Chemically modified babassu coconut (<Emphasis Type="Italic">Orbignya sp.)</Emphasis> biopolymer: characterization and development of a thin film for its application in electrochemical sensors

The babassu coconut is a plant very abundant in northeast of Brazil and other countries, and any part of plant and fruit becomes residue. In this study, babassu mesocarp (Orbignya sp) (BM) was chemically modified with phthalic anhydride (BMPA) to increase its solubility in an aqueous medium, and thus facilitate its processing in the form of thin films. The reaction of modification of the babassu mesocarp with phthalic anhydride (PA), obtaining BMPA, was confirmed by FTIR, XRD, TG/DTG, Zeta Potential and SEM analysis, from the differences in the bands of the FTIR spectra, increase in crystallinity, new thermal profile, changes in zeta potential value and morphology, respectively. The thin monolayer films of BM and BMPA were produced by the self-assembly monolayer (SAM) technique, and adsorbed onto conductive glass substrates (tin-doped indium oxide, ITO). The electroactive properties of these thin films were evaluated by cyclic voltammetry (CV). BM exhibited a pair redox pair process of +0.57 V(oxidation) and?+?0.19 V (reduction) for BM. In BMPA these redox processes were observed at +0.37 V (oxidation) and 0.24 V vs. ECS (reduction), verifying that both BM and BMPA are electroactive materials that can be used in the construction of sensor platforms, without the necessity of being conjugated with other electroactive materials, such as conductive polymers, metal phthalocyanines, or dyes. Furthermore, under the experimental conditions used, the BMPA presented a more reversible redox process and higher electrochemical stability in comparison to BM. This effect occurs because BMPA has higher solubility in aqueous media, which favors the preparation of films with smaller grain sizes compared to BM films, as observed by Atomic Force Microscopy (AFM). This study showed that BMPA is a new material with potential for applications in electrochemical sensors.

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Graphical abstract Obtaining and modifying babassu mesocarp for the electrochemical studies

     

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.     

Crystallization of porcine insulin with carbon dioxide as acidifying agent

Recent studies on the use of volatile electrolytes such as CO₂ in protein precipitation showed that these agents are a promising alternative to the conventional acids. This use of volatile electrolytes prevents protein denaturation due to local pH extremes, and saline effluent generation is greatly reduced, as the volatile electrolyte may be separated and recovered from solution just by pressure release. In this work, insulin was successfully crystallized in the presence of zinc using CO₂ as acidifying agent. The crystals obtained were rhombohedral, a common shape for porcine insulin crystals that contain zinc in their structure, and their average size varied with the mixing applied.     

Optimization of Oil Oxidation by Response Surface Methodology and the Application of this Model to Evaluate Antioxidants

The oxidative stability of oils is a complex process influenced by several factors, making the evaluation of antioxidant effects of new compounds difficult. Thus, the objective of this study was to apply a factorial design to obtain the combination of factors that maximizes the formation of oil oxidation products, and use this model to evaluate the antioxidant activity of different compounds. Temperature, Fe²⁺ and ascorbyl palmitate were evaluated in two full-factorial designs (2³ and 3²). The validated optimized oxidation model was obtained by adding 1.47 mmol/L of Fe²⁺ and 1.54 mmol/L of ascorbyl palmitate to flaxseed oil stripped of tocopherol kept at 40 °C for 8 days. Antioxidant activities of six compounds were evaluated using this model. All antioxidant samples were statistically different (p < 0.001) at 200 ppm concentration, indicating the efficiency of the optimized model to evaluate the antioxidant action of natural and synthetic compounds.     

Anticoagulant, Antioxidant and Antitumor Activities of Heterofucans from the Seaweed Dictyopteris delicatula

In the present study, six families of sulfated polysaccharides were obtained from seaweed Dictyopteris delicatula by proteolytic digestion, followed by acetone fractionation and molecular sieving on Sephadex G-100. Chemical analyses demonstrated that all polysaccharides contain heterofucans composed mainly of fucose, xylose, glucose, galactose, uronic acid, and sulfate. The fucans F0.5v and F0.7v at 1.0 mg/mL showed high ferric chelating activity (～45%), whereas fucans F1.3v (0.5 mg/mL) showed considerable reducing power, about 53.2% of the activity of vitamin C. The fucan F1.5v presented the most prominent anticoagulant activity. The best antiproliferative activity was found with fucans F1.3v and F0.7v. However, F1.3v activity was much higher than F0.7v inhibiting almost 100% of HeLa cell proliferation. These fucans have been selected for further studies on structural characterization as well as in vivo experiments, which are already in progress.     

XANES investigation of the enhanced chemical stability of Pd in supported Pd–Mo catalysts

The XANES (X-ray absorption near edge structure) technique was used to study Pd and Mo catalysts deposited on supported Al₂O₃/SiO₂ and Al₂O₃/Si-MCM-41 in the form of monometallic and bimetallic systems. The results indicate that Pd has stronger chemical stability when in the presence of Mo and is always in the metallic form, which is surprising, because the samples were not subjected to reducing conditions prior to the measurements. The increased stability was attributed to the formation of a core-shell structure with a Pd rich core and a Mo rich surface.     

Preliminary Results on an Approach for the Quantification of Lignin-Carbohydrate Complexes (LCC) in Hardwood Pulps

Abstract

The literature on biomass research contains many references to lignin-carbohydrate complexes (LCC) decreasing the rate of delignification in chemical pulp production, decreasing the yield of cellulosic ethanol via fermentation, and decreasing forage digestibility. However, it is difficult to find correlations between rates of the processes above and initial LCC concentration. One of the main reasons for the lack of such correlations is the absence of methods for accurate quantification of LCC. In this investigation, repeatable and reproducible determinations of bound sugars at monomeric concentrations as low as 0.3 wt% on enzymatic lignin (EL) have been achieved. The bound sugars are hydrolyzed by H₂SO₄, most likely as low molecular weight oligomers. In the same H₂SO₄ treatment, the oligomers are hydrolyzed to monomers which are subsequently quantified by ¹H NMR analyses. A significant enrichment of bound arabinan was previously reported when a crude milled wood lignin (MWL) was compared to the starting wood meal. A similar arabinan enrichment was observed for ELs from kraft and soda-AQ (SAQ) pulps in the present study. Also, well-resolved cross-peaks have been obtained in 2D HSQC NMR analyses of ELs. It has so far been confirmed that the EL from a 30.6 kappa number SAQ pulp from sugar maple contained ～30% more benzyl ethers linked to primary-OH groups in sugar units than the corresponding EL from a 33.7 kappa number kraft pulp.     

Oxygen Reduction on Structurally Well Defined,Bimetallic PtRu Surfaces: Monolayer PtxRu1−x/Ru(0001) Surface Alloys Versus Pt Film Covered Ru(0001)

The electrocatalytic activity of different, structurally well defined bimetallic PtRu surfaces in the oxygen reduction reaction was investigated by a combination of scanning tunnelling microscopy and electrochemical measurements performed under controlled mass transport conditions in a flow cell. We compare the effect of pseudomorphic Pt cover layers, mimicking the situation in a core–shell Pt/Ru nanoparticle, and of mixed Pt_xRu_1?x monolayer surface alloys, reflecting the situation in an alloyed nanoparticle. The results unambiguously demonstrate that these bimetallic surfaces can reach activities well in excess of that of Pt(111), both for the film surfaces and the surface alloys, by optimizing the Pt surface content (surface alloys) or the Pt film thickness (film surfaces). The results are compared with simulated kinetic current–potential profiles based on existent density functional theory calculations (Greeley and Nørskov, J Phys Chem C 113:4932, 2009; Lischka et al., Electrochim Acta 52:2219, 2007) revealing very good agreement in trends. Potential and limits of this approach are discussed.     

Bacterial polymers as materials for the development of micro/nanoparticles

Bacterial polysaccharides and polyhydroxyalkanoates present physical and chemical characteristics that impart them diverse functional properties, including the ability to produce structures from nano- to macroscale (e.g., spheres, capsules, beads). Such structures may be specially designed to fulfill the requirements of specific applications in different areas, either alone or conjugated with other polymers by means of ionic interactions, hydrogen bonding, or chemical reactions. The interest on using such biomaterials has been increasing due to their unique functional properties, nontoxicity, biodegradability, and biocompatibility. The fields of application of bacterial polymers-based structures include drug delivery, biomedicine, food products, environment, and agriculture, among others.