Supercritical carbon dioxide extraction of bioactive compounds from microalgae and volatile oils from aromatic plants

A discussion of the most interesting results obtained in our laboratories, during the supercritical CO(2) extraction of bioactive compounds from microalgae and volatile oils from aromatic plants, was carried out. Concerning the microalgae, the studies on Botryococcus braunii and Chlorella vulgaris were selected. Hydrocarbons from the first microalgae, which are mainly linear alkadienes (C(23)-C(31)) with an odd number of carbon atoms, were selectively extracted at 313 K increasing the pressure up to 30.0 MPa. These hydrocarbons are easily extracted at this pressure, since they are located outside the cellular walls. The extraction of carotenoids, mainly canthaxanthin and astaxanthin, from C. vulgaris is more difficult. The extraction yield of these components at 313 K and 35.0 MPa increased with the degree of crushing of the microalga, since they are not extracellular. On the other hand, for the extraction of volatile oils from aromatic plants, studies on Mentha pulegium and Satureja montana L were chosen. For the first aromatic plant, the composition of the volatile and essential oils was similar, the main components being the pulegone and menthone. However, this volatile oil contained small amounts of waxes, which content decreased with decreasing particle size of the plant matrix. For S. montana L it was also observed that both oils have a similar composition, the main components being carvacrol and thymol. The main difference is the relative amount of thymoquinone, which content can be 15 times higher in volatile oil. This oxygenated monoterpene has important biological activities. Moreover, experimental studies on anticholinesterase activity of supercritical extracts of S. montana were also carried out. The supercritical nonvolatile fraction, which presented the highest content of the protocatechuic, vanilic, chlorogenic and (+)-catechin acids, is the most promising inhibitor of the enzyme butyrylcholinesterase. In contrast, the Soxhlet acetone extract did not affect the activity of this enzyme at the concentrations tested. (C) 2011 Elsevier B.V. All rights reserved.

Biodiesel production from waste frying oils over lime catalysts

Biodiesel production from semi-refined oils (SRO) and waste frying oils (WFO) was studied using commercial CaO as heterogeneous catalyst. The methanolysis tests were carried out in mild reaction conditions (62 A degrees C, atmospheric pressure). With such conditions, SRO (soybean and rapeseed) allowed to produce a biodiesel containing 97-98 % of methyl esters (FAME), whereas WFO only provided 86-87 % of FAME. The lower FAME yield for WFO oil is ascribable to the partial neutralization of the catalyst by free fatty acids. Also, soaps formation from the WFO oil reduced the weight yield of the oil phase (containing FAME) obtained and increased the MONG content of the glycerin phase. The catalysts stability tests showed high stability even when WFO oil was processed. Catalytic tests performed with blends of WFO/semi-refined oils showed blending as a good strategy to process low value raw oils with minor decay of the catalyst performance. Both WFO and semi-refined oils showed S-shape kinetics curves thus discarding significant differences of the reaction mechanisms.

Lethal and sublethal effects of essential oils from Pittosporum undulatum and Hedychium gardnerianum on the egg parasitoid Trichogramma cordubensis (Hymenoptera: Trichogrammatidae

Dissertação de Mestrado, Biotecnologia em Controlo Biológico, 6 de Junho de 2013, Universidade dos Açores.

Simulation and life cycle assessment of process design alternatives for biodiesel production from waste vegetable oils

This study uses the process simulator ASPEN Plus and Life Cycle Assessment (LCA) to compare three process design alternatives for biodiesel production from waste vegetable oils that are: the conventional alkali-catalyzed process including a free fatty acids (FFAs) pre-treatment, the acid-catalyzed process, and the supercritical methanol process using propane as co-solvent. Results show that the supercritical methanol process using propane as co-solvent is the most environmentally favorable alternative. Its smaller steam consumption in comparison with the other process design alternatives leads to a lower contribution to the potential environmental impacts (PEI’s). The acid-catalyzed process generally shows the highest PEI’s, in particular due to the high energy requirements associated with methanol recovery operations.

Film thickness in a ball-on-disc contact lubricated with greases, bleed oils and base oils

Three different lubricating greases and their bleed and base oils were compared in terms of film thickness in a ball-on-disc test rig through optical interferometry. The theoretical values calculated according to Hamrock's equation are in close agreement with the base oil film thickness measurements, which validates the selected experimental methodology. The grease and bleed oil film thickness under fully flooded lubrication conditions presented quite similar behaviour and levels. Therefore, the grease film thickness under full film conditions might be predicted using their bleed oil properties, namely the viscosity and pressure-viscosity coefficient. The base and bleed oil lubricant parameter LP are proportional to the measured film thickness. A relationship between grease and the corresponding bleed oil film thickness was evidenced.

Aliphatic bio-oils from corks: a Py-Gc/MS study

Cork samples from Betula pendula, Quercus suber and Quercus cerris were submitted to Py-GC-MS/FID at temperatures between 550 degrees C and 900 degrees C and the pyrolysis-derived compounds (py-products) were identified and quantified. Corks were compared with wood samples. Py-products include suberin, lignin and carbohydrates derivatives. Suberin py-products are dominated by unsaturated aliphatics. Corks pyrolysis yield and composition were dramatically influenced by temperature in contrast to wood that showed stable results across temperatures. At 850-900 degrees C the peaks area of cork pyrograms were approximately two times higher than at 550 degrees C, for which yield was about half of the woods, and cork py-products were dominated by suberin-derived short chain aliphatics, namely 1-alkenes, while at 550 degrees C composition was dominated by lignin derivatives. Lignin and carbohydrate derived products decreased dramatically over 750 degrees C while the opposite was observed for unsaturated aliphatics. Cork materials show a high potential as feedstock for production of aliphatic-rich pyrolytic biofuels or as a source of olefins. (C) 2014 Elsevier B.V. All rights reserved.

Potential of biologically active plant oils to control mosquito larvae (Culex pipiens, Diptera: Culicidae) from an egyptian locality

The insecticidal effect of six commercially available plant oils was tested against 4th larval instars of Culex pipiens. Larvae were originally collected from Meit El-Attar, Qalyubia Governorate, Egypt, and then reared in the laboratory until F1 generation. The LC50 values were 32.42, 47.17, 71.37, 83.36, 86.06, and 152.94 ppm for fenugreek (Trigonella foenum-grecum), earth almond (Cyperus esculentus), mustard (Brassica compestris), olibanum (Boswellia serrata), rocket (Eruca sativa), and parsley (Carum ptroselinum), respectively. The tested oils altered some biological aspects of C. pipiens, for instance, developmental periods, pupation rates, and adult emergences. The lowest concentrations of olibanum and fenugreek oils caused remarkable prolongation of larval and pupal durations. Data also showed that the increase of concentrations was directly proportional to reduction in pupation rates and adult emergences. Remarkable decrease in pupation rate was achieved by mustard oil at 1000 ppm. Adult emergence was suppressed by earth almond and fenugreek oils at 25 ppm. In addition, the tested plant oils exhibited various morphological abnormalities on larvae, pupae, and adult stages. Consequently, fenugreek was the most potent oil and the major cause of malformation of both larval and pupal stages. Potency of the applied plant oils provided an excellent potential for controlling C. pipiens.

Molluscicidal and Mosquitocidal Activities of the Essential oils of Thymus capitatus Hoff. et Link. and Marrubium vulgare L.

Steam distillation of essential oils of aerial parts of Thymus capitatus and Marrubium vulgare L. collected at North cost of Egypt yielded 0.5% and 0.2%, respectively. Results of Gas chromatography-mass spectrometry analyses of the two samples identified 96.27% and 90.19% of the total oil composition for T. capitatus and M. vulgare, respectively. The two oil samples appeared dominated by the oxygenated constituents (88.22% for T. capitatus and 57.50% for M. vulgare), composed of phenols, mainly carvacrol (32.98%) and thymol (32.82%) in essential oil of T. capitatus, and thymol (34.55%) in essential oil of M. vulgare. It was evaluated the molluscicidal activity of T. capitatus and M. vulgare essential oils on adult and eggs of Biomphalaria alexandrina as well as their mosquitocidal activity on Culex pipiens. The LC50 and LC90 of T. capitatus essential oil against adult snails was 200 and 400 ppm/3hrs, respectively, while for M. vulgare it was 50 and 100 ppm/3hrs, respectively. Moreover, M. vulgare showed LC100 ovicidal activity at 200 ppm/24 hrs while T. capitatus oil showed no ovicidal activity. It was verified mosquitocidal activity, with LC50 and LC90 of 100 and 200 ppm/12hrs respectively for larvae, and 200 and 400 ppm/12hrs respectively for pupae of C. pipiens.

Larvicidal activity of oils, fatty acids, and methyl esters from ripe and unripe fruit of Solanum lycocarpum (Solanaceae) against the vector Culex quinquefasciatus (Diptera: Culicidae)

ABSTRACTINTRODUCTION:The larvicidal activity of oils, fatty acids, and methyl esters of Solanum lycocarpum fruit against Culex quinquefasciatus is unknown.METHODS:The larvicidal activity of samples of ripe and unripe fruit from S. lycocarpum was evaluated against third and fourth instar larvae of C. quinquefasciatus .RESULTS:The oils, fatty acids, and methyl esters of S. lycocarpum showed the greatest larvicidal effect (57.1-95.0%) at a concentration of 100mg/L (LC 50values between 0.70 and 27.54mg/L).CONCLUSIONS:Solanum lycocarpum fruit may be a good source of new natural products with larvicidal activity.

On the occurrence of cyanolipids In Paullinia carpopodea cambess And P. cupana Kunth seed oils

Paullinia carpopodea seed oil contains 70% type Icyanolipids with cyanogenetic properties, as proven by chemical and spectrometric techniques. P. cupana seed oil also contains cyanogenic type I cyanolipids, according to its 1Ή-NMR spectrum. The existing controversy in the literature about the presence and/or type of cyanolipids in P. cupana seed oil is probably due to the low amount of these compounds (0.2%) in the seeds.

Chemical composition and acaricidal activity of the leaf and fruit essential oils of Protium heptaphyllum (Aubl.) Marchand (Burseraceae)

Essential oils from leaves and fruits of Protiumheptaphyllum collected in Tamandaré beach Pernambuco/Brazil were analysed by GC/MS and tested for toxicity and repellent effect against the two spotted spider mite (Tetranychus urticae). The major constituent identified in the fruits was alpha-terpinene (47.6 %) whereas oil from leaf contained mainly sesquiterpenes such as 9-epi-caryophyllene (21.4 %), trans-isolongifolanone (10.7 %) and 14-hydroxi-9-epi-caryophyllene (16.7 %). The fruit oil was found to be more effective against the mite when compared to the leaf oil. Both showed mortality properties and oviposition deterrence in higher concentration (10 µl.l-1 air), but only the essential oil from fruits induced repellence on T. urticae.

Chemical composition of the essential oils from two subspecies of Protium heptaphyllum

Qualitative and quantitative analyses of the volatile constituents from resin of Protium heptaphyllum (Aubl.) Marchand subsp. ulei (Swat) Daly (PHU), and Protium heptaphyllum (Aubl.) Marchand subsp. heptaphyllum (PHH), Burseraceae were performed using GC-MS and GC-FID. The resins were collected around the city of Cruzeiro do Sul, state of Acre, Brazil. Essential oils from the two subspecies were extracted by hydrodistillation with a yield of 8.6% (PHU) and 11.3% (PHH); the main components were terpinolene (42.31%) and p-cymene (39.93%) for subspecies ulei (PHU) and heptaphyllum (PHH), respectively.

Sensory intensity assessment of olive oils using an electronic tongue

Olive oils may be commercialized as intense, medium or light, according to the intensity perception of fruitiness, bitterness and pungency attributes, assessed by a sensory panel. In this work, the capability of an electronic tongue to correctly classify olive oils according to the sensory intensity perception levels was evaluated. Cross-sensitivity and non-specific lipid polymeric membranes were used as sensors. The sensor device was firstly tested using quinine monohydrochloride standard solutions. Mean sensitivities of 14±2 to 25±6 mV/decade, depending on the type of plasticizer used in the lipid membranes, were obtained showing the device capability for evaluating bitterness. Then, linear discriminant models based on sub-sets of sensors, selected by a meta-heuristic simulated annealing algorithm, were established enabling to correctly classify 91% of olive oils according to their intensity sensory grade (leave-one-out cross-validation procedure). This capability was further evaluated using a repeated K-fold cross-validation procedure, showing that the electronic tongue allowed an average correct classification of 80% of the olive oils used for internal-validation. So, the electronic tongue can be seen as a taste sensor, allowing differentiating olive oils with different sensory intensities, and could be used as a preliminary, complementary and practical tool for panelists during olive oil sensory analysis.

Toxicity and repellency of essential oils to Zabrotes subfasciatus (Boheman) (Coleoptera, Chrysomelidae, Bruchinae) in Phaseolus vulgaris L

The effects of tangerine (Phaseolus vulgaris Blanco), lemon (Citrus medica limonum Lush), pear orange (Citrus sinensis L. Osbeck), red copaiba (Copaifera langsdorffii Desf.), rosemary (Baccharis dracunculifolia De Candole), Eucalyptus (Eucalyptus globulus Labillardière and E. citriodora Hook), lemongrass (Cymbopogon citratus Stapf.) and citronella (Cimbopogon nardus Linnaeus) oils at several concentrations on Zabrotes subfasciatus (Boheman) were studied. In toxicity tests, grains of Phaseolus vulgaris L. cv. Rajadinho were impregnated with oils and infested with adults of Z. subfasciatus up to 24 hours old. All tested oils were effective in reducing the viable egg-laying and adult emergence of this pest, in function of the concentrations used, highlighting E. citriodora and E. globulus oils which caused 100% effectiveness from 0.5 mL Kg-1 concentration. In repellency tests, two arenas consisting of plastic containers, connected symmetrically to a central box by two plastic tubes were used. In one of the boxes, untreated beans were placed and on the other ones beans treated with each oil concentration were used. In the central box, five couples of Z. subfasciatus were released. Grains of P. vulgaris treated with oils of E. citriodora, C. citratus and C. oleifera reduced the attraction percentage of Z. subfasciatus adults, while the E. globulus increased this percentage. The percentages of reduced viable eggs ranged from 17.9% (C. medica limonum) to 93.3% (C. nardus), while the reduction on the number of emerged insects was 23.9% and 95.9%, respectively for these same oils.

Essential oils of the Sextonia rubra (Mez ) van der Werff (Lauraceae)

The essential oils of the leaves and branches of Sextonia rubra were obtained by hydrodistillation and analyzed by GC-FID and GC-MS. In the leaves were identified as the major constituents α-pinene (21.7%), β-pinene (15.4%), α-copaene (12.5%) and germacrene D (12.1%). In the branches essential oil, α-copaene (22.9%), β-selinene (7.9%) and β-elemene (7.2%) were identified as the most abundant constituents. This paper describes for the first time the composition of these essential oils.