Wood chemotaxonomy via ESI-MS profiles of phytochemical markers: the challenging case of african versus brazilian mahogany woods

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)The harvesting of Brazilian mahogany (Swietenia macrophylla) is a main cause of the Brazilian Amazon deforestation and has been therefore prohibited. African mahogany (Khaya ivorensis) was then introduced for Amazon reforestation and the commercialization of such wood is legal, thus creating a challenging problem for wood certification. Herein we report that a wood chemotaxonomic method based on distinct profiles of phytochemical markers is able to promptly characterize both the native and foreign mahogany species. This challenging task has been performed via a simple, fast and unambiguous methodology using direct electrospray ionization mass spectrometry (ESI-MS) analysis of a simple methanolic extract of a tiny wood chip. Typical limonoids such as khivorin, khayanolide A and mexicanolide for African mahogany and phragmalin-type limonoids for the native Brazilian species, as well as distinct polyphenols such as catechin derivatives and cinchonain, form the characteristic phytochemical marker pools for both species. This rapid methodology could therefore be used to monitor legal and illegal mahogany tree harvesting, and hence to control Amazon deforestation. It could also be applied to create a wood certification program for African and Brazilian mahogany trees, as well as for wood certification in general.The harvesting of Brazilian mahogany (Swietenia macrophylla) is a main cause of the Brazilian Amazon deforestation and has been therefore prohibited. African mahogany (Khaya ivorensis) was then introduced for Amazon reforestation and the commercialization72085768583FAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOFINEP - FINANCIADORA DE ESTUDOS E PROJETOSFundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)sem informaçãosem informaçãosem informaçã

Selective and Efficient Mitochondrial Staining with Designed 2,1,3-Benzothiadiazole Derivatives as Live Cell Fluorescence Imaging Probes

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Novel designed 2,1,3-benzothiadiazole fluorescent probes were synthesized, characterized and applied as live cell fluorescence imaging probe staining only mitochondria in mammalian cancer cell lines (MCF-7). The efficiency of these new probes was found to be much superior to that of the commercially available MitoTracker (R) Red. Cellular and in vitro experiments allowed better understanding of the relationship between the planned molecular architecture of the new dyes and the observed cellular selectivity.234770781Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Fundacao de Apoio a Pesquisa do Distrito Federal (FAPDF)INCT-CatalysisBrasilia Fundacao de Empreendimentos Cientificos e Tecnologicos (Finatec)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)PetrobrasDPP-UnBQuiCSI TeamLMC (IQ-UnB)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP

Analysis of 31 Hydrazones of Carbonyl Compounds by RRLC-UV and RRLC-MS(/MS): A Comparison of Methods

Aldehydes and ketones are volatile organic compounds (VOC) emitted into the atmosphere by a large number of natural and anthropogenic sources. Carbonyl compounds (CC) are atmospheric pollutants with known damaging effects for the human’s health. In this work, the separation of 31 carbonyl compounds (CC) in their 2,4-dinitrophenylhydrazones form was optimized by rapid resolution liquid chromatography in 9 minutes and simultaneously detected by ultraviolet and mass spectrometry with an APCI(−) as ionization source. The mass spectra of hydrazones presented the [M-H]− ions as base peak, but the MS/MS spectra showed fragments related to different structural classes of aldehydes and ketones, representing an important tool to assist structure elucidation of unknown CC in real samples. Multiple reactions monitoring (MRM) improved the sensitivity and selectivity for the quantitation method. Analytical parameters using both UV and MS (linearity, determination coefficients, detection limits, and sensitivity) were compared. The detection methods are complementary and a powerful analytical tool for the detection and quantitation of CC in complex environmental samples

Chemical Composition of Pyroligneous Acid Obtained from Eucalyptus GG100 Clone

The present study aimed to characterize the chemical composition of pyroligneous acid (PA) obtained from slow pyrolysis of the clone GG100 of Eucalyptus urophylla × Eucalyptus grandis. The efficiency of extraction of organic compounds by using different solvents—dichloromethane (DCM), diethyl ether (DE) and ethyl acetate (EA)—was evaluated. Wood discs were collected and carbonized at a heating rate of 1.25 °C/min until 450 °C. Pyrolysis gases were trapped and condensed, yielding a crude liquid product (CLP), which was refined to obtain pure PA. Then liquid–liquid extraction was carried out. Each extracted fraction was analyzed by GC-MS and the chemical compounds were identified. Experimental results showed that a larger number of chemical compounds could be extracted by using DCM and EA in comparison to diethyl ether DE. A total number of 93 compounds were identified, with phenolic compounds being the major group, followed by aldehydes and ketones, furans, pyrans and esters. Higher contents of guaiacol, phenol, cresols and furfural seem to explain the antibacterial and antifungal activity shown by PA, as reported previously in the literature. Experimental data indicated that the organic phase extracted from GG100 PA consists of a mixture of compounds similar to liquid smokes regularly used in the food industry

Separation of isomeric disaccharides by traveling wave ion mobility mass spectrometry using CO2 as drift gas

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)The use of CO2 as a massive and polarizable drift gas is shown to greatly improve peak-to-peak resolution (Rp-p), as compared with N2, for the separation of disaccharides in a Synapt G2 traveling wave ion mobility cell. Near or baseline Rp-p was achieved for three pairs of sodiated molecules of disaccharide isomers, that is, cellobiose and sucrose (Rp-p?=?0.76), maltose and sucrose (Rp-p?=?1.04), and maltose and lactose (Rp-p?=?0.74). Ion mobility mass spectrometry using CO2 as the drift gas offers therefore an attractive alternative for fast and efficient separation of isomeric disaccharides. Copyright (c) 2012 John Wiley & Sons, Ltd.471216431647Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Brazilian science foundation FINEPFundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES

Petroleomics By Traveling Wave Ion Mobility-mass Spectrometry Using Co 2 As A Drift Gas

The technique of choice for petroleomics has been ultra-high-resolution and high-accuracy Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), but other techniques such as ion mobility have been shown to provide additional or alternative information about crude oil composition. Using the traveling wave ion mobility (TWIM) cell of a hybrid Q-TWIM-TOF first-generation Synapt instrument and electrospray ionization in both the positive and negative ion modes, different crude oil samples with different polar compound profiles and petro fuels (diesel and gasoline) with or without additives were analyzed using either CO2 or N2 as the drift gas. Parameters such as gas pressure, velocity, and wave height were optimized for each type of crude oil or fuel sample. The ability of TWIM-MS to separate crude oil components according to their classes was verified by comparison with FT-ICR data. 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Baseline resolution of isomers by traveling wave ion mobility mass spectrometry: investigating the effects of polarizable drift gases and ionic charge distribution

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)We have studied the behavior of isomers and analogues by traveling wave ion mobility mass spectrometry (TWIM-MS) using drift-gases with varying masses and polarizabilities. Despite the reduced length of the cell (18cm), a pair of constitutional isomers, N-butylaniline and para-butylaniline, with theoretical collision cross-section values in helium ((He)) differing by as little as 1.2 angstrom(2) (1.5%) but possessing contrasting charge distribution, showed baseline peak-to-peak resolution (Rp-p) for their protonated molecules, using carbon dioxide (CO2), nitrous oxide (N2O) and ethene (C2H4) as the TWIM drift-gas. Near baseline Rp-p was also obtained in CO2 for a group of protonated haloanilines (para-chloroaniline, para-bromoaniline and para-iodoaniline) which display contrasting masses and theoretical (He), which differ by as much as 15.7 angstrom(2) (19.5%) but similar charge distributions. The deprotonated isomeric pair of trans-oleic acid and cis-oleic acid possessing nearly identical theoretical (He) and (N2) as well as similar charge distributions, remained unresolved. Interestingly, an inversion of drift-times were observed for the 1,3-dialkylimidazolium ions when comparing He, N-2 and N2O. Using density functional theory as a means of examining the ions electronic structure, and He and N-2-based trajectory method algorithm, we discuss the effect of the long-range charge induced dipole attractive and short-range Van der Waals forces involved in the TWIM separation in drift-gases of differing polarizabilities. We therefore propose that examining the electronic structure of the ions under investigation may potentially indicate whether the use of more polarizable drift-gases could improve separation and the overall success of TWIM-MS analysis. Copyright (c) 2013 John Wiley & Sons, Ltd.489989997Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Brazilian Science Foundation FINEPFundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq

The influence of different referencing methods on the accuracy of δ13C value measurement of ethanol fuel by gas chromatography/combustion/isotope ratio mass spectrometry

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)RationaleBrazil is the largest producer of sugar cane bioethanol in the world. Isotope ratio mass spectrometry (IRMS) is the technique of choice to certify the origin/raw materials for ethanol production, but the lack of certified reference materials (CRMs) for accurate measurements of C-13 values traceable to Vienna Pee Dee Belemnite (VPDB), the international zero point for C-13/C-12 measurements, certified and compatible with gas chromatography (GC)/IRMS instruments may compromise the accuracy of C-13 determinations. MethodsWe evaluated the influence of methods for the calibration and normalization of raw C-13 values of ethanol samples. Samples were analyzed by GC/C/IRMS using two different GC columns. Different substances were used as isotopic standards for the working gas calibration. The C-13 values obtained with the three methods of normalization were statistically compared with those obtained with elemental analyzer (EA)/IRMS, since the C-13 results obtained using EA are traceable to VPDB via the NBS 22 reference material. ResultsIt was observed that both the isotopic reference material for CO2 calibration and the GC column have a major effect on the C-13 measurements, leading to a bias of almost 2-3 in the C-13 values. All three methods of normalization were equivalent in performance, enabling an improvement in the GC/C/IRMS accuracy, compared with the EA/IRMS reference values for the samples. ConclusionsAll the methods of CO2 calibration, chromatography and normalization presented in this work demonstrated several sources of traceability and accuracy loss for the determination of C-13 values in ethanol fuel samples by GC/C/IRMS. This work has also shown the importance of using proper CRMs traceable to VPBD that should be compatible and certified using GC/C/IRMS, ideally in a wide range of C-13 values. This is important not only for bioethanol fuel samples, but also for many analytes commonly analyzed by IRMS. Copyright (c) 2015 John Wiley & Sons, Ltd.Brazil is the largest producer of sugar cane bioethanol in the world. Isotope ratio mass spectrometry (IRMS) is the technique of choice to certify the origin/raw materials for ethanol production, but the lack of certified reference materials (CRMs) for ac292119381946FAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOFAPERJ - FUNDAÇÃO DE AMPARO A PESQUISA DO ESTADO DO RIO DE JANEIROCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOFINEP - FINANCIADORA DE ESTUDOS E PROJETOSFundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)sem informaçãosem informaçãosem informaçãosem informaçãoWe thank the State of São Paulo Research Foundation (FAPESP), State of Rio de Janeiro Research Foundation (FAPERJ), the Brazilian National Council for Scientific and Technological Development (CNPq) and the Financing Agency of Studies and Projects (FINEP

Investigating the potential of ion mobility-mass spectrometry for microalgae biomass characterization

Algae biomass is formed by an extremely complex set of metabolites, and its molecular characterization has been very challenging. We report the characterization of microalgae extracts via traveling wave ion mobility-mass spectrometry (TWIM-MS) by two different analysis strategies. First, the extracts were analyzed by direct infusion electrospray ionization (ESI) with no previous chromatographic separation (DI-ESI-TVVIM-MS). Second, the samples were screened for metabolites and lipids using an untargeted high-throughput method that employs ultrahigh-performance liquid chromatography (UHPLC) using data-independent analysis (DIA) MSE (UHPLC-HDMSE). Sixteen different microalgae biomasses were evaluated by both strategies. DI-ESI-TWIM-MS was able, via distinct drift times, to set apart different classes of metabolites, with the differences in the profiles of each microalga readily evident. With the UHPLC-HDMSE approach, 1251 different compounds were putatively annotated across 16 samples with 210 classified as lipids. From the normalized abundance for each annotated compound category, a detailed profiling in terms of metabolites, lipids, and lipid classes of each sample was performed. The reported workflow represents a powerful tool to determine the most suitable biotechnological applications for a given alga type and may allow for real-time monitoring of the algae composition distribution as a function of growth conditions, feedstocks, and the like. The determination of collision cross section results in improved confidence in the identification of triacylglycerols in samples, highly applicable to biofuels production. The two analysis strategies explored in this work offer powerful tools for the biomass industry by aiding in the identification of ideal strains and culture conditions for a specific application, saving analysis time and facilitating identification of a large number of constituents at once911492669276CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO - CNPQFINANCIADORA DE ESTUDOS E PROJETOS - FINEPFUNDAÇÃO CARLOS CHAGAS FILHO DE AMPARO À PESQUISA DO ESTADO DO RIO DE JANEIRO - FAPERJFUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULO - FAPESPnão temnão temnão temnão te