Microwave-assisted generation and reactivity of aza- and diazafulvenium methides: heterocycles via pericyclic reactions

Azafulvenium methides and diazafulvenium methides have been generated under microwave irradiation from 2,2-dioxo-1H,3H-pyrrolo[1,2-c]thiazoles and 2,2-dioxo-1H,3H-pyrazolo[1,5-c]thiazoles, respectively. Pericyclic reactions of these 1,7-dipole intermediates, namely, sigmatropic [1,8]H shifts, 1,7-electrocyclization or [8[pi]+2[pi]] cycloaddition led to the synthesis of a range of pyrrole and pyrazole derivatives. The first evidence for the azafulvenium methides by intermolecular trapping via [8[pi]+2[pi]] cycloaddition is reported.http://www.sciencedirect.com/science/article/B6THS-4SP3SM3-6/1/d6303d9db78919cfe9cd796c1a17d44

Degradable particulate composite reinforced with nanofibres for biomedical applications

Nanofibre-based structures and their composites are increasingly being studied for many biomedical applications, including tissue engineering scaffolds. These materials enable architectures resembling the extracellular matrix to be obtained. The search for optimized supports and carriers of cells is still a major challenge for the tissue engineering field. The main purpose of this work is to develop a novel composite structure that combines microparticles and nanofibres in reinforced polymeric microfibres. This innovative combination of materials is obtained by melting extrusion of a particulate composite reinforced with chitosan nanofibre meshes (0.05 wt.%) produced by the electrospinning technique. The reinforced microfibres were analysed by scanning electron microscopy and showed a considerable alignment of the chitosan nanofibres along the longitudinal main axis of the microfibre composite structure. The tensile mechanical properties revealed that the introduction of the nanofibre reinforcement in the particulate microfibre composite increased the tensile modulus by up to 70%. The various structures were subjected to swelling and degradation tests immersed in an isotonic saline solution at 37 C. The presence of chitosan nanofibres in the particulate microfibres enhances the water uptake by up to 24%. The combination of good mechanical properties and enhanced degradability of the developed structures is believed to have great potential for various biomedical applications, including three-dimensional fibre mesh scaffolds to be applied in the field of bone tissue engineering.This work was partially supported by the EU Integrated Project GENOSTEM (No. LSH503161) and by project Micro-Nano (POCI/CTM/48040/2002), financed by the Portuguese Foundation for Science and Technology (FCT). A.M. would like to thank FCT for his PhD grant (SFRH/BD/24382/2005)

Gene expression of antioxidant enzymes and coffee seed quality during pre-and post- physiological maturity.

Seeds collected at different maturation stages vary in physiological quality and patterns of protective antioxidant systems against deterioration. In this study we investigated the expression of genes that codify catalase (CAT), dismutase superoxide (SOD), and polyphenol oxidase (PPO) during the pre- and post-physiological maturation phases in whole seeds and in endosperms and embryos extracted from the seeds. Coffea arabica L. berries were collected at the green, yellowish-green, cherry, over-ripe, and dry stages, and the seeds were examined physiologically. The transcription levels of the genes were quantified by quantitative real-time polymerase chain reaction using coffee-specific primers. The highest level of SOD expression was observed in the endosperm at the cherry and over-ripe stages; in addition, these seeds presented the greatest physiological quality (assessed via germination test). The highest CAT3 transcript expression was observed at the green stage in whole seeds, and at the green and over-ripe stages in the embryos and endosperms High expression of the PPO transcript was observed at the green and yellowish-green stages in whole seeds. In embryos and endosperms, peak expression of the PPO transcript was observed at the green stage; subsequently, peaks at the cherry and over-ripe stages were observed. We concluded that the expression patterns of the SOD and CAT3 transcripts were similar at the more advanced maturation stages, which corresponded to enhanced physiological seed quality. High expression of the PPO transcript at the over-ripe stage, also observed in the embryos and endosperms at the cherry stage, coincided with the highest physiological seed quality

Capacidade de armazenamento de sementes de Coffea arabica L. em diferentes estádios de maturação e submetidas à diferentes métodos de secagem.

O momento da colheita e os métodos de secagem podem influenciar a qualidade de sementes de cafeeiro durante o armazenamento. Este trabalho foi realizado com o objetivo de estabelecer os efeitos do estádio de desenvolvimento e do método de secagem sobre a qualidade fisiológica e a capacidade de armazenamento de sementes de cafeeiro. Os ensaios foram realizados nos Laboratórios de Análise de Sementes e Eletroforese do Departamento de Agricultura da UFLA. Os frutos do cultivar Rubi foram colhidos, despolpados, desmucilados por fermentação à 30ºC por 24 horas e as sementes lavadas e deixadas sobre papel para retirada da água superficial, antes de serem submetidas à secagem convencional (à sombra) e secagem em secador estacionário à temperatura de 35ºC. Como testemunha foram analisadas sementes sem secagem. As avaliações foram feitas imediatamente após os tratamentos de secagem e após quatro e oito meses de armazenamento. As sementes foram armazenadas a 10ºC em embalagens plásticas e herméticas. Foram realizados os testes de germinação, de protrusão radicular, de matéria seca de plântulas, de índice de velocidade de emergência, de condutividade elétrica, além de análises eletroforéticas da enzima endobmananase e de proteínas resistentes ao calor. O delineamento foi inteiramente ao acaso em esquema fatorial 2 (estádios de desenvolvimento) x 3 (secagens) x 3 (tempo de armazenamento), com 4 repetições. As sementes submetidas à secagem perderam vigor e viabilidade, principalmente quando colhidas no estádio verdecana, sendo que a secagem a 35ºC se mostrou mais prejudicial à qualidade fisiológica das sementes. A presença ou intensidade de bandas de proteínas resistentes ao calor estão associadas à secagem das sementes. Há maior atividade da enzima endoßmananase em sementes colhidas no estádio cereja que em sementes do estádio verdecana. Há um aumento da atividade da enzima na medida em que se aumenta o período de armazenamento

New chemistry of diazafulvenium methides: one way to pyrazoles

Diazafulvenium methides generated from the solution pyrolysis of pyrazolo[1,5-c][1,3]thiazole-2,2-dioxides participate in [8[pi]+2[pi]] cycloadditions giving pyrazolo[1,5-a]pyridine derivatives. 1-Methyl-diazafulvenium, generated under flash vacuum pyrolysis reaction conditions, undergoes an intramolecular sigmatropic [1,8]H shift giving 1-vinyl-1H-pyrazoles.http://www.sciencedirect.com/science/article/B6THS-4HR7298-7/1/af0dd8d679e7977f53bc0d4af9a5b68

Synthesis and reactivity of 2-halo-2H-azirines towards nucleophiles

Nucleophilic substitution reactions of 2-halo-2H-azirine with potassium phthalimide and aniline allowed the preparation of new substituted 2H-azirines. The reactions of 2-bromo-3-phenyl-2H-azirine-2-carboxylate with methylamine led to the synthesis of [alpha]-diimines and from the reaction with water, a 3-oxazoline was obtained.http://www.sciencedirect.com/science/article/B6THS-4152YMR-K/1/e94005b66b66b6820ad27458f2562ed