Constituintes químicos de Melaleuca alternifolia (Myrtaceae)

The first chemical study of non-volatile constituents from the bark and stem of Melaleuca alternifolia (Myrtaceae) led to the isolation and identification of 3,3'-O-dimethylellagic acid (1) and five pentacyclic triterpenes: 2alpha,3beta,23-trihydroxyolean-12-en-28-oic acid (arjunolic acid, 2), 3beta-hydroxylup-20(29)-en-27,28-dioic acid (melaleucic acid, 3), betulinic acid (4), betuline (5), 3beta-O-acetylurs-12-en-28-oic acid (6), a mixture of fatty acids and esters, and several hydrocarbons. For 2alpha,3beta,23-trihydroxyolean-12-en-28-oic acid (2) and 3beta-O-acetylurs-12-en-28-oic acid (6) a first detailed assignment of ¹H NMR is presented.

Influência de métodos de digestão e massa de amostra na recuperação de nutrientes em resíduos orgânicos

The influence of nitric-perchloric, aqua regia, dry ashing and microwave digestion methods, in combination with 100 and 200 mg of sample, on the characterization and recovery of nutrients in samples of sludge sewage, poultry, swine, quail and bovine manures, organic compost, organic substrate and humic material were studied. Nitric-perchloric digestion with 200 mg samples recovered the higher nutrient contents. The nitric-perchloric method recovered also low levels of K. Dry ashing caused S volatilization and microwave digestion produced dark color extracts and this impaired S determination. Aqua regia recovered the lowest contents of nutrients in the organic residues evaluated.

Bioreduction of substituted a-tetralones promoted by Daucus carota root

The bioreduction of a series of substituted a-tetralones, carried out using Daucus carota root (carrot), afforded the corresponding homochiral a-tetralols in variable conversions (9 to 90%) and excellent enantiomeric excesses. Two of the assayed a-tetralones were resistant to the bioreduction conditions. The absolute configurations of four a-tetralols were assigned as being (S), by comparison to the (S)-enantiomers obtained by kinetic resolution promoted by CALB-catalysed acetylation. Additionally, the new 5-methoxy-6-methyl-1-tetralone was synthesized in seven steps from 3-methylsalicylic acid.

Otimização de método para determinação de flavonóis e flavonas em frutas por cromatografia líquida de alta eficiência utilizando delineamento estatístico e análise de superfície de resposta

This work optimized the HPLC conditions for the simultaneous determination of luteolin, apigenin, myricetin, quercetin and kaempferol in aglycone form, as well defined the best conditions for hydrolysis/extraction of these flavonoids in fruits, using the statistical central composite design and response surface analysis. A reverse phase method was developed using a gradient of methanol/water acidified with 0.3% formic acid as mobile phase and a photodiode array detector. The samples were extracted with methanol/water (50:50 v/v) at 90 ºC. The optimum time and HCl concentration varied for the different fruits investigated, demonstrating the necessity of optimizing these conditions for each fruit analyzed. Good recovery (87.1 to 96.3%), repeatability and linearity were obtained.

Atividade biológica do lapachol e de alguns derivados sobre o desenvolvimento fúngico e em germinação de sementes

The natural quinones lapachol, α-lapachone and β-lapachone, and the synthetic derivative β-lapachone-3-sulfonic-acid were assayed for inhibition of fungal growth (Fusarium oxysporum) and germination of lettuce seeds (Lactuca sativa L.). β-Lapachone has the strongest activity as a germination inhibitor and lapachol shows no effect. β-Lapachone, followed by lapachol, are the most active in reducing fungal growth.

Steroidal and phenolic compounds from Sidastrum paniculatum (L.) Fryxell and evaluation of cytotoxic and anti-inflammatory activities

Sidastrum paniculatum (L.) Fryxell belongs to the family Malvaceae and is popularly known as "malva roxa" or "malvavisco". The phytochemical study of the hexane, CHCl3 and EtOAc phases from the crude ethanol extract of S. paniculatum led to the isolation of six compounds: a mixture of β-sitosterol and stigmasterol, 4-methoxy-3-hydroxybenzoic acid, 4-methoxy-3-hydroxybenzaldehyde, N-trans-feruloyltyramine and kaempferol-3-O-β-D-(6''-E-p -coumaroyl) glucoside. The structural identification of the compounds was made on the basis of spectroscopic methods such as IR, ¹H and 13C NMR with the aid of including two-dimensional techniques, besides comparison with literature data. The β-sitosterol and stigmasterol mixture showed a significant anti-inflammatory activity.

Leaf and root volatiles produced by tissue cultures of Alpinia zerumbet (pers.) Burtt & Smith under the influence of different plant growth regulators

Volatiles produced by plantlets of Alpinia zerumbet were obtained by means of simultaneous distillation-extraction (SDE). The effects of indole-3-acetic acid, kinetin, thidiazuron and 6-benzylaminopurine on leaf and root volatile composition obtained by tissue cultures were investigated. A higher content of b-pinene and a lower content of sabinene were observed in leaf volatile of plantlets cultured in control, IAA and IAA+ TDZ media, as compared with those of donor plants. In vitro conditions were favorable to increase caryophyllene content. Volatile compounds from the root were characterized mainly by camphene, fenchyl-acetate and bornyl acetate; which constitute about 60% of total volatile.

Determinação simultânea de ácido kójico e hidroquinona por espectrofotometria visível e calibração multivariada

A multivariate spectrophotometric method was developed for analysis of kojic acid/hydroquinone associations in skin whitening cosmetics. The method is based on the reaction between kojic acid and Fe3+ and on the reduction of Fe3+ by hydroquinone and further complexation of Fe2+ with 1,10-phenanthroline. The multivariate model was developed by Partial Least Squares Regression (PLSR), using 25 synthetic mixtures and mean-centered spectral data (350-380 nm). The use of 3 (kojic acid) and 2 (hydroquinone) latent variables permits the observation of mean errors of about 5% in the external validation phase.

Análise dos produtos de degradação do esfenvalerato por SBSE/CLAE-UV/DAD utilizando planejamento fatorial fracionário

A simple procedure based on stir bar sorptive extraction and high-performance liquid chromatography-ultraviolet/photodiode array detection (SBSE/LC-UV/PAD) to determine intermediates and by-products of esfenvalerate is described. The influence of organic modifier, ionic strength, extraction time, temperature and pH were simultaneously evaluated by using a factorial experimental design. The utilization of different organic solvents and desorption times were also investigated to establish the optimal conditions for SBSE liquid desorption. Among the ten different peaks (intermediates and by-products) detected after degradation of esfenvalerate, eight (including 3-phenoxybenzoic acid and 3-phenoxybenzaldehyde) were successfully extracted by SBSE under the optimized conditions.

Avaliação da labilidade de alumínio em infusões de erva-mate empregando voltametria adsortiva de redissolução catódica

Infusions of yerba mate obtained at different stages of industrialization were evaluated to determine the bioavailable fraction of Al. Adsorptive Cathodic Stripping Voltammetry using DASA (complexing agent) was applied to determine the labile fraction of Al at pH 5.0 and pH 8.0 for the total fraction of dissolved Al. The results indicate that on average 60% of Al is complexed with organic compounds, minimizing their bioavailability; however, the labile fraction exceeds by up to 4 times the maximum weekly intake recommended by the World Health Organization.

Phytochemical investigation of Wissadula periplocifolia (L.) C. Presl and evaluation of its antibacterial activity

A phytochemical study on the aerial parts of Wissadula periplocifolia using chromatographic techniques has led to the isolation of sitosterol (1a), stigmasterol (1b), sitosterol 3-O-β-D-glucopyranoside (2a), stigmasterol 3-O-β-D-glucopyranoside (2b), phaeophytin A (3), 13²-hydroxy-(13²-S)-phaeophytin A (4), phaeophytin B (5), 17³-ethoxyphaeophorbide (6), 3,4-seco-urs-4(23),20(30)-dien-3-oic acid (7), 3-oxo-21β-H-hop-22(29)-ene (8), dammaradienone (9a), and taraxastenone (9b). The isolated compounds were characterised by spectroscopic analysis. A preliminary assay to evaluate the antibacterial activity of W. periplocifolia extracts and fractions showed that the dichloromethane, ethyl acetate, and n-butanol fractions were active against Enterococcus faecalis.

Salacia crassifolia (Celastraceae): CHEMICAL CONSTITUENTS AND ANTIMICROBIAL ACTIVITY

The phytochemical study of hexane extract from leaves of Salacia crassifolia resulted in the isolation of 3β-palmitoxy-urs-12-ene, 3-oxofriedelane, 3β-hydroxyfriedelane, 3-oxo-28-hydroxyfriedelane, 3-oxo-29-hydroxyfriedelane, 28,29-dihydroxyfriedelan-3-one, 3,4-seco-friedelan-3-oic acid, 3β-hydroxy-olean-9(11):12-diene and the mixture of α-amirin and β-amirin. β-sitosterol, the polymer gutta-percha, squalene and eicosanoic acid were also isolated. The chemical structures of these constituents were established by IR, 1H and 13C NMR spectral data. Crude extracts and the triterpenes were tested against Entamoeba histolytica, Giardia lamblia and Trichomonas vaginalis and no activity was observed under the in vitro assay conditions. The hexane, chloroform, ethyl acetate and ethanol crude extracts, and the constituent 3,4-seco-friedelan-3-oic acid and 28,29-dihydroxyfriedelan-3-one showed in vitro antimicrobial activity against Salmonella typhimurium, Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, Bacillus cereus, Listeria monocytogenes, Streptococcus sanguinis and Candida albicans.

COMPOSIÇÃO QUÍMICA E TEMPERATURA DE CRISTALIZAÇÃO DE ÉSTERES OBTIDOS DE QUATRO ÓLEOS VEGETAIS EXTRAÍDOS DE SEMENTES DE PLANTAS DO CERRADO

The seed oils from four plants (Scheelea phalerata, Butia capitata, Syagrus romanzoffiana, Terminalia cattapa) found in Mato Grosso do Sul were extracted at good yields. Alkaline transesterification of these seed oils to esters using methanol and ethanol was studied and also produced good yields. Oleic acid (30.5/32.3%), lauric acid (30.7/32.9%) methyl and ethyl esters, were the main components of transesterification of the oils from Scheelea phalerata and Syagrus romanzoffiana. Lauric acid (42.2%), capric acid (15.9%) and caprylic acid (14.6%) methyl and ethyl esters were the main ester components of transesterification of the oil from Butia capitata. Oleic acid (37.8%), palmitic acid (33.5%) and linoleic acid (22.6%) methyl and ethyl esters were the main components of transesterification of oil from Terminalia catappa. Based on differential scanning calorimetry (DSC) studies, the first crystallization peak temperature of esters was observed. Esters derived from oils of the family Arecaceae (Scheelea phalerata, Butia capitata, Syagrus romanzoffiana) showed the lowest points of crystallization, despite having high levels of saturated fat. Esters of Terminalia cattapa oil, rich in unsaturated fat, showed the highest crystallization temperature. This difference in behavior is probably related to the high concentration of esters derived from lauric acid and palmitic acid.

CARBOXYLATION OF SILVER NANOPARTICLES FOR THE IMMOBILIZATION OF β-GALACTOSIDASE AND ITS EFFICACY IN GALACTO-OLIGOSACCHARIDES PRODUCTION

The present study investigated the carboxylation of silver nanoparticles (AgNPs) by 1:3 nitric acid-sulfuric acid mixtures for immobilizing Aspergillus oryzae β-galactosidase. Carboxylated AgNPs retained 93% enzyme upon immobilization and the enzyme did not leach out appreciably from the modified nanosupport in the presence of 100 mmol L-1 NaCl. Atomic force micrograph revealed the binding of β-galactosidase on the modified AgNPs. The optimal pH for soluble and carboxylated AgNPs adsorbed β-galactosidase (IβG) was observed at pH 4.5 while the optimal operating temperature was broadened from 50 ºC to 60 ºC for IβG. Michaelis constant, Km was increased two and a half fold for IβG while Vmax decreases slightly as compared to soluble enzyme. β-galactosidase immobilized on surface functionalized AgNPs retained 70% biocatalytic activity even at 4% galactose concentration as compared to enzyme in solution. Our study showed that IβG produces greater amount of galacto-oligosaccharides at higher temperatures (50 ºC and 60 ºC) from 0.1 mol L-1 lactose solution at pH 4.5 as compared to previous reports.

COMPOSIÇÃO QUÍMICA DAS CASCAS DAS RAÍZES E FLORES DEPoincianella pyramidalis (Fabaceae)

Chemical investigation of the MeOH extract of root barks of P. pyramidallis (Tul.) L. P. Queiroz resulted in the isolation of 3,3'-dimethylellagic acid and 3,3'-dimethylellagic acid-4'-O-β-D-xyloside. Lupeol, β-sitosterol/stigmasterol and the mixture of fatty acid methyl ester derivatives were also obtained. Chromatographic procedures of the MeOH extract of the flowers of this species led to obtain an unusual mixture of fatty alcohols, β-sitosterol/stigmasterol, α-amyrin, β-amyrin and methyl gallate. The structures of the isolates were established by spectral data analysis. This is the first occurrence of 3,3'-dimethylellagic acid, 3,3'-dimethylellagic acid-4'- O-β-D-xyloside and free fatty alcohols in the Fabaceae family.