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

Corrole Isomers: Intrinsic Gas-phase Shapes Via Traveling Wave Ion Mobility Mass Spectrometry And Dissociation Chemistries Via Tandem Mass Spectrometry.

Corrole and four of its isomers with subtle structural changes promoted by exchange of nitrogen and carbon atoms in the corrole ring have been studied by traveling wave ion mobility mass spectrometry and collision induced dissociation experiments. Significant differences in shapes and charge distributions for their protonated molecules were found to lead to contrasting gas phase mobilities, most particularly for corrorin, the most confused isomer. Accordingly, corrorin was predicted by B3LYP/6-31g(d,p) and collisional cross section calculations to display the most compact tri-dimensional structure, whereas NCC4 and corrole were found to be the most planar isomers. Better resolution between the corrole isomers was achieved using the more polarizable and massive CO(2) as the drift gas. Sequential losses of HF molecules were found to dominate the dissociation chemistry of the protonated molecules of these corrole isomers, but their unique structures caused contrasting labilities towards CID, whereas NCC4 showed a peculiar and structurally diagnostic loss of NH(3), allowing its prompt differentiation from the other isomers.108396-40

Corrole isomers: intrinsic gas-phase shapes via traveling wave ion mobility mass spectrometry and dissociation chemistries via tandem mass spectrometry

Corrole and four of its isomers with subtle structural changes promoted by exchange of nitrogen and carbon atoms in the corrole ring have been studied by traveling wave ion mobility mass spectrometry and collision induced dissociation experiments. Significant differences in shapes and charge distributions for their protonated molecules were found to lead to contrasting gas phase mobilities, most particularly for corrorin, the most "confused" isomer. Accordingly, corrorin was predicted by B3LYP/6-31g(d,p) and collisional cross section calculations to display the most compact tri-dimensional structure, whereas NCC4 and corrole were found to be the most planar isomers. Better resolution between the corrole isomers was achieved using the more polarizable and massive CO2 as the drift gas. Sequential losses of HF molecules were found to dominate the dissociation chemistry of the protonated molecules of these corrole isomers, but their unique structures caused contrasting labilities towards CID, whereas NCC4 showed a peculiar and structurally diagnostic loss of NH3, allowing its prompt differentiation from the other isomers

Analysis Of Fuels Via Easy Ambient Sonic-spray Ionization Mass Spectrometry.

The desorption and ionization of analytes directly from surfaces or natural matrices under ambient conditions has greatly simplified chemical analysis by mass spectrometry. Among the currently available set of such techniques, easy ambient sonic-spray ionization (EASI) is one of the simplest and most easily implemented. Fuels are among the most important and most complex classes of chemical mixtures and a challenge for fast and comprehensive chemical analysis. This review summarizes the applications of EASI-MS for fast, simple and nearly sample-preparation-free analysis of various fuels, focusing in typification, adulteration and quality control.65915-2

The carbon isotopic (13C/12C) signature of sugarcane bioethanol: certifying the major source of renewable fuel from Brazil

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Ethanol has been increasingly used worldwide as a major renewable fuel. Since it can be produced from several matrixes such as sugarcane, corn, wheat, grape and beet, it has become important for certification purposes to verify the geographical origin and the different raw materials used for ethanol production. In this work, isotope ratio mass spectrometry, coupled to gas chromatography, was used to measure the carbon isotopic signature (delta C-13(V-PDB)) of Brazilian sugar cane bioethanol. Statistical data analysis was also applied to establish a probabilistic profile for the isotopic signature of major renewable Brazilian fuel. Other bioethanol samples produced from different raw materials in the USA and France were also analysed, for comparison.Ethanol has been increasingly used worldwide as a major renewable fuel. Since it can be produced from several matrixes such as sugarcane, corn, wheat, grape and beet, it has become important for certification purposes to verify the geographical origin and71147804785FAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOFAPERJ - FUNDAÇÃO DE AMPARO À 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

Resolution of isomeric multi‐ruthenated porphyrins by travelling wave ion mobility mass spectrometry

The ability of travelling wave ion mobility mass spectrometry (TWIM‐MS) to resolve cationic meta/para and cis/trans isomers of mono‐, di‐, tri‐ and tetra‐ruthenated supramolecular porphyrins was investigated. All meta isomers were found to be more compact than the para isomers and therefore mixtures of all isomeric pairs could be properly resolved with baseline or close to baseline peak‐to‐peak resolution (Rp‐p). Di‐substituted cis/trans isomers were found, however, to present very similar drift times and could not be resolved. N2 and CO2 were tested as the drift gas, and similar α but considerably better values of Rp and Rp‐p were always observed for CO2263263268CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO - CNPQCOORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIOR - CAPESFUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULO - FAPESPNão temNão temNão te

Resolution Of Isomeric Multi-ruthenated Porphyrins By Travelling Wave Ion Mobility Mass Spectrometry.

The ability of travelling wave ion mobility mass spectrometry (TWIM-MS) to resolve cationic meta/para and cis/trans isomers of mono-, di-, tri- and tetra-ruthenated supramolecular porphyrins was investigated. All meta isomers were found to be more compact than the para isomers and therefore mixtures of all isomeric pairs could be properly resolved with baseline or close to baseline peak-to-peak resolution (R(p-p)). Di-substituted cis/trans isomers were found, however, to present very similar drift times and could not be resolved. N(2) and CO(2) were tested as the drift gas, and similar α but considerably better values of R(p) and R(p-p) were always observed for CO(2).26263-

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

Resolution of isomeric multi-ruthenated porphyrins by travelling wave ion mobility mass spectrometry

The ability of travelling wave ion mobility mass spectrometry (TWIM-MS) to resolve cationic meta/para and cis/trans isomers of mono-, di-, tri- and tetra-ruthenated supramolecular porphyrins was investigated. All meta isomers were found to be more compact than the para isomers and therefore mixtures of all isomeric pairs could be properly resolved with baseline or close to baseline peak-to-peak resolution (Rp-p). Di-substituted cis/trans isomers were found, however, to present very similar drift times and could not be resolved. N-2 and CO2 were tested as the drift gas, and similar a but considerably better values of R-p and Rp-p were always observed for CO2. Copyright (C) 2012 John Wiley & Sons, Ltd.FAPESPFAPESPCNPqCNPqCAPESCAPESINOMATINOMA

Protomers: Formation, Separation And Characterization Via Travelling Wave Ion Mobility Mass Spectrometry.

Travelling wave ion mobility mass spectrometry (TWIM-MS) with post-TWIM and pre-TWIM collision-induced dissociation (CID) experiments were used to form, separate and characterize protomers sampled directly from solutions or generated in the gas phase via CID. When in solution equilibria, these species were transferred to the gas phase via electrospray ionization, and then separated by TWIM-MS. CID performed after TWIM separation (post-TWIM) allowed the characterization of both protomers via structurally diagnostic fragments. Protonated aniline (1) sampled from solution was found to be constituted of a ca. 5:1 mixture of two gaseous protomers, that is, the N-protonated (1a) and ring protonated (1b) molecules, respectively. When dissociated, 1a nearly exclusively loses NH(3) , whereas 1b displays a much diverse set of fragments. When formed via CID, varying populations of 1a and 1b were detected. Two co-existing protomers of two isomeric porphyrins were also separated and characterized via post-TWIM CID. A deprotonated porphyrin sampled from a basic methanolic solution was found to be constituted predominantly of the protomer arising from deprotonation at the carboxyl group, which dissociates promptly by CO(2) loss, but a CID-resistant protomer arising from deprotonation at a porphyrinic ring NH was also detected and characterized. The doubly deprotonated porphyrin was found to be constituted predominantly of a single protomer arising from deprotonation of two carboxyl groups.47712-