A mass transfer model applied to the supercritical extraction with CO2 of curcumins from turmeric rhizomes (Curcuma longa L)

ABSTRACT: Increasing restrictions on the use of artificial pigments in the food industry, imposed by the international market, have increased the importance of raw materials containing natural pigments. Of those natural substances with potential applications turmeric rhizomes (Curcuma longa L), are one of the most important natural sources of yellow coloring. Three different pigments (curcumin, desmetoxycurcumin, and bis-desmetoxycurcumin) constitute the curcuminoids. These pigments are largely used in the food industry as substitutes for synthetic dyes like tartrazin. Extraction of curcuminoids from tumeric rhizomes with supercritical CO2 can be applied as an alternative method to obtain curcuminoids, as natural pigments are in general unstable, and hence degrade when submitted to extraction with organic solvents at high temperatures. Extraction experiments were carried out in a supercritical extraction pilot plant at pressures between 25 and 30 MPa and a temperature of 318 K. The influence of drying pretreatment on extraction yield was evaluated by analyzing the mass transfer kinetics and the content of curcuminoids in the extracts during the course of extraction. The chemical identification of curcuminoids in both the extract and the residual solid was performed by spectrophotometry. Mass transfer within the solid matrix was described by a linear first-order desorption model, while that in the gas phase was described by a convective mass transfer model. Experimental results showed that the concentration profile for curcuminoids during the supercritical extraction process was higher when the turmeric rhizomes were submitted to a drying pretreatment at 343 K.

Supercritical extraction of pupunha (Guilielma speciosa) oil in a fixed bed using carbon dioxide

The pupunha (Guilielma speciosa) is the fruit of a palm tree typical of the Brazilian Northern region, whose stem is used as a source of heart of palm. The fruit, which is about 65% pulp, is a source of oil and carotenes. In the present work, an analysis of the kinetics of supercritical extraction of oil from the pupunha pulp is presented. Carbon dioxide was used as solvent. The extractions were carried out at 25 MPa and 323 K and 30 MPa and 318 K. The chemical composition of the extracts in terms of fatty acids was determined by gas chromatography. The amount of oleic acid, a saturated fatty acid, in the CO2 extracts was larger than that in the extract obtained with hexane. The overall extraction curves were modeled using the single-parameter model proposed in the literature to describe the desorption of toluene from activated coal.

Extraction mechanism of La3+ from hydrochloric acid solution using Cyanex 302

The solvent extraction of La3+ from hydrochloric acid solutions was investigated using his (2, 4, 4-trimethylpentyl) monothiophosphinic acid (Cyanex 302, HL) as an extractant. The effect of equilibrium of aqueous acidity on extraction of La3+ using Cyanex 302 In different diluents was discussed. The effects of extractant concentration and chloride ion on the extraction reaction were also studied. Stoichiometry of the extraction reactions and the nature of metal complexes formed were determined using slope analysis technique and IR measurement.

Tetrabutylammonium methacrylate as a novel receptor for selective extraction of sulphonylurea drugs from biological fluids using molecular imprinting

Glibenclamide (GLIB), an oral antidiabetic medication of the sulphonylurea drugs family, was stoichiometrically imprinted using tetrabutylammonium methacrylate as the functional monomer, for the first time in molecular imprinting, and utilising the sulphonylurea affinity for carboxylate anions. Solution association between the drug and the novel functional monomer was studied by 1H-NMR titrations, whereby evidence of sulphonylurea deprotonation followed by the formation of “narcissistic” GLIB dimers was found when tested in CDCl3, while an affinity constant in excess of 105 L mol-1 was measured in DMSO-d6. Detailed analysis of GLIB binding on the subsequently prepared imprinted and non-imprinted polymers confirmed deactivation of binding sites by exchange of a proton between GLIB and methacrylate, followed by extraction of the tetrabutylammonium counterion from the polymer matrix, resulting in overall reduced binding capacities and affinities by the imprinted material under equilibrium conditions. An optimised MI-SPE protocol, which included a binding site re-activation step, was developed for the extraction of GLIB from blood serum, whereby recoveries of up to 92.4% were obtained with exceptional sample clean-up.

Deep separation of benzene from cyclohexane by liquid extraction using ionic liquids as the solvent

Separation of benzene and cyclohexane is one of the most important and difficult processes in the petrochemical industry, especially for low benzene concentration. In this work, three ionic liquids (ILs), [Bmim][BF ₄], [Bpy][BF ₄], and [Bmim][SCN], were investigated as the solvent in the extraction of benzene from cyclohexane. The corresponding ternary liquid-liquid equilibria (LLE) were experimentally determined at T = 298.15 K and atmospheric pressure. The LLE data were correlated with the nonrandom two-liquid model, and the parameters were fitted. The separation capabilities of the ILs were evaluated in terms of the benzene distribution coefficient and solvent selectivity. The effect of the IL structure on the separation was explained based on a well-founded physical model, COSMO-RS. Finally, the extraction processes were defined, and the operation parameters were analyzed. It shows that the ILs studied are suitable solvents for the extractive separation of benzene and cyclohexane, and their separation efficiency can be generally ranked as [Bmim][BF ₄] > [Bpy][BF ₄] > [Bmim][SCN]. The extraction process for a feed with 15 mol % benzene was optimized. High product purity (cyclohexane 0.997) and high recovery efficiency (cyclohexane 96.9% and benzene 98.1%) can be reached. © 2012 American Chemical Society.

Removal of arsenic from contaminated soils using different salt extractants

This study presents an environmental-friendly and cost effective method for the extraction of arsenic from contaminated soils.<br />Laboratory experiments using inorganic salts, potassium phosphate (KH2PO4), potassium chloride (KCl), potassium nitrate (KNO3), potassium sulfate (K2SO4), and sodium perchlorate (NaClO4) were evaluated as arsenic extractants. An Andosol soil was artificially contaminated with arsenite [As(III)] and arsenate [As(V)]. The soil was washed in a batch process with different salt solutions in the pH range 3–11 for 24 hours at 20◦C. Among the various potassium and sodium salts tested, KH2PO4 was found to be highly effective in extracting arsenic from As(III)-soil attaining more than 80% and 40% from As(V)-soil in neutral pH range. Other salts were particularly ineffective in extraction of arsenic from both soils. More arsenic was extracted more from the As(III)-soil than the As(V)-soil.<br />

Generation of Testing Source Code for Object-Oriented Programs

Красимир Манев, Антон Желязков, Станимир Бойчев - В статията е представена имплементацията на последната фаза на автоматичен генератор на тестови данни за структурно тестване на софтуер, написан на обектно-ориентиран език за програмиране – генерирането на изходен код на тестващия модул. Някои детайли от имплементацията на останалите фази, които са важни за имплементацията на последната фаза, са представени първо. След това е описан и алгоритъмът за генериране на кода на тестващия модул.

Automating the extraction of quantities

The Automated Estimator and LCADesign are two early examples of nD modelling software which both rely on the extraction of quantities from CAD models to support their further processing. The issues of building information modelling (BIM), quantity takeoff for different purposes and automating quantity takeoff are discussed by comparing the aims and use of the two programs. The technical features of the two programs are also described. The technical issues around the use of 3D models is described together with implementation issues and comments about the implementation of the IFC specifications. Some user issues that emerged through the development process are described, with a summary of the generic research tasks which are necessary to fully support the use of BIM and nD modelling.

Automated surface sampling of lipids from worn contact lenses coupled with tandem mass spectrometry

The deposition of biological material (biofouling) onto polymeric contact lenses is thought to be a major contributor to lens discomfort and hence discontinuation of wear. We describe a method to characterize lipid deposits directly from worn contact lenses utilizing liquid extraction surface analysis coupled to tandem mass spectrometry (LESA-MS/MS). This technique effected facile and reproducible extraction of lipids from the contact lens surfaces and identified lipid molecular species representing all major classes present in human tear film. Our data show that LESA-MS/MS is a rapid and comprehensive technique for the characterization of lipid-related biofouling on polymer surfaces.

Selective Extraction of Mercury(II) by 1-Naphthylthiourea-Methyl Isobutyl Ketone System

Selective extraction of Mercury(II) using 1-naphthylthiourea-methyl isobutyl ketone (ANTU-MIBK) system from hydrochloric acid solutions (0.1-10 M) has been studied. Influence of foreign ions, acid and ligand concentrations has been investigated. Addition of ANTU in MIBK enhanced, extraction capacity of MIBK to several times. Low effect of foreign ions and high separation factors for a number of metal ions determined at 0.5 M hydrochloric acid concentration evaluated the proposed method efficient and selective. The experimental data obtained from application of the method for extraction of mercury from a synthetic aqueous solution reveal that more than 99% mercury can be separated from cadmium, zinc and selenium in a single step with five minutes equilibration

Water-compatible imprinted polymers for selective depletion of riboflavine from beverages

Artificial riboflavin receptors adapted to aqueous environments were studied for their ability to selectively extract riboflavine (Rf) from three types of beverages i.e. milk, beer and a multivitamin mixture. The basic receptor was first prepared by molecular imprinting in nonaqueous medium using a hydrogen-bond donor-acceptor-donor functional monomer (2,6-bis(acrylamido)pyridine), complementary to the imide motif of the template, riboflavin tetra-acetate as template and pentaerythritol triacrylate (PETA) as a hydrophilic cross-linking monomer. The polymer was then packed in columns and used for extraction of riboflavine from beverages. Riboflavine (Rf) was selectively removed from milk and an artificial vitamin mixture but the nonspecific binding was still significant, as judged from the binding of Rf to a control nonimprinted polymer. In order to suppress this nonspecific binding, attempts to hydrolytically hydrophilize the polymer matrix were performed. The preferred approach consisted in a controlled base hydrolysis of pendent unreacted acrylate groups, using hydroxides with differently sized counterions as reagents. This resulted in a decreased binding of Rf to both polymers, but to an equal extent implying a preferential suppression of the nonspecific contribution to the binding. The hydrophilized polymers, when subjected to beer, showed larger imprinting factors at lower phase ratios compared to the nontreated polymers and a maximum removal of 86% compared to 47% for the nonimprinted control polymer.

Antifungal activity of extracts from Atacama Desert fungi against Paracoccidioides brasiliensis and identification of Aspergillus felis as a promising source of natural bioactive compounds

Fungi of the genus Paracoccidioides are responsible for paracoccidioidomycosis. The occurrence of drug toxicity and relapse in this disease justify the development of new antifungal agents. Compounds extracted from fungal extract have showing antifungal activity. Extracts of 78 fungi isolated from rocks of the Atacama Desert were tested in a microdilution assay against Paracoccidioides brasiliensis Pb18. Approximately 18% (5) of the extracts showed minimum inhibitory concentration (MIC) values ≤ 125.0 μg/mL. Among these, extract from the fungus UFMGCB 8030 demonstrated the best results, with an MIC of 15.6 μg/mL. This isolate was identified as Aspergillus felis (by macro and micromorphologies, and internal transcribed spacer, β-tubulin, and ribosomal polymerase II gene analyses) and was grown in five different culture media and extracted with various solvents to optimise its antifungal activity. Potato dextrose agar culture and dichloromethane extraction resulted in an MIC of 1.9 μg/mL against P. brasiliensis and did not show cytotoxicity at the concentrations tested in normal mammalian cell (Vero). This extract was subjected to bioassay-guided fractionation using analytical C18RP-high-performance liquid chromatography (HPLC) and an antifungal assay using P. brasiliensis. Analysis of the active fractions by HPLC-high resolution mass spectrometry allowed us to identify the antifungal agents present in the A. felis extracts cytochalasins. These results reveal the potential of A. felis as a producer of bioactive compounds with antifungal activity.

Evaluation of a pilot-scale oil extraction from microalgae for biodiesel production

Biodiesel derived from microalgae is one of a suite of potential solutions to meet the increasing demand for a renewable, carbon-neutral energy source. However, there are numerous challenges that must be addressed before algae biodiesel can become commercially viable. These challenges include the economic feasibility of harvesting and dewatering the biomass and the extraction of lipids and their conversion into biodiesel. Therefore, it is essential to find a suitable extraction process given these processes presently contribute significantly to the total production costs which, at this stage, inhibit the ability of biodiesel to compete financially with petroleum diesel. This study focuses on pilot-scale (100 kg dried microalgae) solvent extraction of lipids from microalgae and subsequent transesterification to biodiesel. Three different solvents (hexane, isopropanol (IPA) and hexane + IPA (1:1)) were used with two different extraction methods (static and Soxhlet) at bench-scale to find the most suitable solvent extraction process for the pilot-scale. The Soxhlet method extracted only 4.2% more lipid compared to the static method. However, the fatty acid profiles of different extraction methods with different solvents are similar, suggesting that none of the solvents or extraction processes were biased for extraction of particular fatty acids. Considering the cost and availability of the solvents, hexane was chosen for pilot-scale extraction using static extraction. At pilot-scale the lipid yield was found to be 20.3% of total biomass which is 2.5% less than from bench scale. Extracted fatty acids were dominated by polyunsaturated fatty acids (PUFAs) (68.94±0.17%) including 47.7±0.43 and 17.86±0.42% being docosahexaenoic acid (DHA) (C22:6) and docosapentaenoic acid (DPA) (C22:5, ω-3), respectively. These high amounts of long chain poly unsaturated fatty acids are unique to some marine microalgae and protists and vary with environmental conditions, culture age and nutrient status, as well as with cultivation process. Calculated physical and chemical properties of density, viscosity of transesterified fatty acid methyl esters (FAMEs) were within the limits of the biodiesel standard specifications as per ASTM D6751-2012 and EN 14214. The calculated cetane number was, however, significantly lower (17.8~18.6) compared to ASTM D6751-2012 or EN 14214-specified minimal requirements. We conclude that the obtained microalgal biodiesel would likely only be suitable for blending with petroleum diesel to a maximum of 5 to 20%.