Interactions underpinning the plasticization of a polymer matrix: a dynamic and structural analysis of DMP-plasticized cellulose acetate

This work establishes that the plasticization effect of a classical petrochemical plasticizer, dimethyl phthalate (DMP), on a polymer matrix, cellulose acetate (CA), is due to the development of intermolecular interactions of dipolar type. Plasticized cellulose acetate films are studied with regard to the interactions between the polymer and plasticizer at the macroscopic scale by thermogravimetric analysis and differential scanning calorimetry. At the molecular level, Fourier transform infrared spectroscopy and dielectric relaxation spectroscopy are used to elucidate the nature of interactions that are responsible for the plasticizing effects. These static and dynamic complementary analyses evidenced that DMP does not establish H-bonding interactions with the polymer chains of cellulose acetate but rather weaker interactions of dipolar type. These dipole–dipole interactions that develop between acetyl side groups of CA and the ester phthalate moieties of DMP increase the overall mobility of CA chains and also locally influence the molecular mobility and the water uptake tendency.     

Analysis of an Emulsification Process Using Fractional Experimental Design

ABSTRACT

Soy oil-in-water emulsions (30% oil) with soy lecithin as emulsifier (4%) were prepared using a stirred vessel under batch conditions. The effects of 7 process variables (impeller-to-tank diameter ratio, temperature, agitation speed, mode of cooling and also pre-emulsification mixing rate, pre-emulsification mixing time and resting time before emulsification) were studied according to a fractional factorial design 2^7?3. The droplet size distributions of the emulsions were measured and the kinetics of destabilization were monitored during 3 months. In the experimental domain, the mixing rate was found to be the most significant variable affecting both the size distribution and the stability. It was followed by the temperature, and the impeller-to-tank ratio depending on the Sauter mean diameter or the half-life time of the emulsions. Interaction of the temperature with the agitation speed and with the impeller-to-tank diameter ratio was also observed.     

Elimination Reactions of 2-Deoxy 2-C-Methyl Sugars : Application to the Synthesis of Methyl 2,3,4-Trideoxy-2,4-Di-C-Methyl-6-O-Triphenylmethyl α-D-Lyxo Hexopyranoside and its X Ray Crystal Structure

Abstract

A facile and regiospecific dehydration of 2-deoxy 2-C-methyl sugars using the triphenylphosphine-diethylazodicarboxylate reagent is reported. This reaction allowed us to prepare the title compound which is a crucial intermediate in the total synthesis of natural products. Its absolute configuration is firmly established by X Ray analysis.     

Direct amplification of ultrashort pulses in μ-pulling-down Yb:YAG single crystal fibers

We demonstrated that Yb:YAG single crystal fibers have a strong potential for the amplification of femtosecond pulses. Seeded by 230?fs pulses with an average power of 400?mW at 30?MHz delivered by a passively mode-locked Yb:KYW oscillator, the system produced 330?fs pulses with an average power of 12?W. This is the shortest pulse duration ever produced by an Yb:YAG amplifier. The gain in the single crystal fiber reached a value as high as 30 in a simple double-pass configuration.     

Synthetic investigations of (1,3′)-bistetrahydroisoquinolines: towards pentacyclic analogues of piperazine core alkaloids

Synthetic investigations of (1,3′)-bistetrahydroisoquinolines are reported as the key intermediates for the synthesis of ecteinascidin and phthalascidin pentacyclic structure analogues through successive Pictet-Spengler cyclization and intramolecular peptide coupling. The direct Pictet-Spengler reaction between a derivative of l-DOPA and N-protected-α-aminoaldehyde was first extended to the synthesis of cis-(1,3′)-bistetrahydroisoquinoline. After introduction of the required amino acid moiety, an efficient six-membered ring intramolecular peptide coupling gave rise to piperazine derivative structures. Complete structural assignments were corroborated by NMR and X-ray spectroscopic methods. Nevertheless, the optical integrity of the N-protected-α-aminoaldehyde seems to be sensitive to the reaction conditions. Pentacylic structures, having an anti C3-C11 backbone stereochemistry, were obtained from cyclization para- and ortho- to the 3-OH group of the l-DOPA derivative.     

The discrete Frenkel-Kontorova model and its extensions: I. Exact results for the ground-states

We present a rigorous study of the classical ground-states under boundary conditions of a class of one-dimensional models generalizing the discrete Frenkel-Kontorova model. The extremalization equations of the energy of these models turn out to define area preserving twist maps which exhibits periodic, quasi-periodic and chaotic orbits. For all boundary conditions, we select among all the extremum solutions of the energy of the model, those which correspond to the ground-states of the infinite system. We prove that these ground-states are either periodic (commensurate) or quasi-periodic (incommensurate) but are never chaotic. We also prove the existence of elementary discommensurations which are minimum energy configuration of the model for certain special boundary conditions. The topological structure of the whole set of ground-states is described in details. In addition to physical applications, consequences for twist map homeomorphisms are mentioned. Part II (S. Aubry, P.Y. LeDaeron and G. Andre) will be mostly devoted to exact results on the transition by breaking of analyticity which occurs on the incommensurate ground states when the model parameters vary and on its connection with the stochasticity threshold in the corresponding twist map.     

High power tunable dual frequency laser system

Construction and performance characteristics of a dual frequency oscillator-amplifier system, pumped by the second harmonic of a Nd-YAG laser are described. With 250 mJ pump energy, output energies up to 115 mJ with Rh 6 G have been achieved. Linewidth was 1.2 pm at 589 nm with a 25 ns pump pulse duration.     

Concentrating particles on drop surfaces using external electric fields

We propose to use an externally applied uniform electric field to alter the distribution of particles on the surface of a drop immersed in another immiscible liquid. Specifically, we seek to generate well-defined concentrated regions at the drop surface while leaving the rest of the surface particle free. Experiments show that when the dielectric constant of the drop is greater than that of the ambient liquid the particles for which the Clausius-Mossotti factor is positive move along the drop surface to the two poles of the drop. Particles with a negative Clausius-Mossotti factor, on the other hand, move along the drop surface to form a ring near the drop equator. The opposite takes place when the dielectric constant of the drop is smaller than that of the ambient liquid, namely particles for which the Clausius-Mossotti factor is positive form a ring near the equator while those for which such a factor is negative move to the poles. This motion is due to the dielectrophoretic force that acts upon particles because the electric field on the surface of the drop is nonuniform, despite the uniformity of the applied electric field. Experiments also show that when small particles collect at the poles of a deformed drop the electric field needed to break the drop is smaller than without particles. These phenomena could be useful to concentrate particles at a drop surface within well-defined regions (poles and equator), separate two types of particles at the surface of a drop or increase the drop deformation to accelerate drop breakup.