamic and hydrodynamic behavior. Due to the weak magnetic interactions, the liquidlike structure is governed by screened Coulomb interactions. The hydrodynamic interactions of the measured systems are significantly stronger than predicted by current theories.     

Structure and stability of VO2+ in aqueous solution: a Car-Parrinello and static ab initio study

Quantum chemical calculations have been carried out to get some insight concerning the effects of temperature and solvent acidity on the structure and stability of solvated VO2+ as the elementary chemical unit involved in the nucleation of vanadophosphates. First, because some recent theoretical studies have suggested a tendency of density functional theory (DFT) to favor lower coordination numbers for such systems, static calculations have been performed on [VO2(H2O)(4-n)]+.nH2O (n=0-2) conformers at the MP2 and DFT level of theory, using two different combinations of basis sets. The results of two pure-GGA (BP86 and PBEPBE), two hybrid-GGA (PBE1PBE and mPWPW91), and two hybrid-meta-GGA (mPW1B95 and B1B95) functionals were analyzed on these systems. The comparison of the results indicates that the stability differences between the two methodologies are resolved when hydration energy is taken into account, provided that some amount of HF exchange is introduced in the DFT calculations. In a second step, Car-Parrinello simulations have been carried out starting from VO2(H2O)4+ surrounded by water molecules. The calculations at 300 K show the natural tendency of VO2(H2O)4+ to decompose to VO2(OH)2- and the requirements to work with an already acidified medium to be able to investigate the coordination sphere of VO2+ for an extended period of time. Under such conditions, we have obtained a clear preference for a five-coordinated vanadium. The molecular dynamics simulations performed at 500 K starting from hydrated VO2+ in a protonated medium found VO(OH)3 to be the most stable structure, whereas this ideal candidate for oxolation reactions is expected to be a very minor species at room temperature.     

NMR parameters in alkali, alkaline earth and rare earth fluorides from first principle calculations

(19)F isotropic chemical shifts for alkali, alkaline earth and rare earth of column 3 basic fluorides are measured and the corresponding isotropic chemical shieldings are calculated using the GIPAW method. When using the PBE exchange-correlation functional for the treatment of the cationic localized empty orbitals of Ca(2+), Sc(3+) (3d) and La(3+) (4f), a correction is needed to accurately calculate (19)F chemical shieldings. We show that the correlation between experimental isotropic chemical shifts and calculated isotropic chemical shieldings established for the studied compounds allows us to predict (19)F NMR spectra of crystalline compounds with a relatively good accuracy. In addition, we experimentally determine the quadrupolar parameters of (25)Mg in MgF(2) and calculate the electric field gradients of (25)Mg in MgF(2) and (139)La in LaF(3) using both PAW and LAPW methods. The orientation of the EFG components in the crystallographic frame, provided by DFT calculations, is analysed in terms of electron densities. It is shown that consideration of the quadrupolar charge deformation is essential for the analysis of slightly distorted environments or highly irregular polyhedra.     

The effect of lip-reading on primary stream segregation

Lip-reading has been shown to improve the intelligibility of speech in multitalker situations, where auditory stream segregation naturally takes place. This study investigated whether the benefit of lip-reading is a result of a primary audiovisual interaction that enhances the obligatory streaming mechanism. Two behavioral experiments were conducted involving sequences of French vowels that alternated in fundamental frequency. In Experiment 1, subjects attempted to identify the order of items in a sequence. In Experiment 2, subjects attempted to detect a disruption to temporal isochrony across alternate items. Both tasks are disrupted by streaming, thus providing a measure of primary or obligatory streaming. Visual lip gestures articulating alternate vowels were synchronized with the auditory sequence. Overall, the results were consistent with the hypothesis that visual lip gestures enhance segregation by affecting primary auditory streaming. Moreover, increases in the naturalness of visual lip gestures and auditory vowels, and corresponding increases in audiovisual congruence may potentially lead to increases in the effect of visual lip gestures on streaming.     

Bacteria love our sugars: Interaction between soluble lectins and human fucosylated glycans,structures, thermodynamics and design of competing glycocompounds

The specific recognition of host epithelial surfaces by pathogen receptors is often the first step of infection. Bacterial carbohydrate-binding proteins, called adhesins or lectins, specifically recognize glycoconjugates on host tissues. Opportunistic pathogens responsible for lung infections, such as some Pseudomonas and Burkholderia species, produce soluble lectins that bind to human fucosylated oligosaccharides. Among these targets, the observed variations in ABO and Lewis histo-blood group phenotypes are proposed to be a result of co-evolution between pathogens and mammals. The analysis of the available crystal structures of bacterial lectins helps deciphering the structure/function relationship involving this important class of protein. The high affinity observed between bacterial lectins and fucosylated oligosaccharides can be reached by different strategies in term of structures and thermodynamics. Structure-based design of glycomimetics and glycodendrimers resulted in very high affinity ligands that open the route towards novel anti-infectious strategies.     

Solving Non-Linear Constraint Satisfaction Problems Involving Time-Dependant Functions

In this paper, we consider the resolution of non-linear constraint satisfaction problems where the variables of the systems are trajectories (functions from \({\mathbb{R}}\) to \({\mathbb{R}^{n}}\) ). We introduce the notion of tubes as intervals of functions, for which the lower and upper bounds are trajectories with respect to the inclusion. We then define basic operators and prove propositions verified by tubes. We show the possibility to build contractors on tubes and propagate constraints to solve problems involving time-dependant functions as the unknown variables. We show that the approach is particularly powerful when inter-temporal equations (e.g. delays) are involved. Finally, in order to illustrate the principle and efficiency of the approach, several test cases are provided.     

Synthesis and structure resolution of RbLaF4

The synthesis and structure resolution of RbLaF(4) are described. RbLaF(4) is synthesized by solid-state reaction between RbF and LaF(3) at 425 °C under a nonoxidizing atmosphere. Its crystal structure has been resolved by combining neutron and synchrotron powder diffraction data refinements (Pnma,a = 6.46281(2) ?, b = 3.86498(1) ?, c = 16.17629(4) ?, Z = 4). One-dimensional (87)Rb, (139)La, and (19)F MAS NMR spectra have been recorded and are in agreement with the proposed structural model. Assignment of the (19)F resonances is performed on the basis of both (19)F-(139)La J-coupling multiplet patterns observed in a heteronuclear DQ-filtered J-resolved spectrum and (19)F-(87)Rb HMQC MAS experiments. DFT calculations of both the (19)F isotropic chemical shieldings and the (87)Rb, (139)La electric field gradient tensors using the GIPAW and PAW methods implemented in the CASTEP code are in good agreement with the experimental values and support the proposed structural model. Finally, the conductivity of RbLaF(4) and luminescence properties of Eu-doped LaRbF(4) are investigated.