Effects of polypyrrole modified electrode functionalization on potentiometric pH responses

Two functionalized polypyrrole films, poly(11-N-pyrrolylundecanoic) acid and poly(N-undecylpyrrole), were used as sensitive layers for pH sensors. The functionalized pyrrole monomers were first synthesized before carrying out their electropolymerization onto non-oxidizable electrodes. The deposits were characterized by SEM imaging, XPS and PM-IRRAS to study surface structure and composition. Poly(11-N-pyrrolylundecanoic) acid coating yielded very promising results as sensitive layer in pH sensors. Indeed, the potentiometric responses from pH 4.0 to 9.0 appeared linear, reversible, stable in time over a period of 1 month and highly selective for H⁺ ions. This behavior was attributed to carboxylic acid groups which are sensitive to proton concentration changes. This was confirmed by the fact that poly(N-undecylpyrrole) film led to potentiometric responses being pH dependent only from pH 6.0 to 9.0 with low sensitivity. Poly(11-N-pyrrolylundecanoic) acid is thus promoted to be used as sensitive layer in pH sensors.     

Carbonic anhydrase inhibitors: design of membrane-impermeant copper(II) complexes of DTPA-, DOTA-, and TETA-tailed sulfonamides targeting the tumor-associated transmembrane isoform IX

The synthesis and carbonic anhydrase (CA, EC 4.2.1.1) inhibitory activity of two series of aromatic sulfonamides and their Cu(II) derivatives, incorporating metal-complexing moieties of the DTPA, DOTA, and TETA type are reported. The new compounds were designed in such a way as to possess high affinity for Cu(II) ions, exploiting four pendant carboxylate moieties in the DTPA derivatives, as well as the cyclen/cyclam macrocyles, and three pendant acetate moieties in the DOTA and TETA derivatives. The new derivatives showed modest inhibition of the cytosolic isoform CA I (K(I) values in the range of 66-2130 nM), were better CA II inhibitors (K(I) values in the range of 21-360 nM), and excellent inhibitors of the tumor-associated isoform CA IX (K(I) values in the range of 4.1-110 nM), with selectivity ratios for the inhibition of the tumor (CA IX) over the cytosolic (CA II) isozyme in the range of 10.74-20.88 for the best derivatives. Copper complexes were more inhibitory than the corresponding ligand sulfonamides, and showed membrane impermeability, thus, having the possibility to specifically target the transmembrane CA IX that has an extracellular active site. Incorporation of radioactive copper isotopes in this type of CA inhibitor may lead to interesting diagnostic/therapeutic applications for such compounds.     

Miniemulsion polymerization for synthesis of structured clay/polymer nanocomposites: Short review and recent advances

This review intends to present different aspects concerning clay/polymer nanocomposites produced by heterophase polymerization in aqueous media. This paper highlights the ability of miniemulsion polymerization to produce clay/polymer nanoparticles with tailored nanostructures. Indeed, this polymerization route enables the synthesis of composite nanoparticles with the clay platelets located either on the surface of the polymer particle or embedded inside the polymer particle. A focus is given on the influence of these nanostructures on the properties of the final material through a direct comparison of the composites obtained after water evaporation from these structured nanoparticles. Indeed, the film obtained from the film forming process of these nanoparticles present significantly different nanostructures and exhibit totally different mechanical behaviours and water uptakes. By comparing experimental results and modeling approaches, it is demonstrated that their properties are clearly related to the clay dispersion and contacts. It is also evidenced that the main drawback of miniemulsion from the coating application point of view, is the large water uptake promoted by the surfactant presence whose localization is strongly influenced by nanostructuration. This stresses the need for the further development of surfactant free miniemulsion polymerization using advantageously the clay presence to stabilize the emulsion.     

Prediction and optimization of electroplated Ni-based coating composition and thickness using central composite design and artificial neural network

Journal of Applied Electrochemistry - The choice of the electroplating conditions of Ni-based alloys has always been a serious research question. In this study, an artificial neural network based...     

Mechanism of action of Melaleuca armillaris (Sol. Ex Gaertu) Sm. essential oil on six LAB strains as assessed by multiparametric flow cytometry and automated microtiter-based assay

Little is known concerning the effects of essential oils (EOs) against lactic acid bacteria (LAB), either of the human gastrointestinal microflora or those involved in industrial processes. GC and GC/MS analysis of Melaleuca armillaris EO resulted in the identification of 68 compounds comprising 99.6% of the oil. Eucalyptol (1,8-cineole) was the major compound (68.9%) and the composition was largely dominated by the oxygenated monoterpenes fraction (77.3%). The anti-LAB activities of the EO were first checked by the disc diffusion assay. In a second phase, time-survival kinetics of each strain incubated with increasing concentrations of the EO (0.25, 2.5, 5 and 25 μg/ml) were established using an automated microtiter assay (Bioscreen C). Bacteriostatic or bactericidal effects were noticed depending on the studied strain and on the applied concentration of the EO. The mathematical modelling of the kinetics showed that in presence of increasing concentrations of M. armillaris EO, the lag phases of growth were extended (0.69%–97.5%) and both the growth rate and final cell density were reduced. Variations depending on the strain were noticed.     

Relation between the redox state of iron-based nanoparticles and their cytotoxicity toward Escherichia coli

Iron-based nanoparticles have been proposed for an increasing number of biomedical or environmental applications although in vitro toxicity has been observed. The aim of this study was to understand the relationship between the redox state of iron-based nanoparticles and their cytotoxicity toward a Gram-negative bacterium, Escherichia coli. While chemically stable nanoparticles (gammaFe2O3) have no apparent cytotoxicity, nanoparticles containing ferrous and, particularly, zerovalent iron are cytotoxic. The cytotoxic effects appear to be associated principally with an oxidative stress as demonstrated using a mutant strain of E. coli completely devoid of superoxide dismutase activity. This stress can result from the generation of reactive oxygen species with the interplay of oxygen with reduced iron species (Fe(II) and/or Fe(0)) or from the disturbance of the electronic and/or ionic transport chains due to the strong affinity of the nanoparticles for the cell membrane.     

Effect of seed coat fragments on cotton yarn structure: impact of fragment size,attached fibres and position within yarn core

Seed coat fragments are a major source of cotton yarn imperfections. This article discusses the factors influencing the disruption caused by seed coat fragments in ring-spun yarn structure with a focus on three characteristics: the fragment's size, the amount of fibres attached to it and its position relative to the yarn core. The three characteristics were investigated through two experiments involving various types of yarn defects and a range of ring-spun yarn counts. Results presented in this article indicate that the three factors considered have a significant influence on the intensity of the disruption the seed coat fragment causes in the yarn structure, and are determinant of the type of defect that this disruption engenders (short/long defect).     

Nouveau type structural dans la chimie des phosphures : Le compose ternaire Ni20Zr6P13. Preparation,structure et proprietes

Two new compounds Ni₁₂Zr₂P₇ and Ni₂₀Zr₆P₁₃ were synthesized in the NiZrP system by reacting the constituent elements. Ni₁₂Zr₂P₇ is of the Fe₁₂Zr₂P₇-type while Ni₂₀Zr₆P₁₃ appears as a new structural type in the chemistry of transition metal phosphides. Its unit cell is hexagonal with space group P6̄ and contains one formula unit. The X-ray structure was studied from three-dimensional single-crystal counter data and was refined down to R = 0.040 for 221 independent reflections. The structure of Ni₂₀Zr₆P₁₃ can be described as built up by two groups of three phosphorus trigonal prisms occupied by the zirconium atoms. In each group, the |ZrP₆| prisms are linked together by common edges in order to generate triangular phosphorus sites occupied by nickel atoms. In addition, nickel atoms are also in tetrahedral and square-planar pyramidal phosphorus sites. A comparative study with the Fe₂P- and Co₄Hf₂P₃-type structures having the same metal/non metal ratio as in Ni₁₂Zr₂P₇ and Ni₂₀Zr₆P₁₃ is also discussed. A nearly temperature independent paramagetism and a metallic conduction deducted from magnetic and electrical measurements exhibit the metallic behavior for these new compounds.     

Geometry of Interaction V: Logic in the hyperfinite factor

Geometry of Interaction is a transcendental syntax developed in the framework of operator algebras. This fifth installment of the program takes place inside a von Neumann algebra, the hyperfinite factor. It provides a built-in interpretation of cut-elimination as well as an explanation for light, i.e., complexity sensitive, logics.