Evaluation of laser induced breakdown spectroscopy for cadmium determination in soils

Cadmium is known to be a toxic agent that accumulates in the living organisms and present high toxicity potential over lifetime. Efforts towards the development of methods for microanalysis of environmental samples, including the determination of this element by graphite furnace atomic absorption spectrometry (GFAAS). inductively coupled plasma optical emission spectrometry (ICP OES), and inductively coupled plasma-mass spectrometry (ICP-MS) techniques, have been increasing. Laser induced breakdown spectroscopy (UBS) is an emerging technique dedicated to microanalysis and there is a lack of information dealing with the determination of cadmium. The aim of this work is to demonstrate the feasibility of LIBS for cadmium detection in soils. The experimental setup was designed using a laser Q-switched (Nd:YAG, 10 Hz, lambda = 1064 nm) and the emission signals were collimated by lenses into an optical fiber Coupled to a high-resolution intensified charge-coupled device (ICCD)-echelle spectrometer. Samples were cryogenically ground and thereafter pelletized before LIBS analysis. Best results were achieved by exploring a test portion (i.e. sampling spots) with larger surface area, which contributes to diminish the uncertainty due to element specific microheterogeneity. Calibration curves for cadmium determination were achieved using certified reference materials. The metrological figures of merit indicate that LIBS can be recommended for screening of cadmium contamination in soils. (C) 2009 Elsevier B.V. All rights reserved.

Characterization of different fruit wines made from cacao, cupuassu, gabiroba, jaboticaba and umbu

The main aim of this work was to produce fruit wines from pulp of gabiroba, cacao, umbu, cupuassu and jaboticaba and characterize them using gas chromatography-mass spectrometry for determination of minor compounds and gas chromatography-flame ionization detection for major compounds. Ninety-nine compounds (C(6) compounds, alcohols, monoterpenic alcohols, monoterpenic oxides, ethyl esters, acetates, volatile phenols, acids, carbonyl compounds, sulfur compounds and sugars) were identified in fruit wines. The typical composition for each fruit wine was evidenced by principal component analysis and Tukey test. The yeast UFLA CA 1162 was efficient in the fermentation of the fruit pulp used in this work. The identification and quantification of the compounds allowed a good characterization of the fruit wines. With our results, we conclude that the use of tropical fruits in the production of fruit wines is a viable alternative that allows the use of harvest surpluses and other underused fruits, resulting in the introduction of new products into the market. (C) 2010 Elsevier Ltd. All rights reserved.

Fermentative behavior of Saccharomyces strains during microvinification of raspberry juice (Rubus idaeus L.)

Sixteen different strains of Saccharomyces cerevisiae and Saccharomyces bayanus were evaluated in the production of raspberry fruit wine. Raspberry juice sugar concentrations were adjusted to 16 degrees Brix with a sucrose solution, and batch fermentations were performed at 22 degrees C. Various kinetic parameters, such as the conversion factors of the substrates into ethanol (Y(p/s)), biomass (Y(x/s)), glycerol (Y(g/s)) and acetic acid (Y(ac/s)), the volumetric productivity of ethanol (Q(p)), the biomass productivity (P(x)), and the fermentation efficiency (E(f)) were calculated. Volatile compounds (alcohols, ethyl esters, acetates of higher alcohols and volatile fatty acids) were determined by gas chromatography (GC-FID). The highest values for the E(f), Y(p/s), Y(g/s), and Y(x/s) parameters were obtained when strains commonly used in the fuel ethanol industry (S. cerevisiae PE-2, BG, SA, CAT-1, and VR-1) were used to ferment raspberry juice. S. cerevisiae strain UFLA FW 15, isolated from fruit, displayed similar results. Twenty-one volatile compounds were identified in raspberry wines. The highest concentrations of total volatile compounds were found in wines produced with S. cerevisiae strains UFLA FW 15 (87,435 mu g/L), CAT-1 (80,317.01 mu g/L), VR-1 (67,573.99 mu g/L) and S. bayanus CBS 1505 (71,660.32 mu g/L). The highest concentrations of ethyl esters were 454.33 mu g/L, 440.33 mu g/L and 438 mu g/L for S. cerevisiae strains UFLA FW 15, VR-1 and BG, respectively. Similar to concentrations of ethyl esters, the highest concentrations of acetates (1927.67 mu g/L) and higher alcohols (83,996.33 mu g/L) were produced in raspberry wine from S. cerevisiae UFLA FW 15. The maximum concentration of volatile fatty acids was found in raspberry wine produced by S. cerevisiae strain VR-1. We conclude that S. cerevisiae strain UFLA FW 15 fermented raspberry juice and produced a fruit wine with low concentrations of acids and high concentrations of acetates, higher alcohols and ethyl esters. (c) 2010 Elsevier B.V. All rights reserved.

Identification of new ozonation disinfection byproducts of 17 beta-estradiol and estrone in water

Estrogens are a class of micro-pollutants found in water at low concentrations (in the ng L(-1) range), but often sufficient to exert estrogenic effects due to their high estrogenic potency. Disinfection of waters containing estrogens through oxidative processes has been shown to lead to the formation of disinfection byproducts, which may also be estrogenic. The present work investigates the formation of disinfection byproducts of 17 beta-estradiol (E2) and estrone (E1) in the treatment of water with ozone. Experiments have been carried out at two different concentrations of the estrogens in ground water (100 ng L(-1) and 100 mu g L(-1)) and at varying ozone dosages (0-30 mg L(-1)). Detection of the estrogens and their disinfection byproducts in the water samples has been performed by means of ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) with a triple quadrupole (QqQ) and a quadrupole-time of flight (QqTOF) instrument. Both E2 and El have been found to form two main byproducts, with molecular mass (MM) 288 and 278 in the case of E2, and 286 and 276 in the case of El, following presumably the same reaction pathways. The E2 byproduct with MM 288 has been identified as 10epsilon-17beta-dihydroxy-1,4-estradieno-3-one (DEO), in agreement with previously published results. The molecular structures and the formation pathways of the other three newly identified byproducts have been suggested. These byproducts have been found to be formed at both high and low concentrations of the estrogens and to be persistent even after application of high ozone dosages. (C) 2011 Elsevier Ltd. All rights reserved.

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.

Isolation and analysis of bioactive isoflavonoids and chalcone from a new type of Brazilian propolis

Activity-directed fractionation and purification processes were employed to identify isoflavonoids with antioxidant and antimicrobial activities from Brazilian red propolis. Crude propolis was extracted with ethanol (80%. v/v) and fractioned by liquid-liquid extraction technique using hexane and chloroform. Since chloroform fraction showed strong antioxidant and antimicrobial activities it was purified and isolated using various chromatographic techniques. Comparing our spectral data (UV, NMR, and mass spectrometry) with values found in the literature, we identified two bioactive isoflavonoids (vestitol and neovestitol), together with one chalcone (isoliquiritigenin). Vestitol presented higher antioxidant activity against beta-carotene consumption than neovestitol. The antimicrobial activity of these three compounds against Staphylococcus aureus, Streptococcus mutans, and Actinomyces naeslundii was evaluated and we concluded that isoliquiritigenin was the most active one with lower MIC, ranging from 15.6 to 62.5 mu g/mL. Our results showed that Brazilian red propolis has biologically active isoflavonoids that may be used as a mild antioxidant and antimicrobial for food preservation. (C) 2010 Elsevier B.V. All rights reserved.

Metallomics and chemical speciation: towards a better understanding of metal-induced stress in plants

Most metal ions are toxic to plants, even at low concentrations, despite the fact that some are essential for growth and play key roles in metabolism. The majority of metals induce the formation of reactive oxygen species, which require the synthesis of additional antoxidant compounds and enzymes for their removal. New techniques that have greatly improved the identification, localisation and quantification of metals within plant tissues have led to the science of metallomics. This advancement in knowledge should eventually allow the characterisation of plants used in the process of phytoremediation of soils contaminated with toxic metals.

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.

Long-Chain Acyl-Homoserine Lactones from Methylobacterium mesophilicum: Synthesis and Absolute Configuration

The acyl-homoserine lactones (acyl-HSLs) produced by Methylobacterium mesophilicum isolated from orange trees infected with the citrus variegated chlorosis (CVC) disease have been studied, revealing the occurrence of six long-chain acyl-HSLs, i.e., the saturated homologues (S)-N-dodecanoyl (1) and (S)-N-tetradecanoyl-HSL (5), the uncommon odd-chain N-tridecanoyl-HSL (3), the new natural product (S)-N-(2E)-dodecenoyl-HSL (2), and the rare unsaturated homologues (S)-N-(7Z)-tetradecenoyl (4) and (S)-N-(2E,7Z)-tetradecadienyl-HSL (6). The absolute configurations of all HSLs were determined as 3S. Compounds 2 and 6 were synthesized for the first time. Antimicrobial assays with synthetic acyl-HSLs against Gram-positive bacterial endophytes co-isolated with M. mesophilicum from CVC-infected trees revealed low or no antibacterial activity.

Influence of ethylene on carotenoid biosynthesis during papaya postharvesting ripening

The carotenoid composition was evaluated during ripening of papaya cv. `Golden` under untreated (control) conditions and treated with ethylene and 1-methylcyclopropene (1-MCP). At the end of the experiments, the total carotenoid content in the control group (2194.4 mu g/100 g) was twice as high as that found in ethylene (1018.1 mu g/100 g) and 1-MCP (654.5 mu g/100 g) gas-treated samples. Separation of 21 carotenoids by HPLC connected to photodiode array and mass spectrometry detectors showed that no minor carotenoids seemed to be particularly favoured by the treatments. Lycopene was the major carotenoid in all untreated and gas-treated samples, ranging from 461.5 to 1321.6 mu g/100 g at the end of the experiments. According to the proposed biosynthetic pathway, lycopene is the central compound, since it is the most abundant carotenoid indicating a high stimulation of its upstream steps during ripening, and it is the source for the synthesis of other derivative compounds, such as beta-cryptoxanthin. The influence of both gas treatments on the carotenoid biosynthetic pathway was considered. (C) 2011 Elsevier Inc. All rights reserved.

Phenolic composition and antioxidant activity of culms and sugarcane (Saccharum officinarum L.) products

The present work reports amounts of flavonoids and phenylpropanoids of culms of three sugarcane varieties and of raw juice, syrup, molasse and VHP sugar. The antioxidant activity of those materials was evaluated by the DPPH and beta-carotene/linoleic acid methods. The predominant phenolics in culms were phenylpropanoids (caffeic, chlorogenic and coumaric acids), while flavones (apigenin, tricin and luteolin derivatives) appeared in lower amounts. Differences were noted either among phenolic profiles of sugarcane culms or between culms and sugarcane products. The antioxidant activities of solutions from most samples were similar or higher than a 80 mu M Trolox solution. (C) 2010 Elsevier Ltd All rights reserved.

Evaluation of gamma-radiation on green tea odor volatiles

The aim of this study was to evaluate the gamma radiation effects on green tea odor volatiles in green tea at doses of 0, 5, 10, 15 and 20 kGy. The volatile organic compounds were extracted by hydrodistillation and analyzed by GC/MS. The green tea had a large influence on radiation effects, increasing the identified volatiles in relation to control samples. The dose of 10 kGy was responsible to form the majority of new odor compounds following by 5 and 20 kGy. However, the dose of 5 kGy was the dose that degraded the majority of volatiles in non-irradiated samples, following by 20 kGy. The dose of 15 kGy showed has no effect on odor volatiles. The gamma radiation, at dose up to 20 kGy, showed statistically no difference between irradiated and non irradiated green tea on odors compounds. (C) 2010 Elsevier Ltd. All rights reserved.

Cultivar influence on carotenoid composition of loquats from Brazil

Cultivar, growing conditions and geographical origin are factors that influence the carotenoid composition in fruits. Because the loquat cultivars evaluated in this study, CentenAria, Mizauto, Mizuho, Mizumo and Nectar de Cristal, have not previously been investigated, the present work was carried out to determine and compare the carotenoid composition of these five loquat cultivars, by applying high-performance liquid chromatography connected to a photodiode array and mass spectrometry detectors (HPLC-PDA-MS/MS). Twenty-five carotenoids were separated on a C(30) column, and 23 of them were identified. All-trans-beta-carotene (19-55%), all-trans-beta-cryptoxanthin (18-28%), 5,6:5`,6`-diepoxy-beta-cryptoxantilin (9-18%) and 5,6-epoxy-beta-cryptoxanthin (7-10%) were the main carotenoids. The total carotenoid content ranged from 196 mu g/100 g (cv. Nectar de Cristal) to 3020 mu g/100 g (CV. Mizumo). The carotenoid profile of cv. Nectar de Cristal was different from the other cultivars, which was in agreement with its cream pulp colour, in contrast to the other four cultivars with orange pulp colour. Cultivars Mizauto, Mizuho, Mizumo and CentenAria showed provitamin A values between 89 and 162 mu g RAE/100 g, and can be considered good source of this provitamin. (C) 2009 Elsevier Inc. All rights reserved.

Composition of phenolic acids content in apple (Malus sp) pomace

The present work aimed the study of phenolic acids composition in apple pomace of Gala and Fuji cultivars. Phenolic acids were fractionated in phenolic acids, esterified and insoluble and analyzed by gas chromatography-mass spectrometry (GC-MS). Sixteen phenolic acids were identified in apple pomace samples. Total phenolic acids in apple pomace from Gala and Fuji cultivars were, in dry weight, 93.94 mg/g and 68.38 mg/g, respectively. Content of free phenolic acids in apple pomace from Gala cultivar was 29.11 mg/g and the following acids were identified: salicylic, protocatequinic, quinic, p-coumaric, gallic, propylgallate and synapic. Content of free phenolic acids in apple pomace from Fuji cultivar was 16.03 mg/g and the following acids were identified: salicylic, protocatequinic, gallic, ferulic and sinapic. Salicylic was the predominant free phenolic acids found in both cultivars, consisting of 91.67% and 63.57% of the free phenolic acids in Gala and Fuji cultivars, respectively. Chlorogenic acid (1.147 mg/g) was found only in apple pomace from Fuji cultivar. Content of esterified phenolic acids in apple pomace from Gala and Fuji cultivars were 53.75 mg/g and 48.29 mg/g, respectively. It was verified that the predominant esterified phenolic acid in pomace from apple Gala is derived from salicylic acid (52.76 mg/g). Acids derived from gallic acid (0.175 mg/g), propylgallate acid (0.198 mg/g), ferulic acid (0.159 mg/g) and sinapic acid (0.140 mg/g) were also found in Gala cultivar. Regarding to pomace from cultivar Fuji, the main esterified phenolic acid found is also derived from salicylic acid (47.42 mg/g) followed by gallic acid (0.270 mg/g), benzoic acid (0.194 mg/g) and sinapic acid (0.115 mg/g). Content of insoluble phenolic acids in apple pomace from Gala and Fugi cultivars were, in dry weight, 11.08 mg/g and 4.05 mg/g, respectively Insoluble phenolic acids derived from salicylic acid were found in higher concentrations in apple pomace from both cultivars.

Cannabinoid contents in cannabis products seized in Sao Paulo, Brazil, 2006-2007

A rapid and simple method was optimized for determination of Delta(9)-tetrahydrocannabinol (Delta(9)-THC), cannabidiol (CBD), and cannabinol (CBN) contents in cannabis products by gas chromatography with flame-ionization detection (GC-FID), using diazepam as internal standard. All parameters of validation of the method such as linearity, intraassay precision, and limits of detection and quantification of the analytes were satisfactory. Using the described method, cannabinoid contents of 55 cannabis product samples seized in Sao Paulo City, Brazil, in 2006 and 2007 were measured. Delta(9)-THC content in marijuana and hashish samples varied between 0.08% and 5.5%, with an average of 2.5%. The phenotypic ratio showed that the products were able to be designated as ""drug type.""