Polymethacrylates: Pour point depressants in diesel oil

A variety of techniques have been employed in order to reduce problems caused by the crystallization of paraffin during the production and/or transportation of paraffin oils and derivatives. Methacrylate copolymers are known as additives which reduce the pour point of these oils. This paper describes the synthesis, characterization and performance evaluation of these copolymers, having as an initial step the synthesis of the alkyl methacrylate monomers by transesterification of methyl methacrylate (MMA) with C₁₄, C₁₆ and C₁₈ fatty alcohols. The copolymerization of these monomers with MMA was then performed, with molar ratios of 30:70, 50:50 and 70:30 for alkyl methacrylate:methyl methacrylate. All products were characterized by FTIR, ¹H NMR and gel permeation chromatography (GPC). All the methacrylic copolymers lead to a large reduction in the pour point of samples of Brazilian diesel oil. Oil samples containing 50 ppm of the polymeric additive with ca. 70% octadecyl methacrylate units showed a 22 °C reduction in their pour points, thus establishing the large efficiency of the products synthesized in this work.     

An extension of Mercer’s theory to L p

Let X be a topological space, either locally compact or first countable, endowed with a strictly positive measure ?? and ${\mathcal{K}:L^2(X,\nu)\to L^2(X,\nu)}$ an integral operator generated by a Mercer like kernel K. In this paper we extend Mercer??s theory for K and ${\mathcal{K}}$ under the assumption that the function ${x\in X\to K(x,x)}$ belongs to some L ^p/2(X, ??), p??? 1. In particular, we obtain series representations for K and some powers of ${\mathcal{K}}$ , with convergence in the p-mean, and show that the range of certain powers of ${\mathcal{K}}$ contains continuous functions only. These results are used to estimate the approximation numbers of a modified version of ${\mathcal{K}}$ acting on L ^p (X, ??).     

Elemental composition of freshwater sponges Drulia uruguayensis and Drulia cristata collected in the Tapajós River

Sponges are aquatic, predominantly marine animals, but are also represented by several families that inhabit freshwater environments. All freshwater sponges are included in the Demospongiae class and so have skeletons composed of silicious spicules. Because they are filter feeders, they have high potential for bioaccumulation of metals, with various implications and applications in environmental chemistry. This study describes the inorganic chemical composition of two Amazonian species of freshwater sponges: Drulla cristata and Drulla uruguayensis, using energy dispersive X‐ray fluorescence. In both species, the major constituent was silicon (36.75% and 36.05%, respectively), followed by aluminum. Elements such as sulfur, chlorine, copper, and titanium were selectively accumulated and were detected only in the species D. cristata, suggesting its use in environmental characterization studies. Copyright © 2012 John Wiley & Sons, Ltd.     

Electrochemical study and voltammetric determination of sodium diethyldithiocarbamate using silver nanoparticles solid amalgam electrode

We report in this work, for the first time, the voltammetric study and the development of an electroanalytical method for the determination of sodium diethyldithiocarbamate (Na-DDC) using solid amalgam electrode fabricated with silver nanoparticles. The experimental parameters were studied and the best voltammetric response was reached when using 0.02 mol L^–1 Britton–Robinson buffer (pH = 5.5). Cyclic voltammograms of the substance presented two voltammetric signals: one cathodic peak at E_p = – 0.55 V and one anodic peak at E_p = – 0.49 V. The redox process of Na-DDC showed itself as an adsorption-controlled and quasi-reversible system. A mechanism for this electrochemical reaction was proposed. The analytical studies employed square-wave adsorptive stripping voltammetry (SWAdSV) and were based on the cathodic signal given by Na-DDC. Good linearity was observed in the concentration range from 2.83 × 10^–7 mol L^–1 to 6.89 × 10^–6 mol L^–1. The obtained limit of detection was 7.26 × 10^–8 mol L^–1. The electroanalytical approach described here was successfully employed for the determination of Na-DDC in river water at levels of concentration from 1.46 × 10^–7 mol L^–1 to 1.46 × 10^–6 mol L^–1 with good repeatability and reproducibility (RSD values of 4.2% and 5.9%, respectively). The values found during these determinations presented good concordance when compared with the expected values. According to the data presented here, the solid amalgam electrode fabricated with silver nanoparticles may be seen as an effective and green tool for the electrochemical analysis of Na-DDC and also other reducible compounds that usually require mercury-based electrode surfaces.     

A necessary and sufficient condition for strictly positive definite functions on spheres

We give a necessary and sufficient condition for the strict positive-definiteness of real and continuous functions on spheres of dimension greater than one.

     

Voltammetric determination of herbicide molinate in river water and rice samples using solid silver amalgam electrode fabricated with nanoparticles

The evaluation of the voltammetric behaviour and the determination of herbicide molinate were performed for the first time over the surface of solid amalgam electrode fabricated with silver nanoparticles using cyclic voltammetry and square-wave voltammetry techniques. The experimental and instrumental parameters were evaluated to reach the maximum analytical response for molinate. It was achieved when a medium composed of 0.04 mol L^?1 Britton–Robinson buffer at the pH value of 4.0 was used. Under these conditions, molinate showed one pronounced reduction peak at E_p = ?0.37 V (vs. Ag/AgCl 3 mol L^?1) that was characterised as an irreversible system. An analytical curve was constructed at the concentration range from 9.36 to 243.49 µg L^?1 and a limit of detection of 2.34 µg L^?1 was obtained. The amalgam electrode presented good stability during the measurements with relative standard deviation (RSD) values of 2.9% for the repeatability and 5.4% for the reproducibility. The voltammetric method developed here could be conveniently applied for the determination of molinate in river water and rice spiked samples at levels below those established on the legislations of European Union and Brazil with good accuracy (RSD of less than 5% for all samples). Comparison with HPLC technique was carried out and the results indicated satisfactory concordance. According to the results depicted here, the silver nanoparticles solid amalgam electrode showed itself highly sensitive and an interesting alternative for the routine analysis of molinate in water and food samples. Furthermore, it introduces an environmentally acceptable alternative to the mercury electrodes, most commonly used for determination of reducible pesticides.     

Evaluation of DNA damage and cytotoxicity of polyurethane-based nano- and microparticles as promising biomaterials for drug delivery systems

The in vitro cytotoxicity and DNA damage evaluation of biodegradable polyurethane-based micro- and nanoparticles were carried out on animal fibroblasts. For cytotoxicity measurement and primary DNA damage evaluation, MTT and Comet assays were used, respectively. Different formulations were tested to evaluate the influence of chemical composition and physicochemical characteristics of particles on cell toxicity. No inhibition of cells growth surrounding the polyurethane particles was observed. On the other hand, a decrease of cell viability was verified when the anionic surfactant sodium dodecyl sulfate (SDS) was used as droplets stabilizer of monomeric phase. Polyurethane nanoparticles stabilized with Tween 80 and Pluronic F68 caused minor cytotoxic effects. These results indicated that the surface charge plays an important role on cytotoxicity. Particles synthesized from MDI displayed a higher cytotoxicity than those synthesized from IPDI. Size and physicochemical properties of the particles may explain the higher degree of DNA damage produced by two tested formulations. In this way, a rational choice of particles’ constituents based on their cytotoxicity and genotoxicity could be very useful for conceiving biomaterials to be used as drug delivering systems.     

Voltammetric determination of some organic compounds of arsenic reduced at the mercury electrode

Cyclic voltammetric scans for methylarsonic acid, dimethylarsinic acid and 3-acetamido-4-hydroxyphenylarsonic acid at a mercury electrode in an acidic medium show anodic adsorption waves when the starting potential is sufficiently negative; the related arsines are formed on the electrode. Detection limits are at the micromolar level for the absorption peak found at about ?0.1 V vs. SCE for all three compounds. Interferences are discussed.     

Electroanalytical Determination of Lidocaine in Pharmaceutical Preparations Using Boron‐Doped Diamond Electrodes

A new electroanalytical procedure was developed for the determination of lidocaine in commercial local anesthetics products containing lidocaine as the active ingredient. The procedure is based on the use of electrochemical methods as cyclic and square‐wave voltammetry, with boron‐doped diamond electrodes. The oxidation of lidocaine in Britton–Robinson buffer (0.1 mol L^?1) using this type of electrode gives rise to one irreversible peak in 1.68 V (versus Ag/AgCl). The detection and quantification limits obtained from pure water were 10.0 and 34.4 μg/L, respectively. The proposed electrochemical method was also successfully applied to the analysis of commercially available pharmaceutical preparations. The electrochemical responses of pharmaceutical preparations (gels) were identical to those of standard lidocaine. No influence of propyleneglycol present in the gels on the voltammetric responses was observed. Lidocaine recoveries ranged from 97.6% to 99.2%.     

Thermal Degradation of Natural Polymers

The thermal degradation of sodium hyaluronate, xanthan and methylcellulose was evaluated by thermogravimetric and infrared analysis. Kinetic parameters such as activation energy and pre-exponential factor were determined considering the Ozawa and Freeman–Carroll methods. The results suggest changes in the degradation mechanism with the fraction of mass loss for both the studied polysaccharides. The activation energy values determined by the Freeman–Carroll method are higher than those obtained by the Ozawa method under the same conditions, probably because in the first method a first order reaction was assumed and the thermal history effects were eliminated since only one TG curve was used to determine the kinetic parameters. Low thermal stability was observed for polyanions e.g. sodium hyaluronate (Na-Hy) and xanthan(XT) in comparison with methylcellulose (MC) which is a neutral polysaccharide. By infrared spectroscopy, it was observed that at low temperatures there occured only the scission of the exocyclic groups for both polysaccharides and that the scission of strong links in the backbone occurred at high temperatures, in agreement with the kinetic parameters determined for the degradation reaction. This revised version was published online in July 2006 with corrections to the Cover Date.