Petroleomics by ion mobility mass spectrometry: resolution and characterization of contaminants and additives in crude oils and petrofuels

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Ion mobility-mass spectrometry (IM-MS), performed with exceptional resolution and sensitivity in a new uniform-field drift tube ion mobility quadrupole time-of-flight (IM-QTOF) instrument, is shown to provide a useful tool for resolving and characterizing crude oils and their contaminants, as well as petrofuels and their additives. Whereas direct analysis of a crude oil sample contaminated with demulsifiers by the classical ESI(+/-)-FTICR-MS petroleomic approach was unsatisfactory since it responds only with abundance and m/z, and ionization is impaired due to suppression of polar compounds of crude oil by additives likely used in petroleum industry, IM-MS enables mobility separation of ions, particularly of double bond equivalent (DBE) series for a giving CnX class providing separated spectra which are typical obtained either for the crude oil or the contaminants, even suffering of ion suppression or low ionization efficiency. The combination of improved IM resolution and high mass resolving power (40,000@400) of the QTOF instrument provides useful information on class (N, NO, NS, etc.), carbon number (C-n), and unsaturation (DBE) levels for crude oils, allowing one to infer geochemical properties from DBE trends that can be compared with IM-MS data. As demonstrated by results of gasoline samples with additives, the IM-MS system also allows efficient separation and characterization of additives and contaminants in petrofuels.Ion mobility-mass spectrometry (IM-MS), performed with exceptional resolution and sensitivity in a new uniform-field drift tube ion mobility quadrupole time-of-flight (IM-QTOF) instrument, is shown to provide a useful tool for resolving and characterizing71144504463FAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIORCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOFundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)FAPESP [2013/19161-4]2013/19161-4sem informaçãosem informaçãoWe would like to thank the Fundação de Amparo a Pesquisa do Estado de São Paulo (FAPESP) for the scholarship awarded to J.M.S. (process number 2013/19161-4), Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) and Conselho Nacional de Des

Sucrose and color profiles in sugarcane (saccharum sp.) juice analyzed by UFLC-ELSD and synapt high-definition mass spectrometry during radiation treatment

This work evaluated the effect of electron beam irradiation (E-beam) on sugarcane juice and compared the results with preliminary tests performed on sugarcane juice treated with gamma irradiation. The samples were irradiated at 5, 10 and 20 kGy doses and results were compared wile control samples without irradiation. The results showed a significant increase (p≤0.05) of phenolic compounds in both treatments. We also observed increased contents of reducing sugars (glucose and fructose) for the samples irradiated with gamma rays and E-beam measured by the DNS methods. However, there was no significant difference of sugars content measured by chromatographic analyses performed in the sugarcane juice treated with E-beam. Therefore reducing sugars content could be overestimated by the DNS method because salts in sugarcane juice. The treatments were able to reduce sugarcane juice ICUMSA color intensity in both treatments with irradiation. E-beam reduced sugarcane juice color by roughly 49% compared the control, while gamma irradiation reduced it by 30%. © 2016 Elsevier Ltd.This work evaluated the effect of electron beam irradiation (E-beam) on sugarcane juice and compared the results with preliminary tests performed on sugarcane juice treated with gamma irradiation. The samples were irradiated at 5, 10 and 20 kGy doses and12199105FAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO2009/54635-1sem informaçãoAgudo, J.A.G., Cubero, M.T.G., Benito, G.G., Miranda, M.P., Removal of coulored compounds from sugar solutions by adsorption onto anionic resins: equilibrium and kinects study (2002) Sep. Purif. Technol., 29 (3), pp. 1-6Araújo, F.A.D., Processo de clarificação do caldo de cana pelo método da bicarbonatação (2007) Rev. Cienc. 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Differentiation of two morphologically similar Amazonian Aniba species by mass spectrometry leaf fingerprinting

The wood of the Amazonian tree Aniba rosaeodora Ducke has been intensively exploited since the 1920s and remains a much valued material in the perfume industry, leading to its classification as a plant at risk of extinction. Another Amazonian tree, Aniba parviflora, is morphologically highly similar to the much more valuable A. rosaeodora and is illegally commercialized in the seedling stage as counterfeit samples of the much more valuable A. rosaeodora. A technique that would be able to perform rapid, versatile and reliable differentiation of the two species would therefore be valuable to detect such illegal practice. Herein we describe unequivocal differentiation between the two morphologically similar Amazonian Aniba species by leaf mass spectrometry fingerprinting using a small fragment of the leaf. Two ionization techniques were tested (ESI and VL-EASI), and mass spectra obtained from many leaves and at different points on the leaf surface belonging to the same species were very similar and reproducible, whereas spectra between the two species were markedly different. Marker ions detected in each spectrum were structurally characterized based on the accurate mass measurements, MS/MS fragmentation patterns and comparison of the results with reported data. Principal component analysis (PCA) was used to validate the differentiation of the spectra. MS leaf fingerprinting using both ESI and VL-EASI offers therefore a rapid, versatile and reliable method to differentiate morphologically similar plant species, as demonstrated herein for the two Amazonian Aniba species at the seedling stage. This journal is © The Royal Society of Chemistry

Antioxidative, Antiproliferative and Antimicrobial Activities of Phenolic Compounds from Three Myrcia Species

Myrcia bella Cambess., Myrcia fallax (Rich.) DC. and Myrcia guianensis (Aubl.) DC. (Myrtaceae) are trees found in Brazilian Cerrado. They have been widely used in folk medicine for the treatment of gastrointestinal disorders, hemorrhagic and infectious diseases. Few reports have been found in the literature connecting their phenolic composition and biological activities. In this regard, we have profiled the main phenolic constituents of Myrcia spp. leaves extracts by ESI(−)Q-TOF-MS. The main constituents found were ellagic acid (M. bella), galloyl glucose isomers (M. guianensis) and hexahydroxydiphenic (HHDP) acid derivatives (M. fallax). In addition, quercetin and myricetin derivatives were also found in all Myrcia spp. extracts. The most promising antioxidant activity, measured by 2,2-diphenyl-1-picrylhydrazyl (DPPH) scavenging activity, was found for M. fallax extracts (EC50 8.61 ± 0.22 µg·mL−1), being slightly less active than quercetin and gallic acid (EC50 2.96 ± 0.17 and 2.03 ± 0.02 µg·mL−1, respectively). For in vitro antiproliferative activity, M. guianensis showed good activity against leukemia (K562 TGI = 7.45 µg·mL−1). The best antimicrobial activity was observed for M. bella and M. fallax to Escherichia coli (300 and 250 µg·mL−1, respectively). In conclusion, the activities found are closely related to the phenolic composition of these plants