Optimization of the physical refining of sunflower oil concerning the final contents of trans-fatty acids

The final contents of total and individual trans-fatty acids of sunflower oil, produced during the deacidification step of physical refining were obtained using a computational simulation program that considered cis-trans isomerization reaction features for oleic, linoleic, and linolenic acids attached to the glycerol part of triacylglycerols. The impact of process variables, such as temperature and liquid flow rate, and of equipment configuration parameters, such as liquid height, diameter, and number of stages, that influence the retention time of the oil in the equipment was analyzed using the response-surface methodology (RSM). The computational simulation and the RSM results were used in two different optimization methods, aiming to minimize final levels of total and individual trans-fatty acids (trans-FA), while keeping neutral oil loss and final oil acidity at low values. The main goal of this work was to indicate that computational simulation, based on a careful modeling of the reaction system, combined with optimization could be an important tool for indicating better processing conditions in industrial physical refining plants of vegetable oils, concerning trans-FA formation.

A Graphite-Polyurethane Composite Electrode for the Analysis of Furosemide

A graphite-polyurethane composite electrode has been used for the determination of furosemide, a antihypertensive drug, in pharmaceutical samples by anodic oxidation. Cyclic voltammetry and electrochemical impedance spectroscopy were used to characterize the electrooxidation process at +1.0 V vs. SCE over a wide pH range, with the result that no adsorption of analyte or products occurs, unlike at other carbon-based electrode materials. Quantification was carried out using cyclic voltammetry, differential pulse voltammetry, and square-wave voltammetry. Linear ranges were determined (up to 21 mu mol L-1 with cyclic voltammetry) as well as limits of detection (0.15 mu mol L-1 by differential pulse voltammetry). Four different types of commercial samples were successfully analyzed. Recovery tests were performed which agreed with those obtained by spectrophotometric evaluation. The advantages of this electrode material for repetitive analyzes, due to the fact that no electrode surface renewal is needed owing to the lack of adsorption, are highlighted.

Electrochemical Behavior of Verapamil at Graphite-Polyurethane Composite Electrodes: Determination of Release Profiles in Pharmaceutical Samples

A solid graphite-polyurethane composite electrode has been used to determine release profiles of verapamil, a calcium-channel blocker. The electro-oxidation process was characterized by cyclic voltammetry and electrochemical impedance spectroscopy and showed no adsorption of analyte or oxidation products, unlike at other carbon-based electrodes. Quantification gave linear ranges up to 40molL-1 with cyclic voltammetry and detection limits of 0.7molL-1 by differential pulse and square-wave voltammetry. Commercial product samples were successfully analyzed with results equal to those from spectrophotometry. Because no electrode surface renewal is needed, this electrode material has many advantages.

Silver Nanoparticles Obtained in PAH/PAA-Based Multilayers by Photochemical Reaction

Carboxylic acid groups in PAH/PAA-based multilayers bind silver cations by ion exchange with the acid protons. The aggregation and spatial distribution of the nanoparticles proved to be dependent oil the process used to reduce the silver acetate aqueous solution. The reducing method with ambient light formed larger nanoparticles with diameters ranging from 4-50 nm in comparison with the reduction method using UV light, which gave particles with diameters of 2-4 nm The high toughness of samples reduced by ambient light is a result of two population distributions of particle sizes caused by different mechanisms when compared with the UV light process. According to these phenomena, a judicious choice of the spectral source call be used as a way to control the type and size of silver nanoparticles formed on PEMs. Depending on the energy of the light source, the Ag nanoparticles present cubic and/or hexagonal crystallographic structures, as confirmed by XRD. Beyond the kinetically controlled process of UV photoinduced cluster formation, the annealing produced by UV light allowed a second mechanism to modify the growth rates, spatial distribution, and phases.

Insuring cleaner oceans: the economics of oil pollution prevention

The current system of controlling oil spills involves a complex relationship of international, federal and state law, which has not proven to be very effective. The multiple layers of regulation often leave shipowners unsure of the laws facing them. Furthemore, nations have had difficulty enforcing these legal requirements. This thesis deals with the role marine insurance can play within the existing system of legislation to provide a strong preventative influence that is simple and cost-effective to enforce. In principle, insurance has two ways of enforcing higher safety standards and limiting the risk of an accident occurring. The first is through the use of insurance premiums that are based on the level of care taken by the insured. This means that a person engaging in riskier behavior faces a higher insurance premium, because their actions increase the probability of an accident occurring. The second method, available to the insurer, is collectively known as cancellation provisions or underwriting clauses. These are clauses written into an insurance contract that invalidates the agreement when certain conditions are not met by the insured The problem has been that obtaining information about the behavior of an insured party requires monitoring and that incurs a cost to the insurer. The application of these principles proves to be a more complicated matter. The modern marine insurance industry is a complicated system of multiple contracts, through different insurers, that covers the many facets of oil transportation. Their business practices have resulted in policy packages that cross the neat bounds of individual, specific insurance coverage. This paper shows that insurance can improve safety standards in three general areas -crew training, hull and equipment construction and maintenance, and routing schemes and exclusionary zones. With crew, hull and equipment, underwriting clauses can be used to ensure that minimum standards are met by the insured. Premiums can then be structured to reflect the additional care taken by the insured above and beyond these minimum standards. Routing schemes are traffic flow systems applied to congested waterways, such as the entrance to New York harbor. Using natural obstacles or manmade dividers, ships are separated into two lanes of opposing traffic, similar to a road. Exclusionary zones are marine areas designated off limits to tanker traffic either because of a sensitive ecosystem or because local knowledge is required of the region to ensure safe navigation. Underwriting clauses can be used to nullify an insurance contract when a tanker is not in compliance with established exclusionary zones or routing schemes.

Ontology-based metadata for e-learning content

Nowadays, the popularity of the Web encourages the development of Hypermedia Systems dedicated to e-learning. Nevertheless, most of the available Web teaching systems apply the traditional paper-based learning resources presented as HTML pages making no use of the new capabilities provided by the Web. There is a challenge to develop educative systems that adapt the educative content to the style of learning, context and background of each student. Another research issue is the capacity to interoperate on the Web reusing learning objects. This work presents an approach to address these two issues by using the technologies of the Semantic Web. The approach presented here models the knowledge of the educative content and the learner’s profile with ontologies whose vocabularies are a refinement of those defined on standards situated on the Web as reference points to provide semantics. Ontologies enable the representation of metadata concerning simple learning objects and the rules that define the way that they can feasibly be assembled to configure more complex ones. These complex learning objects could be created dynamically according to the learners’ profile by intelligent agents that use the ontologies as the source of their beliefs. Interoperability issues were addressed by using an application profile of the IEEE LOM- Learning Object Metadata standard.

Pricing and hedging of oil futures : a unifying approach

We develop and empirically test a continuous time equilibrium model for the pricing of oil futures. The model provides a link between no-arbitrage models and expectation oriented models. It highlights the role of inventories for the identification of different pricing regimes. In an empirical study the hedging performance of our model is compared with five other one- and two-factor pricing models. The hedging problem considered is related to Metallgesellschaft´s strategy to hedge long-term forward commitments with short-term futures. The results show that the downside risk distribution of our inventory based model stochastically dominates those of the other models.

Energy balance for biodiesel production by the castor bean crop (Ricinus communis L.)

The castor bean crop (Ricinus communis L.) has acquired prestige due to industries interest in the oil quality and recently for new sources of energy demand. The experiment that served as basis for the data used in this study was conducted at the Lageado Experimental Farm, in Botucatu - SP, 2008. This study aimed to avaluate the crop viability through energy balance and energy efficiency since the implantation until biodiesel production using parameters of consumption in operational management for installation and maintenance of culture harvest and oil production. The soil management operations, sow and harvest consumed the total of 266.20 MJ ha(-1), gathering with the fertilizers, pesticides, fuels, lubricants, labor, seed and industrial processing totaled 56,808 MJ ha(-1) of energy inputs. The energy production was 72,814.00 MJ ha(-1). The industry still lacks studies thal would contribution data collection and more specific energy coefficients. The castor beans cultivation was considered efficient allowing again of 15983.44 MJ ha(-1) equivalent to about 415 liters of diesel oil.

Enhancement of thermal stability, strength and extensibility of lipid-based polyurethanes with cellulose-based nanofibers

Cellulose was extracted from lignocellulosic fibers and nanocrystalline cellulose (NC) prepared by alkali treatment of the fiber, steam explosion of the mercerized fiber, bleaching of the steam exploded fiber and finally acid treatment by 5% oxalic acid followed again by steam explosion. The average length and diameter of the NC were between 200-250 nm and 4-5 nm, respectively, in a monodisperse distribution. Different concentrations of the NC (0.1, 0.5, 1.0, 1.5, 2.0 and 2.5% by weight) were dispersed non-covalently into a completely bio-based thermoplastic polyurethane (TPU) derived entirely from oleic acid. The physical properties of the TPU nanocomposites were assessed by Fourier Transform Infra-Red spectroscopy (FTIR), Thermo-Gravimetric Analysis (TGA), Differential Scanning Calorimetry (DSC), X-Ray Diffraction (XRD), Dynamic Mechanical Analysis (DMA) and Mechanical Properties Analysis. The nanocomposites demonstrated enhanced stress and elongation at break and improved thermal stability compared to the neat TPU. The best results were obtained with 0.5% of NC in the TPU. The elongation at break of this sample was improved from 178% to 269% and its stress at break from 29.3 to 40.5 MPa. In this and all other samples the glass transition temperature, melting temperature and crystallization behavior were essentially unaffected. This finding suggests a potential method of increasing the strength and the elongation at break of typically brittle and weak lipid-based TPUs without alteration of the other physico-chemical properties of the polymer. (C) 2012 Elsevier Ltd. All rights reserved.

Synthesis and physical properties of lipid-based poly(ester-urethane)s, I: Effect of varying polyester segment length

Four aliphatic thermoplastic poly(ester-urethane)s (PEUs) with similar molecular weights but varying polyesters molecular weight (534-1488 g/mol) were prepared from polyester diols, obtained by melt condensation of Azelaic acid and 1,9-Nonanediol, and 1,7-heptamethylene di-isocyanate (HPMDI) all sourced from vegetable oil feedstock. The thermal, and mechanical properties, and crystal structure of PEUs were investigated using DSC, TGA, DMA, tensile analysis and WAXD. For sufficiently long polyester chain, WAXD data indicated no hydrogen bonds polyethylene (PE)-like crystalline packing and for short polyester chains, small crystal domains with significant H-bonded polyamide (PA)-like packing. Crystallinity decreased with decreasing polyester molecular weights. The polymorphism of PEUs and consequently their melting characteristics were found to be largely controlled by polyester segment length. TGA of the PEUs indicated improved thermal stability with decreasing polyester chain length, suggesting a stabilization effect by urethane groups. Mechanical properties investigated by DMA and tensile analysis were found to scale predictably with the overall crystallinity of PEUs. (C) 2012 Elsevier Ltd. All rights reserved.

Narrow row spacing and high plant population to short height castor genotypes in two cropping seasons

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

An electrochemical sensor for (L)-dopa based on oxovanadium-salen thin film electrode applied flow injection system

An oxovanadium-salen complex (NAP-ethylene-bis(salicylidenciminato) oxovanadium) thin film deposited on a graphite-polyurethane electrode was investigated with regard to its potential use for detection of L-dopa in flow injection system. The oxovanadium(IV)/oxovanadium(V) redox couple of the modified electrode was found to mediate the L-dopa oxidation before its use in the FIA system. Experimental parameters, such as pH of the carrier solution, flow rate, sample volume injection and probable interferents were investigated. Under the optimized FIA conditions, the amperometric signal was linearly dependent on the L-dopa concentration over the range 1.0 x 10(-1) to 1.0 x 10(-4) mol L-1 (I-anodic, mu A) = 0.01 + 0.25 [L-dopa mu mol L-1]) with a detection limit (S/N = 3) of 8.0 x 10(-7) mol L-1 and a sampling frequency of 90 h(-1) was achieved. For a concentration of 1.0 x 10(-5) mol L-1 L-dopa, the R.S.D. of nine consecutive measurements was 3.7%. (c) 2006 Elsevier B.V. All rights reserved.

Structural Properties Induced by the Composition of Biocompatible Phospholipid-Based Microemulsion and Amphotericin B Association

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Mathematical modeling of the ester oil-refrigerant R134A mixture two-phase flow with foam formation through a small diameter tube

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Genotoxicity and mutagenicity of Rosmarinus officinalis (Labiatae) essential oil in mammalian cells in vivo

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)