Fate of Magnetic Nanoparticles during Stimulated Healing of Thermoplastic Elastomers.

We have investigated the heating mechanism in industrially relevant, multi-block copolymers filled with Fe nanoparticles and subjected to an oscillatory magnetic field that enables polymer healing in a contactless manner. While this procedure aims to extend the lifetime of a wide range of thermoplastic polymers, repeated or prolonged stimulus healing is likely to modify their structure, mechanics, and ability to heat, which must therefore be characterized in depth. In particular, our work sheds light on the physical origin of the secondary heating mechanism detected in soft systems subjected to magnetic hyperthermia and triggered by copolymer chain dissociation. In spite of earlier observations, the origin of this additional heating remained unclear. By using both static and dynamic X-ray scattering methods (small-angle X-ray scattering and X-ray photon correlation spectroscopy, respectively), we demonstrate that beyond magnetic hysteresis losses, the enormous drop of viscosity at the polymer melting temperature enables motion of nanoparticles that generates additional heat through friction. Additionally, we show that applying induction heating for a few minutes is found to magnetize the nanoparticles, which causes them to align in dipolar chains and leads to nonmonotonic translational dynamics. By extrapolating these observations to rotational dynamics and the corresponding amount of heat generated through friction, we not only clarify the origin of the secondary heating mechanism but also rationalize the presence of a possible temperature maximum observed during induction heating.

Isostructural softening of vulcanized nanocomposites.

Following previous work evidencing that short poly-propylene glycol (PPG) chains incorporated into crude SBR/silica nanocomposites act as filler-network softeners without changing their structure, we propose in the present report to examine more operative cross-linked materials. We first evidence that the adsorption of PPG onto silica deactivates progressively the particle's catalytic effect on vulcanization, without perturbing however the cross-link density distribution that we investigate through multiple-quantum NMR. In addition, electron microscopy confirms that the silica structure is conserved after vulcanization and that it does not depend on the PPG content either. Composites containing various amounts of PPG can thus be seen as structurally identical, both from a matrix and filler point of view - which is confirmed by small and medium amplitude oscillation shear rheology showing strikingly identical viscoelastic properties. The PPG signature only appears above 100% in tensile deformation where it is observed to soften dramatically the filler network. Our discovery makes it consequently possible to decorrelate the mechanical behavior of reinforced rubbers under normal conditions of use and urgent needs of energy dissipation.

Isostructural softening of the filler network in SBR/silica nanocomposites.

A new formulation of the widely used nanocomposites based on SBR (ca. 250 kg mol-1) and fractal silica fillers is proposed by substituting the usual covering and coupling agents with short chains (4 kg mol-1) of polypropylene glycol (PPG). We study in a systematic way the structural evolution and the changes in the linear and non-linear mechanical properties of two series of samples varying: (i) the silica volume fraction (Φsi = 0, 5, 10 and 15 vol%) in PPG-free samples and (ii) the amount of PPG for a given silica content Φsi = 15 vol%. While the first series is used as a reference, showing expected trends (e.g. the enhancement of the plateau modulus), the second series reveals in contrast, a surprising PPG insensitivity, both in terms of the filler structure (investigated by means of SAXS, SEM and TEM) and properties "at rest" (linear rheology). However, increasing the strain amplitude (both in shear and tensile tests) discloses the great effect of the oligomers, opening possibly the way to a fruitful decorrelation between the low and high deformation performances of tires. Although this study is limited to the investigation of uncrosslinked materials, it will be extended to more operative industrial formulations in due course.

Towards quantitative analysis of enamel erosion by focused ion beam tomography.

OBJECTIVES: The purpose of this work is a proof of concept to introduce a new quantitative 3D-analysis of dental erosion obtained by focused ion beam (FIB) tomography associated with silver nitrate penetration into porosities in etched enamel. METHODS: One sample selected was sound enamel after removal of the aprismatic surface. The other was studied after applying an additional attack with orthophosphoric acid. Both surfaces were infiltrated with silver nitrate via immersion. After dehydration, samples were observed in a dual column FIB/SEM station. Serial FIB sectioning was conducted with a current of 3nA at 30keV and an increment step of 20nm for the healthy enamel and of 40nm for the etched one. 3D analysis was performed with Fiji software and BoneJ plugin and several parameters were obtained to characterize the tissue: non-mineralized phase content (NMP), connected porosity fraction (CPF) and degree of anisotropy (DA) of the NMP. RESULTS: Healthy enamel showed an NMP content of 0.5vol.%, with a bimodal distribution of non-mineralized regions, inside the prisms and between the prisms. No silver penetration was noticed in the healthy enamel, demonstrating the absence of open porosity. In contrast, silver nitrate penetration after acidic exposure was observed, up to a depth of 12µm, which allowed the calculation of an interconnected porosity volume fraction (CPF) of 3.1vol.%, mostly between the prisms. Values for DA of 0.56 for sound enamel and 0.81 for acid-etched surface were determined, highlighting a higher degree of anisotropy in the latter. SIGNIFICANCE: Quantitative analysis of FIB tomography using NMP, CPF and DA should contribute to a better understanding and follow up of dental erosion, correlation between erosion and attrition or abrasion process, and the ability to develop enamel remineralization procedures.

Novel phosphorus-containing cyclodextrin polymers and their affinity for calcium cations and hydroxyapatite.

Novel phosphorous-containing ß-cyclodextrin (ßCD) polymers (CDP) were synthesized easily under "green chemistry" conditions. A simple polycondensation between the hydroxyl groups of ßCD and non-toxic sodium trimetaphosphate (STMP) under basic conditions led to soluble, non-reticulated CDPs with molecular weights (Mw) higher than 10(4) g mol(-1), the actual value depending on the NaOH:ßCD and STMP:ßCD weight ratios. The presence of both ßCD and phosphate groups in the polymer allows for strong interactions with amphiphilic probes, such as 1-adamantyl acetic acid, or with divalent cations, such as Ca(2+), whose strengths were characterized by isothermal titration microcalorimetry. The obtained phosphated compounds also display high affinity towards hydroxyapatite (HA), leading to HA nanoparticles that could easily be recovered by CDPs, as demonstrated by transmission electron microscopy and quantitative determination of the total amount of phosphated molecules fixed on HA.

Zirconocene Dichloride: An Efficient Cleavable Photoinitiator Allowing the in Situ Production of Zr-Based Nanoparticles Under Air.

Cp2ZrCl2 is presented as both an effective photoinitiator and additive for radical photopolymerization reactions in aerated conditions. This compound is characterized by remarkable properties: (i) an efficiency higher than that of a reference Type I photoinitiator (2,2-dimethoxy-2-phenylacetophenone, DMPA), (ii) an excellent ability, when added to DMPA, to overcome the oxygen inhibition of the polymerization, and (iii) a never reported in situ photoinduced and oxygen-mediated formation of zirconium-based nanoparticles (diameter ranging from 50 to 70 nm). The photochemical properties of Cp2ZrCl2 are investigated by steady state photolysis and electron spin resonance (ESR) experiments. The high reactivity of this compound is ascribed to a bimolecular homolytic substitution SH2 (clearly characterized by molecular orbital calculations) which converts the peroxyls into new polymerization-initiating radicals and oxygenated Zr-based nanoparticles.

Evaluation of a cationic calix[4]arene: Solubilization and self-aggregation ability.

Water-soluble calixarenes are promising macrocyclic compounds which have found numerous applications in chemistry and biology. However, these compounds have been less studied in regard to their behavior in aqueous solutions and mechanisms of drug solubilization. The present work is devoted to the evaluation of the solubilizing properties and estimation of self-aggregation ability of positively charged 5,11,17,23-tetrakis(trimethylammoniomethyl)-25,26,27,28-tetrapropoxy-calix[4]arene tetrachloride (aminocalix), including comparisons with a series of pharmaceutically relevant cyclodextrins. Phase-solubility measurements of the drugs with aminocalix and various cyclodextrins were carried out. Aminocalix showed a solubilizing ability comparable to the cyclodextrins. The drug solubility enhancement caused by the aminocalix was studied and was found to be maximal for steroid drugs. An attempt to understand the solubilizing mechanism of aminocalix was undertaken based on correlation analysis between physical and physico-chemical properties of the drugs from one side and the solubilizing ability of aminocalix from the other. Correlation analysis supports the supposition that the solubilizing effect of aminocalix is based on interaction of the drug with aminocalix aggregates rather than on inclusion complexation. UV-absorbance, osmolality and surface tension concentration dependences of aminocalix showed an inflection at 1% (w/v) which was initially related to the transition from monomers to micelles. However, dynamic light scattering and transmission electron microscopy measurements revealed that likely vesicles of diverse size exist at 0.1% (w/v) concentration. Thus the 1% (w/v) inflection point was interpreted to be spontaneous reordering of the vesicles between two different size populations.

Direct small-angle-neutron-scattering observation of stretched chain conformation in nanocomposites: more insight on polymer contributions in mechanical reinforcement.

In this paper we present a direct measurement of stretched chain conformation in polymer nanocomposites in a large range of deformation using a specific contrast-matched small angle neutron scatttering (SANS) method. Whatever are the filler structure and the chain length the results show a clear identity of chain deformation in pure and reinforced polymer and offer more insight on the polymer chain contribution in the mechanical reinforcement. It suggests that glassy layer or glassy paths, recently proposed, should involve only a small fraction of chains. As a result, the remaining filler contribution appears strikingly constant with deformation as explained by continuous locking-unlocking rearrangement process of the particles.

Biomimetic models of the actin cytoskeleton.

The cytoskeleton is a complex polymer network that plays an essential role in the functionality of eukaryotic cells. It endows cells with mechanical stability, adaptability, and motility. To identify and understand the mechanisms underlying this large variety of capabilities and to possibly transfer them to engineered networks makes it necessary to have in vitro and in silico model systems of the cytoskeleton. These models must be realistic representatives of the cellular network and at the same time be controllable and reproducible. Here, an approach to design complementary experimental and numerical model systems of the actin cytoskeleton is presented and some of their properties discussed.