Aqueous extracts of green yerba maté (Ilex paraguariensis) and green tea (Camellia sinensis) are good sources of phenolic antioxidants, as already described in the literature. The subject of this study were organic extracts from yerba maté, both green and roasted, and from green tea. Their phenolic profiles were characterized by direct infusion electrospray insertion mass spectrometry (ESI-MS) and their free radical scavenging activity was determined by the DPPH assay. Organic extracts containing phenolic antioxidants might be used as natural antioxidants by the food industry, replacing the synthetic phenolic additives used nowadays. Ethanolic and aqueous extracts from green yerba maté, roasted yerba maté and green tea showed excellent DPPH scavenging activity (>89%). The ether extracts from green and roasted yerba maté displayed a weak scavenging activity, different from the behavior observed for the green tea ether extract. The main phenolic compounds identified in green yerba maté water and ethanolic extracts were: caffeic acid, quinic acid, caffeoyl glucose, caffeoylquinic acid, feruloylquinic acid, dicaffeoylquinic acid and rutin. After the roasting process two new Molecules 2007, 12 424 compounds were formed: caffeoylshikimic acid and dicaffeoylshikimic acid. The ethanolic extracts from yerba maté, both roasted and green, with lower content of phenolic compounds (3.80 and 2.83 mg/mL) presented high antioxidant activity and even at very low phenolic concentrations, ether extract from GT (0.07 mg/mL) inhibited DPPH over 90%.

An improved approach for the direct infusion electrospray ionization mass spectrometry (ESI-MS) analysis of vegetable oils is described. The more polar components of the oils, including the fatty acids, are simply extracted with methanol/water (1:1) solution and analyzed by direct infusion ESI-MS in both the negative and positive ion modes. This fingerprinting analysis was applied to genuine samples of olive, soybean, corn, canola, sunflower, and cottonseed oil, to admixtures of these oils, and samples of aged soybean oil. ESI-MS fingerprints in the positive ion mode of the extracts divide the oils into well-defined groups, as confirmed by principal component analysis, whereas ESI-MS fingerprints in the negative ion mode clearly differentiate olive oil from the five other refined oils. The method is also shown to detect aging and adulteration of vegetable oils.

Crude ethanolic extracts of propolis, a natural resin, have been directly analysed using electrospray ionization mass (ESI-MS) and tandem mass spectrometry (ESI-MS/MS) in the negative ion mode. European, North American and African samples have been analyzed, but emphasis has been given to Brazilian propolis which displays diverse and region-dependent chemical composition. ESI-MS provides characteristic fingerprint mass spectra, with propolis samples being divided into well-defined groups directly related to their geographical origins. Chemometric multivariate analysis statistically demonstrates the reliability of the ESI-MS fingerprinting method for propolis. On-line ESI-MS/MS tandem mass spectrometry of characteristic [M - H](-) ion markers provides an additional dimension of fingerprinting selectivity, while structurally characterizing the ESI-MS marker components of propolis. By comparison with standards, eight such markers have been identified: para-coumaric acid, 3-methoxy-4-hydroxycinnamaldehyde, 2,2-dimethyl-6-carboxyethenyl-2H-1-benzopyran, 3-prenyl-4-hydroxycinnamic acid, chrysin, pinocembrin, 3,5-diprenyl-4-hydroxycinnamic acid and dicaffeoylquinic acid. The negative mode ESI-MS fingerprinting method is capable of discerning distinct composition patterns to typify, to screen the sample origin and to reveal characteristic details of the more polar and acidic chemical components of propolis samples from different regions of the world.

Abstract:The antioxidant activity of flavonoids is believed to increase when they are coordinated with transition metal ions. However, the literature on this subject is contradictory and the outcome seems to largely depend on the experimental conditions. In order to understand the contribution of the metal coordination and the type of interaction between a flavonoid and the metal ion, in this study a new metal complex of Cu (II) with naringin was synthesized and characterized by FT-IR, UV-VIS, mass spectrometry (ESI-MS/MS), elemental analysis and 1 H-NMR. The results of these analyses indicate that the complex has a Cu (II) ion coordinated via positions 4 and 5 of the flavonoid. The antioxidant, anti-inflammatory and antimicrobial activities of this complex were studied and compared with the activity of free naringin. The Naringin-Cu (II) complex 1 showed higher antioxidant, anti-inflammatory and tumor cell cytoxicity activities than free naringin without reducing cell viability.

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A simple, fast, and sensitive method for the extraction through direct saponification, separation, quantification, and identification of 12 cholesterol oxidation products (COPs) and cholesterol in a single isocratic, normal-phase, high-performance liquid chromatography (HPLC) was developed. Three detectors were compared for determination of COPs and cholesterol in fish samples: refractive index (RI), ultraviolet (UV), and atmospheric pressure chemical ionization mass spectrometry (APCI-MS). The results did not show significant differences (p > 0.05) between the concentration of the cholesterol oxides and cholesterol obtained with these detectors. The present study demonstrated the presence of 19-hydroxycholesterol, 22"R"-hydroxycholesterol, 22"S"-hydroxycholesterol, 24"S"-hydroxycholesterol, and 25"R"-hydroxycholesterol for the first time in fish samples.

Durante a extração de própolis foram variados alguns fatores para determinar como eles afetam o rendimento e o teor de fenóis totais. Seis amostras diferentes da região sudeste do Brasil foram testadas. Os resultados indicam que os maiores rendimentos de extratos de própolis obtidos por maceração, que também apresentam o maior número de componentes, foram aqueles usando 70% (v/v) ou maior proporção de etanol no solvente. A extração em Soxhlet resultou em um maior rendimento. Não foram observadas diferenças entre extratos de macerações com ou sem luz. Um aumento no rendimento da extração foi observado entre os extratos obtidos por maceração durante 10 e 30 dias, porém o teor de fenóis não variou significativamente nesses extratos. O teor de fenóis totais de todos os extratos variou entre 6,41 e 15,24% mas nenhuma correlação direta foi encontrada com qualquer um dos fatores testados.During the extraction of propolis several factors were varied in order to determine how they affected the yield and phenolic composition of the obtained extracts. Six samples of green propolis from the Southeastern region of Brazil were tested. The results indicate that the highest yield of propolis extracts obtained by maceration, which also had the greatest number of components, were those using 70% (v/v) ethanol or more as a solvent. The Soxhlet extraction procedure resulted in even higher yields. No differences were observed between extracts macerated in the presence or absence of light. An increase in yield was observed between extracts macerated for 10 and 30 days although the phenolic content did not vary significantly. The total phenolic content of all extracts varied from 6.41 to 15.24 % but no direct correlation could be found between any of the factors tested. Keywords: propolis, extraction techniques, high performance liquid chromatography IntroductionPropolis, a resinous substance collected by bees from plants around the hive, is masticated by the bees, salivary enzymes and beeswax added, then applied to the combs and walls of the hive, 1 thereby insulating and reinforcing the hives as well as making the environment aseptic. For beekeepers, propolis is a by-product obtained by scraping the walls of the hives. Crude propolis is composed basically of 55% vegetable resins and balsam, 30% bee wax, 10% essential oil and 5% pollen. 2 Due to its antibiotic and anti-fungal activity, propolis has been used in folk medicine for many centuries 3 and is presently used in health food and various pharmaceutical and cosmetic products such as mouthwash preparations, face creams, lotions and tablets. 1 Traditionally, the fraction soluble in 70% ethanol was extracted and referred to as propolis balsam. 3 In order to avoid the characteristic ethanolic smell and solubility problems of this product, propolis extracts using water 4 or other solvents such as glycerol, edible oils and propylene glycol 5 are presently found on the market. There is no standard either for extractive procedure or composition of products that contain propolis extracts...

Lignin is a polymer found in the cell wall of plants and is one of the main obstacles to the implementation of second-generation ethanol production because it confers the recalcitrance of the lignocellulosic material. The recalcitrance of biomass is affected by the amount of lignin, by its monomer composition, and the way the monomers are arranged in the plant cell wall. Analysis of lignin structure demands mass spectrometry analysis, and identification of oligomers is usually based on libraries produced by laborious protocols. A robust method to build a do-it-yourself lignin oligomer library was tested. This library can be built using commercially available enzymes, standards, and reagents and is relatively easy to accomplish. An ultrahigh performance liquid chromatography–tandem mass spectrometry (UPLC–MS/MS) method for the separation and characterization of monomers and oligomers was developed and was equally applicable to the synthetic lignin and to soluble lignin extracted from a sample of sugar cane.