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.

ENZYMATIC RESOLUTION OF ANTIDEPRESSANT DRUG PRECURSORS IN AN UNDERGRADUATE LABORATORY

The use of biocatalysts in synthetic chemistry is a conventional methodology for preparing enantiomerically enriched compounds. Despite this fact, the number of experiments in chemical teaching laboratories that demonstrate the potential of enzymes in synthetic organic chemistry is limited. We describe a laboratory experiment in which students synthesized a chiral secondary alcohol that can be used in the preparation of antidepressant drugs. This experiment was conducted by individual students as part of a Drug Synthesis course held at the Pharmacy Faculty, Lisbon University. This laboratory experiment requires six laboratory periods, each lasting four hours. During the first four laboratory periods, students synthesized and characterized a racemic ester using nuclear magnetic resonance spectroscopy and gas chromatography. During the last two laboratory periods, they performed enzymatic hydrolysis resolution of the racemic ester using Candida antarctica lipase B to yield enantiomerically enriched secondary alcohol. Students successfully prepared the racemic ester with a 70%-81% overall yield in three steps. The enzymatic hydrolysis afforded (R)- secondary alcohol with good enantioselectivity (90%-95%) and reasonable yields (10%-19%). In these experiments, students were exposed to theoretical and practical concepts of aromatic acylation, ketone reduction, esterification, and enzymatic hydrolysis.

CHEMICAL CONSTITUENTS, ANTI-INFLAMMATORY, AND FREE-RADICAL SCAVENGING ACTIVITIES OF Guettarda viburnoides CHAM. & SCHLTDL. (RUBIACEAE)

Chemical investigation of Guettarda viburnoides (leaves) led to the isolation of ursolic acid, uncaric acid, secoxyloganin, and grandifloroside, along with a mixture of quercetin-3-O-β-D-galactopyranoside and quercetin-3-O-β-D-glucopyranoside, and of β-sitosterol and stigmasterol. The structures of the isolated compounds were elucidated on the basis of their NMR data. The crude extract, ethyl acetate fraction, aqueous-methanol fraction, and grandifloroside showed significant DPPH free-radical scavenging activities with IC50 ranging from 18.92 to 26.47 µg mL-1. The topical administration of the crude extract and fractions markedly reduced the croton oil-induced mice ear edema in 67.0%-99.0%. Inhibition of tissue MPO activity was also observed, which demonstrated an anti-inflammatory effect of the G. viburnoides species.

PYROLIGNEOUS LIQUOR PRODUCED FROM ACACIA MEARNSII DE WILD WOOD UNDER CONTROLLED CONDITIONS AS A RENEWABLE SOURCE OF CHEMICALS

Acacia mearnsii de Wild (black wattle) is one of the most important trees planted in Southern Brazil for tannin extraction and charcoal production. The pyrolysis of the black wattle wood used for obtaining charcoal is performed in brick ovens, with the gas fraction being sent directly into the environment. The present study examines the condensable compounds present in the liquor produced from black wattle wood at different thermal degradation conditions, using gas chromatography coupled with mass spectrometry (GC/MS). Branches of black wattle were thermally degraded at controlled ambient and temperature conditions. Overall, a higher variety of compounds were obtained under atmospheric air pressure than under synthetic air pressure. Most of the tentatively identified compounds, such as carboxylic acids, phenols, aldehydes, and low molecular mass lignin fragments, such as guayacol, syringol, and eugenol, were products of lignin thermoconversion. Substituted aromatic compounds, such as vanillin, ethyl vanillin, and 2-methoxy-4-propeny-phenol, were also identified. At temperatures above 200 ºC, furan, 2-acetylfuran, methyl-2-furoate, and furfural, amongst others, were identified as polysaccharide derivatives from cellulose and hemicellulose depolymerization. This study evidences the need for adequate management of the condensable by-products of charcoal production, both for economic reasons and for controlling their potential environmental impact.

PRODUÇÃO DE BIODIESEL A PARTIR DE ÁCIDOS GRAXOS PROVENIENTES DO REFINO DE ÓLEOS VEGETAIS VIA CATÁLISE ÁCIDA HETEROGENEA E MICRO-ONDAS

This work presents the biofuel production results of the esterification of fatty acids (C12-C18) and high-acid-content waste vegetable oils from different soap stocks (soybean, palm, and coconut) with methanol, ethanol, and butanol by acid catalysis. We used Amberlyst-35 (A35) sulfonic resin as a heterogeneous acid catalyst and p-toluenesulfonic acid as a homogeneous catalyst for comparison. Both the heterogeneous (A35) and homogeneous (p-toluenesulfonic acid) reactions were performed with 5% w/w of catalyst. The final products were analyzed by proton nuclear magnetic resonance (1H NMR). The homogeneous catalyzed esterification of fatty acids with methanol, ethanol, and butanol produced esters with yields higher than 90%. In the reaction with fatty acids and methanol catalyzed by A35, the best results were achieved with lauric acid and methanol, with a yield of 97%. An increase in the hydrocarbon chain decreased the rate of conversion and yield for stearic acid with methanol, which was 90%. Maximum biodiesel production was achieved from coconut and soybean soap stocks and methanol (96%-98%), which showed conversions very close to those obtained from their respective fatty acids. Microwave irradiation reduced the reaction time from 6 to 1 h in the esterification reaction of fatty acids with butanol.

ESTUDO FITOQUÍMICO, ATIVIDADE ANTIMICROBIANA E CITOTÓXICA DE ESPÉCIMES DE Leonotis nepetifolia L. R. (Br)

Specimens of Leonotis nepetiflolia were obtained from cultivated and wild environments to verify their influences in chemical composition. Phytochemical analyses were conducted for the ethyl acetate phase obtained by partitioning the crude ethanol extract from the cultivated leaves of L. nepetifolia. In doing so, flavonoid 3',4',5-trimethoxy-6,7-dihidroxyflavone (cirsiliol), a chemotaxonomic marker of the family Lamiaceae, was isolated. The results reveal that all phases and extracts tested exhibited weak to moderate antimicrobial activity against the strains of bacteria tested. The evaluation of in vitrocytotoxic and antitumor activity showed that the ethyl acetate phases obtained from both wild and cultivated leaves exhibit high potential cytotoxic and antitumor (> 78.0% of inhibition) activity. The major component of these phases was identified by high-performance liquid chromatography-diode array detector and nuclear magnetic resonance analyses using both 1D and 2D methods. The results further indicate that the flavonoid cirsiliol is the agent responsible for the activity observed in these phases.

DERIVATIZACIÓN Y CARACTERIZACIÓN ESPECTROSCÓPICA DE UN BIOPOLÍMERO A BASE DE L -LISINA CON ANÁLOGOS DE LA D-BIOTINA: CO -POLI(L-LISINA)-GRAFT -(ε-N-[X-D -BIOTINIL]-L-LISINA)

We report the single-step derivatization reaction of a biopolymer based onL -lysine with D -biotin analogs:Co -poly(L -lysine)-graft-(ε-N -[X-D-biotinyl]-L -lysine) (PLL-X-Biotin). The valeric acid carboxylate of D -biotin is activated to an NHS ester for direct modification of amine groups in proteins and other macromolecules. NHS esters react by nucleophilic attack of an amine in the carbonyl group, releasing the NHS group, and forming a stable amide linkage. NHS-X-Biotin is the simplest biotinylation reagent commercially available. In contrast withD -biotin, it has a longer spacer arm off the valeric acid side chain allowing better binding potential for avidin or streptavidin probes. Derivatization of poly(L -lysine) (PLL) with NHS-X-Biotin led to a copolymer PLL-X-Biotin. UV-Visible, IR-FT and 1H NMR characteristics derived from synthesis are briefly discussed.

FAST GC-FID METHOD FOR MONITORING ACIDIC AND BASIC CATALYTIC TRANSESTERIFICATION REACTIONS IN VEGETABLE OILS TO METHYL ESTER BIODIESEL PREPARATION

A fast gas chromatography with a flame ionisation detector (GC-FID) method for the simultaneous analysis of methyl palmitate (C16:0), stearate (C18:0), oleate (C18:1), linoleate (C18:2) and linolenate (C18:3) in biodiesel samples was proposed. The analysis was conducted in a customised ionic-liquid stationary-phase capillary, SLB-IL 111, with a length of 14 m, an internal diameter of 0.10 mm, a film thickness of 0.08 µm and operated isothermally at 160 °C using hydrogen as the carrier gas at a rate of 50 cm s-1 in run time about 3 min. Once methyl myristate (C14:0) is present lower than 0.5% m/m in real samples it was used as an internal standard. The method was successful applied to monitoring basic and acidic catalysis transesterification reactions of vegetable oils such as soybean, canola, corn, sunflower and those used in frying process.

Determination of herbicides residues in soil by small scale extraction

Herbicides such as trifluralin, simazine, atrazine, metribuzin and metolachlor are used in Brazilian agriculture. The efficiency of a small scale method for determination of these herbicides and two degradation products (deisopropylatrazine and deethylatrazine) in soil samples was evaluated. The compounds were extracted from soil samples (5 g) with 20 ml of ethyl acetate in a mechanical shaker for 50 min. Following the extraction, the supernatant was dried through anhydrous sodium sulphate, concentrated and analysed by high resolution gas chromatography (HRGC) with thermionic specific detection (TSD). Mean recoveries obtained from soil samples fortified at three different levels ranged from 81 to 115% with relative standard deviation (RSD) values varying from 1.2 to 12.7%. The method detection limits ranged from 0.01 to 0.06 mg kg-1. The methodology was applied using soil samples from farms located near the town of Araraquara, in the State of São Paulo, Brazil.

Nematicidal effect of volatile organic compounds (VOCs) on the plant-parasitic nematode Meloidogyne javanica

Previous studies have demonstrated that volatile organic compounds (VOCs), produced by the yeast Saccharomyces cerevisiae, were able to inhibit the development of phytopathogenic fungi. In this context, the nematicidal potential of the synthetic mixture of VOCs, constituted of alcohols and esters, was evaluated for the control of the root-knot nematode Meloidogyne javanica, which causes losses to crops of high economic value. The fumigation of substrate containing second-stage juveniles with VOCs exhibited nematicidal effect higher than 30% for the lowest concentration tested (33.3 µL g-1 substrate), whereas at 66.6 and 133.3 µL g-1 substrate, the nematode mortality was 100%. The present results stimulate other studies on VOCs for nematode management.

Segurança das condições de trabalho de tratorista em aplicações de herbicidas em soja e amendoim e eficiência de equipamentos de proteção individual

Teve-se o objetivo de avaliar a eficiência de um conjunto de equipamentos de proteção individual no controle das exposições proporcionadas ao tratorista aplicando herbicidas nas culturas de soja e de amendoim com o pulverizador de barra e a segurança dessas condições de trabalho. Os pulverizadores utilizados foram os convencionais empregados nas duas culturas para as aplicações de herbicidas em pré-plantio incorporado (ppi), em pré-emergência (pré) e em pós-emergência inicial (pós), com volumes de 200 L ha-1, e 150 L ha-1 apenas na aplicação em pós, na cultura de soja. As exposições sem EPIs foram de 102,77 mL de calda por dia nas aplicações em ppi, 39,62 em pré e 47,14 em pós-emergência. A eficiência dos EPIs no controle das exposições dérmicas foi de 76,5% em ppi, 50,9% em pré e 75,3% em pós-emergência. Na cultura de soja, foram seguras para o tratorista, sem ou com EPIs, as aplicações de pendimethalin, imazaquin e flumetsulam em ppi; de pendimethalin, acetochlor, clomazone, flumioxazin, imazaquin, metribuzin, sulfentrazone, dimethenamid e flumetsulamem em pré, e de bentazone, glyphosate, imazethapyr, quizalofop-ethyl, chlorimuron ethyl e oxasulfuron em pós. Na cultura de amendoim, sem e com EPIs, foi segura a aplicação de pendimethalin em ppi; em pré, a aplicação de alachlor foi classificada como insegura, sem ou com o uso dos EPIs.

Eficiência e qualidade da aplicação de misturas em tanque com adjuvantes na dessecação de corda-de-viola

O objetivo do trabalho foi avaliar se a utilização de adjuvantes nas misturas em tanque de glyphosate + chlorimuron-ethyl e glyphosate + carfentrazone-ethyl influenciam na qualidade da aplicação e eficiência de controle de Ipomoea grandifolia. Treze tratamentos, dispostos em delineamento inteiramente casualizado, foram constituídos pelas misturas em tanque de glyphosate + chlorimuron-ethyl (1.440 + 12,5 g ha-1) e glyphosate + carfentrazone-ethyl (1.440 + 10 g ha-1) isoladas e associados aos adjuvantes Nimbus®, Joint Oil®, Naturl'Oil®, Triunfo 515® e All Fix ®, e uma testemunha sem aplicação. Os adjuvantes utilizados foram eficientes na redução da tensão superficial das caldas; no entanto, não influenciaram nos valores de deposição e na eficiência do controle. Os adjuvantes proporcionaram efeitos distintos na redução da tensão superficial, no pH e na qualidade da aplicação (diâmetro mediano volumétrico, densidade de gotas, potencial de perdas por deriva, área coberta e diâmetro médio das gotas) das misturas em tanque de glyphosate + chlorimuron-ethyl e glyphosate + carfentrazone-ethyl, mas não interferiram na deposição da calda de pulverização sobre os alvos I. grandifolia e lâminas de vidro. Glyphosate + carfentrazone-ethyl apresentou maior velocidade de controle de I. grandifolia em relação ao glyphosate + chlorimuron-ethyl, na ausência ou na presença dos adjuvantes, apesar de o glyphosate + carfentrazone-ethyl associado com Nimbus® e Joint Oil® terem proporcionado às plantas-alvo início de desenvolvimento de novas folhas.

Injúria potencial de herbicidas de solo ao girassol: IV - rendimento de aquênios e componentes do rendimento

Conduziu-se um ensaio em campo na Estação Experimental Agronômica da Universidade Federal do Rio Grande do Sul, em Eldorado do Sul, RS, em 1989/90. O objetivo foi determinar o efeito dos herbicidas clomazone, chlorimuronethyl, imazaquin e imazethaphyr, aplicados em três doses à superfície do solo (PRE) ou incorporados no mesmo (PPI), sobre o rendimento de aquênios de girassol e seus componentes. Os herbicidas de solo para controle de plantas daninhas na cultura da soja com maior potencial de dano ao girassol cultivado em sucessão, conforme indicado pelo rendimento de aquênios, foram os seguintes, em ordem decrescente: imazaquin > clomazone > imazethapyr> chlorimuron-ethyl. O efeito mais pronunciado dos herbicidas foi a redução da população de plantas. Este foi o fator que mais influenciou no rendimento do girassol.

Seletividade de herbicidas do grupo químico das ariloxifenoxipropionatos a cereais de inverno

O objetivo deste trabalho foi investigar o grau de tolerância de cultivares de trigo e aveia aos herbicidas diclofop-methyl, fenoxaprop-ethyl e haloxyfop-methyl, visando a utilização seletiva desses produtos para controlar espécies gramíneas infestantes dessas culturas. Foi instalado um experimento de campo e outro de casa-de-vegetação. Os tratamentos testados no experimento de campo foram diclofop-methyl (540 g/ha), fenoxaprop-ethyl (180 g/ha), haloxyfop-methyl (120 g/ha) e uma testemunha sem tratamento herbicida, aplicados sobre as cultivares 'CTC-1', 'UFRGS-7' e 'UPF-16' de aveia branca, e em aveia-preta. No experimento de casa-de-vegetação testaram-se três doses de fenoxaprop-ethyl (0, 90 e 120 g/ha), aplicadas sobre sete cultivares de trigo ('BR-23', 'BR-35', 'BR-38', 'E-16', 'E-40', 'E-49' e 'E-52'), aveia-branca, aveia-preta e azevém. Como resultados do ensaio de campo, constatou-se que todos os herbicidas testados controlaram com eficiência (acima de 90%) as cultivares de aveia-branca. A aveia-preta mostrou alta sensibilidade ao fenoxaprop-ethyl e ao haloxyfop-methyl e alguma tolerância ao diclofop-methyl; já o trigo mostrou-se tolerante ao diclofop-methyl e ao fenoxaprop-ethyl. Em casa-de-vegetação, as cultivares de trigo 'BR-38', 'E-16', 'E-49' e 'E-52' apresentaram níveis aceitáveis de fitotoxicidade para fenoxaprop-ethyl a 90 g/ha, enquanto as demais cultivares ('BR-23', 'BR-35' e 'E-40') apresentaram danos moderados ao herbicida. Já fenoxaprop-ethyl a 120 g/ha causou aumento no nível de fitotoxicidade para as cultivares de trigo, exceto para 'E-16' e 'E-52'. O azevém mostrou-se tolerante ao herbicida fenoxaprop-ethyl. Conclui-se que existe potencial de uso do herbicida fenoxaprop-ethyl em lavouras de trigo para controlar seletivamente aveia-branca e aveia-preta. O herbicida diclofop-methyl apresenta controle elevado de aveia-branca e reduzido de aveia-preta. Haloxyfop-methyl não evidenciou seletividade ao trigo, controlando com eficiência as gramíneas testadas.

Controle químico de plantas daninhas na cultura do arroz irrigado no estado do Ceará

A presente pesquisa foi conduzida, em condições de irrigação por inundação, em um solo de aluvião eutrófico da Fazenda Experimental Vale do Curu, Pentecoste-CE, em 1995. Teve como objetivo verificar a ação dos herbicidas propanil (4,80 kg/ha de i.a.), fenoxaprop-ethyl (0,14 kg/ha de i.a.), fenoxaprop-p-ethyl (0,11 kg/ha de i.a.), oxadiazon (0,62 kg/ha de i.a.) e as misturas: propanil + molinate (2,52 kg/ha de i.a. + 2,52 kg /ha de i.a.) e propanil + 2,4-D (2,72 kg/ha de i.a. + 2,52 kg/ha de i.a.), no controle das plantas daninhas e efeito fitotoxico sobre as plantas das cultivares de arroz CICA-8 e METICA-1. Foi avaliado também o efeito dos herbicidas sobre a produção de arroz em casca e outros componentes da produção de grãos. Os herbicidas mais eficientes no controle das plantas daninhas foram: propanil e as misturas propanil + 2,4-D e propanil + molinate, com 90%, 98% e 95% de controle, respectivamente. Esses herbicidas proporcionaram também as maiores produções de arroz em casca, semelhantes à testemunha capinada. A altura da planta; o número de dias para o início de floração; o comprimento da panícula e o peso de 1.000 sementes, não foram afetados pelos herbicidas testados. Os sintomas de fitotoxidade causados pelos herbicidas as plantas de arroz, variaram de leve a muito leve, tendo o propanil se mostrado o mais severo, porém sem causar decréscimo significativo a produção de arroz em casca.