Quantification of Sterol and Triterpenol Biomarkers in Sediments of the Cananéia-Iguape Estuarine-Lagoonal System (Brazil) by UHPLC-MS/MS

Sterols and triterpenols present in sedimentary cores from 12 stations along the Cananéia-Iguape estuarine-lagoonal system were investigated by ultra-high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS). Ten sterols and three triterpenols were identified and quantified, indicating both natural and anthropogenic sources. The relative distributions of sterol and triterpenol showed that the study area is submitted to organic matter (OM) from the Ribeira de Iguape River, seawater, surrounding vegetation, and plankton production. The contribution of these sources depends on the region of the estuarine-lagoonal system and the depth of sediment. Regarding anthropogenic sources, only the samples submitted to freshwater flow from the Ribeira de Iguape River presented concentration of coprostanol higher than the threshold value and diagnostic ratios, coprostanol/(coprostanol + cholestanol) and coprostanol/cholesterol, that indicate moderate contamination by domestic sewage in that area of the estuarine-lagoonal system. Therefore, the approach used herein identified the OM sources and its transport along the Cananéia-Iguape estuarine-lagoonal system (Brazil), which is a complex of lagoonal channels located in a United Nations Educational, Scientific and Cultural Organization (UNESCO) Biosphere Reserve

The use of tucumã of amazonas kernel oil in the biodiesel production

The shortage of electricity is a major reason for the low Human Development Index of isolated communities located in the Amazon basin. The biodiesel produced from vegetable oils extracted from oil seeds native species, in a sustainable way, is one of the best alternative energy for the region. The \x93tucumã of amazonas\x94, Astrocaryum aculeatum, is an Amazon palm tree that produces a much appreciated fruit in the region, from which it obtains kernels that have high content in oil. In this study, we evaluated the production of ethyl biodiesel, from different batches of oil obtained from \x93tucumã of amazonas\x94 kernels with high and low acidity by the transesterification process acidic and basic catalysis, respectively. Different acid catalysts (HCl and H2SO4) and concentrations of each acid (from 0.0625 to 1.000 M) were tested, with ethanol at molar ratio of 1:6 at 90º C for 24 h. In the basic catalysis, NaOH and KOH were tested at the concentration range of 0.5 to 2.0 % with anhydrous ethanol with molar ratio 1:12 and the reactions took place at 80º C for 2 h. The conversion into biodiesel and its quality was analyzed by means reversed-phase high performance liquid chromatography (RP-HPLC) and specific gravity. Chromatographic analysis indicated that the best conversions were achieved by samples of biodiesel with lowest specific gravity (0.87 g.cm-1). The samples of biodiesel with best quality were obtained with acid catalysis at 1.0 M with yield above 90 %. In the basic catalysis, it could be obtained biodiesel with good quality with NaOH at 2.0 %, but at lower yields. However in both types of catalysis, it was possible to identify an excellent potential for the production of this important biofuel from tucumã kernel oil.A falta de disponibilidade de energia elétrica é um dos principais motivos pelo baixo Índice de Desenvolvimento Humano das comunidades isoladas localizadas na Amazônia. O biodiesel produzido a partir de óleos vegetais extraídos de espécies oleaginosas nativas de forma sustentada é uma das melhores alternativas energéticas para a região. O tucumã do amazonas, Astrocaryum aculeatum, é uma espécie de palmeira que produz um fruto muito apreciado na região, a partir do qual se obtém uma amêndoa com alto teor de óleo. Nesse estudo, foi avaliada a produção de biodiesel etílico, a partir de diferentes lotes de óleos de tucumã do amazonas, com índices de acidez baixos e elevados, pela transesterificação por catálise básica e ácida homogêneas, respectivamente. Na catálise ácida, foram testados HCl e H2SO4 como catalisadores nas concentrações de 0,0625 a 1,000 M, empregando etanol hidratado na proporção molar de 1:6 e a reação conduzida a 90 ºC por 24 h. Na catálise básica, foram testados NaOH e KOH, nas proporções de 0,5 a 2,0 %, empregando etanol anidro na proporção molar de 1:12 e a reação conduzida a 80 ºC por 2 h. O biodiesel obtido em cada experimento foi analisado por métodos físicos (massa específica) e cromatográficos (CLAE em fase reversa). Análises cromatográficas indicaram que as melhores conversões foram alcançadas por amostras de biodiesel com massas específicas inferiores a 0,87 g.cm-1. As amostras de biodiesel obtidas com melhor qualidade foram obtidas utilizando-se os catalisadores ácidos a 1,0 M com rendimentos superiores a 90%. No caso da catálise básica, obteve-se biodiesel de boa qualidade empregando-se o catalisador NaOH a 2,0%, porém com rendimento inferior a 60 %. Contudo, em ambos os casos, foi possível identificar um excelente potencial de produção de biocombustível, a partir do óleo das amêndoas de tucumã

Gas chromatography coupled to high resolution time-of-flight mass spectrometry as a high-throughput tool for characterizing geochemical biomarkers in sediments

FAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOThe performance of gas chromatography coupled to high-resolution time-of-flight mass spectrometry (GC-HRTofMS) for characterizing geochemical biomarkers from sediment samples was evaluated. Two approaches to obtain the geochemical biomarkers were tested:2018FAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOFAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULO2012/21395-0The authors would like to thank FAPESP (scholarship 2012/21395-0) for sponsoring this stud

Cinerascetins, new peptides from Hypsiboas cinerascens : MALDI LIFT-TOF-MS/MS de novo sequence and imaging analysis

The continuous search for antimicrobial candidates pushes the pursuit of compounds in the most diverse organisms. Amphibians are known as a prolific source of antibacterial peptides. Based on the rich biodiversity of the Amazon region the unexplored green-tree frog (Hypsiboas cinerascens) was studied for its skin secretion peptide content. Chromatographic separations and established tandem mass spectrometry (MS/MS) methods were used for sequencing the primary structures of the purified compounds. De novo sequencing lead to the identification of five new peptides related to hylaseptin P1, displaying an aminated C-terminal. Sequencing of the complementary deoxyribonucleic acid (cDNA) analysis allowed the disambiguation of isobaric amino-acids for C-01. Matrix assisted laser desorption ionization (MALDI) was carried out, demonstrating the in situ co-occurrence of the identified peptides in the dorsal skin. The major peptide C-01 was synthesized and assayed against a selection of microorganisms displaying minimal inhibitory concentrations (MICs) ranging from 4 to 16 µM

Određivanje fizikalno-kemijskih svojstava, stabilnosti i citotoksičnosti plavog bojila dobivenog iz ploda jague (Genipa americana L.)

Research background. The current commercial scenario indicates an increase in the demand for natural dyes. Compared to synthetic dyes, natural ones have the advantage of being sustainable, making them of great interest for the food and cosmetic industries. The development of new natural dyes is necessary, as well as the carrying out of complementary research regarding the existing ones. Experimental approach. The present study aims to characterize the physicochemical and biological characteristics of the dye obtained from dehydrated endocarp of the genipap (Genipa americana) fruit, as well as perform the relevant stability and cytotoxicity tests. The chemical characterization was performed by HPLC-MS/MS analyses. The stability studies were carried out by spectrophotometry and cytotoxicity assays using cell culture and fluorometric methods. Results and conclusions. After dehydration and milling of the fruit endocarp, water was added to the obtained powder (in the ratio 4:1) to extract the dye. Five compounds were elucidated using HPLC-MS/MS and confirmed the presence of the geniposide as its main compound. With the X-ray diffraction and electron microscopy analysis, we characterised the obtained powder as being amorphous and of porous structure with a variable size. The thermogravimetric analysis indicated a maximum loss of 61% mass after exposure to a temperature range from 240 to 760 °C. The obtained blue dye was stable in the absence of light, at room temperature and had neutral pH. In the cytotoxicity assay, (95.0±1.3) % of viable human fibroblasts were observed after exposure to this dye. The genipap fruit can be a viable alternative to produce a natural blue dye, since it is easy to obtain and has very low toxicity in food, pharmaceutical or cosmetic products. Novelty and scientific contribution. This study demonstrates for the first time the physicochemical and biological properties of a natural blue dye from G. americana fruit.Pozadina istraživanja. Na tržištu se povećala potražnja za prirodnim bojilima. Njihova je prednost nad sintetičkima ta da potječu iz održivih izvora, pa su od velikog interesa za prehrambenu i kozmetičku industriju. Stoga je bitno razvijati nova prirodna bojila, te dodatno ispitati postojeća. Eksperimentalni pristup. Svrha je ovoga rada bila ispitati fizikalno-kemijska i biološka svojstva bojila dobivenog ektrakcijom dehidriranog endokarpa ploda biljke jagua (Genipa americana), te testirati njegovu stabilnosti i citotoksičnost. Kemijska svojstva određena su spregnutim sustavom visokodjelotvorne tekućinske kromatografije i tandemne spektrometrije masa (HPLC-MS/MS). Stabilnost je ispitana spektrofotometrijom, a citotoksičnost pomoću staničnih kultura i fluorometrijom. Rezultati i zaključci. Nakon dehidriranja i meljave endokarpa jague, za ekstrakciju bojila dobiveni je prah pomiješan s 20 % vode. Metodom HPLC-MS/MS detektirano je pet spojeva, te je potvrđena prisutnost genipozida kao glavnog sastojka. Rendgenskom difrakcijom i elektronskom mikroskopijom struktura dobivenog praha okarakterizirana je kao amorfna i porozna, s česticama različitih veličina. Termogravimetrijskom je analizom utvrđen gubitak od 61 % mase praha nakon izlaganja temperaturama između 240 i 760 °C. Dobiveno je bojilo bilo stabilno u mraku, pri sobnoj temperaturi i neutralnoj pH-vrijednosti. U testu citotoksičnosti utvrđena je stopa preživljavanja fibroblasta od (95,0±1,3) % nakon njihovog izlaganja bojilu. Stoga je zaključeno da plod voćke jagua može poslužiti kao izvor prirodnog bojila za primjenu u prehrambenoj, farmaceutskoj i kozmetičkoj industriji, jer se jednostavno dobiva i ima vrlo malu toksičnost. Novina i znanstveni doprinos. U ovom su radu po prvi put opisana fizikalno-kemijska i biološka svojstva prirodnog bojila dobivenog iz ploda voćke G. americana

Analgesic, Anti-Inflammatory, and Antioxidant Activities of Byrsonima duckeana

Background. Byrsonima is a promising neotropical genus, rich in flavonoids and triterpenes, with several proven pharmacological properties. Nevertheless, Byrsonima duckeana W. R. Anderson is an Amazonian species almost not studied. Objective. To assess the antioxidant, anti-inflammatory, and analgesic activities of Byrsonima duckeana leaves. Materials and Methods. We analyzed an ethanol extract and its fractions for polyphenol content and UHPLC-MS/MS, phosphomolybdenum, DPPH, TBARS antioxidant tests, formalin-induced pain, carrageenan-induced peritonitis, acetic acid-induced abdominal writhings, and hot plate assays. Results. All the samples showed high polyphenol content and antioxidant capacity in the phosphomolybdenum, DPPH, and TBARS tests. We identified ethyl gallate, quinic acid, gallic acid, catechin, epicatechin, quercetrin, and quercetin in the samples. B. duckeana was able to reduce leukocyte migration in the carrageenan-induced peritonitis by 43% and the licking time in the formalin test by 57%. In the acetic acid-induced writhing test, the chloroform (FCL) and ethyl acetate (FEA) fractions were the most active samples. FEA was selected for the hot plate test, where all the dosages tested (5, 50, and 200 mg·kg−1) showed significant analgesic activity. Conclusion. B. duckeana has interesting analgesic and antioxidant activities, due to its high phenolic content, especially phenolic acids

Integrative analysis based on HPLC-DAD-MS/MS and NMR of Bertholletia excelsa Bark Biomass Residues: Determination of ellagic acid derivatives

Bertholletia excelsa Bonpl. (Lecythidaceae) is a South American tree worldwide known for providing the Brazil nuts. In the Amazon Region, B. excelsa is found in monocultures, integrating agroforestries and providing raw materials for food and timber industries. Through the application of an integrative analysis based on high-performance liquid chromatography coupled with diode array detector and tandem mass spectrometry (HPLC-DAD-MS/MS) and nuclear magnetic resonance (NMR) techniques, the present study showed that B. excelsa bark biomass residues contain large quantities of ellagic acid (EA) and its derivatives. Qualitatively, five compounds were characterized for the first time in this species. Quantitations were carried out to determine the total amount of these compounds in outer and inner bark tissues. A total of 4.96 and 44.09 g of EA derivatives per kg of dry residues was determined for the outer and inner barks, respectively. Among the EA derivatives, eschweilenol C, ellagic acid and valoneic acid dilactone were the main compounds. These results pointed B. excelsa barks as a valuable biomass residue with potential to be source of health-promoting compounds. Therefore, a potential raw material as source of valuable bioactive phenolic compounds is described herein. © 2019 Sociedade Brasileira de Química

The bitter end: primate avoidance of caterpillar-infested trees in a central Amazon flooded forest.

Animal-plant interactions are often mediated by chemical compounds. It has been widely reported that herbivore damage to plants induces chemical defenses which may then affect subsequent interactions with both invertebrate and vertebrate herbivores. Our study investigated the effects of the interaction between larvae of an unindentified Nymphalid butterfly and the tanimbuca tree (Buchenavia ochroprumna Eichler Combretaceae) on subsequent folivory by a primate, the golden-backed uacari (Cacajao ouakary Spix, 1823, Pitheciidae). Primate feeding observations, records of the extent of Nymphalid/Buchenavia interactions and tree distribution occurred in JaĂş National Park, Amazonas State, Brazil. Ivlev Electivity Index values showed that uacaris strongly rejected trees infested by caterpillars (- 0.68), while uninfested trees were highly selected by them (+ 0.84). Given this behavior, we suggest that uacari monkeys may be deterred by (i) caterpillars; (ii) change in leaf chemical composition induced by caterpillars; (iii) or a combination of both.The accepted manuscript in pdf format is listed with the files at the bottom of this page. The presentation of the authors' names and (or) special characters in the title of the manuscript may differ slightly between what is listed on this page and what is listed in the pdf file of the accepted manuscript; that in the pdf file of the accepted manuscript is what was submitted by the author