Tailoring the chemo-resistive response of self-assembled polysaccharide-CNT sensors by chain conformation at tunnel junctions

The performances of the e-noses used for the detection of toxic volatiles or anticipated diagnosis of diseases are closely related to the nanostructure of their conductive polymer composite (CPC) vapour sensors. It is attractive to be able to adjust a nanometric parameter such as the tunnel junctions’ gap between nanofillers in the percolated network of CPC sensors, to tune their macroscopic chemo-resistive properties, i.e., sensitivity and selectivity to organic vapours. Therefore, three types of transducers (multiwalled carbon nanotubes (CNTs), CNT functionalized by amylose, and CNT functionalized by amylopectine) were hierarchically assembled by spray layer by layer and exposed to water, methanol and toluene vapours. Amylose and amylopectine macromolecules, which have the same chemical nature but a different structure, linear and highly branched, are found (by atomic force microscopy) to adsorb in different conformations on CNT surface, helical and random, respectively. Interestingly, amylose is enhancing the sensitivity of CNT transducers to water by a factor 5, whereas amylopectine increases the sensitivity to toluene by a factor 1.5. These results suggest that changing the conformation of the polysaccharides adsorbed on CNT not only allows to tailor CPC chemo-resistive sensors sensitivity but also their selectivity by a specific orientation of chemical groups.     

Electrochemical treatment of bisphenol-A using response surface methodology

The decomposition of bisphenol-A (BPA) in synthetic solution and in municipal effluent was investigated using an electro-oxidation process. Electrolysis was conducted using a cylindrical electrolytic cell containing two circular anodes (expanded metal) and two circular cathodes (stainless steel) alternated in the electrode pack. Different anode materials (Ti/SnO₂, Ti/IrO₂ and Ti/PbO₂) were tested, and Ti/PbO₂ was found to be the most effective electrode for BPA degradation. An experimental design methodology (2³ Box–Behnken design) was applied to determine the optimal experimental conditions in terms of cost effectiveness. The BPA concentration (C ₀ = 1.0 mg l⁻¹) could be optimally diminished by up to 90% by applying a current intensity of 2.0 A for a 100-min reaction period in the presence of 250 mg Na₂SO₄ l⁻¹ (used as a supporting electrolyte). Then, the optimal conditions were applied on a municipal wastewater effluent (sampled after secondary treatment) artificially contaminated with 1 mg BPA l⁻¹ without the addition of a supporting electrolyte. The treatment was more effective with the municipal effluent due to the presence of a high concentration of chloride ions that could easily be transformed into active chlorine. BPA could be oxidized by both direct anodic electrochemical oxidation (by means of OH·) and indirect electrochemical oxidation via mediators, such as hypochlorous acid generated by chloride oxidation. Both actions (direct and indirect effects) lead to the formation of powerful oxidizing agents capable of rapidly oxidizing BPA.     

Comparing the growth of a molecular semiconductor on amorphous and semi-crystalline polycarbonate substrates

Polymeric substrates are of importance in plastic electronics. However, polymeric surfaces can exhibit different morphologies depending on whether they are amorphous or semi-crystalline. This work focuses on the impact of the surface structure of bisphenol A polycarbonate substrates on the nucleation and growth of a p-type semi-conductor, namely zinc phthalocyanine (ZnPc). ZnPc films were deposited under high vacuum at different substrate temperatures on oriented semi-crystalline as well as amorphous substrates of PC. The oriented substrates of PC were prepared by a method combining mechanical rubbing and solvent induced crystallization: the substrates show a periodic and regular alternation of oriented crystalline lamellae. Grazing incidence X-ray diffraction shows that the crystalline lamellae of PC have a preferential (a, c) contact plane. Moreover, the substrates show a bilayer structure made of a 60 nm-thick semi-crystalline overlayer atop an amorphous underlayer. UV–vis spectroscopy shows that the polymorphism of the ZnPc films is not modified by the surface structure of the PC substrate (amorphous versus semi-crystalline). However, the statistical analysis of domain size and density versus substrate temperature T_s evidences different apparent activation energies of the growth mechanism. High Resolution Transmission Electron Microscopy suggests that twinning along a (2 ?1 0) plane accounts for the bifurcations of the in-plane b-axis direction of the ZnPc nanocrystals. On oriented substrates of PC, such bifurcations are partly suppressed by the nanocorrugation of the surface, resulting in larger apparent domain sizes and unidirectional in-plane orientation.     

Canadian dietitians' use and perceptions of glycemic index in diabetes management.

PURPOSE: Several health organizations, including the Canadian Diabetes Association, advocate use of the glycemic index (GI) in the nutritional management of diabetes. However, the clinical utility and applications of the GI remain controversial. Our goal was to determine, via a postal survey, whether dietitians were using the GI and barriers to its use if they were not. METHODS: This cross-sectional study was conducted in 2003. Members of Dietitians of Canada and the Ordre professionnel des diététistes du Québec (n=6,060) were first contacted by mail to identify those working with individuals with diabetes. Among respondents (n=2,857), 1,805 worked with individuals with diabetes and were sent a questionnaire. Using Chi-square analyses, users and nonusers were compared for their professional characteristics, perceived benefits, barriers, general knowledge about the concept, and confidence in teaching the GI. RESULTS: Among questionnaire respondents (n=1,057), 39% (n=415) used the GI and 61% (n=642) did not. Overall, users were more likely to have a greater diabetes patient caseload, perceived greater benefits and had greater confidence in teaching the concept. Nonusers cited lack of teaching tools and lack of knowledge on how to teach the concept as major barriers. CONCLUSIONS: Further research is required to identify the clinical reasoning that triggers dietitians to apply the concept in their practice.     

Assembly and degradation of low-fouling click-functionalized poly(ethylene glycol)-based multilayer films and capsules

Nano-/micrometer-scaled films and capsules made of low-fouling materials such as poly(ethylene glycol) (PEG) are of interest for drug delivery and tissue engineering applications. Herein, the assembly and degradation of low-fouling, alkyne-functionalized PEG (PEG(Alk) ) multilayer films and capsules, which are prepared by combining layer-by-layer (LbL) assembly and click chemistry, are reported. A nonlinear, temperature-responsive PEG(Alk) is synthesized, and is then used to form hydrogen-bonded multilayers with poly(methacrylic acid) (PMA) at pH 5. The thermoresponsive behavior of PEG(Alk) is exploited to tailor film buildup by adjusting the assembly conditions. Using alkyne-azide click chemistry, PEG(Alk)/PMA multilayers are crosslinked with a bisazide linker that contains a disulfide bond, rendering these films and capsules redox-responsive. At pH 7, by disrupting the hydrogen bonding between the polymers, PEG(Alk) LbL films and PEG(Alk) -based capsules are obtained. These films exhibit specific deconstruction properties under simulated intracellular reducing conditions, but remain stable at physiological pH, suggesting potential applications in controlled drug release. The low-fouling properties of the PEG films are confirmed by incubation with human serum and a blood clot. Additionally, these capsules showed negligible toxicity to human cells.     

Thermal and refining processes, not fermentation, tend to reduce lipotropic capacity of plant-based foods

Plant-based foods (PBF) are relevant and diversified sources of lipotropes, which are compounds preventing excess hepatic fat deposits. In a first study, we defined the lipotropic capacity (LC, %) of raw PBF as the means of 8 lipotrope densities (LD, mg/100 kcal), each expressed relative to that of a reference food ranking the highest considering its mean 8 LD ranks (LC(raw asparagus)=100%) (A. Fardet, J.-F. Martin and J. M. Chardigny, J. Food Comp. Anal., 2011, DOI: 10.1016/j.jfca.2011.1003.1013). We showed that vegetables appeared as the best source of lipotropes on a 100 kcal-basis compared to legumes, cereals, fruits and nuts. The main objective of this second study was to quantify the effect of processing on LD and LC of raw PBF based on lipotrope contents collected in a USDA (United State Department of Agriculture) database and the literature, i.e. betaine, choline, myo-inositol, methionine, magnesium, niacin, pantothenic acid and folate contents. Choline and betaine densities were not significantly affected by processing while methionine and lipotropic micronutrient densities were significantly decreased, especially for magnesium, pantothenate and folates. Myo-inositol density decreases were insignificant due to lower product number resulting from limited literature data. Lipotropic micronutrient densities were more affected by processing than other densities. Fermentations increased betaine (median change of +32%) and choline (+34%) densities. Canning and boiling vegetables increased choline densities (+26%). Globally, processing significantly reduced LC by ～20%, fermentations being less drastic (median change of -5%) than refining (-33%) and thermal treatments (-16%). More specifically, canning increased LC of beetroot (536 vs 390%) and common bean (40 vs 36%) as fermentation towards LC grape (14 vs 7% for wine). Results were then mainly discussed based on percentages of lipotrope content changes on a dry-weight basis. Results of this study also showed that the LC is quite a relevant index to estimate effect of processing on lipotropic potential of PBF.     

Influence of EGR unequal distribution from cylinder to cylinder on NOx–PM trade-off of a HSDI automotive Diesel engine

The influence of cylinder-to-cylinder variation in EGR distribution on the NOx–PM trade-off (while varying EGR rate) is studied on an automotive high-speed direct injection Diesel engine. Experiments have been conducted on an engine test bench with and without air-EGR mixer and demonstrate that variations in cylinder-to-cylinder EGR distribution results in a deteriorated NOx–PM trade-off (increased NOx emissions level at a given PM emissions level, or increased PM emissions level at a given NOx emissions level) compared to the well mixed configuration with equal EGR rate for all the cylinders. A qualitative study as well an original experiment is conducted to explain this emissions increase induced by unequal distribution of EGR. When recirculating hot exhaust gases, the emissions increase is due to cylinder-to-cylinder variations in intake gas composition and temperature.     

Selecting a battery of bioassays for ecotoxicological characterization of wastes

This study was conducted in France within the context of waste classification (Hazardous Waste Council Directive 91/689/EEC), and focused on "ecotoxic" property (H14). In 1998, an experimental test strategy was developed to assess ecotoxicological properties of wastes using a battery of six standardized bioassays. This combined direct and indirect approaches integrating two solid-phase tests: emergence and growth inhibition of Lactuca sativa (14 days), mortality of Eisenia fetida (14 days) and four standardized tests performed on water extracts from wastes: growth inhibition of Pseudokirchneriella subcapitata (3 days), inhibition of mobility of Daphnia magna (48 h), inhibition of reproduction of Ceriodaphnia dubia (7 days), inhibition of light emission of Vibrio fischeri (30 min). This study aimed to set up preliminary conclusions on relevancy of this experimental test strategy, based on data obtained since 1998. Results were analyzed from the combined use of Hierarchical Cluster Analysis, Principal Component Analysis and Nonlinear Mapping. These multivariate analyses clearly showed that it was possible to reduce this number of tests without changing the typology of the wastes. A battery of bioassays including one solid phase test and two tests performed on water extracts (L. sativa, V. fischeri and C. dubia) was found as an optimal solution for characterizing the toxicity of the studied wastes. This optimal battery represents a good basis for determining the H14 property.     

Al2O3-ZrO2 Finely Structured Multilayer Architectures from Suspension Plasma Spraying

Suspension plasma spraying (SPS) is an alternative to conventional atmospheric plasma spraying (APS) aiming at manufacturing thinner layers (i.e., 10-100 μm) due to the specific size of the feedstock particles, from a few tens of nanometers to a few micrometers. The staking of lamellae and particles, which present a diameter ranging from 0.1 to 2.0 μm and an average thickness from 20 to 300 nm, permits to manufacture finely structured layers. Moreover, it appears as a versatile process able to manufacture different coating architectures according to the operating parameters (suspension properties, injection configuration, plasma properties, spray distance, torch scan velocity, scanning step, etc.). However, the different parameters controlling the properties of the coating, and their interdependences, are not yet fully identified. Thus, the aim of this paper is, on the one hand, to better understand the influence of operating parameters on the coating manufacturing mechanisms (in particular, the plasma gas mixture effect) and, on the other hand, to produce Al₂O₃-ZrO₂ finely structured layers with large varieties of architectures. For this purpose, a simple theoretical model was used to describe the plasma torch operating conditions at the nozzle exit, based on experimental data (mass enthalpy, arc current intensity, thermophysical properties of plasma forming gases, etc.) and the influences of the spray parameters were determined by mean of the study of sizes and shapes of spray beads. The results enabled then to reach a better understanding of involved phenomena and their interactions on the final coating architectures permitting to manufacture several types of microstructures.     

Design,Synthesis and Evaluation of a Series of 1,5-Diaryl-1,2,3-triazole-4-carbohydrazones as Inhibitors of the YAP-TAZ/TEAD Complex

Starting from our previously reported hit, a series of 1,5-diaryl-1,2,3-triazole-4-carbohydrazones were synthesized and evaluated as inhibitors of the YAP/TAZ-TEAD complex. Their binding to hTEAD2 was confirmed by nanodifferential scanning fluorimetry, and some of the compounds were also found to moderately disrupt the YAP-TEAD interaction, as assessed by a fluorescence polarization assay. A TEAD luciferase gene reporter assay performed in HEK293T cells and RTqPCR measurements in MDA-MB231 cells showed that these compounds inhibit YAP/TAZ-TEAD activity to cells in the micromolar range. In spite of the cytotoxic effects displayed by some of the compounds of this series, they are still good starting points and can be suitably modified into an effective and viable YAP-TEAD disruptor in the future.