Pequi (Caryocar brasiliense Camb.), a typical fruit of Brazilian Cerrado, is well known in regional cookery and used in folk medicine to treat various illnesses. Mass spectrometry and chromatographic methods have identified the organic composition of pequi fruit pulp; however, NMR spectroscopy is used for the first time to characterize the nutritional components of organic and aqueous-ethanolic extracts. This spectroscopic technique determined the triacylglycerols in the pequi organic fraction, which is constituted mainly by oleate and palmitate esters, and detected the carbohydrate mixtures as the major components of aqueous and ethanolic fractions, respectively. In this study, presence of phenolic compounds was only evidenced in the ethanolic fraction.

Abstract The objective of this research was to suggest a systematic model of wood identification through metabolomic analysis by 13C NMR, toward a data bank formation. In this work cyclohexane extracts from wood of E. urograndis were used. Four specimes with aproximately 15 years old were colected from differents regions. The data of 13C NMR showed that spectra of hexane extractes from heartwood (DAP), were considered the most representative for the study for the E. urograndis, due to the largest number of existing spectrum signals. After the data it was possible to identify a common spectral profile for each anatomic region of wood (sapwood, transition zone and heartwood) of E. urograndis.

Resumo O objetivo da pesquisa foi propor um modelo sistemático de identificação de madeiras através de análise metabolômica por Ressonância Magnética Nuclear do 13C (RMN 13C) constituindo um banco de dados de 13C. Neste trabalho foram utilizados os extratos obtidos com ciclohexano de madeiras do híbrido E. urograndis. Quatro espécimes com aproximadamente 15 anos de idades foram coletados em diferentes localidades. Os dados de RMN 13C mostraram que os espectros dos extratos ciclohexano da madeira do cerne (DAP) foram os mais representativos para o estudo do E. urograndis devido ao número de absorções verificadas. Com os dados foi possível traçar o perfil espectral comum para o híbrido do E. urograndis de cada região anatômica (alburno, zona de transição e cerne).

The structure of mullite obtained by thermal decomposition of topaz at 1340 °C and after additional thermal treatment at 1600 °C was characterized by 29Si and 27Al MAS NMR spectroscopy and x ray diffraction. No amorphous phase was detected by these techniques. The 29Si MAS NMR spectra of the mullite samples showed four resonance peaks at -81, -86, -90 and -94 ppm. The peak at -81 ppm corresponded to silicon near oxygen vacancies in the mullite structure. The peak at 86 ppm was related to a sillimanite-type site and was the major contribution, ranging from 42 to 50%. The two other peaks, at -90.0 ppm and -94 ppm, were interpreted as resulting from rearrangements of the sillimanite-type site by the replacement of AlO4 by SiO4 tetrahedra16. The 27Al MAS NMR data of the two samples exhibited three different peaks, two of which were attributed to tetrahedral sites at 40 -45 and 63 -67 ppm, while the third was assigned to an octahedral site at about -6 ppm. The ratio of tetrahedral to octahedral aluminum sites was found to depend on the temperature applied during the preparation of the mullite and was higher at 1600 °C.

A Fig. 1 descreve um método geral para preparação de feromônios de insetos. Vários componentes de feromônios de insetos, junto de seus isômeros geométricos e/ou posicionais, foram preparados a partir de Z-lactonas 2a-d, que são facilmente acessíveis pela hidrogenação estereosseletiva (Lindlar Pd, H2) dos precursores acetilênicos 1a-d, sendo estes já sintetizados a partir de cicloalcanonas. A isomerização de acetatos de Z-alquenilas 6a-d aos respectivos esteres de E-alquenilas 8a-d, foi realizada tanto pela técnica catalítica (NaNO2, HNO3, D) como pelo método de inversão química (NBS, TFA; NaI, DMF, D). O álcool (E)-6-decenílico (7b) foi também preparado diretamente do ester acetilênico (15b) pela redução, em trans, com hidreto de lítio-alumínio (LiAlH4), por refluxo em diglima. Os acetatos de decila (18) e hexadecila (19), componentes dos feromônios de mariposa do nabo (Agrotis segetum; turnip moth) e da borboleta Lycorea ceres ceres, respectivamente, foram obtidos pela hidrogenação catalítica (Pd, H2) dos acetatos de Z-alquenilas correspondentes.

Figure 1 describes a general method for the preparation of insect pheromones. Several members of the title compounds, along with their geometric and/or positional isomers, have been prepared from Z-lactones 2a-d, which are easily available from the corresponding acetylenic lactones 1a-d, prepared earlier from cycloalkanones. The Z to E isomerization of alkenyl acetates 6a-d to 8a-d was carried out both by a catalytic technique (NaNO2, HNO3, D) and the chemical inversion procedure (NBS, TFA; NaI, DMF, D). (E)-6-Decenyl alcohol (7b) was also prepared from the acetylenic ester 15b by the trans reduction with LiAlH4 in refluxing diglyme. decyl acetate (18) and hexadecyl acetate (19), pheromone components of the turnip moth (Agrotis segetum) and the male butterfly Lycorea ceres ceres, respectively, were obtained by the catalytic hydrogenation (Pd, H2) of the corresponding Z-alkenyl acetates.

Lactonas acetilênicas de tamanho médio e macrocíclico 15a-e 6-decin-9-olídeo (15a), 7-undecin-10-olídeo (15b), 8-dodecin-11-olídeo (15c), 12-hexadecin-15-olídeo (15d) e 5-decin-9-olídeo (15e) foram preparadas a partir de oxabiciclo-alquenonas 7a-d e 2, respectivamente, pela expansão de anel das tosil-hidrazonas 16a-e, efetuada pela reação com N-bromo-succinimida, sob condições rigorosamente controladas. A hidrogenação (Pd-C, H2) completa da ligação tripla forneceu lactonas racêmicas saturadas: 9-decanolídeo (foracantolídeo I, 6, de 15a e 15e), 10-undecanolídeo, 11-dodecanolídeo (di-hidro-recifeiolídeo) e 15-hexadecanolídeo. As tentativas de converter di-hidropironas 7a,d nas respectivas lactonas acetilênicas 15a,d, via cloro-hidrinas 8a,d e/ou clorocetolactonas 9a,d, foram apenas parcialmente bem sucedidas.

Medium to macrocyclic acetylenic lactones 15a-e 6-decyn-9-olide (15a), 7-undecyn-10-olide (15b), 8-dodecyn-11-olide (15c), 12-hexadecyn-15-olide (15d), and 5-decyn-9-olide (15e) were prepared from oxabicycloalkenones 7a-d and 2, respectively, by the ring expansion of their tosylhydrazones 16a-e, carried out by reaction with N-bromosuccinimide, under strictly controlled conditions. Complete hydrogenation (Pd-C, H2) of the triple bond gave the racemic saturated lactones: 9-decanolide (phoracantholide I, 6, from 15a and 15e), 10-undecanolide, 11-dodecanolide (dihydrorecifeiolide), and 15-hexadecanolide. The attempts at the conversion of dihydropyrones 7a,d into the respective acetylenic lactones 15a,d, via chlorohydrins 8a,d and/or chloroketolactones 9a,d, were only partially successful.