A convenient procedure for the synthesis and expansion of bicyclic rings has been developed for the production of probable precursors of non-racemic pyrenophorin, an antibiotic dilactone. The major highlight for this new synthetic methodology came from the use of a readily available reagent of easy manipulation, 9-oxabicyclo[3.3.1]nonane-2,6-diol, for the preparation of the bicyclic intermediate, which sequentially was subjected to oxidative cleavage with butyl nitrite resulted in an isomeric mixture, a dioximedilactone and diisoxazoledilactone.

Um método analítico por cromatografia líquida de alto rendimento com detecção ultravioleta (HPLC-UV) (método A) foi utilizado na determinação simultânea dos valores totais de triacilglicerídeos, diacilglicerídeos, monoacilglicerídeos e ésteres metílicos de ácidos graxos na alcólise de diferentes óleos (algodão, canola, girassol, milho e soja). As análises foram realizadas a 40 ºC por 20 min usando gradiente de metanol (MeOH) e 2-propanol-hexano 5:4 (v/v) (PrHex): 100% de MeOH em 0 min, 50% de MeOH e 50% de PrHex em 10 min mantido com eluição isocrática por 10 min. Outro método por HPLC-UV (método B) com eluição isocrática de acetonitrila por 34 min foi utilizado na determinação da composição de ácidos graxos de óleos analisando seus derivados de éster metílico. Os conteúdos foram analisados com satisfatória repetibilidade (desvio padrão relativo, RSD < 3%), linearidade (r² > 0,99) e sensibilidade (limite de quantificação). O método B foi comparado com o método oficial cromatográfico gasoso com detecção através de ionização por chama (GC-FID) da American Oil Chemists' Society (AOCS) na determinação de ésteres metílicos de ácidos graxos (FAME) em amostras reais de biodiesel

An analytical method using high performance liquid chromatography with UV detection (HPLC‑UV) (method A) was used for simultaneous determination of total amounts of triacylglycerides, diacylglycerides, monoacylglycerides and fatty acid methyl esters in alcoholysis of different oil (cotton, canola, sunflower, corn and soybean) samples. Analyses were carried out at 40 °C for 20 min using a gradient of methanol (MeOH) and 2-propanol-hexane 5:4 (v/v) (PrHex): 100% of MeOH in 0 min, 50% of MeOH and 50% of PrHex in 10 min maintained with isocratic elution for 10 min. Another HPLC-UV method (method B) with acetonitrile isocratic elution for 34 min was used to determine the fatty acid composition of oils analyzing their methyl ester derivatives. Contents were determined with satisfactory repeatability (relative standard deviation, RSD < 3%), linearity (r² > 0.99) and sensitivity (limit of quantification). Method B was compared with an official gas chromatographic method with flame ionization detection (GC-FID) from American Oil Chemists' Society (AOCS) in the determination of fatty acid methyl esters (FAME) in biodiesel real samples.

Poliestireno (PS) é um dos materiais descartáveis mais usados no nosso cotidiano, mas ele não se decompõe facilmente. A adição de amido de mandioca ao PS pode melhorar a sua degradabilidade, tendo em vista ser o amido um polímero biodegradável. O objetivo deste trabalho foi desenvolver blendas de PS e (amido termoplástico) TPS usando dois diferentes plastificantes: glicerol e óleo de buriti, sendo esse óleo um plastificante natural e original para o amido. As blendas PS/TPS foram preparadas em diversas composições por casting e em seguida caracterizadas por termogravimetria (TG), calorimetria exploratória diferencial (DSC), análise termomecânica (TMA) e ressonância magnética nuclear (RMN) 13C. As blendas PS/TPS com óleo de buriti apresentaram uma contínua redução em suas Tg e Ta. Nas blendas com glicerol esses parâmetros permaneceram praticamente constantes. As blendas também foram submetidas a testes de degradação no solo e depois analisadas por TG e RMN. A análise das blendas PS/TPS com óleo de buriti mostrou que houve um aumento da perda de massa nas curvas TG. Nos espectros de RMN 13C, todos os picos referentes ao amido desapareceram, depois do teste de aterro, sugerindo que houve consumo do amido das blendas por microorganismos. De acordo com as análises realizadas, a adição do TPS produzido com óleo de buriti pode melhorar a degradabilidade do PS.

Polystyrene (PS) is one of the most used disposable materials in our daily life, but it does not decompose easily. The addition of cassava starch to PS can improve its degradability since starch is a biodegradable polymer. The aim of this work was to develop blends of PS and thermoplastic starch (TPS) using two different plasticizers: buriti glycerol and buriti oil, a novel and natural plasticizer for starch. PS/TPS blends were prepared in various contents with the casting technique and analyzed by thermogravimetry (TG), differential scanning calorimetry (DSC), thermomechanical analysis (TMA) and 13C nuclear magnetic resonance (NMR). PS/TPS blends with buriti oil presented a continuous reduction in Tg and Ta. For blends with glycerol these parameters remained practically constant. PS/TPS blends were submitted to degradation by soil burial testing and then analyzed by TG and 13C NMR. The analysis of PS/TPS blends with buriti oil indicated an increase in weight loss in the TG curves. All NMR peaks associated with starch disappeared after the soil burying test, probably due to the consumption of starch by microorganisms. The results showed that addition of TPS produced with buriti oil to PS can probably improve its degradability.

The daily consumption of natural antioxidants protects against oxidative damage caused by reactive oxygen species (ROS), including DNA damage, and can reduce the risk of cancer, atherosclerosis and other degenerative diseases. The pulp of pequi (Caryocar brasiliense Camb.) fruit, a tree native to the Brazilian savannah, contains several compounds with antioxidant properties, including carotenoids, vitamin C, phenolic compounds such as flavonoids, saponins and tannins, and essential oils. In this work, we examined the ability of organic and aqueous extracts of pequi fruit pulp to protect against the genotoxicity induced by two antineoplastic drugs, cyclophosphamide (CP) and bleomycin (BLM). Micronucleus tests with mouse bone marrow cells and single-cell gel electrophoresis (comet assay) with peripheral blood leukocytes were used to examine the effects of CP and BLM, respectively. The antioxidant activity of the extracts was assessed by measuring lipid peroxidation with the TBARS method in mouse plasma. The fruit pulp extracts had no clastogenic or genotoxic effects in the cells studied, but both extracts protected against oxidative DNA damage caused by BLM or CP, indicating an ability to inhibit chemical mutagenesis in vivo. However, the protective effect against oxidative DNA damage depended on the dose of extract used. At the doses tested, the aqueous extract enhanced lipid peroxidation in mice of both sexes, especially in males. In contrast, the organic extract enhanced lipid peroxidation only in male mice, with no significant effect in females. These results suggest that, with adequate adjustment of the dose, an organic extract of pequi fruit pulp could be a useful dietary supplement with natural antioxidant activity, at least in females.

The effectiveness of an aqueous extract of Caryocar brasiliense (Caryocaraceae) Camb pulp, popularly known in Brazil as pequi, against clastogenicity induced by cyclophosphamide and bleomycin was evaluated using an in vivo mouse bone marrow cell micronuclei test, an in vitro Chinese hamster ovary cell (CHO-K1) chromosome aberration test and an in vitro antioxidant assay based on the oxidative damage to 2-deoxy-D-ribose (2-DR) induced by hydroxyl radicals (•OH) generated by the reaction between ascorbic acid and (Fe III)-EDTA. In mouse bone marrow cells the extract showed a protective effect against micronuclei induced by cyclophosphamide and bleomycin but did not interfere with polychromatic bone marrow erythrocyte proliferation, except when the mice had been treated with the highest dose of cyclophosphamide. When CHO-K1 cells were pretreated by adding 0.01, 0.05 or 0.1 mL of extract per mL of cell culture medium 24 or 48 h before bleomycin or cyclophosphamide there was a protective effect against chromosome breaks and a significant decrease in the mitotic index (a measure of cytotoxicity) of the CHO-K1 cells. The extract also had a protective effect against oxidative hydroxyl radical damage to 2-DR. This study suggests that C. brasiliense pulp aqueous extract has anticlastogenic potential, possibly due to its antioxidative properties.

(-)-exo-Isobrevicomina (1) e (+)-exo-brevicomina (2) são substâncias voláteis produzidas pelos besouros machos Dendroctonus ponderosae, os quais habitam árvores do gênero Pinus encontradas no hemisfério norte, freqüentemente causando a morte dos hospedeiros. Objetivando a obtenção desses feromônios de agregação, que apresentam a estrutura 6,8-dioxabiciclo[3.2.1]octano, as estratégias sintéticas utilizadas nesse trabalho tiveram como etapas-chaves a di-hidroxilação assimétrica de Sharpless e a adição conjugada, promovida pela liga Zn(Cu) em meio aquoso e acelerada por ultra-som. A adição conjugada dos acetonídeos 13 e 14 às respectivas cetonas insaturadas (metil-vinil-cetona e etil-vinil-cetona) gerou os adutos 15 e 16. A ciclização intramolecular catalisada dos compostos 15 e 16 com ácido fosfotungstico (H3PW12O40) forneceu a exo-isobrevicomina (1) e a exo-brevicomina (2).

(-)-exo-Isobrevicomin (1) and (+)-exo-brevicomin (2) are volatile substances produced by males of the beetles Dendroctonus ponderosae, which inhabit pine trees found in the northern hemisphere, frequently causing the death of their host. In order to obtain these aggregation pheromones, which present the 6,8-dioxabicyclo[3.2.1]octane structure, the synthetic strategies utilized in this work had as key steps the Sharpless asymmetric dihydroxylation and the conjugated addition, promoted by the Zn(Cu) couple in aqueous medium and accelerated by ultrasound. The conjugated addition of acetonides 13 and 14 to the respective unsaturated ketones (methyl vinyl ketone and ethyl vinyl ketone) furnished the adducts 15 and 16. The intramolecular catalyzed cyclization of compounds 15 and 16 with phosphotungstic acid (H3PW12O40) produced exo-isobrevicomin (1) and exo-brevicomin (2).