The Human Milk Bank undergo human milk to pasteurization, followed by storage in a freezer at -18º C for up to six months to thus keep available the stocks of this product in maternal and infant hospitals. The objective of this study was to evaluate the effects of processing on the lipid fraction of human milk. A sample of human milk was obtained from a donor and was subdivided into ten sub-samples that was subjected to the following treatments: LC = raw milk; T0 = milk after pasteurization; T30 = milk after pasteurization and freezing for 30 days; T60 = milk after pasteurization and freeze for 60 days, and so on every 30 days until T240 = milk after pasteurization and freezing for 240 days, with 3 repetitions for each treatment. Lipids were extracted, methylated and fatty acid profiles determined by gas chromatography. The fatty acids were characterized by nuclear magnetic resonance and functional groups were identified by infrared spectroscopy. There were variations in the concentration of fatty acids. For unsaturated fatty acids there was increasing trend in their concentrations. The IR and NMR analyze characterized and identified functional groups presents in fatty acids.

Los Bancos de Leche Humana someten la leche la pasteurización, seguido del almacenamiento en un congelador a -18 grados por até seis meses, para así disponerlo a los Hospitales Materno Infantiles. El objetivo de este estudio fue evaluar los efectos del procesamiento de la fracción lipídica de la leche humana. Para esto, una muestra obtenida de una donante y sometida a diez diferentes tratamientos: LC = leche cruda; TO = leche después de la pasteurización; T30 = leche después de la pasteurización y congelación por 30 días; T60 = leche después de la pasteurización y congelación por 60 días y así sucesivamente a cada 30 días hasta T240 = leche después de la pasteurización y congelación por 240 días, con tres repeticiones a cada tratamiento. Los lípidos fueron extraídos y los ácidos grasos metilados fueron determinados por cromatografía gaseosa. Los ácidos grasos fueron caracterizados por resonancia magnética nuclear y los grupos funcionales identificados por espectroscopia infrarroja. Hubo variaciones en las concentraciones de ácidos grasos. Para los ácidos grasos insaturados hubo un aumento en sus concentraciones. Sin embargo, los grupos funcionales se caracterizaron por espectroscopia infrarroja y resonancia magnética nuclear, RMN.

A obtenção de óleos essenciais de espécies nativas no Brasil ainda é pequena, apesar das suas florestas apresentarem grande potencial para a exploração desses produtos. No caso do Cerrado, até agora apenas algumas espécies foram estudadas quanto à presença de óleos essenciais, sendo necessárias mais pesquisas para verificar o potencial desse importante Bioma. Objetivou-se, nesta pesquisa, avaliar o potencial de plantas arbóreas e arbustivas do Cerrado para a produção de óleos essenciais, determinando o rendimento e a composição química preliminar de óleos de algumas espécies do Bioma. Foram selecionadas em campo as espécies Baccharis sp. (assa-peixe), Blepharocalyx salicifolius (maria preta), Psidium myrsinites (araçá do cerrado) e Protium ovatum (almecega). Essa seleção foi feita com base em estudos prévios sobre famílias botânicas produtoras de óleos essenciais, junto com a constatação da presença de odores nas folhas maceradas das plantas. A extração dos óleos foi feita com um minidestilador por arraste de vapor utilizando as folhas das plantas no processo. Para analisar quimicamente cada óleo, primeiramente, foi realizada a separação das fases orgânica e aquosa dos hidrolatos com o solvente acetato de etila. Posteriormente, foram feitas análises cromatográficas (cromatografia em camada delgada, CCD) e espectroscópicas de Ressonância Magnética Nuclear (RMN) de ¹H e ¹³C e Infravermelho (IV). Foram obtidos rendimentos de 0,06% para Baccharis sp., 0,12% para Blepharocalyx salicifolius, 0,10% para Protium ovatum e 0,13% para Psidium myrsinites. Nas análises espectroscópicas foi observado que esses óleos são misturas complexas de hidrocarbonetos saturados (grupos alifáticos) e insaturados (olefinas ou alquenos) e oxigenados (aldeídos, cetonas, ésteres, dentre outros). As espécies Psidium myrsinites e Blepharocalyx salicifolius apresentaram sinais característicos de carbonilas de cetonas. A primeira apresentou o componente linalol, enquanto a segunda apresentou forte odor característico. Pelos resultados mostrou-se o potencial das plantas do Cerrado como produtoras de óleos essenciais. Com a análise química, observou-se que esses óleos essenciais são constituídos por complexas misturas que devem ser melhor estudadas para avaliar, detalhadamente, a composição de cada óleo.

The production of essential oils from the species of the Brazilian native forests is still low, even thought its high biodiversity. Specifically for the Brazilian Savannah, a few species has been studied so far, then the research effort concerning essential oil should be raised. This paper aimed at evaluating the potential of some species from the Brazilian Savannah to produce essential oil by calculating the yield and determining the preliminary chemical composition. Leaves from Baccharis sp., Blepharocalyx salicifolius, Psidium myrsinites and Protium ovatum were collected at Fazenda Água Limpa, the ecologic experimental area of the University of Brasília. The essential oil from the material was extracted by steam distillation for 90 minutes, using laboratory distillatory equipment. The fresh distillate was collected and the essential oil was separated from the hydrosol by using a solvent. The preliminary chemical composition of the essential oils was determined by TLC (thin layer chromatography) and ¹H and 13C Nuclear Magnetic Ressonance (NMR) and Infrared (IR) analyses. According to the results the essential oil yield of Baccharis sp., Blepharocalyx salicifolius, Psidium myrsinites and Protium ovatum was 0.06%, 0.12%, 0.10% and 0.13%, respectively. The observed yield values can be considered suitable for maintaining the research efforts. Chemical analysis showed that the essential oils obtained are composed by a complex mixture of compounds which should be studied more deeply.

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.

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.

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.