Optimization of atmospheric pressure photoionization for the crude oil analysis using ultra-high resolution mass spectrometry

FAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULODesign of experiments (DOE) applied to mass spectrometry (MS), mainly focusing on the optimization of ionization techniques, has been applied to optimize experiments in order to provide the highest amount of information with the lowest number of experimen304819829FAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOFAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULO2013/19161-

Absolute and general assignment of constitutional isomers by mass spectrometry: the case of methylpiperidines

An absolute method is described via mass spectrometry (MS) for the structural assignment of isomers within the class of methylpiperidines. The method explores both the unimolecular and bimolecular gas phase behavior of structurally diagnostic fragment ions (SDFI). For the methylpiperidnes, the isomeric 2-methyl, 3-methyl and 4-methyl 2-azabutadienyl cations are found to function as SDFI. These fragment ions are expected to be formed from all members within the class, to be stable and to retain the structural information of the precursor molecule, and to not interconvert into one another. To characterize these SDFI, both the collision induced dissociation (CID) in argon and bimolecular ion/molecule chemistry with ethyl vinyl ether were compared.1721Fundação 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

Comparing crude oils with different API gravities on a molecular level using mass spectrometric analysis. Part 2: resins and asphaltenes

FAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOThe combination of fractionation methods for crude oils, such as saturate, aromatic, resin and asphaltene (SARA) fractionation, in combination with analysis by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) has been used for reduc1110FAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOFAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULO2013/19161-42015/05818-

Chloroform formation by chlorination of aqueous algae suspensions: online monitoring via membrane introduction mass spectrometry

Membrane introduction mass spectrometry (MIMS) was used to perform on-line monitoring of the chloroform formation via the chlorination of aqueous suspensions of several green and blue-green Brazilian algae (Microcystis panniformis, Selenastrum sp., Scenedesmus sp., Monoraphidium sp. (strain 354), Monoraphidium sp. (strain 960), and Staurastrum sp.). The influence of major parameters, such as temperature, pH, initial concentration of sodium hypochloride, filtration, and reaction time, on chloroform formation was evaluated. It was verified that the chloroform formation is strongly dependent on the alga type and is favored by high temperatures, pH, sodium hypochloride initial concentration and reaction time. Finally, filtered algae samples produce smaller amounts of chloroform in comparison to the rough suspension.A técnica MIMS (membrane introduction mass spectrometry) foi utilizada para monitorar a formação de clorofórmio durante a cloração de suspensões aquosas de várias espécies brasileiras de algas verdes e azuis (Microcystis panniformis, Selenastrum sp., Scenedesmus sp., Monoraphidium sp. (strain 354), Monoraphidium sp. (strain 960), and Staurastrum sp.). Foram avaliadas as influências de parâmetros como temperatura, pH, concentração inicial de hipoclorito de sódio, filtração e tempo de reação. Foi constatado que o teor de clorofórmio é fortemente dependente da espécie de alga e também é favorecido com o aumento da temperatura, pH, dosagem de cloro inicial e do tempo de reação. Amostras de suspensões de algas submetidas a filtração produziram menores quantidades de clorofórmio em comparação com as amostras brutas.950955Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq

Dba-free" Palladium Intermediates Of The Heck-matsuda Reaction."

The dba-free Heck-Matsuda reaction was investigated via direct ESI-MS(/MS) monitoring. Palladium species involved in the reduction of Pd(II) during a Wacker type reaction and several dba-free arylpalladium transient complexes were detected and characterized. Based on these findings, a more comprehensible catalytic cycle for this pivotal reaction is suggested.113277-8

On The Mechanism Of The Aza-morita-baylis-hillman Reaction: Esi-ms Interception Of A Unique New Intermediate.

Solutions of aza-Morita-Baylis-Hillman (aza-MBH) reactions were directly monitored by ESI(+)-MS(/MS) spectrometry to obtain information on their mechanism. A unique bis-sulfonamide intermediate was intercepted and characterized and, based on this novel species, a mechanism that rationalizes the uniqueness of aza-MBH reactions is proposed.476593-

Food Quality And Authenticity Screening Via Easy Ambient Sonic-spray Ionization Mass Spectrometry.

This review is the first to summarize a decade of studies testing the use of easy ambient sonic-spray ionization mass spectrometry (EASI-MS) and its several sister techniques, Venturi (V-EASI), thermal imprinting (TI-EASI) and Spartan (S-EASI) mass spectrometry in food quality control and authentication. Since minimal or no sample preparation is required, such ambient desorption/ionization techniques have been shown to provide direct, fast and selective fingerprinting characterization at the molecular level based on the pools of the most typical components. They have also been found to be applicable on intact, undisturbed samples or on simple solvent extracts. Fundamentals of EASI-MS and its sister techniques, including mechanisms, devices, parameters and strategies, as well as the many applications reported for food analysis, are summarized and discussed.1411172-118

Rápida identificação de agentes causadores de mastite por espectrometria de massas MALDI-TOF

FAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOMatrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) has been shown to be an alternative method for identification of bacteria via their protein profile spectra, being able to identify bacteria at the genus, species384586594FAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOFAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULO2011/01867-

Distribution and sources of aliphatic and polycyclic aromatic hydrocarbons in surface sediments of Itajaí-Açu estuarine system in Brazil

The Itajaí-Açu estuarine system, located in southern Brazil, has great economic importance due to the presence of two ports (Itajaí and Navegantes). This system is affected by industrial and dredging activities, which can cause the remobilization of pollutants accumulated over time in the sediment. In this context, hydrocarbons were assessed in twelve surface sediment samples. n-Alkane and polycyclic aromatic hydrocarbons (PAH) concentrations were determined by gas chromatography and their sources assessed. Total concentrations ranged between 0.50 ± 0.04 and 69.70 ± 3.90 μg g-1 dry weight (d.w.) for n-alkanes and from 63.9 ± 12.1 to 1459.0 ± 43.5 ng g-1 d.w. for PAH. Most of the sediment samples presented carbon preference index (CPI) values close to unity, indicating that the area is submitted to petroleum-related sources, mainly close to Itajaí harbor, where an intense unresolved complex mixture (UCM) was observed. The presence at all stations of αβ-hopane biomarkers also indicated petrogenic input. Based on selected PAH ratios, the sedimentary PAH composition reflects a mixture of both petrogenic and pyrolytic sources. A comparison of the PAH concentrations found in this study with those listed in the sediment quality guidelines (SQGs) indicated that adverse biological effects on the biota are rarely expected.The Itajaí-Açu estuarine system, located in southern Brazil, has great economic importance due to the presence of two ports (Itajaí and Navegantes). This system is affected by industrial and dredging activities, which can cause the remobilization of pollu28460361

Structural Studies on Alkylisocyanate Polymers by Thermal Degradation Tandem Mass Spectrometry

AbstractHomopolymers and copolymers of alkylisocyanates having n-hexyl, 2,6-dimethylheptyl, 3,7-dimethyloctyl, and (2,2-dimethyl-1,3-dioxolan-4-yl)methyl substituents underwent thermal degradation in the course of desorption electron ionization to yield trimers and monomers that were characterized in situ by tandem mass spectrometry. The trimers were trisubstituted cyanuric acids, the protonated molecules displaying a characteristic series of alkene eliminations on collision-induced dissociation to yield protonated cyanuric acid, m/z 130. Confirmation of the identity of the pyrolysates was obtained by using two types of MS3 experiments: the reaction intermediate scan and the two-dimensional familial scan. The ion chemistry of the trimers and of the protonated monomer, the alkylisocyanate, was elucidated. Among the many interesting fragmentation processes undergone by the ionized trimers were α and β CC bond cleavages and charge-remote fragmentations, which provided information on branching in the alkyl substituent. The dioxolane-containing substituent showed unique ion chemistry. The monomer distribution in the copolymers was deduced from the abundances of the various protonated trimers. The distribution was found to be random in all copolymers except that containing the dioxolane substituent