Application of Fluorescence to the Study of Crude Petroleum

Crude petroleum oils are complex mixtures of different compounds (mainly organic), which are obtained from an extensive range of different geological sources. The fluorescence of crude petroleum oils derives largely from the aromatic hydrocarbon fraction, and this fluorescence emission is strongly influenced by the chemical composition (e.g., fluorophore and quencher concentrations) and physical characteristics (e.g., viscosity and optical density) of the oil. The fluorescence spectroscopy (FS) is increasingly used in petroleum technology due the availability of better optical detection techniques, because FS offers high sensitivity, good diagnostic potential, and relatively simple instrumentation. In this work we analyzed crude petroleum at different dilution in Nujol, a transparent mineral oil. The main objective of this work was to verify the possibility to measure crude oil emission spectroscopic without use of volatile solvents. The mixtures of nujol with different -crude oil concentrations were measured with a 10 mm optical path cuvette thus simplifying the fluorescence spectroscopy signal detection. The emission spectra were obtained by exciting the samples with a 400 W Xenon lamp at 350 nm, 450 nm and 532 nm. The emissions of the samples were collected perpendicularly with the excitation axis.

Modeling the kinetics of the coalescence of water droplets in crude oil emulsions subject to an electric field, with the cellular automata technique

In this study, the concept of cellular automata is applied in an innovative way to simulate the separation of phases in a water/oil emulsion. The velocity of the water droplets is calculated by the balance of forces acting on a pair of droplets in a group, and cellular automata is used to simulate the whole group of droplets. Thus, it is possible to solve the problem stochastically and to show the sequence of collisions of droplets and coalescence phenomena. This methodology enables the calculation of the amount of water that can be separated from the emulsion under different operating conditions, thus enabling the process to be optimized. Comparisons between the results obtained from the developed model and the operational performance of an actual desalting unit are carried out. The accuracy observed shows that the developed model is a good representation of the actual process. (C) 2010 Published by Elsevier Ltd.

Prediction of Crude Oil Properties and Chemical Composition by Means of Steady-State and Time-Resolved Fluorescence

Steady-state and time-resolved fluorescence measurements are reported for several crude oils and their saturates, aromatics, resins, and asphaltenes (SARA) fractions (saturates, aromatics and resins), isolated from maltene after pentane precipitation of the asphaltenes. There is a clear relationship between the American Petroleum Institute (API) grade of the crude oils and their fluorescence emission intensity and maxima. Dilution of the crude oil samples with cyclohexane results in a significant increase of emission intensity and a blue shift, which is a clear indication of the presence of energy-transfer processes between the emissive chromophores present in the crude oil. Both the fluorescence spectra and the mean fluorescence lifetimes of the three SARA fractions and their mixtures indicate that the aromatics and resins are the major contributors to the emission of crude oils. Total synchronous fluorescence scan (TSFS) spectral maps are preferable to steady-state fluorescence spectra for discriminating between the fractions, making TSFS maps a particularly interesting choice for the development of fluorescence-based methods for the characterization and classification of crude oils. More detailed studies, using a much wider range of excitation and emission wavelengths, are necessary to determine the utility of time-resolved fluorescence (TRF) data for this purpose. Preliminary models constructed using TSFS spectra from 21 crude oil samples show a very good correlation (R(2) > 0.88) between the calculated and measured values of API and the SARA fraction concentrations. The use of models based on a fast fluorescence measurement may thus be an alternative to tedious and time-consuming chemical analysis in refineries.

Coalescence of Water Droplets in Crude Oil Emulsions: Analytical Solution

In petroleum refineries, water is used in desalting units to remove the salt contained in crude oil. Typically, 7% of the volume of hot crude oil is water, forming a water-and-oil emulsion. The emulsion flows between two electrodes and is subjected to an electric field. The electrical forces promote the coalescence of small droplets of water dispersed in crude oil, and these form bigger droplets. This paper calculates the forces acting on the droplets, highlighting particularly the mechanisms proposed for droplet-droplet coalescence under the influence of an applied electric field. Moreover, a model is developed in order to calculate the displacement speed of the droplets and the time between droplet collisions. Thus, it is possible to simulate and optimize the process by changing the operational variables (temperature, electrical field, and water quantity). The main advantage of this study is to show that it is feasible to increase the volume of water recycled in desalting processes, thus reducing the use of freshwater and the generation of liquid effluents in refineries.

Wine industry residues extracts as natural antioxidants in raw and cooked chicken meat during frozen storage

The effect of Isabel (IGE) and Niagara (NGE) grape seed and peel extracts on lipid oxidation, instrumental colour, pH and sensory properties of raw and cooked processed chicken meat stored at -18 degrees C for nine months was evaluated. The pH of raw and cooked samples was not affected by the addition of grape extracts. IGE and NGE were effective in inhibiting the lipid oxidation of raw and cooked chicken meat, with results comparable to synthetic antioxidants. The extracts caused alterations in colour, as evidenced by the instrumental (darkening and lower intensity of red and yellow colour) and sensory results of cooked samples. In the sensory evaluation of odour and flavour, IGE produced satisfactory results, which did not differ from synthetic antioxidants. These findings suggest that the ICE and NGE are effective in retarding lipid oxidation of raw and cooked chicken meat during frozen storage. (c) 2011 Elsevier Ltd. All rights reserved.

Sweet Basil (Ocimum basilicum) Extracts Obtained by Supercritical Fluid Extraction (SFE): Global Yields, Chemical Composition, Antioxidant Activity, and Estimation of the Cost of Manufacturing

In this work, supercritical technology was used to obtain extracts from Ocimum basilicum (sweet basil) with CO(2) and the cosolvent H(2)O at 1, 10, and 20% (w/w). The raw material was obtained from hydroponic cultivation. The extract`s global yield isotherms, chemical compositions, antioxidant activity, and cost of manufacturing were determined. The extraction assays were done for pressures of 10 to 30 MPa at 303 to 323 K. The identification of the compounds present in the extracts was made by GC-MS and ESI-MS. The antioxidant activity of extracts was determined using the coupled reaction of beta-carotene and linolenic acid. At 1% of cosolvent, the largest global yield was obtained at 10 MPa and 303 K (2%, dry basis-d.b.); at 10% of cosolvent the largest global yield was obtained at 10 and 15 MPa (11%, d.b.), and at 20% of cosolvent the largest global yield was detected at 30 MPa and 303 K (24%, d.b.). The main components identified in the extracts were eugenol, germacrene-D, epi-alpha-cadinol, malic acid, tartaric acid, ramnose, caffeic acid, quinic acid, kaempferol, caffeoylquinic acid, and kaempferol 3-O-glucoside. Sweet basil extracts exhibited high antioxidant activity compared to beta-carotene. Three types of SFE extracts from sweet basil were produced, for which the estimated cost of manufacturing (class 5 type) varied from US$ 47.96 to US$ 1,049.58 per kilogram of dry extract.

Foundation and Perspectives of the Use of Plant Extracts as Performance Enhancers in Broilers

Feed is responsible for about 70% of broilers production costs, leading to an increasing number of studies on alternative dietary products that benefit bird performance and lower production costs. Since the 1950s, antimicrobial additives are the most frequently used performance enhancers in animal production and their positive results are observed even in high-challenge conditions. Since the 1990s, due to the ban of the use of some antibiotics as growth promoters and the growing trend of the public to consume natural products, plant extracts have been researched as alternatives to antibiotic growth promoters. The first study that evaluated the antibacterial activities of plant extracts was carried out in 1881; however, they started to be used as flavor enhancers only during the next decades. With the emergence of antibiotics in the 1950s, the use of plant extracts as antimicrobial agents almost disappeared. There are several studies in literature assessing the use of plant extracts, individually or in combination, as antimicrobials, antioxidants, or digestibility enhancers in animal feeds. Research results on the factors affecting their action, such as plant variety, harvest time, processing, extraction, as well as the technology employed to manufacture the commercial product and dietary inclusion levels show controversial results, warranting the need of further research and standardization for the effective use of plant extracts as performance enhancers, when added to animal feeds. This article aims at presenting plant extracts as alternatives to antibiotics, explaining their main modes of action as performance enhancers in broiler production.

Phenolic compounds and antioxidant activity of seed and skin extracts of red grape (Vitis vinifera and Vitis labrusca) pomace from Brazilian winemaking

The phenolic compounds content and antioxidant activity of seed and skin of pomace from the vinification of grape varieties widely produced in Brazil were investigated with a view to their exploitation as a potential source of natural antioxidants. There was a greater concentration of phenolic compounds in the seeds (2128 to 16,518 mg of catechin equivalents (CE)/100 g) than in the skins (660 to 1839 mg CE/100 g). The highest antioxidant activity values determined as DPPH radical-scavenging ability and ferric reducing-antioxidant power (FRAP) were found for the seeds of the Pinot Noir variety (16,925 mu mol Trolox equivalents (TE)/100 g and 21,492 mu mol Fe(2+)/100 g, respectively) and in the skin extracts of the Isabel variety (3640 mu mol TE/100 g and 4362 mu mol Fe(2+)/100 g, respectively). The skin of Cabernet Sauvignon and Primitivo varieties had the highest contents of anthocyanins (935 and 832 mg/100 g, respectively). The grape seed extracts were rich in oligomeric and polymeric flavanols. The data suggested that grape seed and skin extracts may be exploited as antioxidant agents. (C) 2011 Elsevier Ltd. All rights reserved.

Antioxidant capacity of the striped sunflower (Helianthus annuus L.) seed extracts evaluated by three in vitro methods

The antioxidant capacity of the striped sunflower seed cotyledon extracts, obtained by sequential extraction with different polarities of solvents, was evaluated by three different in vitro methods: ferric reducing/antioxidant power (FRAP), 2.2-diphenyl-1-picrylhydrazyl radical (DPPH) and oxygen radical absorbance capacity (ORAC) assays. In the three methods, the aqueous extract at 30 mu g/ml showed a higher antioxidant capacity value (FRAP, 45.27 mu mol; DPPH, 50.18%; ORAC, 1.5 Trolox equivalents) than the ethanolic extract (FRAP, 32.17 mu mol; DPPH, 15.21%; ORAC, 0.50 Trolox equivalents). When compared with the synthetic antioxidant butylated hydroxyl toluene, the antioxidant capacity of the aqueous extract varied from 45% to 66%, according to the used method. The high antioxidant capacity observed for the aqueous extract of the studied sunflower seed suggests that the intake of this seed may prevent in vivo oxidative reactions responsible for the development of several diseases, such as cancer.

Standardization and determination of photostability of leaf extracts of Pothomorphe umbellata L. Miq (pariparoba) and evaluation of the inhibition in vitro of metalloproteinases 2 and 9 in skin

Most researches that have been done until today about the beneficial effects of hariparoha (Pothomorphe umbellata L. Miq) have been done with root extract of this species, but the use in large scale would compromise the sustainable exploration of this natutral resource. In this sense, the utilization of pariparoha leaves, substituting the roots, in the cosmetic industry does not put in risk the existence of the species. In this work the concentration of 4-nerolidyl-cathecol (4-NC) in leaf extract was determined by the analytical methodology validated in our laboratory. The concentration of 4-NC in leaf extract was around 30% less than that of root extract, obtained in the same way. Concerning the study of the photostability of a leaves extract solution containing 4-NC did not demonstrate meaningful alterations in the spectrometry, profile after 2 hours of exposure under UVB radiation, showing its stability under this conditions. Metalloproteinases (MMPs) cure endopeptidases that are zinc-dependent, involved in remodeling extracellular matrix (ECM), that are important in the appearance of typical photoaging wrinkles. In this work the capacity of leaf extract of P. umbellata to inhibit MMP-2 and 9 activities of hairless mouse skin in vitro by zymography gel was also evalutated. The leaf extract (0,1 mg/mL) inhibit in 80% activity of this enzymes, according to the densitometric zymography evaluation.

Skin Penetration of Epigallocatechin-3-Gallate and Quercetin from Green Tea and Ginkgo biloba Extracts Vehiculated in Cosmetic Formulations

Green tea (Camellia sinensis) and Ginkgo biloba extracts in cosmetic formulations have been suggested to protect the skin against UV-induced damage and skin ageing. Thus, it is very important to assess the human skin penetration of their major flavonoids to verify if they penetrate and remain in the skin to exert their proposed effects. The aim of this study was to evaluate the human skin penetration of epigallocatechin-3-gallate (EGCG) and quercetin from green tea and G. biloba extracts vehiculated in cosmetic formulations. This study was conducted with fresh dermatomed human Caucasian skin from abdominal surgery mounted on static Franz diffusion cells. Skin samples were mounted between two diffusion half-cells and 10 mg/cm(2) of formulations supplemented with 6% of green tea or G. biloba extract were applied on the skin surface. The receptor fluid was removed after 6 and 24 h and analyzed by high-performance liquid chromatography for the quantification of the flavonoids. The stratum corneum was removed by tape stripping and immersed in methanol and the epidermis was mechanically separated from the dermis and triturated in methanol to extract EGCG and quercetin. The results showed that the flavonoids under study penetrated into the skin, without reaching the receptor fluid. The majority of EGCG was quantified in the stratum corneum (0.87 mu g/cm(2)), which was statistically higher than the EGCG concentrations found in viable epidermis (0.54 mu g/cm(2)) and in the dermis (0.38 mu g/cm(2)). The majority of quercetin was quantified in the viable epidermis (0.23 mu g/cm(2)), which was statistically higher than the EGCG concentration found in the stratum corneum layer (0.17 mu g/cm(2)). Finally, it can be concluded that EGCG and quercetin from green tea and G. biloba extracts vehiculated in cosmetic formulations presented good skin penetration and retention, which can favor their skin effects. Copyright (C) 2009 S. Karger AG, Basel

Production and characteristics comparison of crude beta-glucosidases produced by microorganisms Thermoascus aurantiacus e Aureobasidium pullulans in agricultural wastes

The purified beta-glucosidase of Aureobasidium pullulans ER-16 is one of more thermostable enzyme reported to date. Considering the unfeasibility of using purified enzyme for industrial application, it was interesting to analyze this property for the crude enzyme. Thermophilic fungus Thermoascus aurantiacus CBMAI-756 and mesophilic A. pullulans ER-16 were cultivated in different hemicellulosic materials on solid-state cultivation for beta-glucosidase production. Wheat bran was most appropriate for beta-glucosidase production by both microorganisms. T. aurantiacus exhibited maximum enzyme production (7.0 U/ml or 70 U/g) at 48-72 h and A. pullulans a maximum (1.3 U/ml or 13 U/g) at 120 h. Maximum activities were at 75 degrees C with optimum pH at 4.5 and 4.0, for T aurantiacus and A. pullulans, respectively. A. pullulans`s beta-glucosidase was more pH stable (4.5-10.0 against 4.5-8.0) and more thermostable (90% after 1 h at 75 degrees C against 85% after 1 h at 70 degrees C) than the enzyme from the thermophilic T. aurantiacus. The t((1/2)) at 80 degrees C were 50 and 12.5 min for A. pullulans and T. aurantiascus, respectively. These data confirm the high thermostability of crude beta-glucosidase from A. pullulans. Both beta-glucosidases were strongly inhibited by glucose, but ethanol significantly increased the activity of the enzyme from T. aurantiacus. (C) 2008 Elsevier Inc. All rights reserved.

Evaluation of the antioxidant activity as an additional parameter to attain the functional quality of natural extracts

Due to differences in the functional quality of natural extracts, we have also faced differences in their effectiveness. So, it was intended to assess the antioxidant activity of natural extracts in order to attain their functional quality. It was observed that all the extracts (brown and green propolis, Ginkgo biloba and Isoflavin Beta (R)) and the standard used (quercetin) showed antioxidant activity in a dose-dependent manner with IC50 values ranging from 0.21 to 155.28 mu g mL(-1) (inhibition of lipid peroxidation and scavenging of the DPPH center dot assays). We observed a high correlation (r(2)= 0.9913) among the antioxidant methods; on the other hand, the antioxidant activity was not related to the polyphenol and flavonoid content. As the DPPH center dot assay is a fast method, presents low costs and even has a high correlation with other antioxidant methods, it could be applied as an additional parameter in the quality control of natural extracts.

Spray Drying of Extracts from Red Yeast Fermentation Broth

Red yeast rice is a pigmented material that is traditionally used in Asia as a food colorant. In addition to food applications, red yeast rice is known in traditional Chinese medicine for its therapeutic actions. The aim of this work was to study the quality interactions during spray drying of extracts from the Monascus ruber van Tiegham fermentation broth. The quality indicators used for the dry powder properties were the levels of monacolin K, ratio of red to yellow pigments, as well as their antioxidant activity. The experiments followed a Box-Behnken design to study the effects of the adjuvant/drug ratio, adjuvant incorporation time, and oulet drying temperature on the pharmacotechnical, chemical, and biological properties of the dry extract. The influences of these factors on the characteristics of the dry powder were evaluated by the bulk density, tapped density, Carr index, Hausner factor, residual moisture content, water activity, antioxidant activity, monacolin K, yellow-to-red pigment ratio, and antioxidant activity. The analysis of variance (ANOVA) on experimental data revealed that an increase in drying temperature significantly increased the dry powder yield and caused an improvement in powder flow properties, which may be related to lower moisture contents. The drying temperature did not affect the monacolin K content in dry powder but showed a complex influence on its antioxidant activity. The increase in drying adjuvant-to-drug ratio affected the yield and also indicated a protective effect on the monacolin K content. The duration of drying adjuvant incorporation had little or negligible effect on powder properties. The dry extracts of red yeast rice showed adequate properties and the process proposed herein can be used to prepare nutraceutical products.

Stability Testing of Spray- and Spouted Bed-Dried Extracts of Passiflora alata

The aim of this research was to perform a stability testing of spray- and spouted bed-dried extracts of Passiflora alata Dryander (Passion flower) under stress storage conditions. Spouted bed- and spray-dried extracts were characterized by determination of the average particle diameter (dP), apparent moisture content (XP), total flavonoid content (TF), and vitexin content. Smaller and more irregular particles were generated by the spouted bed system due to a higher attrition rate (surface erosion) inside the dryer. The SB dryer resulted in an end product with higher concentration of flavonoids (approximate to 10%) and lower moisture content (1.6%, dry basis) than the spray dryer, even with both dryers working at similar inlet drying air temperature and ratio between the extract feed flow rate to drying air flow rate (Ws/Wg). Samples of the spouted bed- and spray-dried extracts were stored at two different temperatures (34 and 45 degrees C) and two different relative humidities (52 and 63% RH for 34 degrees C; 52 and 60% RH for 45 degrees C) in order to perform the stability testing. The dried extracts were stored for 28 days and were analyzed every 4 days. The flavonoid vitexin served as the marker compound, which was assayed during the storage period. Results revealed shelf lives ranging from 9 to 184 days, depending on the drying process and storage conditions.