Photopolymerization of Pollen Based Biosourced Composites and Applications in 3D and 4D Printing

Pollen have the potential to be effective plant-based biorenewable reinforcing fillers for polymers due to their chemical stability and unique micro- or nano-structured surfaces. Pollen-polymer composites can form the basis for a new class of light-weight and sustainable materials if compatible polymer-filler systems can be engineered through photopolymerization, but this idea is previously unexplored. The first demonstration of photopolymerization and 3D printing with the incorporation of pine pollen as filler in poly(ethylene glycol) diacrylate are presented. The filler properties affecting the related depth of cure and the mechanical, thermal, and functional properties are examined in detail. In addition, the lithography technique is applied to the photocomposites for the production of 3D patterns. 4D printing behavior is also possible through the water swelling and dehydration induced actuation of the 3D printed composites with spatial resolution features. This work is expected to provide a new way to a field for photopolymerization reactions in natural material-resin composites and thereby to expand potential applications in 3D and 4D printing.     

α-Al2O3 (0001) Surfaces: Atomic and Electronic Structure

New results on the     R ± 9° reconstructed α-Al₂O₃ (0001) surface, which can be obtained after heating at high temperature (1400°C) under vacuum, are presented. The atomic structure has been studied by combining low-energy electron diffractometry and grazing incidence X-ray scattering. The surface structure is found to be perfectly commensurable with the underlying bulk lattice. The surface consists of hexagonal zones of two, nearly perfect, close-packed Al (111) planes separated by a defect of hexagonal periodicity with a parameter of 26.44 Å. This model is consistent with previous surface studies of this reconstruction. The electronic structure has been investigated using valence band photoemission spectroscopy, X-ray absorption spectroscopy at the O K edge, electron energy loss spectroscopy, and X-ray-induced Auger electron spectroscopy. Interpretation of these experimental data in the frame of a self-consistent, tight-binding calculation leads to the conclusion that the     R ± 9° reconstructed surface is more covalent than the (1 × 1) surface. Significant changes in the; Al-O hybridizations are observed; these are likely due to a difference in the interatomic distances along the [0001] axis (relaxations). The increase of covalent character is mainly due to a strong decrease of the Madelung field on the reconstructed surface.     

Pilot scale preparation of wheat gluten protein fractions: II. Technological properties of the fractions

Fractions differing in prolamin compositions were obtained on a pilot scale when wheat gluten proteins were separated by differential extraction in dilute acetic acid. The soluble fractions were enriched in gliadins and the insoluble ones were richer in glutenins. The effects of the gluten fractions on the technological properties of wheat flours were investigated using an alveographic test and a comparison was made with gluten-added flours. Gliadin-rich fractions increased the extensibility of the dough and reduced its resistance to deformation. On the other hand, glutenin-rich fractions had an opposite effect and increased the dough resistance more than that of equally-concentrated whole gluten. The magnitude of the effects was strongly related to the gliadin and glutenin contents of the fractions. Prediction of technological effects is thus possible using composition analyses based on protein extractibility or size-exclusion chromatography. Finally, the improving effects of the gliadin-rich and of the glutenin-rich fractions were observed at different stages of the breadmaking process.     

Comparison of the fluoride,arsenate and nitrate anions water depollution potential of a calcined quintinite,a layered double hydroxide compound

The potential for removing anionic pollutants such as F⁻, HAsO₄²⁻, and NO₃⁻ from water by mixed oxides issued from the moderate thermal treatment of quintinite (Mg₄Al₂ LDH) has been studied. This compound shows good trapping properties for F⁻ and HAsO₄²⁻, and a low potential for NO₃⁻, due to the competition with OH⁻. The competition between these three anions and CO₃²⁻ has been envisaged and shows that CO₃²⁻ is able to easily replace F⁻ and NO₃⁻, making the mixed oxides issued from MgAl LDH an inappropriate trap for F⁻ and NO₃⁻. However, only small amounts of arsenic are released after the CO₃²⁻ introduction in water. Moreover, arsenates are able to replace carbonates even at lower concentrations. This means that HAsO₄²⁻ anions present a stronger affinity than CO₃²⁻ for the LDH structure. This makes mixed oxides issued from MgAl LDH very promising materials for the removal of arsenic in polluted waters.     

Nanoscale observation of the distribution of the polarization orientation of ferroelectric domains in lithium niobate thin films

In this paper, an Atomic Force Microscope (AFM) in the so-called piezoresponse mode is used to image the ferroelectric domains in radio frequency sputtered lithium niobate (LiNbO₃) thin films. It is shown that ferroelectric domains are clearly detectable and most of the time confined in the grains. The vertical and the lateral motion of the vibration of the tip in response to the applied alternating voltage is recorded in order to reconstruct a cartography of the orientation of the ferroelectric domains, allowing us to observe the distribution of the orientation of the polarization in the polycrystalline film and providing additional information about the direction of the polarization, although it is not a fully 3D cartography. From Piezoresponse Force Microscopy images, it is clear that the dispersion of the orientation of the polarization vector in the studied LiNbO₃ sample is very high. It is shown that the AFM quasi-3D mapping of the distribution of orientation in the material provides a valuable information and may help understanding the fundamental phenomena which govern the growth of the material.     

Validation of a new pertinent packing coefficient to estimate flow properties of pharmaceutical powders at a very early development stage, by comparison with mercury intrusion and classical flowability methods

The present study compares four characterisation techniques, such as packing and rearrangement under pressure methods or shear cell measurement methods, used to evaluate powder flow properties. The reduction of the powder bed volume under low pressures is analysed using mercury porosimetry and two compressibility methods (uniaxial press and volumenometer). Flow functions, deduced from shear cell measurements, are determined using a Johanson Indicizer^TM Tester. The examination of the reduction of the powder bed volume leads to new parameters such as the packing coefficient (C _t) and the volume of mercury intruded (V _hg). The packing coefficient appears to be a reliable approximation of powder flow properties, whatever cohesive or free flowing : it is actually well correlated with shear cell measurements and it is more accurate than classical flowability tests recommended by the European Pharmacopoeia. Furthermore, this method is easy to use and consumes a small amount of powders (<1 g). All together, this method is able to give—very early in the development—a quite accurate estimation of powder flow properties of new drug substances. This may be very helpful for an early determination of the optimum particle granulometry or for a rapid development of a feasible industrial process.     

Transport process in thin SiO2 films with an embedded 2-D array of Si nanocrystals

This work deals with the electrical characteristics and physical properties of novel dielectric systems based on silicon nanocrystals embedded in SiO₂ matrices. In particular, the transport phenomena of 10 nm thick SiO₂ capacitors with an embedded thin layer (5 nm) of LPCVD Si nanocrystals, located at different tunneling distances from the oxide–substrate interface, are studied. An original model based on an elastic tunneling phenomenon, which allows an efficient evaluation of the main structural characteristics of Si dots, is proposed.     

The In Vivo Radiosensitizing Effect of Gold Nanoparticles Based MRI Contrast Agents

Owing to the high atomic number (Z) of gold element, the gold nanoparticles appear as very promising radiosensitizing agents. This character can be exploited for improving the selectivity of radiotherapy. However, such an improvement is possible only if irradiation is performed when the gold content is high in the tumor and low in the surrounding healthy tissue. As a result, the beneficial action of irradiation (the eradication of the tumor) should occur while the deleterious side effects of radiotherapy should be limited by sparing the healthy tissue. The location of the radiosensitizers is therefore required to initiate the radiotherapy. Designing gold nanoparticles for monitoring their distribution by magnetic resonance imaging (MRI) is an asset due to the high resolution of MRI which permits the accurate location of particles and therefore the determination of the optimal time for the irradiation. We recently demonstrated that ultrasmall gold nanoparticles coated by gadolinium chelates (Au@DTDTPA‐Gd) can be followed up by MRI after intravenous injection. Herein, Au@DTDTPA and Au@DTDTPA‐Gd were prepared in order to evaluate their potential for radiosensitization. Comet assays and in vivo experiments suggest that these particles appear well suited for improving the selectivity of the radiotherapy. The dose which is used for inducing similar levels of DNA alteration is divided by two when cells are incubated with the gold nanoparticles prior to the irradiation. Moreover, the increase in the lifespan of tumor bearing rats is more important when the irradiation is performed after the injection of the gold nanoparticles. In the case of treatment of rats with a brain tumor (9L gliosarcoma, a radio‐resistant tumor in a radiosensitive organ), the delay between the intravenous injection and the irradiation was determined by MRI.     

Detection and discrimination of cereal and leguminous species in chestnut flour by duplex PCR

Chestnut and chestnut-derived products are quite expensive and thus a possible target for fraudulent labeling. To obtain a French Label of Origin, chestnut producers need to certify the purity of their products. Chestnut-derived products are consumed by people who may suffer from celiac disease or are allergic to cereals. For these reasons, we developed a qualitative PCR-based method to detect cereal and leguminous species in chestnut flour. The presence of common wheat and barley was determined by amplifying part of the puroindoline-a gene, the presence of rye by amplifying part of the secaloindoline-a gene, the presence of durum wheat, rice, maize and chickpea by amplifying part of lipid transfer protein genes, the presence of oat by amplifying part of a thionin gene, the presence of kidney bean by amplifying part of a late embryogenesis-abundant protein, the presence of soybean by amplifying part of a lectin gene and the presence of fava bean by amplifying part of a nodulin gene. A chestnut thaumatine gene was used as control. PCR conditions were optimized to detect 1% of adulteration. Duplex PCR and specially designed sets of primers that allow amplification of several related species limited the number and cost of analyses required. Interpretation of the results is facilitated by using a decision tree.