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International audience; Iron (Fe) is a major micronutrient and is required for plant growth and development. Nongrass species have evolved a reduction-based strategy to solubilize and take up Fe. The secretion of Fe-mobilizing coumarins (e.g. fraxetin, esculetin and sideretin) by plant roots plays an important role in this process. Although the biochemical mechanisms leading to their biosynthesis have been well described, very little is known about their cellular and subcellular localization or their mobility within plant tissues. Spectral imaging was used to monitor, in Arabidopsis thaliana, the in planta localization of Fe-mobilizing coumarins and scopolin. Molecular, genetic and biochemical approaches were also used to investigate the dynamics of coumarin accumulation in roots. These approaches showed that root hairs play a major role in scopoletin secretion, whereas fraxetin and esculetin secretion occurs through all epidermis cells. The findings of this study also showed that the transport of coumarins from the cortex to the rhizosphere relies on the PDR9 transporter under Fe-deficient conditions. Additional experiments support the idea that coumarins move throughout the plant body via the xylem sap and that several plant species can take up coumarins present in the surrounding media. Altogether, the data presented here demonstrate that coumarin storage and accumulation in roots is a highly complex and dynamic process.

Metal–Insulator–Metal (MIM) capacitors based on high-k oxides require stability with the applied electric field. However, experiment reveals a nonlinear behavior of capacitance with ac or dc bias. In this work, we measure capacitance–voltage nonlinearities for Au/10-nm HfO2/M (where M = TiN, Pt, W, and AlCu alloys). It is observed that ac capacitance is strongly dependent on the bottom electrode material. This dependency is discussed through the correlated barrier hopping (CBH) model. Accordingly, the ac nonlinearity is ascribed to the polarization of isolated defect pairs, which in turn increase as the maximum barrier height decreases. This induces higher nonlinearity as compared to the dc one. For the dc bias, oxygen affinity of active metal electrode may describe the origin of dc nonlinearities.

The present work highlights the crucial role of the interfacial compatibilization on the design of polylactic acid (PLA)/Magnesium (Mg) composites for bone regeneration applications. In this regard, an amphiphilic poly(ethylene oxide-b-L,L-lactide) diblock copolymer with predefined composition was synthesised and used as a new interface to provide physical interactions between the metallic filler and the biopolymer matrix. This strategy allowed (i) overcoming the PLA/Mg interfacial adhesion weakness and (ii) modulating the composite hydrophilicity, bioactivity and biological behaviour. First, a full study of the influence of the copolymer incorporation on the morphological, wettability, thermal, thermo-mechanical and mechanical properties of PLA/Mg was investigated. Subsequently, the bioactivity was assessed during an in vitro degradation in simulated body fluid (SBF). Finally, biological studies with stem cells were carried out. The results showed an increase of the interfacial adhesion by the formation of a new interphase between the hydrophobic PLA matrix and the hydrophilic Mg filler. This interface stabilization was confirmed by a decrease in the damping factor (tanδ) following the copolymer addition. The latter also proves the beneficial effect of the composite hydrophilicity by selective surface localization of the hydrophilic PEO leading to a significant increase in the protein adsorption. Furthermore, hydroxyapatite was formed in bulk after 8 weeks of immersion in the SBF, suggesting that the bioactivity will be noticeably improved by the addition of the diblock copolymer. This ceramic could react as a natural bonding junction between the designed implant and the fractured bone during osteoregeneration. On the other hand, a slight decrease of the composite mechanical performances was noted.

International audience; Because of their characteristics, including a d33 of 10–15 pC/N and high stability up to temperatures over 1000 °C, polar glass–ceramics containing fresnoite crystals can be regarded as highly effective materials for applications requiring piezoelectricity at high temperatures. In the present paper we investigate barium substitutions in an Sr-fresnoite (STS) glass–ceramic. Two aspects are studied: first, the effect of the substitution on the preferential orientation of the crystallization, and second, the ability of the glass–ceramics to generate and propagate surface acoustic waves (SAW) at high temperatures. XRD analyses show that a 10 at.% substitution of Ba allows us to keep a strong preferential orientation of the (00l) planes of the fresnoite crystals down to more than 1 mm below the surfaces. Higher substitution levels (25 and 50 at.%), induce a non-oriented volume crystallization mechanism that competes with the surface mechanism. SAW devices were fabricated from glass–ceramic substrates with 0, 10 and 25 at.% Ba substitutions. Temperature testing reveals the high stability of the frequency and delay for all of these devices. The glass–ceramic with a 10 at.% Ba substitution gives the strongest amplitude of the SAW signal. This is attributed to the high (00l) preferential orientation and the absence of disoriented volume crystallization.

We recently presented the elaboration and functional properties of a new generation of hybrid membranes for PEMFC applications showing promising performances and durability. The strategy was to form, inside a commercial sPEEK membrane, via in situ sol–gel (SG) synthesis, a reactive SG phase able to reduce oxidative species generated during FC operation. In order to understand structure-properties interplay, we use a combination of direct space (AFM/3D FIB-SEM) and reciprocal space (SANS/WAXS) techniques to cover dimensional scales ranging from a hundred to few nanometers. AFM modulus images showed the SG phase distributed into spherical domains whose size increases with the SG uptake (ca. 100–200 nm range). Using contrast variation SANS, we observed that the sPEEK nanostructure is mostly unaffected by the insertion of the SG phase which presents a fractal-like multiscale structure. Additionally, the size of both the particles (aggregates/primary) is much too large to be sequestered in the ionic pathways of sPEEK. These findings indicate that the SG-NPs mainly grow within the amorphous interbundle domains. Noticeable rightward shift and widening of the ionomer peak are observed with the SG content, suggesting ion channel compression and greater heterogeneity of the ionic domain size. The SG phase develops in the interbundle regions with a limited impact on the water uptake but leading to a discontinuity of ionic conductivity. This Fourier and real spaces study clarifies the structure of the hybrid membranes and brings into the question the ideal distribution/localization of the SG phase to optimize the membrane's stabilization.

Resistance switching is studied in conductive bridge memory structures made from atomic layer deposited HfO2 and Ag active electrode. Inert electrode is varied by using different substrates (TiN, W, Pt). HfO2 crystallinity is modified by varying the deposition temperature (300/350 °C) and the film thickness (10/20 nm). Current–voltage characteristics, as well as current–time characteristics (to access to the switching kinetics), are studied according to the inert electrode nature and HfO2 structural properties. Results are discussed along resistance transition mechanisms which imply (i) the generation of oxygen vacancies by electronic injection at the inert electrode, (ii) Ag diffusion along oxygen vacancy paths, and (iii) the reduction of silver ions controlled by the inert electrode/HfO2 interface. Best characteristics, in terms of stability, are observed with Pt inert electrode and 10 nm films. Crystalline and amorphous films (10 nm) provide similar characteristics. In 10 nm films, TiN and W inert electrodes lead to variability in electrical properties (parasitic sets during reset, switching time dispersion). Such a variability is related to high electronic injection at the TiN/HfO2 and W/HfO2 interfaces which creates a high density of oxygen vacancy paths (Ag diffusion paths). In thicker and well-crystallized films (20 nm), progressive set is observed. This is ascribed to conduction along oxygen vacancy paths, which dominates over conduction along Ag conductive bridges.

In plants, tetrapyrrole biosynthesis occurs in chloroplasts, the reactions being catalysed by stromal and membrane-bound enzymes. The tetrapyrrole moiety is a backbone for chlorophylls and cofactors such as sirohaems, haems and phytochromobilins. Owing to this diversity, the potential cytotoxicity of some precursors and the associated synthesis costs, a tight control exists to adjust the demand and the fluxes for each molecule. After synthesis, haems and phytochromobilins are incorporated into proteins found in other subcellular compartments. However, there is only very limited information about the chaperones and membrane transporters involved in the trafficking of these molecules. After summarizing evidence indicating that glutathione transferases (GST) may be part of the transport and/or degradation processes of porphyrin derivatives, we provide experimental data indicating that tau glutathione transferases (GSTU) bind protoporphyrin IX and haem moieties and use structural modelling to identify possible residues responsible for their binding in the active site hydrophobic pocket. Finally, we discuss the possible roles associated with the binding, catalytic transformation (i.e. glutathione conjugation) and/or transport of tetrapyrroles by GSTUs, considering their subcellular localization and capacity to interact with ABC transporters. This article is part of the theme issue ‘Retrograde signalling from endosymbiotic organelles’.

International audience; In this work, barium titanate thick films are produced at low-temperature using a modified sol–gel/ceramic powder technology named the composite route. In this process, a commercial BaTiO3 powder, doped or not by Li2O as sintering aid, is mixed with a stabilized titanium (IV) isopropoxide/barium acetate sol to obtain a composite ink. Two sols, using different solvents and chelating agents, are tested. Characterization of the evolution of theses sols with an increase in temperature is realized by thermal analyses (TGA and DTA) and X-ray diffraction. The four type of inks obtained are screen-printed on metallized alumina substrates and sintered. Microstructures and electrical properties of the sintered composite films are compared to those processed from a conventional ink obtained by dispersing the barium titanate powder in an organic vehicle. Measurements of dielectric/piezoelectric properties highlight higher charge coefficients d33 for composite thick films (69 vs. 45 pC/N for conventional thick films at close thickness values) despite a lower relative permittivity (340 vs. 658) certainly due to the presence of a single domain BaTiO3 nano-crystallites.

This paper presents the fabrication of high-performance micro-magnets for the electromagnetic transduction of MEMS. The fabrication method relies on the use of nickel microstructures electroplated onto silicon substrates to control the capillary assembly of cobalt nanorods via magnetophoresis under an external magnetic field. The resulting sub-millimeter size permanent magnets with thicknesses of up to $150\ \mu \mathrm{m}$ produce a stray field of 30 mT at a distance of $100\ \mu \mathrm{m}$ . We demonstrate that this magnetic induction is sufficient to actuate a silicon microcantilever by means of the Lorentz force and that the MEMS resonance frequency can adequately be measured using integrated piezoresistances. This novel room-temperature synthesis approach is foreseen to facilitate the integration of high-performance magnets into MEMS.

Hydrotalcites intercalated with sebacate (HT-SB) were prepared by a coprecipitation method. The synthesized powder was characterized using infrared spectroscopy (FT-IR), X-ray diffraction (XRD), transmission electron microscopy (TEM) and zeta potential measurements. The inhibitor release from HT-SB in a chloride solution has been determined by total organic content (TOC) analysis. The inhibitive action of HT-SB on carbon steel was investigated and compared with hydrotalcites intercalated by benzoate (HT-BZ) and 2-benzothiazolythio-succinic acid (HT-BTSA) using electrochemical measurements and SEM/EDX analysis. The results showed that the zeta potential of modified hydrotalcites and the release of corrosion inhibitors from modified hydrotalcites depend on the chemical structure of inhibitors. The anodic polarization curves showed that the three modified hydrotalcites behave as anodic corrosion inhibitors with an efficiency, at a concentration of 3 g/L, of 94% for HT-SB, 81% for HT-BZ and 92% for HT-BTSA. These efficiencies are higher than those measured for the organic inhibitors in chloride solutions highlighting a synergistic effect due to the combination of the hydrotalcite structure and carboxylate inhibitors. The inhibition effect of modified hydrotalcite depends not only on the intercalated organic inhibitors but also on the capability of adsorption of the hydrotalcite structure on a steel surface. HT-SB was easily dispersed in an epoxy coating improving the barrier properties at concentrations lower than 5 wt.%. The best protection was obtained with 1.5 wt.% HT-SB.

International audience; We describe a process for transferring a 200 nm thick, 200 mm wide monocrystalline silicon (mono c-Si) thin film from a silicon-on-insulator onto a flexible polymer substrate. The result is a stretchable and flexible ultra-thin semiconductor film that can be subjected to tensile stress experiments. The process uses off-the-shelf 200 mm wafers and standard polymer temporary bonding techniques. The backside substrate and buried oxide are removed using grinding and wet etching processes. No cracks or wrinkles are observed on the film prior to the tensile stress experiments. The stretching of the flexible structure results in up to 1.5% uniaxial tensile elastic strain on the thin mono c-Si film.

Polyamides belong to the major class of engineering polymers with very attractive properties but fail in a brittle manner under stress concentrators. PA6/ABS blends are well-established commercial materials due to their stiffness/toughness balance even when stress concentrators are present. The pair PA6/ABS is immiscible and exhibits poor mechanical properties due to unfavorable interactions, thus, an efficient compatibilization is mandatory for practical applications. Deep understanding of the processing-structure-properties interplays requires multiple characterization techniques to provide insights on the impact of the processing/compatibilization on morphology and phases' distribution. In this work an advanced co-localized AFM-Raman strategy was used to study the compatibilization of PA6/ABS blends with SAN-g-Maleic Anhydride. AFM and TEM allowed nanomechanical analysis and characterization of the blends' morphologies. Co-localized AFM-Raman provided new fundamental insights on the compatibilizer's effect on the PA6's γ polymorphic crystallization. The amount and distribution of this γ phase were found to depend on the blending protocol.

The optimization of manufacturing processes and the investigation of polymer materials during their life cycle imply an extended knowledge of the physical and chemical properties of the material. T...

Operando Raman spectroscopy and synchrotron X-ray diffraction were combined to probe the evolution of strain in Li-ion battery anodes made of crystalline silicon nanoparticles. The internal structure of the nanoparticles during two discharge/charge cycles was evaluated by analyzing the intensity and position of Si diffraction peaks and Raman TO-LO phonons. Lithiation/delithiation of the silicon under limited capacity conditions triggers the formation of "crystalline core-amorphous shell" particles, which we evidenced as a stepwise decrease in core size, as well as sequences of compressive/tensile strain due to the stress applied by the shell. In particular, we showed that different sequences occur in the first and the second cycle, due to different lithiation processes. We further evidenced critical experimental conditions for accurate operando Raman spectroscopy measurements due to the different heat conductivity of lithiated and delithiated Si. Values of the stress extracted from both operando XRD and Raman are in excellent agreement. Long-term ex situ measurements confirmed the continuous increase of the internal compressive strain, unfavorable to the Si lithiation and contributing to the capacity fading. Finally, a simple mechanical model was used to estimate the sub-nanometer thickness of the interfacial shell applying the stress on the crystalline core. Our complete operando diagnosis of the strain and stress in SiNPs provides both a detailed scenario of the mechanical consequences of lithiation/delithiation in SiNP and also experimental values that are much needed for the benchmarking of theoretical models and for the further rational design of SiNP-based electrodes.

This paper aims at studying the influence of the reinforcement particle size and morphology on the wear resistance properties of NiCrBSi-based composites. Numerous papers have already been written on this subject but almost all of them studied the “conventional” particle size for laser cladding (i.e. between 20 and 200 μm). The objective of this study is to see the influence of coarser reinforcement particles, up to 1.2 mm, and the influence of the morphology (spherical and random shaped) on the coatings erosive and sliding wear resistance. Laser clad coatings were deposited on low carbon steel substrate S235JR with various amounts of WC/W 2 C particles up to 50 vol.%. The coatings were processed by using a 3.8 kW High Power Diode Laser (HPDL). Spherical tungsten carbide particles from 40 μm up to 1200 μm were used in this study as well as random shaped particles from 40 μm to 400 μm. To assess the influence of the reinforcement particle properties on wear properties, wheel tests and pin-on-disk tests were performed on each composition. From this study, it can be concluded that there is an obvious advantage in using larger particles (750–1200 μm) in harsh conditions while smaller particles (40–160 μm) improve the resistance in sliding conditions. The effect of morphology has not been proved significant.

Via SAXS, herein, we studied how a sPEEK microstructure evolves when it is immersed in water at a wide range of temperatures (20-100 °C) and time scales (from a few hours to dozens of days). In particular, we scrutinized the behavior of sPEEK at the temperature and time associated with the appearance of a well-defined nanosegregated morphology. At 80 °C, we observed nanoscale swelling along with smoothing of the water/polymer interface over a long period of time (several days). Herein, two of the main membrane properties, i.e., water uptake and proton conductivity, were studied for different immersion times and temperatures. It was found that the abovementioned properties were remarkably correlated with the evolution of the membrane microstructure, which was partly conserved after drying. The present findings helped us to understand that the thermally activated evolutions observed at both the nanoscale and macroscale were associated with the sPEEK β-relaxation crossover. Therefore, the very different swelling behaviors of sPEEK and Nafion are correlated to the much higher β-relaxation of sPEEK vs. Nafion (75 °C vs. -20 °C - dry state). From a practical viewpoint, this study emphasizes, for membranes alternative to Nafion, the importance and impact of the membrane pretreatment on their functional properties.

In this work, aqueous solutions of magnetite nanoparticles (NPs) are studied. Magnetite NPs are very useful in biomedicine for magnetic resonance imaging (MRI), for drug delivery therapy, and also for hyperthermia. In order to predict the NP efficiency in these applications, it is crucial to accurately characterize their size distribution and their magnetization. Magnetometry, through the dependence of NP magnetization on the magnetic induction (MB curve), can provide interesting information on these physical properties. In this work, the extraction of the NP size distribution and magnetization from experimental MB curves of aqueous solutions of magnetite NPs is discussed. The results are compared to TEM and XRD characterizations. It is shown that an expression taking into account the size distribution better fits the results than the commonly used simple Langevin function. The size distributions obtained by magnetometry seem comparable to those obtained by TEM measurements. However, a closer look at the results shows some nonnegligible discrepancies: the size distributions obtained by magnetometry vary with the temperature and are closer to the TEM ones at room temperature. Our study suggests that it could be explained by the nonnegligible anisotropy energy of the NPs at low temperature and the lack of NP Brownian rotation below the freezing point of water. This demonstrates that care must be taken when interpreting the results obtained by magnetometry of magnetite NPs: only the size and size distribution obtained at room temperature should be used.

Glutathione transferases (GSTs) belong to a ubiquitous multigenic family of enzymes involved in diverse biological processes including xenobiotic detoxification and secondary metabolism. A canonical GST is formed by two domains, the N-terminal one adopting a thioredoxin (TRX) fold and the C-terminal one an all-helical structure. The most recent genomic and phylogenetic analysis based on this domain organization allowed the classification of the GST family into 14 classes in terrestrial plants. These GSTs are further distinguished based on the presence of the ancestral cysteine (Cys-GSTs) present in TRX family proteins or on its substitution by a serine (Ser-GSTs). Cys-GSTs catalyze the reduction of dehydroascorbate and deglutathionylation reactions whereas Ser-GSTs catalyze glutathione conjugation reactions and eventually have peroxidase activity, both activities being important for stress tolerance or herbicide detoxification. Through non-catalytic, so-called ligandin properties, numerous plant GSTs also participate in the binding and transport of small heterocyclic ligands such as flavonoids including anthocyanins, and polyphenols. So far, this function has likely been underestimated compared to the other documented roles of GSTs. In this review, we compiled data concerning the known enzymatic and structural properties as well as the biochemical and physiological functions associated to plant GSTs having a conserved serine in their active site.

Gold nanoparticles, capped by 3-mercapto propane sulfonate (Au-3MPS), were synthesized inside a swollen sulfonated poly(ether ether ketone) membrane (SPEEK). The formation of the Au-3MPS nanoparticles in the swollen sPEEK membrane was observed by spectroscopic and microscopic techniques. The nanocomposite containing the gold nanoparticles grown in the sPEEK membrane, showed the plasmon resonance λmax at about 520 nm, which remained stable over a testing period of three months. The size distribution of the nanoparticles was assessed, and the sPEEK membrane roughness, both before and after the synthesis of nanoparticles, was studied by AFM. The XPS measurements confirm Au-3MPS formation in the sPEEK membrane. Moreover, AFM experiments recorded in fluid allowed the production of images of the Au-3MPSatsPEEK composite in water at different pH levels, achieving a better understanding of the membrane behavior in a water environment; the dynamic hydration process of the Au-3MPSatsPEEK membrane was investigated. These preliminary results suggest that the newly developed nanocomposite membranes could be promising materials for fuel cell applications.

NiCrBSi/WC composite coatings containing various amounts of WC/W2C particles were laser cladded on low carbon steel substrate S235JR. Coatings were processed using two different laser systems, a 1 kW Nd:YAG and a 3.8 kW high power diode laser (HPDL). Coatings obtained with the Nd:YAG source demonstrate significant changes in the matrix microstructure with WC/W 2 C particle addition. Specific analysis shows the formation of new carbides (W,Cr) x C y and boride phases (W,Cr) x B y resulting from a partial dissolution of the WC/W 2 C particles within the metal matrix. The Brinell macrohardness of the coatings reveals surprisingly low values for coatings containing 10 vol.% and 20 vol.% WC/W 2 C. Through nanoindentation measurements, it is suggested that the low hardness of these new carbide and boride phases most likely counteracts the WC/W 2 C addition and may explain this unexpected behavior. On the contrary, the same coatings deposited using the HPDL source exhibits no change in the microstructure of the NiCrBSi matrix and display an expected monotonic increase of composite hardness with WC/W 2 C amount. It is suggested that the microstructural appearance of new carbide and boride phases may not be related to the type of laser used but to the specific laser energy during the coating process. Contrarily to hardness, measurements show that the erosive wear is marginally affected by the microstructural differences of the coatings. These results demonstrate that evaluating the quality of laser cladded coatings by simply assessing their density and the absence of a crack (as usually done) is insufficient as it does not automatically guarantee reaching optimal mechanical performance.

Dmitry Grishenkov,1–3 Adrian Gonon,3,4 Eddie Weitzberg,5 Jon O Lundberg,5 Johan Harmark,6 Barbara Cerroni,7 Gaio Paradossi,7 Birgitta Janerot-Sjoberg1–3 1Department of Clinical Science, Intervention, and Technology, Karolinska Institutet, Stockholm, Sweden; 2Department of Medical Engineering, KTH, Royal Institute ofTechnology, School of Technology and Health, Stockholm, Sweden; 3Department of Clinical Physiology, Karolinska University Hospital, Stockholm, Sweden; 4Department of Medicine, Karolinska Institutet, Stockholm, Sweden; 5Department of Physiology and Pharmacology, Karolinska Institutet, Stockholm, Sweden; 6Department of Biosciences and Nutrition, Karolinska Institutet, KTH, Royal Institute of Technology, School of Technology and Health, Stockholm, Sweden; 7Department ofChemical Sciences and Technologies, University of Rome Tor Vergata, Rome,Italy Abstract: The current study describes novel multifunctional polymer-shelled microbubbles (MBs) loaded with nitric oxide (NO) for integrated therapeutic and diagnostic applications (ie, theranostics) of myocardial ischemia. We used gas-filled MBs with an average diameter of 4µm stabilized by a biocompatible shell of polyvinyl alcohol. In vitro acoustic tests showed sufficient enhancement of the backscattered power (20dB) acquired from the MBs’ suspension. The values of attenuation coefficient (0.8dB/cmMHz) and phase velocities (1,517m/s) were comparable with those reported for the soft tissue. Moreover, polymer MBs demonstrate increased stability compared with clinically approved contrast agents with a fracture threshold of about 900kPa. In vitro chemiluminescence measurements demonstrated that dry powder of NO-loaded MBs releases its gas content in about 2hours following an exponential decay profile with an exponential time constant equal to 36minutes. The application of high-power ultrasound pulse (mechanical index =1.2) on the MBs resuspended in saline decreases the exponential time constant from 55 to 4minutes in air-saturated solution and from 17 to 10minutes in degassed solution. Thus, ultrasound-triggered release of NO is achieved. Cytotoxicity tests indicate that phagocytosis of the MBs by macrophages starts within 6–8hours. This is a suitable time for initial diagnostics, treatment, and monitoring of the therapeutic effect using a single injection of the proposed multifunctional MBs. Keywords: microbubbles, contrast agent, ultrasound, nitric oxide, myocardial ischemia

New proton-conducting co-networks were synthesized, characterized and tested as Polymer Exchange Membranes for Fuel Cells application. The membranes were obtained from 2-acrylamido-2-methylpropane sulfonic acid (AMPS) copolymerized with a perfluoropolyether oligomer used as crosslinker (Fluorolink ® FMD700). The structure, the thermo-mechanical behavior, the transport properties and the stability were examined in function of the co-network composition, e.g. increasing amount of conductive AMPS. High proton conductivity (1.10 –3 –5.10 −3 S cm −1 ) was reached at a threshold composition of 10 wt% AMPS, which also corresponds to a significant increase in water sorption. The efficiency of proton transfer was shown to directly correlate to the phase-separated nanostructures. On increasing the AMPS content, hydrophilic clusters embedded in the mechanically-robust FMD700 percolate and a co-continuous 3D morphology is formed. Fuel cells tests performed using the high-AMPS content crosslinked membranes showed behaviors comparable to benchmark Nafion ® under similar conditions, with performances significantly improved when the temperature is increased.

Novel polyimide-organosilicate hybrid films were prepared by sol–gel process from a novel functionalized polyimide with alkoxysilanes as pendant groups that increase the affinity between inorganic and organic phases. The synthesis of this functionalized polyimide was carried out by an esterification reaction of a copolyimide containing carboxylic acid groups with allyl alcohol and subsequent hydrosililation. Tetraethoxysilane was used as precursor of silica in different amounts to obtain hybrid membranes with a silica content of 5, 10 and 20 %. The polymers and hybrid membranes were structural, mechanical and thermally characterized. The 29Si-NMR solid state spectroscopy confirmed that silica was covalently bonded to the polyimide. SEM pictures showed a good dispersion of the silica particles and an amorphous morphology was observed by WAXS. DSC analyses revealed an increase in rigidity with the increase in silica content. The mechanical strength of the hybrid membranes decreased with the silica amount, exhibiting a brittle behavior. The evaluation of the gas permeation properties revealed that the film with the lowest silica content showed the highest permeability coefficients for O2, N2, CH4, and CO2 with 34, 8, 6, and 128 barrers respectively, while all hybrid membranes showed similar permselectivities around 4 and 22 for O2/N2 and CO2/CH4 respectively. The fractional free volume of hybrid membranes determined by positron annihilation lifetime spectroscopy followed the same trend that permeability coefficients, confirming that the gas transport properties are mainly governed by the free volume elements.

Aims Vagal nerve stimulation (VNS) protects from myocardial and vascular injury following myocardial ischaemia and reperfusion (IR) via a mechanism involving activation of alpha-7 nicotinic acetylcholine receptor (α7 nAChR) and reduced inflammation. Arginase is involved in development of myocardial IR injury driven by inflammatory mediators. The aim of the study was to clarify whether VNS downregulates myocardial and vascular arginase via a mechanism involving activation of α7 nAChR following myocardial IR. Methods Anaesthetized rats were randomized to (i) sham-operated, (ii) control IR (30-min ischaemia and 2-h reperfusion, (iii) VNS throughout IR, (iv) the arginase inhibitor nor-NOHA+IR, (v) nor-NOHA+VNS+IR, (vi) selective α7 nAChR blockade by methyllycaconitine (MLA) followed by VNS throughout IR and (vii) MLA+IR. Results Infarct size was reduced by VNS compared to control IR (41 ± 3% vs. 67 ± 2% of the myocardium at risk, P < 0.001). Myocardial IR increased myocardial and aortic arginase activity 1.7- and 3.1-fold respectively (P < 0.05). VNS attenuated the increase in arginase activity compared to control IR both in the myocardium and aorta (P < 0.05). MLA partially abolished the cardioprotective effect of VNS and completely abrogated the effect of VNS on arginase activity. Arginase inhibition combined with VNS did not further reduce infarct size. Conclusion Vagal nerve stimulation reduced infarct size and reversed the upregulation of arginase induced by IR both in the myocardium and aorta via a mechanism depending on α7 nAChR activation. The data suggest that the cardioprotective effect of VNS is mediated via reduction in arginase activity.

Background Reduced bioavailability of nitric oxide (NO) is a key factor contributing to myocardial ischemia and reperfusion injury. The mechanism behind the reduction of NO is related to deficiency of the NO synthase (NOS) substrate l-arginine and cofactor tetrahydrobiopterin (BH4) resulting in NOS uncoupling. The aim of the study was to investigate if the combination of l-arginine and BH4 given iv or intracoronary before reperfusion protects from reperfusion injury. Methods Sprague-Dawley rats and pigs were subjected to myocardial ischemia and reperfusion. Rats received vehicle, l-arginine, BH4, l-arginine + BH4 with or without the NOS-inhibitor L-NMMA iv 5 min before reperfusion. Pigs received infusion of vehicle, l-arginine, BH4 or l-arginine + BH4 into the left main coronary artery for 30 min starting 10 min before reperfusion. Results Infarct size was significantly smaller in the rats (50 ± 2%) and pigs (54 ± 5%) given l-arginine + BH4 in comparison with the vehicle groups (rats 65 ± 3% and pigs 86 ± 5%, P < 0.05). Neither l-arginine nor BH4 alone significantly reduced infarct size. Administration of L-NMMA abrogated the cardioprotective effect of l-arginine + BH4. Myocardial BH4 levels were 3.5- to 5-fold higher in pigs given l-arginine + BH4 and BH4 alone. The generation of superoxide in the ischemic-reperfused myocardium was reduced in pigs treated with intracoronary l-arginine + BH4 versus the vehicle group (P < 0.05). Conclusion Administration of l-arginine + BH4 before reperfusion protects the heart from ischemia-reperfusion injury. The cardioprotective effect is mediated via NOS-dependent pathway resulting in diminished superoxide generation. © 2013 Elsevier Ireland Ltd.

This work is focused on the investigation of Au/high k/TiN stacks for Resistive Random Access Memories. A screening of high k oxides, commonly used in advanced metal gates, such as HfO2 and ZrO2, is proposed. These oxides were grown on TiN electrodes using Atomic Layer Deposition and Plasma Enhanced Atomic Layer Deposition. The morphological and structural properties of the films were studied as a function of deposition temperature, film thickness and/or annealing using Atomic Force Microscopy, Grazing Incidence X-ray Diffraction and Attenuated Total Reflectance. An amorphous to crystalline transformation was observed with thickness for HfO2 and ZrO2, with deposition temperature for HfO2 from 300 to 350 °C, and with annealing in N2 for 1 h at 400 °C for ZrO2. According to density measurements obtained using X-ray Reflectometry, HfO2 and ZrO2 are suspected to be stoichiometric whatever the thickness. The film stoichiometry was confirmed using X-ray Spectroscopy. Current–voltage measurements were performed on Au/high k/TiN, where Au and TiN are top and bottom electrodes, respectively. Whatever the high k material, the crystallization increases with thickness or/and temperature without any significant modification of the SET operation. The film annealing, which was proposed as an alternative way to crystallize ZrO2, may cause a modification of the interfaces, leading to a decrease of the switching performance.

In this paper, TiO2 layers grown on RuO2 by atomic layer deposition (ALD) using tetrakis (dimethyla-mino) titanium (TDMAT) and either oxygen plasma or H2O as oxygen source were analyzed using X-ray diffraction (XRD), Raman spectroscopy, and depth-resolved X-ray Photoelectron spectroscopy (XPS). The main objective is to investigate the surface chemical reactions mechanisms and their influence on the TiO2 film properties. The experimental results using XRD show that ALD deposition using H2O leads to anatase TiO2 whereas a rutile TiO2 is obtained when oxygen-plasma is used as oxygen source. Depth-resolved XPS analysis allows to determine the reaction mechanisms at the RuO2 substrate surface after growth of thin TiO2 layers. Indeed, the XPS analysis shows that when H2O assisted ALD process is used, intermediate Ti2O3 layer is obtained and RuO2 is reduced into Ru as evidenced by high resolution transmission electron microscopy. In this case, there is no possibility to re-oxidize the Ru surface into RuO2 due to the weak oxidation character of H2O and an anatase TiO2 layer is therefore grown on Ti2O3. In contrast, when oxygen plasma is used in the ALD process, its strong oxidation character leads to the re-oxidation of the partially reduced RuO2 following the first Ti deposition step. Consequently, the RuO2 surface is regenerated, allowing the growth of rutile TiO2. A surface chemical reaction scheme is proposed that well accounts for the observed experimental results.

International audience; Graphene, a two dimensional material with remarkable electronic properties, has attracted a huge interest among scientist during the last decade. We report the fabrication of Graphene-HfO2-based resistive RAM memories. We insert graphene layers between the oxide layer and the gold top electrode resulting in stabilization of a low resistance state stability without applied voltage, contrary to behaviour observed for identical graphene free memory devices. Graphene here is used as an oxygen reservoir and contribute to the switching mechanism. (C) 2016 Elsevier B.V. All rights reserved.

Resistance switching is studied in HfO2 as a function of the anode metal (Au,Cu, and Ag) in view of its application to resistive memories (resistive random access memories, RRAM). Current-voltage (I-V) and current-time (I-t) characteristics are presented. For Auanodes,resistance transition is controlled by oxygen vacancies (oxygen-based resistive random access memory, OxRRAM). For Aganodes,resistance switching is governed by cation injection (Conducting Bridge random access memory, CBRAM). Cuanodes lead to an intermediate case. I-t experiments are shown to be a valuable tool to distinguish between OxRRAM and CBRAM behaviors. A model is proposed to explain the high-to-low resistance transition in CBRAMs. The model is based on the theory of low-temperature oxidation of metals (Cabrera-Mott theory). Upon electron injection, oxygen vacancies and oxygen ions are generated in the oxide. Oxygen ions are drifted to the anode, and an interfacial oxide is formed at the HfO2/anode interface. If oxygen ion mobility is low in the interfacial oxide, a negative space charge builds-up at the HfO2/oxide interface. This negative space charge is the source of a strong electric field across the interfacial oxide thickness, which pulls out cations from the anode (CBRAM case). Inversely, if oxygen ions migration through the interfacial oxide is important (or if the anode does not oxidize such as Au), bulk oxygen vacancies govern resistance transition (OxRRAM case).

International audience; The electrical reliability of HfO2 based metal–insulator–metal capacitors is investigated under AC stress voltage. The capacitance–time (C–t) and conductance–time (G–t) responses are studied for different stress amplitudes and frequencies. Time-to-breakdown is observed to strongly depend on the electrode nature. Electrical degradation is discussed via a model based on oxygen vacancy/oxygen ions generation. Defect generation is controlled by the injecting nature of electrodes. Partial recovery, and so time-to-breakdown, are controlled by the ability of electrodes to store oxygen.

The research work reported in this paper is an investigation of the behavior of barium titanate powders under selective laser irradiation. Our goal is to determine suitable conditions to sinter the powders and form dense layers usable in some electronic components. On that purpose, compacts of micro/nano BaTiO 3 powder mixes are used for a parametric investigation of the laser scans parameters (power, speed, etc.) with a Nd-YVO 4 laser (23 W). The microstructures obtained after laser treatments are evaluated by XRD, SEM and EDS and compared to a reference specimen manufactured in a conventional way. From this work it can be concluded that a high laser beam power is required to obtain a consolidation of the powder grains and the use of a high scan speed avoids the melting. The scanning speed also influences the final crystallographic state of BaTiO 3 . Optimal parameters were founded in order to form a dense and homogeneous tetragonal BaTiO 3 surface.

Fuel cell tests have been performed on sulfonated Poly(Ether Ether Ketone) (sPEEK) membranes using dry gases. Impact of gas stoichiometry on performance evolution and membrane–electrodes assembly's water distribution optimization (water management) was studied. During the tests, output voltage evolution was recorded as well as impedance spectra, polarization curves and water amount collected at both sides. Fuel cell performances were observed to be influenced by water management which depends on both operating conditions and membrane intrinsic properties. Increasing either hydrogen or oxygen stoichiometry leads to a decrease of performance. This effect was more pronounced for hydrogen increase (anode). This has been ascribed to a global drying of the membrane along with the appearance of a heterogeneous hydration both through the MEA and along the gas channels. Cell performance characterization during the membrane lifespan was mainly based on Electrochemical Impedance Spectroscopy measurements and showed that water distribution heterogeneity increased with operating time for sPEEK membrane, leading to a drop of performance. This was mainly ascribed to the drying of the gas inlet and the increased hydration at the gas outlet. These behaviours were not observed for the better performing Nafion, which underlines the impact of membrane water transport properties on fuel cell performance.

Aim: To investigate whether ischaemic post-conditioning (IPoC) combined with i.v. infusion of the nitric oxide (NO) substrate l-arginine at the onset of reperfusion exerts cardioprotective effect that is superior to either treatment given separately. Methods: Twenty-six anesthetized pigs were subjected to coronary artery (left anterior descending artery, LAD) ligation for 40 min followed by 4 h reperfusion. The pigs were randomized into five different groups receiving either i.v. vehicle, i.v. l-arginine, IPoC 4 × 60 s together with i.v. vehicle or IPoC together with i.v. l-arginine and a group with IPoC 8 × 30 s. All infusions were started 10 min before reperfusion. Results: The infarct size of the vehicle group was 82 ± 4% of the area at risk. l-Arginine alone (79 ± 8%), IPoC 4 × 60 s vehicle (86 ± 3%) or IPoC 8 × 30 s vehicle (94 ± 7%) did not affect infarct size. l-Arginine together with IPoC significantly reduced infarct size to 59 ± 4% (P

D(2)-like antagonists potentiate dopamine release. They also inhibit dopamine uptake by a mechanism yet to be clarified. Here, we monitored dopamine uptake in the striatum of anesthetized mice. The dopamine overflow was evoked by brief electrical stimulation of the medial forebrain bundle (four pulses at 100 Hz) and was monitored with carbon fiber electrodes combined with continuous amperometry. The decay phase of evoked overflows reflects dopamine half-life, which entirely depends on uptake. The D(2)-like antagonists haloperidol and eticlopride enhanced the half-life by 45% and 48%, respectively, a moderate effect as compared to the uptake blocker nomifensine (528%). Both D(2)-like antagonists did not affect dopamine uptake in mice lacking D(2) receptors. Inhibition of tonic dopamine release by gamma-butyrolactone did not mimic the enhancing effect of D(2) antagonists on dopamine half-life. However, prolonged stimulation boosted dopamine uptake and this effect was not observed after haloperidol treatment or in mice lacking D(2) receptors. Therefore, dopamine uptake is accelerated in conditions of excessive D(2) stimulation but not finely tuned in resting conditions. Inhibition of dopamine uptake by D(2) antagonists synergizes with the potentiation of dopamine release to strongly alter the phasic dopamine signaling.

By copolymerization of the disodium-2,2′-disulfonate-4,4′-oxydibenzoic acid (SODBA), the 4,4′-oxybis(benzoic acid) (OBBA) with the bis 3,4-(diaminophenyl)sulfone (BDAPS), a series of high molecular weight sulfonated polybenzimidazoles (sPBI) were prepared by varying the ratio of monomers SODBA/OBBA. Polymers with ion exchange capacity (IEC) ranging from 0 to 3.2 meqH+/g were obtained. The chemical structure of the sPBI was confirmed by NMR, Fourier-transform infra-red (FTIR). Although the sPBI display a very poor solubility in organic solvents, they are, in the ammonium salt form, soluble in polar aprotic solvents such as DMF, NMP, or DMSO. Tough and ductile membranes from solution casting method were prepared. The water uptake and the ionic conductivity were determined at 30 and 90 °C. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1732–1742, 2010

In Parkinson's disease dopamine depletion imbalances the two major output pathways of the striatum. L-DOPA replacement therapy is believed to correct this imbalance by providing effective D1 and D2 receptor stimulation to striatonigral and striatopallidal neurons, respectively. Here we tested this assumption in the rat model of Parkinsonism by monitoring the spike response of identified striatal neurons to cortical stimulation. As predicted, in 6-hydroxydopamine lesioned rats we observed that L-DOPA (6 mg/kg+benserazide), apomorphine and the D2 agonist quinpirole (0.5 mg/kg i.p.) counteract the enhanced responsiveness of striatopallidal neurons. Unexpectedly, the depressed responsiveness of striatonigral neurons was corrected by quinpirole whereas D1 stimulation exerted no (apomorphine, cPB) or worsening effects (L-DOPA, SKF38393 10 mg/kg). Therefore, quinpirole, but not D1 stimulation, restores functional equilibrium between the two striatal output pathways. Our results might explain the therapeutic effect of D2-based medications in Parkinson's disease.

Hydrogenated barium titanate film based metal–insulator–metal (MIM) systems show high dielectric constant and have therefore been proposed as solid state supercapacitors. Hydrogen was incorporated in the dielectric layer during the low temperature deposition process. An investigation of the electrical properties has revealed that hydrogen contributes to the conduction process as mobile ionic species as well as donor trap levels.

Amorphous barium titanate films (a-BTO) were grown by the RF magnetron sputtering technique at low temperature and under various oxygen/argon mixing ratios (OMR). Their dielectric properties (dielectric constant, loss and ac conductivity in the 0.1–105 Hz range), dc leakage currents, and thermally stimulated currents were systematically studied as a function of OMR in the sputtering gas (0% to 20 %). We demonstrate that the presence of oxygen plays a significant role in improving the dielectric properties of a-BTO thin films. The oxygen incorporation successfully suppressed some electrical defects. The bulk conductivity and leakage currents are reduced although a small decrease of dielectric constant has been observed. Films prepared at higher oxygen ratio (20%) have a small leakage current density (3.6 × 10− 7 A/m2) and lower tangent loss (2 × 10− 3).

There is a debate as to what modifications of neuronal activity underlie the clinical manifestations of Parkinson's disease and the efficacy of antiparkinsonian pharmacotherapy. Previous studies suggest that release of GABAergic striatopallidal neurons from D2 receptor-mediated inhibition allows spreading of cortical rhythms to the globus pallidus (GP) in rats with 6-hydroxydopamine-induced nigrostriatal lesions. Here this abnormal spreading was thoroughly investigated. In control urethane-anaesthetized rats most GP neurons were excited during the active part of cortical slow waves ('direct-phase' neurons). Two neuronal populations having opposite phase relationships with cortical and striatal activity coexisted in the GP of 6-hydroxydopamine-lesioned rats. 'Inverse-phase' GP units exhibited reduced firing coupled to striatal activation during slow waves, suggesting that this GP oscillation was driven by striatopallidal hyperactivity. Half of the pallidonigral neurons identified by antidromic stimulation exhibited inverse-phase activity. Therefore, spreading of inverse-phase oscillations through pallidonigral axons might contribute to the abnormal direct-phase cortical entrainment of basal ganglia output described previously. Systemic administration of the D2 agonist quinpirole to 6-hydroxydopamine-lesioned rats reduced GP inverse-phase coupling with slow waves, and this effect was reversed by the D2 antagonist eticlopride. Because striatopallidal hyperactivity was only slightly reduced by quinpirole, other mechanisms might have contributed to the effect of quinpirole on GP oscillations. These results suggest that antiparkinsonian efficacy may rely on other actions of D2 agonists on basal ganglia activity. However, abnormal slow rhythms may promote enduring changes in functional connectivity along the striatopallidal axis, contributing to D2 agonist-resistant clinical signs of parkinsonism.

Conduction mechanisms in BaTiO3 films deposited at low temperatures on Cu-electrodes have been investigated in transient and steady regimes as a function of temperatures and electric field. This work aims to identify possible defects which govern the leakage current. Electrical measurements reveal that Space Charge Limited Current (SCLC) constitutes the main leakage mechanism in both the transient and the steady regimes. Based on the theory of SCLC, two types of defects can be detected. At higher temperatures, oxygen vacancies constitute the main defects which migrate across the film to generate an ionic leakage current. Diffusion of these defects is thermally activated with an activation energy around 1 eV. Moreover, at lower temperatures the J -E measurements reveals the presence of a discrete set of shallow traps at 0.45 eV below the conduction band with an effective density of 4 × 1022 m–3. (© 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

In the present work, a new sulfonated tetraamine and the corresponding sulfonated polybenzimidazoles (sPBI) were synthesized. For the sake of determining the best polymerization conditions, a study involving model compounds was first performed. A strong acid medium was used as polymerization solvent, which allowed to obtain high molecular weight sPBI. A series of polymers with ion exchange capacity (IEC) ranging from 0 to 2.6 mequiv/g were synthesized using a non-sulfonated tetraamine as a comonomer. The chemical structure of those polymers was confirmed by nuclear magnetic resonance (NMR) and Fourier transform infrared (FTIR) as well as by titration. Thermogravimetric analysis (TGA) and viscosity measurement were performed as well. On the other hand, different architectures of the copolymers were prepared, i.e., random, sequenced copolymers, and blends of the homopolymers. The membranes prepared from the sPBI display low water uptake. The ionic conductivities measured in the hydrated state at room temper...

International audience; The design of interpenetrated networks (IPN) membranes for fuel cell applications requires both an electrolyte and a neutral network. The composition and architecture of the latter are of major importance for the final IPN membrane properties. In this work, networks based on a fluorinated diepoxy oligomer (DFODDE) and a non-fluorinated triepoxy monomer (TMPTGE) were synthesized. The network composition was varied from 100% DFODDE to 100% TMPTGE, resulting in an increase of the crosslinking density and concomitantly a decrease of the fluorine content. The curing process was optimized to achieve a total epoxy conversion and the chemical structure of the networks was characterized by Raman and Infrared spectroscopies. The physical, thermal and chemical membrane properties were studied and discussed as a function of the crosslinking density and of the fluorine content. Increasing the crosslinking density led to a decrease of the membrane permeability to oxygen. Water sorption properties depended on both parameters, with a prevailing role of the fluorine content on the water uptake and a major influence of the crosslinking density on the diffusion parameter. The thermal stability increased also with the fluorine content. All materials exhibited a good stability in water at 80 degrees C but a significant weight loss after immersion in a concentrated H2O2 solution. Altogether, these results indicate that networks containing 20% of TMPTGE exhibit an interesting set of properties (low oxygen permeability, high T-g, good chemical and thermal stability) to behave as a neutral partner in an IPN membrane. Moreover, the low water uptake and diffusion rate measured in these networks make them attractive for water barrier membranes.

Resistance switching in HfO 2 metal-insulatormetal devices is investigated through current-voltage (I–V) and current-time (I-t) measurements. Depending on electrodes, a high-to-low resistance transition is observed in I–V characteristics at high or low voltages (OXRAM and CBRAM behaviors). This is correlated in the I-t characteristics to a progressive current increase, or to an abrupt current jump. Following the high-to-low resistance transition, several behaviors are observed: Non-switchable resistance (irreversible breakdown), evanescent low resistance state (spontaneous breakdown recovery), or fully switchable resistance (voltagecontrolled reversible breakdown). The primary mechanism, common to both CBRAM and OXRAM devices, is hot electron injection at the cathode which leads to oxygen vacancies (defects) in the oxide bulk. Anode metal may diffuse along defect paths. In that case, the high-to-low resistance transition is due to the formation of metallic filaments across the oxide thickness (CBRAM case). When the anode metal diffusion is more difficult, the high-to-low resistance transition is ascribed to oxygen vacancy percolation paths (OXRAM case).

Degradation processes of both sulfonated polyimide (sPI) and sulfonated polyetheretherketone (sPEEK) membranes were studied in-situ in fuel cells. Ex-situ ageing protocols were developed for both polymers and model compounds. On the one hand sulfonated polyimides are shown to be mainly sensitive to hydrolysis though an additional thermo activated oxidation process occurs in fuel cell conditions and at least accelerates the degradation. On the other hand sulfonated polyetheretherketone are insensitive to hydrolysis but greatly degraded in an oxidative medium.

Prefrontal cortical (PFC) pyramidal neurons (PN) and fast spiking inter-neurons (FSI) receive dopaminergic (DA) and non-DA inputs from the ventral tegmental area (VTA). Although the responses of PN to VTA stimulation and DA administration have been extensively studied, little is known about the response of FSI to mesocortical activation. We explored this issue using single and double in vivo juxtacellular recordings of medial PFC PN and FSI with chemical VTA stimulation. Electrophysiological characteristics combined with Neurobiotin staining and parvalbumin immunohistochemistry allowed identification of recorded cells as FSI or PN. NMDA injection into the VTA increased firing in all FSI tested (n = 7), whereas most PN (7/11) responded with an inhibition. Furthermore, FSI excitation matching the temporal course of PN inhibition was observed with FSI–PN paired recordings (n = 5). These divergent electrophysiological responses to mesocortical activation could reflect PFC GABAergic inter-neurons contributing to silencing PN. Thus, the mesocortical system could provide a critical control of PFC circuits by simultaneously affecting FSI and PN firing.

The target of this work is to investigate the effects of the relative amounts of the main impurities usually encountered in an alumina powder obtained from the Bayer process. On that purpose, the amounts of Na 2 O and SiO 2 present in a commercial powder, have been modified by doping. The sintering behavior and the microstructure of the sintered ceramics have been investigated. The ratio Na 2 O/SiO 2 strongly influences the shrinkage rates during sintering, the final density and the microstructure. From the commercial powder used (P172SB, Aluminium Pechiney Company, Alcan Group, France), it is shown that an increase in Na 2 O content significantly slows down the densification and also the grain growth. The effect of an increase in SiO 2 additions is less obvious even if the dilatometric curves also show decreases in the sintering rates, particularly in the temperature range 1200–1400 °C. Contrary to Na 2 O, the addition of SiO 2 leads to abnormal grain growth and provokes an increase in the aspect ratio of the grains.

Depth profiles analyses were performed on a cross section of a photoaged BPAPC substrate by measuring the glass transition temperature and the Young modulus at a microscopic scale. The aim was to define the impact of photochemical modifications induced under UV irradiation upon the physical properties of this polymer. It is well known that ageing of BPAPC begins by a direct phototransformation of the macromolecules according to the photo-Fries rearrangements. These reactions lead to an increase of the free volume and, as a consequence, to a decrease of the temperature associated with the glass transition while in the meantime, the Young modulus of the material is not modified. As ageing proceeds (longer irradiation times), oxidation of the polymer takes place. This oxidative degradation leads to the formation of a cross-linked structure on the exposed surface. This oxidative degradation is associated with an increase of the glass transition temperature and of the Young modulus, whereas in the bulk of the material ageing involves chain scissions characterised by a decreased glass transition temperature.

The development of electrochemical recordings with small carbon-fiber electrodes has significantly advanced the understanding of the regulation of catecholamine transmission in various brain areas. Recordings in vivo or in slice preparations monitor diffusion of catecholamine following stimulated synaptic release into the surrounding tissue. This synaptic 'overflow' is defined by the amount of release, by the activity of reuptake, and by the diffusion parameters in brain tissue. Such studies have elucidated the complex regulation of catecholamine release and uptake, and how psychostimulants and anti-psychotic drugs interfere with it. Moreover, recordings with carbon-fiber electrodes from cultured neurons have provided analysis of catecholamine release and its plasticity at the quantal level.