Metal speciation dynamics and bioavailability. 2. Radial diffusion effects in the microorganism range

The free ion activity model for the biouptake of metals from complex media is limited to cases where mass transfer is not flux determining. This paper follows a previous paper (Van Leeuwen, H. P. Environ. Sci. Technol. 1999, 33, 3743) where speciation dynamics and bioavailability of metals are analyzed in terms of bioconversion kinetics and simultaneous metal transport in the medium coupled with dissociation kinetics. Such analysis shows under what conditions labile complex species contribute to the biouptake process or, equivalently, under what conditions the free ion activity model is not obeyed. The present work addresses the theoretical extension of the expressions for the metal flux in the medium by a radial diffusion term so that these are also applicable in the microorganism size range. The transition from macroscopic to microscopic surfaces affects not only the nature of the flux but also the extent of lability of complex species (Van Leeuwen, H. P.; Pinheiro, J. P. J. Electroanal. Chem. 1999, 471, 55), and this can have a dramatic influence on the rate of biouptake of metal ions. Labilities of metal complexes and the ensuing limiting metal fluxes are therefore systematically analyzed for various dimensions of the uptaking surface. Different conditions of bioaffinities and bioconversion capacities are considered, and a number of examples of metal complexes with specified kinetic features are discussed.     

Ca2+ differentially regulates conventional protein kinase Cs' membrane interaction and activation

The regulation of conventional protein kinase Cs by Ca2+ was examined by determining how this cation affects the enzyme's 1) membrane binding and catalytic function and 2) conformation. In the first part, we show that significantly lower concentrations of Ca2+ are required to effect half-maximal membrane binding than to half-maximally activate the enzyme. The disparity between binding and activation kinetics is most striking for protein kinase C betaII, where the concentration of Ca2+ promoting half-maximal membrane binding is approximately 40-fold higher than the apparent Km for Ca2+ for activation. In addition, the Ca2+ requirement for activation of protein kinase C betaII is an order of magnitude greater than that for the alternatively spliced protein kinase C betaI; these isozymes differ only in 50 amino acids at the carboxyl terminus, revealing that residues in the carboxyl terminus influence the enzyme's Ca2+ regulation. In the second part, we use proteases as conformational probes to show that Ca2+dependent membrane binding and Ca2+-dependent activation involve two distinct sets of structural changes in protein kinase C betaII. Three separate domains spanning the entire protein participate in these conformational changes, suggesting significant interdomain interactions. A highly localized hinge motion between the regulatory and catalytic halves of the protein accompanies membrane binding; release of the carboxyl terminus accompanies the low affinity membrane binding mediated by concentrations of Ca2+ too low to promote catalysis; and exposure of the amino-terminal pseudosubstrate and masking of the carboxyl terminus accompany catalysis. In summary, these data reveal that structural determinants unique to each isozyme of protein kinase C dictate the enzyme's Ca2+-dependent affinity for acidic membranes and show that, surprisingly, some of these determinants are in the carboxyl terminus of the enzyme, distal from the Ca2+-binding site in the amino-terminal regulatory domain.     

IgG from Adult Atopic Dermatitis (AD) Patients Induces Thymic IL-22 Production and CLA Expression on CD4+ T Cells: Possible Epigenetic Implications Mediated by miRNA

Atopic dermatitis (AD) is a common relapsing inflammatory skin disorder characterized by immune-mediated inflammation and epidermal barrier dysfunction. The pathogenesis of AD is multifactorial and has not been fully elucidated to date. This study aimed to evaluate whether serum IgG from adult AD patients could modulate the thymic maturation of IL-22-producing T cells and CLA+ T cells of non-atopic infants. Given that miRNAs regulate immune response genes, we evaluated whether miRNA expression is also altered in cultured thymocytes. Thymocytes were cultured with purified IgG from AD patients or control conditions (mock, Intravenous-IgG (IVIg), non-atopic IgG, or atopic non-AD IgG). Using flow cytometry analysis, we assessed the expression of CLA and intracellular levels of IL-4, IFN-γ, and IL-22 on double-positive T cells (DP T), CD4 T cells, or CD8 T cells. We also investigated the frequency of IgG isotypes and their direct interaction with the thymic T cells membrane. The miRNA profiles were evaluated by the Illumina small RNA-seq approach. MiRNA target gene prediction and enrichment analyses were performed using bioinformatics. Increased frequencies of IL-22 and CLA+ producing CD4+ T cells cultured with IgG of AD patients was seen in non-atopic infant thymocytes compared to all control conditions. No alterations were observed in the frequency of IgG isotypes among evaluated IgG pools. Evidence for a direct interaction between IgG and thymic DP T, CD4 T, and CD8 T cells is presented. The small RNA-seq analysis identified ten mature miRNAs that were modulated by AD IgG compared to mock condition (miR-181b-5p, hsa-miR-130b-3p, hsa-miR-26a-5p, hsa-miR-4497, has-miR-146a, hsa-let-7i-5p, hsa-miR-342-3p, has-miR-148a-3p, has-miR-92a and has-miR-4492). The prediction of the targetome of the seven dysregulated miRNAs between AD and mock control revealed 122 putative targets, and functional and pathway enrichment analyses were performed. Our results enhance our understanding of the mechanism by which IgG can collaborate in thymic T cells in the setting of infant AD.     

Amphiphilic Pentablock Copolymers Prepared from Pluronic and ε-Caprolactone by Enzymatic Ring Opening Polymerization

Amphiphilic copolymers are appealing materials because of their interesting architecture and tunable properties. In view of their application in the biomedical field, the preparation of these materials should avoid the use of toxic compounds as catalysts. Therefore, enzymatic catalysis is a suitable alternative to common synthetic routes. Pentablock copolymers (CUC) were synthesized with high yields by ring-opening polymerization of ε-caprolactone (ε-CL) initiated by Pluronic (EPE) and catalyzed by Candida antarctica lipase B enzyme. The variables to study the structure–property relationship were EPEs’ molecular weight and molar ratios between ε-CL monomer and EPE macro-initiator (M/In). The obtained copolymers were chemically characterized, the molecular weight determined, and morphologies evaluated. The results suggest an interaction between the reaction time and M/In variables. There was a correlation between the differential scanning calorimetry data with those of X-ray diffraction (WAXD). The length of the central block of CUC copolymers may have an important role in the crystal formation. WAXD analyses indicated that a micro-phase separation takes place in all the prepared copolymers. Preliminary cytotoxicity experiments on the extracts of the polymer confirmed that these materials are nontoxic.     

Short communication: High frequency of β-lactam-resistant Staphylococcus aureus in artisanal coalho cheese made from goat milk produced in northeastern Brazil

Reports of β-lactam-resistant Staphylococcus aureus in artisanal goat cheese are increasing, and this phenomenon is relevant to public health. The objective of the present study was to determine the prevalence of S. aureus strains carrying the blaZ and mecA resistance genes, as well as the genes encoding the staphylococcal enterotoxins SEA, SEB, SEC, SED, SEE, and TSST-1 in artisanal coalho cheese made from goat milk produced in northeastern Brazil. We used biochemical and molecular tests to characterize 54 S. aureus isolates found in artisanal coalho cheese collected from commercial establishments producing animal products in 11 municipalities of Pernambuco State, Brazil. A PCR analysis revealed that 42.6% (23/54) of the isolates were positive for the blaZ gene, and 7.4% (4/54) were resistant to methicillin by phenotypic testing. We did not detect mecA or any genes encoding enterotoxins. The presence of S. aureus carriers of the blaZ gene and the identification of methicillin-resistant S. aureus strains are of concern for the health of consumers of this type of cheese.     

Cohesive strength of nanocrystalline ZnO:Ga thin films deposited at room temperature

In this study, transparent conducting nanocrystalline ZnO:Ga (GZO) films were deposited by dc magnetron sputtering at room temperature on polymers (and glass for comparison). Electrical resistivities of 8.8 × 10-4 and 2.2 × 10-3 Ω cm were obtained for films deposited on glass and polymers, respectively. The crack onset strain (COS) and the cohesive strength of the coatings were investigated by means of tensile testing. The COS is similar for different GZO coatings and occurs for nominal strains approx. 1%. The cohesive strength of coatings, which was evaluated from the initial part of the crack density evolution, was found to be between 1.3 and 1.4 GPa. For these calculations, a Young's modulus of 112 GPa was used, evaluated by nanoindentation.     

Antioxidant intake among Brazilian adults - The Brazilian Osteoporosis Study (BRAZOS): a cross-sectional study

Background  

Antioxidant nutrient intake and the lesser formation of free radicals seem to contribute to chronic diseases. The aim of the present study was to evaluate the intake profile of the main dietary antioxidants in a representative sample of the adult Brazilian population and discuss the main consequences of a low intake of these micronutrients on overall health.     

SEM study of the morphology of asymmetric cellulose acetate membranes produced from recycled agro-industrial residues: sugarcane bagasse and mango seeds

Cellulose, obtained both from sugarcane bagasse and mango seeds, was used for synthesizing cellulose acetate in order to produce asymmetric membranes. These were compared to membranes of commercial cellulose acetate (Rhodia). All produced membranes were asymmetric, characterized by the presence of a dense skin and a porous support. Differences regarding the morphology of the surfaces as well as of the porous support can be noticed. Scanning Electron Microscopy (SEM) showed that the morphology of the superficial layer, responsible for transport, depends on the different lignin content of the starting material and also on the viscosity average molecular weight of the cellulose acetates produced from sugarcane bagasse, mango seed, and Rhodia’s commercial cellulose acetate.     

Effect of itaconic acid on the wet scrub resistance of highly pigmented paints for architectural coatings

This study investigates the influence of carboxylic monomers, such as itaconic acid (IA), on the colloidal properties of the latexes made by semi-continuous emulsion copolymerization of styrene (STy) with n-butyl acrylate (BA). A number of copolymerization runs were carried out with different IA concentrations. The effect of functional monomer on the overall conversion, the colloidal properties of the latexes, and the distribution of the carboxylic groups (buried, particle surface and aqueous phase) were examined. The carboxylic groups present in the latexes were analyzed using conductimetric and potentiometric titrations. The behavior of the IA on the wet scrub resistance of highly pigmented paints for architectural coatings was examined and correlated with the distribution of the carboxylic groups. The results obtained showed that the properties of highly pigmented paints are greatly dependent on the amount and distribution of the carboxylic groups. The carboxylic acid distributed in the aqueous phase has a strong influence on the wet scrub resistance and on the characteristics of the final products.