Turbulent liquid–liquid dispersion in SMV static mixer at high dispersed phase concentration

The aim of this paper is to investigate the influence of physico-chemical parameters on liquid–liquid dispersion at high dispersed phase concentration in Sulzer SMV™ mixer. Four different oil-in-water systems involving two different surfactants are used in order to evaluate the effect of interfacial tension, densities and viscosities ratio on mean droplets size diameters. Moreover the influence of the dispersed phase concentration on the pressure drop as well as on the droplet size distribution is investigated. Two different droplets size distribution analysis techniques are used in order to compare the resulting Sauter mean diameters. The comparison between residence time in the mixer and surfactants adsorption kinetics leads to take into account the evolution of the interfacial tension between both phases at short times. Finally experimental results are correlated as a function of dimensionless Reynolds and Weber numbers.     

Microcracking of high zirconia refractories after t → m phase transition during cooling: An EBSD study

High zirconia refractories are composed of a zirconia skeleton surrounded by an intergranular glassy phase. In these materials, zirconia undergoes up to two successive phase transitions during the manufacturing process, c → t then t → m. This leads, after complete cooling, to the formation of microcracks.Preliminary observations have enabled to identify the mechanism mostly responsible for the observed microcracking. In particular, SEM imaging emphasizes the link between the positions of cracks and the presence of distinct crystallographic domains.Thus, our work focuses on the arrangement of the monoclinic and tetragonal domains in zirconia dendrites. The assessment by XRD of the thermal expansion coefficients of zirconia at the lattice scale and the analysis of EBSD maps show that cracking is produced by the thermal expansion mismatch between groups of crystallographic variants. The further reconstruction of both cubic and tetragonal - in the case of a presence of monoclinic zirconia at room temperature - parent grains enables to determine the impact of each transition on the final microstructure and the generated microcracking.     

Numerical study of the coupling between reaction and mass transfer for liquid‐liquid slug flow in square microchannels

While the benefits of miniaturization on processes have been widely demonstrated, its impact on microfluidics and local mechanisms such as mass transfer is still little understood. The coupling between reaction and mass transfer in microchannels is simulated for liquid‐liquid slug flow. First, the extrapolation to confined flow of the classical model used to calculate interfacial mass fluxes in reactive infinite media was studied. This model consists in estimating transferred fluxes between two phases as a function of the enhancement factor E. Its expression depends on the model used to represent interfacial mass transfer. In infinite media, Lewis and Whitman's stagnant film theory is generally preferred for its simplicity and its reliability. In the case of confined slug flow, the limitation of such a model to predict interfacial fluxes is highlighted. Second, the case of liquid‐liquid competitive consecutive reactions in microchannels is considered. The unfavorable impact of the length between droplets on selectivity is emphasized. This is a direct consequence of mass‐transport mechanisms in microchannels. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Melt processing of poly(L‐lactic acid) in the presence of organomodified anionic or cationic clays

Poly(L ‐lactic acid) (PLA) films are in use for various types of food packaging; however, a wider range of applications would be possible if the barrier properties of these films could be improved. To make such improvements, combinations of PLA with two nanofillers, laurate‐intercalated Mg‐Al layered double hydroxide (LDH‐C₁₂) and a cationic organomodified montmorillonite (MMT) clay (Cloisite® 30B), were investigated. The dispersion of these fillers in PLA by melt processing was explored using two methods, either by mixing the nanofillers with PLA granulate immediately before extrusion or by preparation and subsequent dilution of PLA‐nanofiller masterbatches. After melt processing of these materials, PLA molecular weight, thermal stability, film transparency, morphology, and permeability characteristics were determined. Direct addition of LDH‐C₁₂ drastically reduced the PLA molecular weight. Although this reduction in molecular weight was still very significant, it was less when a PLA/LDH‐C₁₂ masterbatch was processed. In contrast, there was no significant reduction in PLA molecular weight when processing with Cloisite® 30B. However, film transparency was compromised when either LDH or MMT nanofillers were used. Evidence from DSC analyses showed a significant increase in heat of fusion when LDH‐C₁₂ was dispersed in PLA compared with Cloisite® 30B, likely indicating a difference in nucleating properties. Complementary optical purity analyses suggested that racemization as a result of processing could influence the PLA crystallinity as determined by DSC in certain cases. A reduction in thermal stability when incorporating LDH‐C₁₂ could be a direct result of PLA molecular weight reduction. XRD and TEM analyses showed that both Cloisite® 30B‐ and LDH‐C₁₂‐based PLA composites yielded exfoliated and intercalated morphologies, but nanofiller agglomeration was also seen when LDH‐C₁₂ was used. PLA/Cloisite® 30B nanocomposite films exhibited significant enhancement in oxygen and water vapor barrier properties, but no such improvement was found in PLA/LDH‐C₁₂ nanocomposite films. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Application of the guanidine-acylguanidine bioisosteric approach to argininamide-type NPY Y₂ receptor antagonists

Strongly basic groups such as guanidine moieties are crucial structural elements, but they compromise the drug‐likeness of numerous biologically active compounds, including ligands of G‐protein‐coupled receptors (GPCRs). As part of a project focused on the search for guanidine bioisosteres, argininamide‐type neuropeptide Y (NPY) Y₂ receptor (Y₂R) antagonists related to BIIE0246 were synthesized. Starting from ornithine derivatives, N^G‐acylated argininamides were obtained by guanidinylation with tailor‐made mono‐Boc‐protected N‐acyl‐S‐methylisothioureas. The compounds were investigated for Y₂R antagonism (calcium assays), Y₂R affinity, and NPY receptor subtype selectivity (flow cytometric binding assays). Most of the N^G‐substituted (S)‐argininamides showed Y₂R antagonistic activities and binding affinities similar to those of the parent compound, whereas N^G‐acylated or ‐carbamoylated analogues with a terminal amine were superior (Y₂R: K_i and K_B values in the low nanomolar range). This demonstrates that the basicity of the compounds, although 4–5 orders of magnitude lower than that of guanidines, is sufficient to form key interactions with acidic amino acids of the Y₂R. The acylguanidines bind with high affinity and selectivity to Y₂R over the Y₁, Y₄, and Y₅ receptors. As derivatization of the amino group is tolerated, these compounds can be considered building blocks for the preparation of versatile fluorescent and radiolabeled pharmacological tools for in vitro studies of the Y₂R. The results support the concept of bioisosteric guanidine–acylguanidine exchange as a broadly applicable approach to retain pharmacological activity despite decreased basicity.     

C5-DNA methyltransferase inhibitors: from screening to effects on zebrafish embryo development

DNA methylation is involved in the regulation of gene expression and plays an important role in normal developmental processes and diseases, such as cancer. DNA methyltransferases are the enzymes responsible for DNA methylation on the position 5 of cytidine in a CpG context. In order to identify and characterize novel inhibitors of these enzymes, we developed a fluorescence-based throughput screening by using a short DNA duplex immobilized on 96-well plates. We have screened 114 flavones and flavanones for the inhibition of the murine catalytic Dnmt3a/3L complex and found 36 hits with IC(50) values in the lower micromolar and high nanomolar ranges. The assay, together with inhibition tests on two other methyltransferases, structure-activity relationships and docking studies, gave insights on the mechanism of inhibition. Finally, two derivatives effected zebrafish embryo development, and induced a global demethylation of the genome, at doses lower than the control drug, 5-azacytidine.     

Self-assembly of block copolymer complexes in organic solvents

Micelles have been prepared by mixing poly(styrene)-block-poly(4-vinylpyridine) (PS-b-P4VP) copolymers and poly(acrylic acid) (PAA) homopolymers in organic solvents. Complexation via hydrogen bonding occurs between the P4VP and PAA blocks. Further aggregation of the accordingly formed complexes results in micelles stabilized by a corona of PS blocks. The influence of the relative lengths of the different blocks and of the quality of the solvent towards the complexes on the micellar characteristic features is studied. Soluble, non-aggregating, complexes have been observed in DMF, provided that the complexes are sufficiently small. In all other cases, the complexes were insoluble and aggregated in micelles. The size of those micelles depends strongly on the length of the P4VP blocks but only weakly on the PAA length.     

Microstructural development during transient directional solidification of hypermonotectic Al–Bi alloys

Directional unsteady-state solidification experiments were performed with hypermonotectic Al–5.0 wt%Bi and 7.0 wt%Bi alloys. Thermal parameters such as the growth rate (v) and the thermal gradient (G) were experimentally determined by cooling curves recorded along the casting length. The predominant Bi-rich phase was characterized by droplets embedded in the aluminum matrix. Both the interphase spacing (λ) and the Bi-rich particles diameter (d) were measured along the casting length. These microstructural features were correlated to the solidification thermal parameters: growth rate, cooling rate and thermal gradient. An experimental law expressing λ as a function of both G and v was found to better represent the growth of hypermonotectic Al–Bi alloys. Moreover, it was found that the interphase spacing decreases with increasing alloy bismuth content.