Evaluation of the kinetics of xylose formation from dilute sulfuric acid hydrolysis of forest residues of Eucalyptus grandis

Dilute acid hydrolysis studies were performed on forest residues of Eucalyptus grandis, in a cylindrical reactor of stainless steel. The kinetics of this hydrolysis reaction was investigated employing 0.65% sulfuric acid, a residue/acid solution ratio of 1/9 (w/w), temperatures of 130, 140, 150, and 160 degrees C, and reaction times in the range 20-100 min. The results showed that, under the optimized conditions of acid hydrolysis employed in this study, the variables temperature and reaction time had a strong influence on hemicellulose removal and a small influence on the degree of lignin and cellulose removal. The highest xylose extraction yield was 87.6% attained at 160 degrees C, after 70 min reaction time, simultaneously with the formation of decomposition products, namely 2.8% acetic acid, 0.6% furfural, and 0.06% 5-hydroxymethylfurfural. A similar xylose extraction yield (82.8%) was observed at 150 degrees C after 100 min, with the formation of 3.2% acetic acid, 1.0% furfural, and 0.07% 5-hydroxymethylfurfural. The kinetic parameters determined at 130, 140, 150, and 160 degrees C for degradation of xylan present in the hemicellulose of the eucalyptus forest residue during the formation of xylose were the first-order reaction rate constants (k) for each temperature, 1.22 x 10(-4), 2.12 x 10(-4), 5.43 x 10(-4), and 9.05 x 10(-4) s(-1), respectively, and an activation energy (E-a) of 101.3 kJ mol(-1).

Treatment of Endometriosis with Local Acetylsalicylic Acid Injection: Experimental Study in Rabbits

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Fatty acid composition of mid-trimester amniotic fluid in women of different ethnicities

Objective: To determine whether the fatty acid composition of mid-trimester amniotic fluid differs by ethnicity and pregnancy outcome. Methods: Fatty acid composition was analyzed by gas chromatography in 198 women undergoing amniocentesis at 15-19 weeks gestation. Cytokine levels were determined by ELISA in a subgroup of 52 subjects. Results: The major fatty acids detected were palmitic acid (31.8%) and stearic acid (31.5%). The n-6 polyunsaturated fatty acids (PUFA), linoleic acid (LA, 18: 2) and arachidonic acid (AA, 20: 4), were 11.3%, while the n-3 PUFA fatty acids, alpha linolenic acid (ALA, 18: 3) and docosahexaenoic acid (DHA, 22: 6), were 3.8% of the total. Palmitic acid was a higher percentage in Asians (40.5%) and Whites (34.5%) than in Blacks (22.2%) and Hispanics (23.7%) (p <= 0.0012). Oleic acid (18:1 n-9) was a higher percentage in Blacks (12.2%) and Hispanics (12.1%) than in Whites (9.2%) or Asians (7.5%) (<= 0.0002). LA and AA were higher in Blacks (9.0%, 5.4%) and Hispanics (8.6%, 4.1%) than in Whites (6.1%, 3.7%) and Asians (5.5%, 2.9%) (p <= 0.0002). DHA did not differ among the ethnic groups or according to pregnancy outcome. A reduced palmitic acid percentage was identified in the six women with preeclampsia (p = 0.0233). Tumor necrosis factor-alpha levels were inversely proportional to the palmitic acid percentage (p = 0.0275) and positively associated with the percentages of stearic (18:0) (p = 0.0132) and oleic (p = 0.0290) acids. Conclusions: Amniotic fluid fatty acid composition differed among the ethnic groups and may influence inflammatory mediator production and susceptibility to preeclampsia.

Transdentinal cytotoxic effects of different concentrations of chlorhexidine gel applied on acid-conditioned dentin substrate

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Suppression of TNBS-induced colitis in rats by 4-methylesculetin, a natural coumarin: Comparison with prednisolone and sulphasalazine

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Structure of a Lys49 phospholipase A(2) homologue isolated from the venom of Bothrops nummifer (jumping viper)

Lys49-Phospholipase A(2) (Lys49-PLA(2)) homologues damage membranes by a Ca2+-independent mechanism which does not involve catalytic activity, We have solved the structure of myotoxin-I, a Lys49-PLA(2) homologue isolated from the venom of Bothrops nummifer (jumping viper) at 2.4 Angstrom resolution using molecular replacement techniques. The final model has been refined to a final R-factor of 18.4% (R-free = 23.2%), and shows excellent geometry, the myotoxin-I from Bothrops nummifer is dimeric in the crystalline state as has been observed for other Lys49-PLA(2) homologues. In addition, a continuous electron density in the active site and substrate binding channel could be successfully modeled as a fatty-acid molecule. (C) 1999 Elsevier B.V. Ltd, All rights reserved.

Powder X-ray characterization of lithium thiazoildine-4-carboxylate

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

A chromene and prenylated benzoic acid from Piper aduncum

In addition to nerolidol, 2',6'-dihydroxy-4'-methoxydihydrochalcone, methyl 2,2-dimethyl-8-(3'-methyl-2'-butenyl)-2H-1-chromene-6-carboxylate, methyl 2,2-dimethyl-2H-1-chromene-6-carboxylate and methyl 8-hydroxy-2,2-dimethyl-2H-1-chromene-6-carboxylate, two new natural products were isolated from the leaves of Piper aduncum, 2,2-dimethyl-2H-1-chromene-6-carboxylic acid and 3-(3',7'-dimethyl-2',6 '-octadienyl)-4-methoxybenzoic acid. The structures of the isolates were established based on analysis of spectroscopic data, including ES-MS. The DNA-damaging activity of the isolated compounds was also investigated against mutant strains of Saccharomyces cerevisiae. (C) 1999 Elsevier B.V. Ltd. All rights reserved.

Synthesis, electrochemical behavior and X-ray crystal and molecular structures of [Fe(diene)(CO)(2)PPh3] (diene = chalcone, sorbic acid)

The compounds [Fe(ch)(CO)(2)PP3] (1) (ch = chalcone) and [Fe(sba)(CO)(2)PPh3] (2) (sba = sorbic acid) were prepared by irradiating the tetracarbonyltriphenylphosphineiron(0) complex in benzene in the presence of ch or sba. The compounds were characterized by infrared and P-31 NMR spectroscopies. Their electrochemical behavior was investigated by cyclic voltammetry and the results suggest that their oxidations occur by more than one electrochemical step, producing free ch and sba, free PPh3 and solvated Fe(III). It was observed that sba ligand contributes more effectively to the stabilization of metal center in these complexes, the X-ray crystal and molecular structures of 1 and 2 were determined; it was shown that the Fe atom adopts a distorted octahedral coordinated geometry in which three of the sites are occupied by the ch or sba ligand. The [Fe(ch)(CO)(2)PPh3] complex is a monomer and the unit cell of complex 2 contains exist two identical and crystallographically independent molecules of [Fe(sba)(CO)(2)PPh3] which are linked by short hydrogen bonds O-H . . .O (C) 2001 Published by Elsevier B.V. Ltd.

Biosynthetic origins of the isoprene units of gaudichaudianic acid in Piper gaudichaudianum (Piperaceae)

The biosynthesis of (2S)-2-methyl-2-(4'-methyl-3-pentenyl)-8-(3-methyl-2-butenyl)-2H-1-benzopyran-6-carboxylic acid (gaudichaudianic acid), the major metabolite in leaves and roots of Piper gaudichaudianum Kunth (Piperaceae), has been investigated employing [1(-13) C]-D-glucose as precursor. The labelling pattern in the isolated gaudichaudianic acid was determined by quantitative 13 C NMR spectroscopy analysis and was consistent with involvement of both mevalonic acid and 2-C-methyl-D-erythritol-4-phosphate pathways in the formation of the dimethylallyl- and geranyl-derived moieties. The results confirmed that both plastidic and cytoplasmic pathways are able to provide isopentenyl diphosphate units for prenylation of p-hydroxybenzoic acid. (c) 2007 Elsevier Ltd. All rights reserved.

Effect of modifiers on thermal behaviour of Se in acid digestates and slurries of vegetables by graphite furnace atomic absorption spectrometry

The influence of sample preparation strategy of vegetables on the electrothermal behaviour of Se without and with chemical modifiers such as Pd(NO3)(2), Pd(NO3)(2) + Mg(NO3)(2), Pd(NO3)(2) + Cd(NO3)(2), pre-reduced Pd, Mg(NO3)(2), and Ni(NO3)(2) was investigated. Acid digestates and slurries of vegetables (0.1% m/v in 1% m/v HNO3 + 0.005% v/v of Triton X-100) were used to prepare reference solutions or slurries. For 10 mul of each modifier tested, pyrolysis and atomization temperatures were evaluated using pyrolysis and atomization curves, respectively. Best conditions, such as thermal stability, signal profile, repeatability and sensitivity were attained using Pd(NO3)(2) as chemical modifier. The following heating program (temperature, ramp/hold time) of the graphite tube of the Varian SpectrAA-800Z atomic absorption spectrometer was used: dry step (85 degreesC, 5/0 s; 95 degreesC, 40/0 s; 120 degreesC, 10/.5 s); pyrolysis step (1400 degreesC, 10/3s); atomization step (2200 degreesC, 1/2 s); clean step (2600 degreesC, 2/0 s). This pyrolysis temperature is 800 degreesC higher than when measuring without any modifier. For 20 muL sample volume and 10 mug Pd(NO3)(2), analytical curves in the 3.0-30 mug Se 1(-1) range were obtained. The method was applied for Se determination in acid digestates and slurries of 10 vegetable samples and one standard reference material (rice flower) and results were in agreement at 95% confidence level. Recoveries varied from 89 to 95% for spiked samples. The lifetime of the graphite tube was ca. 250 firings and the relative standard deviations (n = 12) for a typical acid digestate and slurry containing 20 mug Se 1(-1) were 3.8% and 8.3%, respectively. The limits of detection were 2.0 mug Se 1(-1) and 0.6 mug Se 1(-1) Se for digestates and slurries, respectively. (C) 2002 Elsevier B.V. Ltd. All rights reserved.

AMINO-ACID-SEQUENCE OF TSTX-V, AN ALPHA-TOXIN FROM TITYUS-SERRULATUS SCORPION-VENOM, AND ITS EFFECT ON K+ PERMEABILITY OF BETA-CELLS FROM ISOLATED RAT ISLETS OF LANGERHANS

Highly purified Tityustoxin V (TsTX-V), an alpha-toxin isolated from the venom of the Brazilian scorpion Tityus serrulatus, was obtained by ion exchange chromatography on carboxymethylcellulose-52. It was shown to be homogeneous by reverse phase high performance liquid chromatography, N-terminal sequencing (first 39 residues) of the reduced and alkylated protein and by polyacrylamide gel electrophoresis in the presence of sodium dodecylsulfate and tricine. Following enzymatic digestion, the complete amino acid sequence (64 residues) was determined. The sequence showed higher homology with the toxins from the venoms of the North African than with those of the North and South American scorpions. Using the rate of Rb-86(+) release from depolarized rat pancreatic beta-cells as a measure of K+ permeability changes, TsTX-V (5.6 mu g/ml) was found to increase by 2.0-2.4-fold the rate of marker outflow in the presence of 8.3 mM glucose. This effect was persistent and slowly reversible, showing similarity to that induced by 100 mu-M veratridine, an agent that increases the open period of Na+ channels, delaying their inactivation. It is suggested that, by extending the depolarized period, TsTX-V indirectly affects beta-cell voltage-dependent K+ channels, thus increasing K+ permeability.

2,3-Dihydrobenzofuran neolignans from Aristolochia pubescens

From a hexane extract of stems and roots of Aristolochia pubescens, the new neolignans (2S,3S,1'R,2'R)- and (2S,3S, 1'S,2'R)-2,3-dihydro-5-(1',2'-dihydroxypropyl)-2-(4-hydroxy-3-methylbenzofuran) and (2S,3S,1'R,2'R)- and (2S,3S,1'S,2'R)-2,3-dihydro-5-(1',2'-dihydroxypropyl)-2-(3,4-dimethoxyphenyl)-7-methoxy-3-methyl-benzofuran were isolated, together with the known neolignan licarin A, and its bisnor-neolignan aldehyde and acid derivatives. In addition, sitosterol, 8R,9R-oxide-beta-caryophyllene, kobusone, ent-kauran-16 alpha, 17-diol, vanillin, vanillic acid, (+)-sesamin, (+)eudesmin, and (-)-cubebin were isolated. The structures of the new compounds have been elucidated by spectroscopic methods and by chemical transformation using Mosher's acid chloride. (C) 1999 Elsevier B.V. Ltd. All rights reserved.

Determination of rice herbicides, their transformation products and clofibric acid using on-line solid-phase extraction followed by liquid chromatography with diode array and atmospheric pressure chemical ionization mass spectrometric detection

A simultaneous method for the trace determination of acidic, neutral herbicides and their transformation products in estuarine waters has been developed through an on-line solid-phase extraction method followed by liquid chromatography with diode array and mass spectrometric detection. An atmospheric pressure chemical ionization (APCI) interface was used in the negative ionization mode after optimization of the main APCI parameters. Limits of detection ranged from 0.1 to 0.02 ng/ml for 50 mi of acidified estuarine waters preconcentrated into polymeric precolumns and using time-scheduled selected ion monitoring mode. Two degradation products of the acidic herbicides (4-chloro-2-methylphenol and 2,4-dichlorophenol) did not show good signal response using APCI-MS at the concentration studied due to the higher fragmentor voltage needed for their determination For molinate and the major degradation product of propanil, 3,4-dichloroaniline, positive ion mode was needed for APCI-MS detection. The proposed method was applied to the determination of herbicides in drainage waters from rice fields of the Delta del Ebro (Spain). During the S-month monitoring of the herbicides, 8-hydroxybentazone and 4-chloro-2-methylphenoxyacetic acid were successively found in those samples. (C) 2000 Elsevier B.V. B.V. All rights reserved.