Multivariate calibrations in gas chromatographic profiles for prediction of several physicochemical parameters of Brazilian commercial gasoline

Several Brazilian commercial gasoline physicochemical parameters, such as relative density, distillation curve (temperatures related to 10%, 50% and 90% of distilled volume, final boiling point and residue), octane numbers (motor and research octane number and anti-knock index), hydrocarbon compositions (olefins, aromatics and saturates) and anhydrous ethanol and benzene content was predicted from chromatographic profiles obtained by flame ionization detection (GC-FID) and using partial least square regression (PLS). GC-FID is a technique intensively used for fuel quality control due to its convenience, speed, accuracy and simplicity and its profiles are much easier to interpret and understand than results produced by other techniques. Another advantage is that it permits association with multivariate methods of analysis, such as PLS. The chromatogram profiles were recorded and used to deploy PLS models for each property. The standard error of prediction (SEP) has been the main parameter considered to select the "best model". Most of GC-FID-PLS results, when compared to those obtained by the Brazilian Government Petroleum, Natural Gas and Biofuels Agency - ANP Regulation 309 specification methods, were very good. In general, all PLS models developed in these work provide unbiased predictions with lows standard error of prediction and percentage average relative error (below 11.5 and 5.0, respectively). (C) 2007 Elsevier B.V. All rights reserved.

Pesticides in the distilled spirits of wine and its byproducts

The fate of eight fungicides (benalaxyl, fenarimol, iprodione, metalaxyl, myclobutanil, procymidone, triadimefon, and vinclozolin) and five insecticides (dimethoate, fenthion, methidathion, parathion methyl, and quinalphos) in wine and its byproducts (cake and lees) during the production of distilled spirits was studied. Among the pesticides studied, only fenthion, quinalphos, and vinclozolin residues were present in the distilled spirits. During wine distillation, respectively 13% and 5% of the initial residues of fenthion and vinclozolin were transferred to the distilled spirit. Low percentages (2% for fenthion and 0.1% for vinclozolin) of these active ingredients (AI) also passed from the lees to the final-distilled spirit, when samples were fortified at 10.1 and 26.1 ppm for fenthion and vinclozolin, respectively. Quinalphos passed only from the lees to the final-distilled spirit in percentages lower than 1% when samples were fortified at the highest concentration (4.6 ppm).

Essential oil from leaves of Cryptocarya mandioccana Meisner (Lauraceae): Composition and intraspecific chemical variability

The composition of the essential oil from leaves of Cryptocarya mandioccana has been determined by chromatographic fractionation and GC-FID, GC-MS and C-13 NMR analyses, yielding the identification of 64 compounds with predominance of isomeric sesquiterpenes with molecular weights of 204. The main components of the oil obtained by hydrodistillation were beta-caryophyllene, spathulenol, caryophyllene oxide, delta-cadinene, germacrene D, benzaldehyde and bicyclogermacrene. However, the oil obtained by steam distillation contained higher levels of sesquiterpene hydrocarbons, with predominance of P-caryophyllene (C), germacrene D (G) and bicyclogermacrene (B), and was considered to be more representative of the composition of the oil in its natural state. The intraspecific chemical variability of the essential oil obtained by steam distillation was evaluated within populations of trees growing at three separate locations in the state of São Paulo, Brazil. Three distinct chemical groups could be characterised due to differences in the relative percentages of the three main sesquiterpenes from essential oil: CGB [relative contents of C (14-34%), G (5-28%), B (8-15%)], BCG [B (17-34%), C (9-24%), G (12-25%)] and GCB [G (22-42%), C (4-17%), B (7-15%)]. Individuals from groups CGB and BCG were found to be more frequent at south locations while group GCB is predominant in north location. (c) 2006 Elsevier Ltd. All rights reserved.

Resposta de plantas daninhas ao óleo fúsel aplicado em pós-emergência inicial e tardia

This work aimed to study weed response to fusel oil rate applied at early and late post-emergence. The following species were studied at late and early post-emergence: Ipomoea hederifolia, Ipomoea quamoclit, Euphorbia heterophylla, Digitaria spp., Cenchrus echinatus and Panicum maximum.. The experiment was arranged in a completely randomized design with six treatments and four replications. Fusel oil, an alcohol distillation byproduct, was applied at rates of 50, 125, 250, 375 and 500 L ha(-1), plus control without application. The plots were constituted by polyethylene containers with 3 L capacity, filled with topsoil land from a fallow area. Visual symptoms of intoxication were verified at 7 and 30 days after application (DAA) and dry weight at 30 DAA. The variables were submitted to variance analysis according to the design, adjusting the data to obtain the dose-response curve by polynomial regression. The studied species were susceptible only to the application of 500 L ha(-1) of fusel oil at early or late plant post-emergence. The species Digitaria spp. was susceptible and E. heterophylla tolerant to fusel oil applied at early post-emergence, while the other species were moderately tolerant. E. heterophylla was susceptible, Digitaria spp., C. echinatus and P. maximum moderately tolerant and I. hederifolia and I. quamoclit tolerant to fusel oil applied at late post-emergence.

Concentração de flúor e solubilidade em esmalte de dentes decíduos permanentes jovens após aplicações tópicas de soluções fluoretadas.

The aim of this article was to compare, through the distillation method, the incorporated amount of fluoride and the reduction of solubility in the enamel of both deciduous and young permanent teeth, following topical application of a 2% neutral sodium fluoride solution, according to the Knutson's technique and a 1.23% of acidulated solution, according to the Wellock & Brudevold's technique. The greatest fluoride incorporation was observed in the deciduous teeth after the usage of the 2% neutral solution. The amount of calcium and phosphorus liberation by the acid solution was greatest in the control group, followed by the group of teeth treated in acidulated solution and, finally, by those treated in 2% sodium fluoride solution.

Composição fitoquímica dos óleos essenciais de folhas de Lippia alba (Mill.)N.E.Br. em diferentes épocas de colheita e partes do ramo

This work aimed to determine the best harvest time for biomass production, yield and essential oil composition considering the seasonal variation (spring, summer, autumn and winter) on different plant parts (apical, medial and basal). Essential oils were extracted by hydro-distillation with a Clevenger apparatus for both fresh and dry mass obtained in field and lab conditions respectively. The extracted essential oils were analyzed by GS/MS (Shimadzu, QP-5000). The chemical components were identified by comparing their mass spectrum to the patterns filed in the MS computer memory (Wiley,139,Lib.), to the literature references, and by co-injection with authentic standards. Applying phyto-chemical tests on fresh and dry mass, the chemical component percentages of essential oils were calculated and identified as follows: citral (neral and geranial), myrcene, caryophylene and elemene.

Effect of a heat-treatment on the linear dimensional change of a hard chairside reline resin

Statement of problem. Little data are available regarding the effect of heat-treatments on the dimensional stability of hard chairside reline resins. Purpose. The objective of this in vitro study was to evaluate whether a heat-treatment improves the dimensional stability of the reline resin Duraliner II and to compare the linear dimensional changes of this material with the heat-polymerized acrylic resin Lucitone 550. Material and methods. The materials were mixed according to the manufacturer's instructions and packed into a stainless steel split mold (50.0 mm diameter and 0.5 mm thickness) with reference points (A, B, C, and D). Duraliner II specimens were polymerized for 12 minutes in water at 37°C and bench cooled to room temperature before being removed from the mold. Twelve specimens were made and divided into 2 groups: group 1 specimens (n=6) were left untreated, and group 2 specimens (n=6) were submitted to a heat-treatment in a water bath at 55°C for 10 minutes and then bench cooled to room temperature. The 6 Lucitone specimens (control group) were polymerized in a water bath for 9 hours at 71°C. The specimens were removed after the mold reached the room temperature. A Nikon optical comparator was used to measure the distances between the reference points (AB and CD) on the stainless steel mold (baseline readings) and on the specimens to the nearest 0.001 mm. Measurements were made after processing and after the specimens had been stored in distilled water at 37°C for 8 different periods of time. Data were subjected to analysis of variance with repeated measures, followed by Tukey's multiple comparison test (P<.05). Results. All specimens exhibited shrinkage after processing (control, -0.41%; group 1, -0.26%; and group 2, -0.51%). Group 1 specimens showed greater shrinkage (-1.23%) than the control (-0.23%) and group 2 (-0.81%) specimens after 60 days of storage in water (P<.05). Conclusion. Within the limitations of this study, a significant improvement of the long-term dimensional stability of the Duraliner II reline resin was observed when the specimens were heat-treated. However, the shrinkage remained considerably higher than the denture base resin Lucitone 550. Copyright © 2002 by The Editorial Council of The Journal of Prosthetic Dentistry.

Screening for yeast with antibacterial properties from an ethanol distillery

A general screening for the expression of antibacterial activity and non-flocculating type of yeast strains from must and fermented broth of alcohol distilleries was performed. From 60 strains only Saccharomyces sp. M26 presented a inhibitory halo in Lactobacillus fermentum culture and significant reduction in the culture turbidity (71%) and specific growth rate (56%) when compared to the control. Freezing did not affect the antibacterial activity of the Saccharomyces sp. M26 extract and heating at 90°C for 20 min completely destroyed this activity. It is expected the decrease of lactic acid bacteria growth in the S. cerevisiae alcoholic fermentation should allow for better control of these bacteria in the process. © 2003 Elsevier Ltd. All rights reserved.

Caracterização anatômica da folha de Cymbopogon citratus (DC.) Stapf (Poaceae) e perfil químico do óleo essencial

The objective of the work was to accomplish an anatomical and ultrastructural study of mature leaf of Cymbopogon citratus (Poaceae) and analyze the essential oil through Gas Chromatography (GC). For the anatomical study, the material was fixed in FAA, followed bytheethyl dehydration and infiltration of the material in synthetic resin. For the ultrastructural study, the material was fixed and Kamovsky, dehydrated in acetone, dried to the critical point and metallized. For the analysis in GC, the essential oil it was obtained by steam distillation of leaves and analyzed by Gas Chromatography. Through the anatomical study it was observed that the faces of mesophyll are distinctly, the bulliform cells occupy the adaxial surface of the leaf and in the medium region are situated the biggest vascular bundles involved by sclerenchymatous hem with extensions reaching both epidermis. Between the biggest vascular bundles are observed three to five small vascular bundles, linkage only in the abaxial epidermis. Shortly, pointed and unicellular structures, called prickle-hair, had been observed inserted above the veins and micro-hair, that they consist of a long basal cell and an oval distal cell, that are located between the regions of vascular bundles. The chromatogram sample shows that the analyzed essential oil presented three majority components, responsible for 87% of the relative composition of the oil. These components are monoterpenos, justifying the strong smell of the essential oil.

Composition of coriander essential oil from Brazil

Coriander (Coriandrum sativum L.) is an annual and herbaceous plant, belonging to the Apiaceae family. Native of southern Europe and western Mediterranean region, this herb is cultivated world widely. This species, rich in linalool, has potential using as source of essential oil and as a medicinal plant. It has been used as analgesic, carminative, digestive, depurative, anti-rheumatic and antispasmodic agent. Its fruits (commonly called seeds) are used for flavoring candies, in cookery, perfumery, beverage and in tobacco industry. The aim of this study was to analyze the chemical composition of the seed essential oil of this species grown in Botucatu, São Paulo, Brazil. The experiment was carried out in Lageado Experimental Farm, Department of Plant Production, Agronomical Sciences College, São Paulo State University. The fruits were harvest 108 days after sowing. The essential oils were extracted by hydro distillation, in Clevenger apparatus. 50 g of fruits were used in each extraction. Three extractions were performed during three hours. The essential oils were analyzed in Gas Chromatography Mass Spectrometer (CG-MS, Shimadzu, QP-5000), equipped with DB-5 capillary column (30 m × 0,25 mm × 0,25 mm), split 1/20, injector for 240 C°, detector for 230 C°, dragged by gas He (1,7 mL/min), with programmed temperature for 40 C° (5 min)-150 C°, 4 C°/min; 150 C°-280 C°, 8 C°/min. The identification of the compounds was made by comparison of their spectra of masses with data from CG-MS (Nist 62 lib), literature references and retention index of Kovats. The 18 most important components were identified and quantified. The main components of the oil were linalool (77.48 %), γ-terpinene (4.64 %), α-pinene (3.97 %), limonene (1.28 %), geraniol (0.64 %) and 2-decenal (0.16 %).

Shear bond strength of adhesive systems to enamel and dentin. Thermocycling influence

Objectives: The purpose of the this study was to evaluate the influence of thermocycling on shear bond strength on bovine enamel and dentin surfaces of different adhesive systems. Methods: Thirty sound bovine incisors were sectioned in mesiodistal and inciso-cervical direction obtaining 60 incisal surfaces (enamel) and 60 cervical surfaces (dentin). Specimens were randomly assigned to 3 groups of equal size (n = 40), according to the adhesive system used: I-Single Bond; II-Prime & Bond NT/NRC; III-One Coat Bond. After 24-h storage in distilled water at 37 o C, each main group was divided into two subgroups: A- specimens tested after 24 h storage in distilled water at 37°C; B - specimens submitted to thermocycling (500 cycles). Shear bond strength tests were performed. Data were submitted to ANOVA and Tukey test. Results: Means (MPa) of different groups were: I-AE-16.96, AD-17.46; BE-21.60, BD-12.79; II-AE-17.20, AD-11.93; BE-20.67, BD-13.94; III-AE-25.66, AD-17.53; BE-24.20, BD-19.38. Significance: Thermocycling did not influence significantly the shear bond strength of the tested adhesive systems; enamel was the dental substrate that showed larger adhesive strength; One Coat Bond system showed the best adhesive strength averages regardless of substrate or thermocycling. © 2005 Springer Science + Business Media, Inc.

Rendimento de óleo essencial de Salvia officinalis L. sob ação de reguladores vegetais

This study aimed to evaluate the effect of different plant growth regulators on essential oil yield in Salvia officinalis L. plants. The experiment was held in a greenhouse and the experimental design was completely randomized, with 5 treatments and three replications. The Treatments consisted in the application of gibberellic acid (GA3), benzylaminopurine (BAP), 2-chloroethyl phosphonic acid (ethephon), and Stimulate at 2%, compared with control plants (water). Applications of plant growth regulators were performed in three consecutive periods, in turn, 15, 25 and 35 days after transplanting of seeding germinating in the light at 25°C. The dry mass yield of the aerial part and the oil essential content were determined 131 days after the transplant. The aerial part of the plants was dried in an oven at 35°C; after dry mass determination, the oil was extracted by hydrodistillation and its volume was determined. Plants treated with GA 3 and Stimulate showed increase in essential oil content, while plants treated with BAP and ethephon showed decrease in essential oil volume when compared with the control plants.

An alternative process for butanol production: Continuous flash fermentation

The objective of this work is to introduce and demonstrate the technical feasibility of the continuous flash fermentation for the production of butanol. The evaluation was carried out through mathematical modeling and computer simulation which is a good approach in such a process development stage. The process consists of three interconnected units, as follows: the fermentor, the cell retention system (tangential microfiltration) and the vacuum flash vessel (responsible for the continuous recovery of butanol from the broth). The efficiency of this process was experimentally validated for the ethanol fermentation, whose main results are also shown. With the proposed design the concentration of butanol in the fermentor was lowered from 11.3 to 7.8 g/l, which represented a significant reduction in the inhibitory effect. As a result, the final concentration of butanol was 28.2 g/l for a broth with 140 g/l of glucose. Solvents productivity and yield were, respectively, 11.7 g/l.h and 33.5 % for a sugar conversion of 95.6 %. Positive aspects about the flash fermentation process are the solvents productivity, the use of concentrated sugar solution and the final butanol concentration. The last two features can be responsible for a meaningful reduction in the distillation costs and result in environmental benefits due to lower quantities of wastewater generated by the process. © 2008 Berkeley Electronic Press. All rights reserved.

Anaerobic digestion of stillage to produce bioenergy in the sugarcane-to-ethanol industry

Stillage is the main wastewater from ethanol production, containing a high chemical oxygen demand in addition to acidic and corrosive characteristics. Though stillage may be used as a soil fertilizer, its land application may be considered problematic due its high polluting potential. Anaerobic digestion represents an effective alternative treatment to reduce the pollution load of stillage. In addition, the methane gas produced within the process may be converted to energy, which can be directly applied to the treatment plant. The objective of this paper was to investigate the energetic potential of anaerobic digestion applied to stillage in the sugarcane ethanol industry. An overall analysis of the results indicates energy recovery capacity (ERC) values for methane ranging from 3.5% to 10%, respectively, for sugarcane juice and molasses. The processes employed to obtain the fermentable broth, as well as the distillation step, represent the main limiting factors to the energetic potential feasibility. Considering financial aspects the annual savings could reach up to US$ 30 million due to anaerobic digestion of stillage in relatively large-scale distilleries (365,000 m3 of ethanol per year). The best scenarios were verified for the association between anaerobic digestion of stillage and combustion of bagasse. In this case, the fossil fuels consumption in distilleries could be fully ceased, such the ERC of methane could reach values ranging from 140% to 890%. © 2013 Taylor & Francis.

Sugarcane vinasse: Environmental implications of its use

The inadequate and indiscriminate disposal of sugarcane vinasse in soils and water bodies has received much attention since decades ago, due to environmental problems associated to this practice. Vinasse is the final by-product of the biomass distillation, mainly for the production of ethanol, from sugar crops (beet and sugarcane), starch crops (corn, wheat, rice, and cassava), or cellulosic material (harvesting crop residues, sugarcane bagasse, and wood). Because of the large quantities of vinasse produced, alternative treatments and uses have been developed, such as recycling of vinasse in fermentation, fertirrigation, concentration by evaporation, and yeast and energy production. This review was aimed at examining the available data on the subject as a contribution to update the information on sugarcane vinasse, from its characteristics and chemical composition to alternatives uses in Brazil: fertirrigation, concentration by evaporation, energy production; the effects on soil physical, chemical and biological properties; its influence on seed germination, its use as biostimulant and environmental contaminant. The low pH, electric conductivity, and chemical elements present in sugarcane vinasse may cause changes in the chemical and physical-chemical properties of soils, rivers, and lakes with frequent discharges over a long period of time, and also have adverse effects on agricultural soils and biota in general. Thus, new studies and green methods need to be developed aiming at sugarcane vinasse recycling and disposal. © 2013 Elsevier Ltd. All rights reserved.