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

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

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-

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

Metabolização do herbicida sulfentrazona: obtenção e identificação de 3-idroximetilsulfentrazona em urina de mamíferos.

Os agrotóxicos são freqüentemente aplicados no decorrer dos ciclos das culturas para controlar organismos deletérios ou para impedir o crescimento de plantas daninhas. Muitos deles representam uma ameaça toxicológica progressiva para a vida animal e humana (ANG et al., 2005). Entre os herbicidas utilizados nas principais culturas do estado de São Paulo está o sulfentrazona que pode ser aplicado pósplantio ou como pré-emergente em relação às plantas daninhas (FAIRBANKS, 2005). É classificado na categoria toxicológica III, portanto perigoso ao meio ambiente, mas não é carcinogênico. Segundo divulgação do Instituto Brasileiro de Geografia e Estatística, em 2004 o uso de agrotóxicos no Brasil aumentou 22%, passando de 2.3 kg ha-1 para 2.8 kg ha-1 (FELICONIO, 2006). Os herbicidas representam 49% dentro desse total e seu uso está concentrado nas culturas de soja, cana-de-açúcar, milho, arroz e algodão (PACHIONE, 2004). O herbicida sulfentrazona N-[2,4?dicloro-5-[4- (difluorometil)-4,5-dihidro-3-metil-5-oxo-1H-1,2,4-triazol- 1-yl]-fenil] etanossulfonamida, inibe a enzima protoporfirinogênio oxidase (Protox) (DAYAN, et al., 1998). As características deste produto que influem no seu comportamento ambiental são: moderadamente solúvel, não susceptível a hidrólise, extremamente susceptível a fotólise direta em água, muito estável para a fotólise em solo, meia-vida de 1,5 anos sob condições aeróbias, meiavida de nove anos em condições anaeróbias, alta mobilidade em solo, média do coeficiente de partição, Koc= 43, e do coeficiente de sorção, Kd2855 mg.kg-1), este composto foi isolado de urina de rato após a administração do composto parental. Devido à dificuldade de obtenção do metabólito, para uso como padrão em análise de resíduos, e altíssimo custo de síntese, foi objetivo deste trabalho isolá-lo em urina de ratos Wistar, tratados com o agrotóxico, para fins de estudos de degradação do composto parental, pois já está bem estabelecido na literatura que mamíferos, como ratos, são capazes de metabolizar o herbicida

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

Sensory nerve transfers in the upper limb after peripheral nerve injury:a scoping review

Nerve transfer for motor nerve paralysis is an established technique for treating complex nerve injuries. However, nerve transfer for sensory reconstruction has not been widely used, and published research on this topic is limited compared to motor nerve transfer. The indications and outcomes of nerve transfer for the restoration of sensory function remain unproven. This scoping review examines the indications, outcomes and complications of sensory nerve transfer. In total, 22 studies were included; the major finding is that distal sensory nerve transfers are more successful than proximal ones in succeeding protective sensation. Although the risk of extension of the sensory deficit with donor site loss and morbidity from neuromas remain a barrier to wider adoption, these complications were not reported in the review. Further, the scarcity of studies and small patient series limit the ability to determine sensory nerve transfer success. However, sensory restoration remains an opportunity for surgeons to pursue.</p

Sensory nerve transfers in the upper limb after peripheral nerve injury:a scoping review

Nerve transfer for motor nerve paralysis is an established technique for treating complex nerve injuries. However, nerve transfer for sensory reconstruction has not been widely used, and published research on this topic is limited compared to motor nerve transfer. The indications and outcomes of nerve transfer for the restoration of sensory function remain unproven. This scoping review examines the indications, outcomes and complications of sensory nerve transfer. In total, 22 studies were included; the major finding is that distal sensory nerve transfers are more successful than proximal ones in succeeding protective sensation. Although the risk of extension of the sensory deficit with donor site loss and morbidity from neuromas remain a barrier to wider adoption, these complications were not reported in the review. Further, the scarcity of studies and small patient series limit the ability to determine sensory nerve transfer success. However, sensory restoration remains an opportunity for surgeons to pursue.</p

Fingerprinting of propolis by easy ambient sonic-spray ionization mass spectrometry

Chemical profiles of a representative set of 49 propolis ethanolic extracts collected worldwide (North and South America, Europe, Asia and Oceania) were obtained via easy ambient sonic-spray ionization mass spectrometry (EASI-MS). This simple and easily implemented fingerprinting technique analyses directly (without any pre-separation or sample manipulation) a tiny droplet of the ethanolic extract placed on a inert surface under ambient conditions. Data acquisition took about a minute per sample with no substantial sample carry-over. Extraction of propolis with ethanol by using an ultrasonic bath method gave EASI-MS data similar to the traditional maceration method, reducing total analysis time for the crude propolis resin from a week to just ca 1 h. Principal component analysis of the EASI-MS data is shown to group samples according to the plant sources of their resins, which characterizes their geographical origin. © 2009 Elsevier B.V. All rights reserved

MALDI imaging mass spectrometry of fresh water cyanobacteria: spatial distribution of toxins and other metabolites

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)Cyanobacteria are among the most ancient forms of life, yet they are known to synthesize highly sophisticated defense molecules, such as the highly hepatotoxic cyclic peptides microcystins and nodularins produced by the genera Microcystis, Anabaena and Nodularia. These metabolites are released by cyanobacteria to water environments causing episodes of fatalities among animals and humans. To better understand the releasing of these metabolites, imaging mass spectrometry (IMS) using matrix-assisted laser desorption ionization-time of flight (MALDI-TOF) was herein applied to determine the spatial distribution of such toxins directly on agar-based cultures. Other key metabolites such as aeruginosin 602 and the siderophore anachelin were also mapped in mixed cyanobacterial cultures, showing the great potential of IMS to spatially monitor the biochemical details of cyanobacterial defense and interactions.Cyanobacteria are among the most ancient forms of life, yet they are known to synthesize highly sophisticated defense molecules, such as the highly hepatotoxic cyclic peptides microcystins and nodularins produced by the genera Microcystis, Anabaena and No284521528FAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOCAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIORFundação 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)sem informaçãosem informaçãosem informaçã