Slip and Twinning in Polycrystalline Alumina (α-Al2O3) Deformed under Hydrostatic Pressure between 600° and 1000°C

The microstructure of polycrystalline alumina deformed under hydrostatic pressure and at low temperature is investigated by transmission electron microscopy. Deformation occurs mainly by prism plane slip and rhombohedral twinning. Introduction of hydrogen leads to a significant decrease in the yield stress. In large grain size alumina deformed with hydrogen, accommodation of twinning involves dislocation reactions in the twin boundary and in the grains rather than by cracking. Prism plane dislocations decompose into basal dislocations by cross slip probably due to a decrease of Peierls stress for basal slip in the presence of hydrogen.     

Telechelic polydimethylsiloxanes with terminal acetylenic groups prepared by phase-transfer catalysis

Telechelic, hydroxyalkyl terminated polydimethylsiloxanes were obtained under mild conditions via hydrosilylation of allyl alcohol or ethylene glycol monoallyl ether by oligomeric αω-hydride terminated polydimethylsiloxanes, with the use of a platinum catalyst. They were subsequently modified in a phase transfer catalyzed reaction by propargyl bromide, to give telechelic polysiloxanes terminated by acetylenic groups. The synthetic pathway is described and the characterization of the obtained products is presented.     

Effect of GABA,a Bacterial Metabolite,on Pseudomonas fluorescens Surface Properties and Cytotoxicity

Different bacterial species and, particularly Pseudomonas fluorescens, can produce gamma-aminobutyric acid (GABA) and express GABA-binding proteins. In this study, we investigated the effect of GABA on the virulence and biofilm formation activity of different strains of P. fluorescens. Exposure of a psychotropic strain of P. fluorescens (MF37) to GABA (10⁻⁵ M) increased its necrotic-like activity on eukaryotic (glial) cells, but reduced its apoptotic effect. Conversely, muscimol and bicuculline, the selective agonist and antagonist of eukaryote GABA_A receptors, respectively, were ineffective. P. fluorescens MF37 did not produce biosurfactants, and its caseinase, esterase, amylase, hemolytic activity or pyoverdine productions were unchanged. In contrast, the effect of GABA was associated to rearrangements of the lipopolysaccharide (LPS) structure, particularly in the lipid A region. The surface hydrophobicity of MF37 was marginally modified, and GABA reduced its biofilm formation activity on PVC, but not on glass, although the initial adhesion was increased. Five other P. fluorescens strains were studied, and only one, MFP05, a strain isolated from human skin, showed structural differences of biofilm maturation after exposure to GABA. These results reveal that GABA can regulate the LPS structure and cytotoxicity of P. fluorescens, but that this property is specific to some strains.     

Initial Molecular Recognition Steps of McjA Precursor during Microcin J25 Lasso Peptide Maturation

Microcin J25 (MccJ25) has emerged as an excellent model to understand the maturation of ribosomal precursor peptides into the entangled lasso fold. MccJ25 biosynthesis relies on the post‐translational modification of the precursor McjA by the ATP‐dependent protease McjB and the lactam synthetase McjC. Here, using NMR spectroscopy, we showed that McjA is an intrinsically disordered protein without detectable conformational preference, which emphasizes the active role of the maturation machinery on the three‐dimensional folding of MccJ25. We further showed that the N‐terminal region of the leader peptide is involved in interaction with both maturation enzymes and identified a predominant interaction of V43–S55 in the core McjA sequence with McjC. Moreover, we demonstrated that residues K23–Q34 in the N‐terminal McjA leader peptide tend to adopt a helical conformation in the presence of membrane mimics, implying a role in directing McjA to the membrane in the vicinity of the lasso synthetase/export machinery. These data provide valuable insights into the initial molecular recognition steps in the MccJ25 maturation process.     

Influence of H2/NH3 mixtures on the composition of SiCNYO and SiCNAl(O) nanopowders

We performed pyrolysis of SiCNAlH and SiCNYOH nanopowder precursors under a reactive atmosphere (Ar/NH₃/H₂) with various compositions of ammonia (NH₃) and dihydrogen (H₂) to diminish C content, which is deleterious for thermal stability and sintering of the powders. This paper continues a previous work on the fabrication of an Si₃N₄/SiC composite without free C by studying the effect of H₂ on the C/N atomic ratio of the powder. We studied the influence of the nature of the gaseous mixture (Ar/NH₃/H₂) on the powder composition. Elemental analysis showed that the introduction of H₂ in the pyrolysis atmosphere limited the decomposition of NH₃ and allowed for control of the C/N ratio. This behaviour can be explained by the structural evolution observed by ²⁹Si NMR spectrometry but also by Fourier transform infrared and Raman spectroscopy. An Si₃N₄/SiC composite, with traces of free C, was obtained after post-pyrolysis heat treatment of the powders synthesized with 10 wt.% of H₂ and 25 wt.% NH₃.     

Iron oxide magnetic nanoparticles used as probing agents to study the nanostructure of mixed self-assembled monolayers

Self-assembled monolayers (SAMs) of organic molecules are of exceptional technological importance since they represent a convenient, flexible, and simple system for tuning the chemical and physical properties of surfaces. The fine control of surface properties is directly dependent on the structure of mixed SAMs which is difficult to characterize at the nanoscale with usual techniques such as scanning probe microscopies. In this study, we report on a general method to investigate at the nanoscale the structure of molecular patterns which consist in SAMs of two components. Iron oxide nanoparticles (NPs) have been used as probing agents to study indirectly the structure of mixed SAMs. Mixed SAMs were prepared by the replacement of mercaptododecane (MDD) adsorbed by mercaptoundecanoic acid (MUA) molecules on gold substrates. Therefore, the SAM surface displays both chelating carboxylic terminal groups and non-chelating methylene terminal groups. As NPs have been previously demonstrated to specifically interact with carboxylic acid groups, the increasing density in NPs was correlated with the evolution of the COOH/CH(3) terminal groups ratio. Therefore the structure of mixed SAMs was studied indirectly as well as the kinetic of the replacement reaction and its mechanism. With this aim, we took advantage of the SPR properties of the gold substrate and of the high refractive index of iron oxide nanoparticles to follow their assembling on mixed SAMs as a time resolved study. The high sensitivity and tuning of the SPR signal over a wide range of wavelengths are correlated with the NP density. Furthermore, SEM combined with image analysis has allowed studying the replacement rate of MDD by MUA in SAMs. We took also advantages of the magnetic properties of NPs to evaluate qualitatively the replacement of thiol molecules.     

Insight into β-Carotene Thermal Degradation in Oils with Multiresponse Modeling

The aim of this study was to gain further insight into β-carotene thermal degradation in oils. Multiresponse modeling was applied to experimental high-performance liquid chromatography–diode array detection (HPLC–DAD) data (trans-, 13-cis-, and 9-cis-β-carotene concentrations) during the heat treatments (120–180 °C) of two β-carotene-enriched oils, i.e., palm olein and copra. The test of different reaction schemes showed that β-carotene isomerization reactions were dominant and reversible. The resulting cis isomers and trans-β-carotene simultaneously underwent oxidation and cleavage reactions at the same rate constant. From the kinetic analysis, it appeared that—contrary to oxidation and cleavage reactions—isomerization rate constants did not follow the Arrhenius law. However, the isomerization equilibrium constant increased with temperature, favoring isomer production, particularly 9-cis-β-carotene. Its production was shown to be concomitant with oxidation and cleavage reactions, indicating that 9-cis-β-carotene could be a good degradation indicator during oil storage or processing.     

Calorimetric study of fluorinated methacrylic and vinyl polymer blends: part 2: correlation between miscibility, chemical structure and χ12 interaction parameter in binary systems

The miscibility of poly(methylmethacrylate) (PMMA) and (trifluoroethyl methacrylic ester-MMA) copolymers (MMA-MATRIFE) with poly(vinylidene fluoride) (PVDF) and VDF copolymers was studied by differential scanning calorimetry (DSC) as a function of the fluorinated copolymer crystallinity and fluoroalkyl methacrylic ester content in the methacrylic copolymer. Miscibility limits were found identical whatever be the blend preparation technique, although solution mixing induced some polymer fractionation, thus giving slightly higher blend glass transition temperature. The miscibility domain widths are reduced when using MMA-MATRIFE copolymers as compared to PMMA-containing blends and miscibility limits are dependent on the MATRIFE content in the methacrylic copolymer. Moreover, PVDF or VDF copolymer melting enthalpy decrease is associated to a partial dissolution of the semi-crystalline polymer in PMMA or MMA-MATRIFE copolymer above the total miscibility limit. The evolution of dynamic moduli as a function of blends composition confirms the miscibility limits determined by DSC. The Flory-Huggins interaction parameters were determined through the melting point depression analysis and compared to correlate the intensity of inter- or intra-molecular interactions between the polymers to the postulated ‘acidity’ of hydrogen atoms in various VDF-containing polymers. The interaction parameter χ₁₂ increases with the fluoroalkyl methacrylic ester content, corresponding to a prevalence of intra-molecular on inter-molecular interactions in these blends. Similarly, PVDF offers higher χ₁₂ values as compared to VDF-TFE or particularly to VDF-TrFE copolymers. These results highlight the importance of the nature of fluorinated polymers and of the inter- or intra-molecular character of dipolar interactions on both, copolymer miscibility and interaction parameter values.     

Thiol-ene “clickable” carbon-chain polymers based on diallyl cyclopropane-1,1-dicarboxylate

A novel type of clickable polymers with a very high local density of allyl side groups was developed. These polymers were obtained by the anionic ring-opening (co)polymerization of diallyl cyclopropane-1,1-dicarboxylate using as an initiating system a protic precursor whose acid–base reaction with the t-BuP₄ phosphazene base generated the initiator in situ. The obtained polymers display geminated allyl groups on every third carbon alongside the macromolecular backbone. Homopolymers as well as block and statistical copolymers have been synthesized, with controlled molecular weights and narrow molecular weight distributions. The coupling of mercaptans with the allyl CC double bonds has been investigated both thermally and photochemically, with the influence of the type of initiation on the efficiency of the polymer modification being discussed in comparison with other “clickable” systems. Further functionalization by several thiols was performed, leading to a range of functional poly(cyclopropane-1,1-dicarboxylate)s.     

Thioether Analogues of Disulfide‐Bridged Cyclic Peptides Targeting Death Receptor 5: Conformational Analysis,Dimerisation and Consequences for Receptor Activation

Cyclic peptides containing redox‐stable thioether bridges might provide a useful alternative to disulfide‐bridged bioactive peptides. We report the effect of replacing the disulfide bridge with a lanthionine linkage in a 16‐mer cyclic peptide that binds to death receptor 5 (DR5, TRAIL‐R2). Upon covalent oligomerisation, the disulfide‐bridged peptide has previously shown similar behaviour to that of TNF‐related apoptosis inducing ligand (TRAIL), by selectively triggering the DR5 cell death pathway. The structural and biological properties of the DR5‐binding peptide and its desulfurised analogue were compared. Surface plasmon resonance (SPR) data suggest that these peptides bind DR5 with comparable affinities. The same holds true for dimeric versions of these peptides: the thioether is able to induce DR5‐mediated apoptosis of BJAB lymphoma and tumorigenic BJELR cells, albeit to a slightly lower extent compared to its disulfide homologue. NMR analysis revealed subtle variation in the conformations of the two peptides and suggests that the thioether peptide is slightly less folded than its disulfide homologue. These observations could account for the different capability of the two dimers to cluster DR5 receptors on the cell surface and to trigger apoptosis. Nevertheless, our results suggest that the thioether peptide is a potential candidate for evaluation in animal models.