This work presents the biofuel production results of the esterification of fatty acids (C12-C18) and high-acid-content waste vegetable oils from different soap stocks (soybean, palm, and coconut) with methanol, ethanol, and butanol by acid catalysis. We used Amberlyst-35 (A35) sulfonic resin as a heterogeneous acid catalyst and p-toluenesulfonic acid as a homogeneous catalyst for comparison. Both the heterogeneous (A35) and homogeneous (p-toluenesulfonic acid) reactions were performed with 5% w/w of catalyst. The final products were analyzed by proton nuclear magnetic resonance (1H NMR). The homogeneous catalyzed esterification of fatty acids with methanol, ethanol, and butanol produced esters with yields higher than 90%. In the reaction with fatty acids and methanol catalyzed by A35, the best results were achieved with lauric acid and methanol, with a yield of 97%. An increase in the hydrocarbon chain decreased the rate of conversion and yield for stearic acid with methanol, which was 90%. Maximum biodiesel production was achieved from coconut and soybean soap stocks and methanol (96%-98%), which showed conversions very close to those obtained from their respective fatty acids. Microwave irradiation reduced the reaction time from 6 to 1 h in the esterification reaction of fatty acids with butanol.

Commercial and synthetic mesoporous aluminas impregnated with potassium carbonate were characterized by X-ray diffraction (XRD), nitrogen physisorption, infrared spectroscopy and 27Al MAS NMR. The activities in the transesterification reaction of sunflower oil with methanol for biodiesel production were evaluated. 27Al MAS NMR spectra evidenced the presence of AlIV and AlVI in the samples, and also of AlV sites in the mesoporous synthesized alumina, which disappeared after impregnation with potassium salt followed by calcination. All aluminas containing potassium were active for biodiesel production from sunflower seed oil, with high conversions by both conventional heating and microwave irradiation.

Nanopartículas de sílica (NPs) modificadas covalentemente com uma aminonaftoquinona foram sintetizadas e caracterizadas. A aminopropilsilicagelnaftoquinona (APSGNQ) foi obtida por substituição nucleofílica do grupo metóxi da 2-metóxi-1,4-naftoquinona por NPs modificadas com o grupo aminopropil (APSG). Os espectros de ressonância magnética nuclear de 13C e 29Si no estado sólido confirmaram que a naftoquinona encontra-se ligada covalentemente à aminopropilsilicagel. Como o composto APSGNQ é solúvel em solventes orgânicos comuns, foi possível quantificar o ancoramento da naftoquinona na superfície das NPs modificadas por espectroscopia no ultravioleta-visível (0,56 mmol de naftoquinona ancorada por grama de APSGNQ), por comparação com o espectro do composto análogo 2-aminobutil-1,4-naftoquinona (ABNQ). Os dados das análises elementares indicaram que aproximadamente 8% da propilamina presente na superfície do composto APSGNQ não reagiu com a metóxinaftoquinona. Essas NPs de sílica multifuncionais têm potencial para aplicações médicas.

The synthesis and characterization of silica nanoparticles (NPs) covalently modified with an aminonaphthoquinone are reported. The aminopropylsilicagelnaphthoquinone (APSGNQ) was obtained by nucleophilic substitution of 2-methoxy-1,4-naphthoquinone with aminopropylsilicalgel (APSG) NPs. Solid state 13C and 29Si nuclear magnetic resonance spectra confirmed that the naphthoquinone is covalently bonded to APSG. Due to the solubility of APSGNQ in common organic solvents, solution ultraviolet-visible spectroscopy was used to determine the amount of naphthoquinone on the NPs surface (0.56 mmol of incorporated naphthoquinone per gram of APSGNQ) by comparison with the spectrum of 2-aminobutyl-1,4-naphthoquinone (ABNQ). Elemental analysis indicated that about 8% of the surface propylamine remained unreacted in APSGNQ. These multifunctional silica NPs have potential in medical applications.

A atividade catalítica de sólidos ácidos como o fosfato de nióbio e a Amberlyst 35, uma resina trocadora de íons, foi avaliada na acetalização do hexanal com 2-etil-hexanol. Foram avaliadas a concentração do catalisador e a temperatura de reação na conversão do hexanal. A possibilidade de re-utilização do fosfato de nióbio também foi estudada e evidenciou ser possível re-utilizar este catalisador sem perda da atividade. O rendimento em acetal foi acima de 90% em condições brandas de reação.

The catalyst activity of solid acids such as niobium phosphate and Amberlyst 35, an ion exchange resin, was evaluated in the acetalization of hexanal with 2-ethyl-hexanol. The catalyst loading and the reaction temperature were evaluated in the hexanal conversions. The possibility of recycling niobium phosphate was also studied, showing that it was possible to reuse this catalyst without significant loss in its catalytic activity. The yield in acetal was above 90% under mild conditions.

Espectros de ressonância magnética nuclear de 13C com polarização cruzada e rotação no ângulo mágico (RMN-CPMAS de 13C) foram obtidos pela primeira vez para três amostras de âmbar provenientes do Mesozóico da América do Sul. As amostras foram datadas como pertencentes ao Cretáceo Inferior e coletadas em sedimentos das bacias do Amazonas, Araripe e Recôncavo, Brasil. Todas as amostras apresentaram espectros muito similares, o que é consistente com uma fonte paleobotânica em comum. Algumas características dos espectros, tais como sinais mais intensos entre 38-39 ppm, sugerem relação entre os âmbares brasileiros e a família Araucariaceae. Todas as amostras são formadas de estruturas polilabdânicas que permitem associação com resinas de Classe Ib, estruturalmente constituídas por polímeros de diterpenos labdânicos. Informações quanto às mudanças estruturais ocorridas durante a maturação, tais como isomerização de insaturações Δ8(17) e Δ12(13), também foram obtidas pelas análises por RMN-CPMAS de 13C. Os resultados quanto à origem botânica das amostras são concordantes com aqueles alcançados por análises mediante cromatografia gasosa acoplada à espectrometria de massas (GC-MS).

13C cross polarization with magic angle spinning nuclear magnetic resonance (13C CPMAS NMR) spectra have been obtained for the first time to three Cretaceous amber samples from South America. The samples were dated to Lower Cretaceous and collected in sediments from the Amazonas, Araripe and Recôncavo basins, Brazil. All samples have very similar spectra, consistent with a common palaeobotanical source. Some aspects of the spectra suggest a relationship between Brazilian ambers and Araucariaceae family, such as intense resonances at 38-39 ppm. All samples are constituted by polylabdane structure associated to Class Ib resins, constituted by polymers of labdanoid diterpenes. Finally, information concerning some structural changes during maturation, such as isomerization of Δ8(17) and Δ12(13) unsaturations, were obtained by 13C NMR analyses. The results concerning botanical affinities are in accordance with previous results obtained by gas chromatography-mass spectrometry (GC-MS).

{[Pt(eta2-TCNE)]2(µ-TPP)} (1) foi preparado a partir da reação entre o composto de Pt(0) [Pt2(dba)3] (dba = dibenzilidenoacetona), tetracianoetileno (TCNE) e 2,3,5,6-tetraquis(alfa-piridil)pirazina (TPP) na razão estequiométrica 1:2:1, respectivamente. 1 foi caracterizado por análise elementar, espectroscopia no infravermelho, RMN de ¹H em solução e RMN de 13C no estado sólido (CP/MAS). De acordo com os espectros de RMN, o ligante TPP em 1 se coordena a cada centro metálico por dois átomos de nitrogênio piridínicos, segundo um modo de coordenação bis-bidentado já relatado em outros complexos de TPP com PtII. Além dos sinais atribuídos aos átomos de carbono do TPP (delta 128-155) e aos átomos de carbono dos grupos nitrila (delta 115,1), o espectro de RMN de 13C-CP/MAS de 1 exibe na região de menor freqüência um duplo dupleto [delta1 -2,6; ¹J(195Pt-13 C) = 223 Hz e delta2 1,6; ¹J(195Pt-13 C) = 188 Hz]. Estes últimos sinais são atribuídos aos átomos de carbono etilênicos do TCNE ligados a platina e confirmam que a ligação nos fragmentos Pt-eta2-TCNE é melhor descrita segundo o modelo metalaciclopropano.

{[Pt(eta2-TCNE)]2(µ-TPP)} (1) has been prepared from the Pt(0) compound [Pt2(dba)3] (dba = dibenzylideneacetone), tetracyanoethylene (TCNE), and 2,3,5,6-tetrakis(alpha-pyridyl)pyrazine (TPP) in the 1:2:1 stoichiometric ratio, respectively. 1 has been characterized by elemental analysis, infrared spectroscopy, solution ¹H NMR and solid-state 13C (CP/MAS) NMR spectroscopy. According to the NMR spectra of 1, TPP binds to each metal through two pyridine nitrogen atoms. In addition to the signals assigned to the TPP carbon atoms (delta 128-155) and to the nitrile carbon atoms (delta 115.1), the 13C-CP/MAS NMR spectrum of 1 exhibits a double doublet [delta1 -2.6, ¹J(195Pt-13 C) = 223 Hz and delta2 1.6, ¹J(195Pt-13 C) = 188 Hz] in the low frequency region. These signals are assigned to the ethylenic TCNE carbon atoms attached to platinum and confirm that the bonding at the Pt-eta2-TCNE moieties is best described according to the metalacyclopropane model.

A natural clay from Campina Grande region (Paraíba, Brazil), with 8.57% of Fe2O3, was used to study the most appropriate condition to carry out the iron extraction, without altering the clay structure in a significant way. Samples were treated with the Dithionite-Citrate-Bicarbonate method (DCB) for 30 and 120 minutes (pH=9.1), and also with citric acid (pH=1.8; time=15min), at 75°C. Conductivity measurements, X-ray fluorescence, X-ray diffraction, energy-dispersive spectrometry, electron-diffraction with transmission electron microscopy and textural evaluation by nitrogen adsorption were done. The treatment in a basic medium was more selective for iron removal than in acid condition. The time of 30 minutes, with 1.6 g Na2S2O4/10 g clay, was the best condition for the iron extraction.

Al-pillared clay was prepared with a Brazilian bentonite from the Campina Grande region (Paraíba, BRAZIL). It was intercalated at 298 K, during 48 hours, with a solution containing [Al3+] = 0.10 mol/L and molar ratio OH/Al = 2.0 prepared at 333 K, and was calcined at 773K. The catalytic activity was evaluated by alkylation of benzene with 1-dodecene. The characterization methods were: X-ray fluorescence and diffraction analysis; 27Al, 29Si and 23Na MAS NMR and textural analysis by N2 adsorption. The thermal stability of the natural clay was improved by the pillaring procedure, as well as the catalytic activity. The intercalated clay presented the highest initial rate of reaction among the systems tested.