Sulfonated polypropylene ionomers

Polypropylene ionomers have been prepared by sulfonation of copolymers of propene and 7 methyl, 1-6 octadiene, followed by neutralization to cesium salts. Both WAXS and SAXS were used to study the morphology of the samples, while their thermal properties were studied by DSC and their mechanical properties by DMTA. The sulfonation process is shown to cause a further drop in crystallinity in addition to the effect of comonomer incorporation. Ion clustering is observed when the extent of sulfonation is high enough, the limit being dependent on the copolymer composition. The ion pairs which are not incorporated into the cluster cause a small-angle upturn in the WAXS pattern. The mechanical properties are strongly affected by the drop in crystallinity, but may be partly recovered due to ion clustering. No disruption of the ion clusters is observed before thermal decomposition of the polymer.     

Sodium Taurocholate-Induced Lamellar-Micellar Phase Transitions of DPPC

The thermotropic transitions of 1,2-dipalmitoylphosphatidylcholine (DPPC) and the structural changes of its lamellar phases have been studied between 0 and 50°C by both DSC and synchrotron small angle X-ray diffraction/scattering as a function of temperature (XRDT) and sodium taurocholate concentration [TC] in the 0–40 mM range ([DPPC]=50 mM) at pH 7.4. The existence of multiple phase transitions (up to 5 peaks within a 5°C interval) in a narrow domain of temperature between 25 and 42°C depending on the [TC]/[lipid] ratio was observed in the DSC curves. XRDT showed that at low ratios they might correspond to transitions between lamellar phases, the structural characteristics of which are given. At higher ratios a lamellar to micellar transition was observed, and the temperature at which it was observed decreased as a function of the TC content. The relationships with DPPC vesicle bilayer permeabilization and solubilization are discussed.     

Rheology of lyotropic and thermotropic lamellar phases

We investigate the steady-state rheological behaviour of the lamellar phase of a lyotropic system (CpCl, hexanol, brine) and of a thermotropic system (8CB). Power laws characterize the behaviour of the imposed stress as a function of the measured shear rate and similarities are observed for both systems; the same regime γ˙∼σ ^m with m≈1.7 is obtained at low shear stresses corresponding to a texture of oily streaks oriented in the direction of the flow, as shown by microscopic observations. The “onion state” only exists in the case of dilute samples of the lyotropic lamellar phase; the stress then varies as γ˙∼σ ^m with m≈4.8, as already observed by other groups with different systems. Rheological measurements at different temperatures allow determination of different activation energies relating to the still badly understood processes involved in the different rheological regimes. We propose a model which reproduces the experimental power laws and which is based on an analogy with the theory of high-temperature creep in metals and alloys. Received: 19 October 1999/Accepted: 1 November 1999     

DSC And X-Ray Diffraction Coupling

A new technique, that allows simultaneous time-resolved synchrotron X-ray diffraction as a function of temperature (XRDT) and high sensitivity DSC to be carried out in the same apparatus, has been developed. Microcalorimetry and XRDT scans can be performed at any rate between 0.01 and 10°C min^?1 with a 0.01°C temperature resolution in the temperature range, 30–130°C and at lower cooling rates but the same heating rates in the ?30–+30°C range. The use of a single and very small sample (1 to 20 μl) contained in a thin glass capillary for both measurements and simultaneous data collection prevents any temperature shift between recordings and any possible difference in the thermal histories of the samples.     

Investigation of the complex thermal behavior of fats

The thermal behavior of three ural fats (displaying very different composition), cocoa butter (CB)², lard, and a stearin obtained from anhydrous milk-fat (AMF) fractionation, were studied by both DSC and X-ray diffraction as a function of temperature (XRDT). To perform temperature explorations between –30C and +80C, at rates identical to those used for DSC and ranging from 0.1 K min^–1 to 10 K min^–1, a new set of X-ray sample-holders, temperature-controlled by Peltier effect, has been developed. It is shown that the three more stable polymorphic forms of CB were easily characterized by either X-ray diffraction or DSC, and existence of two -3L forms was confirmed. On the contrary, the more complex polymorphism of lard and AMF required combined examination by DSC and XRDT and the brightness of the synchrotron source for studies at the highest heating rates. Quantitative analysis of the long spacings of XRDT recordings is invaluable for interpretation of thermal events. For instance, it was found that the simultaneous formation of two polymorphic forms, of apparent long spacing of 34 and 42 å, at the onset of lard crystallization might explain the difficulty of its fractionation.Special thanks to Courtney P. Mudd (NIH, Bethesda) for his pertinent advice on the mounting and use of thermoelectric devices. The study of lard crystallization was initiated by Valerie Portalier and suggested by Jean-Luc Vendeuvre of CTSCCV (Maisons-Alfort). For the AMF part of this study, stearin was fractionated by ADRIA Normandie, while characterization of its thermal properties was performed as part of a research program funded by ARILAIT Recherches and the French Ministry of Research and Technology.     

DSC and high resolution X-ray diffraction coupling

Adaptive or smart hybrid composites consisting of a polymer matrix reinforced by aramid fibres and incorporating pre-strained Shape Memory Alloy (SMA) wires are able to tune some of their properties, such as their shape, the natural vibration frequency or the damping coefficient, in response to an external stimulus. The functional properties of these systems are directly related to the reversible martensitic transformation in the SMA elements. In this work the transformational behaviour of both free SMA wires and SMA wires embedded in polymer matrix is investigated by means of DSC. The martensitic transformation of the constrained wires is impeded by the polymer matrix, while the interface integrity plays a crucial role.     

Proteocubosomes: nanoporous vehicles with tertiary organized fluid interfaces

Proteocubosomes are nanostructured open-nanochannel hierarchical fluid vehicles characterized by a cubic lattice periodicity of the lipid/protein supramolecular assembly (protein-loaded cubosomes). They are obtained here at very high hydration levels by a three-dimensional (3D) self-assembly process, which exploits a protein-directed 3D patterning and fragmentation to create a new, tertiary-level structural order of fluid lipid/water interfaces. Our freeze-fracture electron microscopy study reveals that the proteocubosome structures are built up by patterned assemblies of nanocubosomes, which comprise 3D nanoporous fracture surfaces throughout. Complex cubosomic architectures, involving arrays of nanodroplets (larger than 20 nm) inside the proteocubosome particles, are established at high resolution. The soft-matter hierarchical nanocompartment formations display internal aqueous pores belonging to the D-type lipid cubic lattice nanochannel system that is proven by synchrotron X-ray diffraction. The reported nanostructured fluid may give rise to novel applications in nanofluidic biomimetic devices, porous protein drug delivery vehicles, nanoscale enzymatic bioreactors, and protein-encapsulating fluid nanomaterials.     

The use of pencil lead as a matrix and calibrant for matrix-assisted laser desorption/ionisation

Pencil lead is shown to be an effective matrix and calibrant in matrix-assisted laser desorption/ionisation (MALDI) mass spectrometry. Various groups of analytes, including peptides, polymers and actinide metals, can be readily ionised using MALDI when deposited onto a pencil lead matrix. The matrix is seen to have advantages in sample preparation relating to its hydrophobic properties and almost complete suppression of the matrix during analysis. Using pencil lead as a matrix is a quick and convenient method of qualitative analysis and has been shown to be quantitative for the isotope ratio analysis of actinide metals.     

Metal-free Brønsted acids catalyzed synthesis of functional 1,4-dihydropyridines

Brønsted acids catalyze the addition of β-enaminoacrylates to α,β-unsaturated aldehydes leading to substituted dihydropyridines in moderate to good yields under mild conditions. The first example of an enantioselective synthesis of a dihydropyridine is also reported.     

Thermal and structural behavior of milk fat. 3. Influence of cooling rate and droplet size on cream crystallization

Crystallization of triacylglycerols (TG) within milk fat globules of creams is studied with an instrument coupling time-resolved synchrotron X-ray diffraction (XRDT) at both small and wide angles and high-sensitivity differential scanning calorimetry (DSC) at cooling rates of -3 and -1 degrees C/min from 60 to -10 degrees C and compared to that of the anhydrous milk fat (AMF). Simultaneous thermal analysis permits correlation of the formation of the different crystalline species monitored by XRDT to the DSC events. Under the above cooling conditions, milk fat TG sequentially crystallize, within the globules, from about 19 degrees C, in three different lamellar structures with double-chain length (2L) stackings of 47 and 42 A and a triple-chain length (3L) stacking of 71 A, all of alpha type, which are correlated to two or three overlapped exothermic peaks recorded by DSC. Compared to what is observed for AMF, TG crystallization in emulsion (i) favors sub-alpha formation at low temperature and (ii) induces layer stacking defects in 3L crystals. Subsequent heating at 2 degrees C/min shows numerous structural rearrangements before final melting, confirming that (i) cooling at -1 degrees C/min leads to the formation of unstable crystalline varieties in the dispersed state and (ii) a monotropic transition alpha-->beta' takes place. Similar behavior is observed for cooling at -3 degrees C/min and subsequent heating. An overall comparison of the thermal and structural properties of the crystalline species formed as a function of the cooling rate, between >1000 and 0.15 degrees C/min, and stabilization time at 4 degrees C is given. Depending on the cooling rate, at least five crystalline subcell species are observed at wide angles, alpha and sub-alpha, two beta' and one beta. At small angles, at least six lamellar stackings are identified, three 3L and three 2L. However, a single subcell packing (e.g., alpha) might correspond to several longitudinal chain stackings, demonstrating the usefulness of the small-angle XRD technique. Reconstituted emulsions homogenized under different pressures are used to determine the influence of droplet size on crystallization. The decrease of droplet size induces (i) a higher supercooling/supersaturation and (ii) a higher disorder and/or a smaller size of TG crystals within the emulsion droplets. At the supramolecular scale, polarized light microscopy shows that various cooling rates applied in situ using a temperature-controlled stage directly influence crystal sizes and their type of organization within milk fat globules. The faster the cooling rate, the smaller the size of the crystals within the globules.