Comparison Of Techniques For The Isolation Of Volatiles From Cashew Apple Juice.

The aim of this study was to compare the performance of the following techniques on the isolation of volatiles of importance for the aroma/flavor of fresh cashew apple juice: dynamic headspace analysis using PorapakQ(®) as trap, solvent extraction with and without further concentration of the isolate, and solid-phase microextraction (fiber DVB/CAR/PDMS). A total of 181 compounds were identified, from which 44 were esters, 20 terpenes, 19 alcohols, 17 hydrocarbons, 15 ketones, 14 aldehydes, among others. Sensory evaluation of the gas chromatography effluents revealed esters (n = 24) and terpenes (n = 10) as the most important aroma compounds. The four techniques were efficient in isolating esters, a chemical class of high impact in the cashew aroma/flavor. However, the dynamic headspace methodology produced an isolate in which the analytes were in greater concentration, which facilitates their identification (gas chromatography-mass spectrometry) and sensory evaluation in the chromatographic effluents. Solvent extraction (dichloromethane) without further concentration of the isolate was the most efficient methodology for the isolation of terpenes. Because these two techniques also isolated in greater concentration the volatiles from other chemical classes important to the cashew aroma, such as aldehydes and alcohols, they were considered the most advantageous for the study of cashew aroma/flavor.

Effect Of Pain Chronification And Chronic Pain On An Endogenous Pain Modulation Circuit In Rats.

We tested the hypothesis that chronic pain development (pain chronification) and ongoing chronic pain (chronic pain) reduce the activity and induce plastic changes in an endogenous analgesia circuit, the ascending nociceptive control. An important mechanism mediating this form of endogenous analgesia, referred to as capsaicin-induced analgesia, is its dependence on nucleus accumbens μ-opioid receptor mechanisms. Therefore, we also investigated whether pain chronification and chronic pain alter the requirement for nucleus accumbens μ-opioid receptor mechanisms in capsaicin-induced analgesia. We used an animal model of pain chronification in which daily subcutaneous prostaglandin E2 (PGE2) injections into the rat's hind paw for 14 days, referred to as the induction period of persistent hyperalgesia, induce a long-lasting state of nociceptor sensitization referred to as the maintenance period of persistent hyperalgesia, that lasts for at least 30 days following the cessation of the PGE2 treatment. The nociceptor hypersensitivity was measured by the shortening of the time interval for the animal to respond to a mechanical stimulation of the hind paw. We found a significant reduction in the duration of capsaicin-induced analgesia during the induction and maintenance period of persistent mechanical hyperalgesia. Intra-accumbens injection of the μ-opioid receptor selective antagonist Cys(2),Tyr(3),Orn(5),Pen(7)amide (CTOP) 10 min before the subcutaneous injection of capsaicin into the rat's fore paw blocked capsaicin-induced analgesia. Taken together, these findings indicate that pain chronification and chronic pain reduce the duration of capsaicin-induced analgesia, without affecting its dependence on nucleus accumbens μ-opioid receptor mechanisms. The attenuation of endogenous analgesia during pain chronification and chronic pain suggests that endogenous pain circuits play an important role in the development and maintenance of chronic pain.

Otimização das condições de produção de ésteres etílicos a partir de óleo de peixe com elevado teor de ácidos graxos ômega-3

The production of ethyl esters by alcoholysis is an alternative for splitting triacylglycerols due to the possibility of using low temperatures, which results in oxidative protection of the polyunsaturated fatty acids. Ethyl esters produced under mild conditions of temperature could be used as substrate for obtaining structured lipids. The reaction parameters of production of ethyl esters from fish oil with high content of omega-3 fatty acids by alcoholysis were optimized using response surface methodology. An experimental design (2³) (with levels +1 and -1, six axial points with levels -alpha and +alpha and three central points) was applied. The variables investigated were concentration of catalyst, amount of ethyl alcohol and temperature. Ethyl ester conversion was monitored by high performance size exclusion chromatography (HPSEC) and the best result obtained was 95% conversion rate. The optimal conditions were 40 °C, 1% of NaOH and 36% of ethanol.

Antinociceptive activity of Ipomoea imperati (Vahl) Griseb., Convolvulaceae

Ipomoea imperati (Vahl) Griseb., Convolvulaceae, is used in folk medicine for the treatment of inflammation, swelling and wounds, as well as to treat pains after childbirth and for stomach problems. Administration of ethanol extract, lipid and aqueous fraction of I. imperati(300, 100 and 200 mg/kg) significantly inhibited the abdominal constriction in mice induced by acetic acid; increased the sleeping time evoked by pentobarbital sodium and showed a significant activity by inhibiting formalin-induced paw edema in mice. The same dose of I. imperatialso raised the pain of mice in the hot-plate test and increased the latency at all observation times. The pre-treatment of the animals with naloxone (5 mg/kg, i.p.) suggested the participation of the opioid system in the antinociceptive effect of Ipomoea imperati.

Morphine infusions into the rostrolateral periaqueductal gray affect maternal behaviors

It is well established that morphine inhibits maternal behaviors. Previous studies by our group have shown activation of the rostrolateral periaqueductal gray (rlPAG) upon inhibition-intended subcutaneous injections of morphine. In this context, we demonstrated that a single naloxone infusion into the rlPAG, following this opioid-induced inhibition, reactivated maternal behaviors. Since these data were obtained by using peripheral morphine injections, the present study was designed to test whether morphine injected directly into the rlPAG would affect maternal behaviors. Our hypothesis that morphine acting through the rlPAG would disrupt maternal behaviors was confirmed with a local infusion of morphine. The mothers showed shorter latency for locomotor behavior to explore the home cage (P = 0.049). Inhibition was especially evident regarding retrieving (P = 0.002), nest building (P = 0.05) and full maternal behavior (P = 0.023). These results support the view that opioidergic transmission plays a behaviorally meaningful inhibitory role in the rostrolateral PAG.

Comparação de técnicas de determinação de ésteres em cachaça

An analytical comparison of three different techniques for quantitative profile of esters in cachaça is reported. The Ministério da Agricultura Pecuária e Abastecimento (MAPA) recommends the use of GC/FID or volumetry. Despite being laborious and lacking in chemical speciation, the volumetric technique for total ester content shows to be appropriate, reproducible, and accurate for the analysis of cachaça. However, the GC/FID suggested by MAPA, considering only ethyl acetate, shows inaccuracy, underestimating the total ester content by a median factor of 72%, mainly due to the absence of ethyl lactate analysis. On the other hand, the GC/MS technique that comprises the analysis and speciation of nine esters, including ethyl lactate, proved to be reproducible, simple, fast and accurate for the analysis of total ester content in cachaça. Thus, the total ester content results obtained using GC/FID must be considered with precaution.

Dipeptide synthesis in biphasic medium: evaluating the use of commercial porcine pancreatic lipase preparations and the involvement of contaminant proteases

Dipeptide syntheses starting from Ac-L-Tyr-OEt or Z-L-X-OMe (X: Asp, Tyr, Phe, Arg, Lys or Thr) and glycine amide in biphasic reaction media were achieved using two commercially available porcine pancreatic lipase (PPL) preparations (crude (cPPL) and purified PPL (pPPL)). Under the mild conditions employed, α-chymotrypsin, a pancreatic protease that also presents esterase activity, catalyzed Ac-L-Tyr-Gly-NH2 synthesis with high productivity. Product hydrolysis also occurred in most of the syntheses studied. Polyacrylamide gel electrophoresis, enzymatic assays employing specific chromogenic substrates and size-exclusion chromatography revealed that cPPL and pPPL contain contaminant proteases and, therefore, exhibit esterase and amidase activities. Overall, these data indicate that those contaminants may be the main catalysts of peptide bond synthesis when Nα-blocked-L-amino acid esters and the commercial PPL preparations are used. On the other hand, such data do not contest the possibility of using such enzyme preparations as an inexpensive source of catalysts for dipeptide synthesis under soft conditions.

Enzymatic kinetic resolution of (RS)-1-(Phenyl)ethanols by Burkholderia cepacia lipase immobilized on magnetic nanoparticles

Lipase from Burkholderia cepacia immobilized on superparamagnetic nanoparticles using adsorption and chemisorption methodologies was efficiently applied as recyclable biocatalyst in the enzymatic kinetic resolution of (RS)-1-(phenyl)ethanols via transesterification reactions. (R)-Esters and the remaining (S)-alcohols were obtained with excellent enantiomeric excess (> 99%), which corresponds to a perfect process of enzymatic kinetic resolution (conversion 50%, E > 200). The transesterification reactions catalysed with B. cepacia lipase immobilized by the glutaraldehyde method showed the best results in terms of reusability, preserving the enzyme activity (conversion 50%, E > 200) for at least 8 successive cycles.

Lipid Metabolism in Subclinical Hypothyroidism: Plasma Kinetics of Triglyceride-Rich Lipoproteins and Lipid Transfers to High-Density Lipoprotein Before and After Levothyroxine Treatment

Background: Subclinical hypothyroidism (SCH) has been associated with atherosclerosis, but the abnormalities in plasma lipids that can contribute to atherogenesis are not prominent. The aim of this study was to test the hypothesis that patients with normocholesterolemic, normotriglyceridemic SCH display abnormalities in plasma lipid metabolism not detected in routine laboratory tests including abnormalities in the intravascular metabolism of triglyceride-rich lipoproteins, lipid transfers to high-density lipoprotein (HDL), and paraoxonase 1 activity. The impact of levothyroxine (LT4) treatment and euthyroidism in these parameters was also tested. Methods: The study included 12 SCH women and 10 matched controls. Plasma kinetics of an artificial triglyceride-rich emulsion labeled with radioactive triglycerides and cholesteryl esters as well as in vitro transfer of four lipids from an artificial donor nanoemulsion to HDL were determined at baseline in both groups and after 4 months of euthyroidism in the SCH group. Results: Fractional clearance rates of triglycerides (SCH 0.035 +/- 0.016 min(-1), controls 0.029 +/- 0.013 min(-1), p=0.336) and cholesteryl esters (SCH 0.009 +/- 0.007 min(-1), controls 0.009 +/- 0.009 min(-1), p=0.906) were equal in SCH and controls and were unchanged by LT4 treatment and euthyroidism in patients with SCH, suggesting that lipolysis and remnant removal of triglyceride-rich lipoproteins were normal. Transfer of triglycerides to HDL (SCH 3.6 +/- 0.48%, controls 4.7 +/- 0.63%, p=0.001) and phospholipids (SCH 16.2 +/- 3.58%, controls 21.2 +/- 3.32%, p=0.004) was reduced when compared with controls. After LT4 treatment, transfers increased and achieved normal values. Transfer of free and esterified cholesterol to HDL, HDL particle size, and paraoxonase 1 activity were similar to controls and were unchanged by treatment. Conclusions: Although intravascular metabolism of triglyceride-rich lipoproteins was normal, patients with SCH showed abnormalities in HDL metabolism that were reversed by LT4 treatment and achievement of euthyroidism.

Understanding solvation

The effects of solvents on different chemical phenomena, including reactivity, spectroscopic data, and swelling of biopolymers can be rationalized by use of solvatochromic probes, substances whose UV-vis spectra, absorption, or emission are sensitive to the properties of the medium. Thermo-solvatochromism refers to the effect of temperature on solvatochromism. The study of both phenomena sheds light on the relative importance of the factors that contribute to solvation, namely, properties of the probe, those of the solvent (acidity, basicity, dipolarity/polarizability, and lipophilicity), and the temperature. Solvation in binary solvent mixtures is complex because of ""preferential solvation"" of the probe by some component of the mixture. A recently introduced solvent exchange model is based on the presence in the binary solvent mixture of the organic component (molecular solvent or ionic liquid), S, water, W, and a 1:1 hydrogen-bonded species (S-W). Solvation by the latter is more efficient than by its precursor solvents, due to probe-solvent hydrogen-bonding and hydrophobic interactions; dimethyl sulfoxide (DMSO)-W is an exception. Solvatochromic data are employed in order to explain apparently disconnected phenomena, namely, medium effect on the pH-independent hydrolysis of esters, (1)H NMR data of water-ionic liquid (IL) mixtures, and the swelling of cellulose.

A flow injection procedure based on solenoid micro-pumps for spectrophotometric determination of free glycerol in biodiesel

A flow system designed with solenoid micro-pumps is proposed for fast and greener spectrophotometric determination of free glycerol in biodiesel. Glycerol was extracted from samples without using organic solvents. The determination involves glycerol oxidation by periodate, yielding formaldehyde followed by formation of the colored (3,5-diacetil-1,4-dihidrolutidine) product upon reaction with acetylacetone. The coefficient of variation, sampling rate and detection limit were estimated as 1.5% (20.0 mg L(-1) glycerol, n =10), 34 h(-1), and 1.0 mg L(-1) (99.7% confidence level), respectively. A linear response was observed from 5 to 50 mg L(-1), with reagent consumption estimated as 345 mu g of KIO(4) and 15 mg of acetylacetone per determination. The procedure was successfully applied to the analysis of biodiesel samples and the results agreed with the batch reference method at the 95% confidence level. (C) 2010 Elsevier B.V. All rights reserved.

Cognitive impairment in cancer pain patients receiving opioids

This study aimed to compare cognitive function of cancer pain patients being given opioids during their cancer treatment (n = 14) with that of patients receiving treatment without opioids (n = 12). Correlations between cognitive function, pain intensity, and opioid dose were analyzed. Patients were assessed 3 times in a I-month period, using the Trail-Making Test, Mini-Mental State Examination, Digit Span, and Brief Cognitive Screening Battery. Opioid use was not associated with clear cognitive impairment. Patients being treated without opioids did perform better in the Digit Span Test reverse-order test (P = .029) and the clock drawing test (P = .023), but the differences arose in just I assessment in each case. Pain intensity correlated negatively with scores in the Mini-Mental State Examination (P = .001) and some Brief Cognitive Screening Battery tests (incidental recall, immediate recall, and late recall; P <= .042) in the group receiving opioids. Opioid dose did not correlate with any of the measures of cognitive performance. However, the patients with the worst performance scores were those with more severe pain. Further studies are needed to clearly distinguish between the effects of opioids versus the effects of pain.

Influence of temperature on continuous high gravity brewing with yeasts immobilized on spent grains

Flavor compounds` formation and fermentative parameters of continuous high gravity brewing with yeasts immobilized on spent grains were evaluated at three different temperatures (7, 10 and 15 degrees C). The assays were performed in a bubble column reactor at constant dilution rate (0.05 h(-1)) and total gas flow rate (240 ml/min of CO(2) and 10 ml/min of air), with high-gravity all-malt wort (15 degrees Plato). The results revealed that as the fermentation temperature was increased from 7 to 15 degrees C, the apparent and real degrees of fermentation, rate of extract consumption, ethanol volumetric productivity and consumption of free amino nitrogen (FAN) increased. In addition, beer produced at 15 degrees C presented a higher alcohols to esters ratio (2.2-2.4:1) similar to the optimum values described in the literature. It was thus concluded that primary high-gravity (15 degrees Plato) all-malt wort fermentation by continuous process with yeasts immobilized on spent grains, can be carried out with a good performance at 15 degrees C.

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.