The feasibility of obtaining cellulose acetate from lignocellulosic precursors is of great interest from the environmental, economic and technological points of view. Herein, sugarcane bagasse and vegetable sponge (Luffa cylindrica ) were used as precursors to produce cellulose using the organosolv extraction procedure. From the extracted celluloses, the production of cellulose acetate was carried out by the homogeneous acetylation method. The obtained materials were characterized by FTIR, solid-state 13C NMR, XRD, TG and DSC techniques. The results revealed the success of both the extraction and the acetylation processes, which provided cellulose with high crystallinity and cellulose acetates with high degrees of substitution (cellulose triacetates).

New Schiff base compound N, N’-bis-(4-hexadecanate)-salicylethylenediamine (named IM) was synthesized, and characterized via infrared and nuclear magnetic ressonance spectroscopies. IM was tested as corrosion inhibitor and antioxidant in soybean biodiesel. Corrosion studies were developed with AISI 1020 carbon steel in a three-step accelerated corrosion assay and IM inhibitory activity was evaluated using microscopic techiniques: optical microscopy (OM), scanning electron microscopy (SEM) and atomic force microscopy (AFM). In 750 ppm concentration, IM showed better inhibitory activity compared to commercial compounds tert-butylhydroquinone and pyrogallol, reducing root-mean-square roughness (Rq) from 37.8 to 11.7 nm and peak-peak height (PP) from 454.1 to 120.2 nm after 8 days of immersion. Antioxidant studies were conducted using the PetroOXY equipment. In 250 ppm concentration, IM showed better antioxidant activity as metal chelator, reducing biodiesel oxidation induced by copper on biodiesel. In this concentration, IM increased the induction period from 3.0 to 5.8 h. Furthermore, the new Schiff base acts as an oxygen scavanger. This is a great property because it reduces oxygen concentration in biodiesel, reducing metal corrosion reactions.

Using niobium compounds as heterogeneous catalysts in biodiesel production is a promising methodology from economic and environmental viewpoints. However, the application of niobium catalysts still is a challenge due to the high temperatures and pressures for moderate biofuel yields. Therefore, easily handled and applied materials have been developed to optimize biofuel production, which is the goal of this study. Nb2O5 and ammonium niobium oxalate (AmNO) were activated in reflux and ultrasound-assisted system. Nb2O5 showed better activity under reflux, using methanol. The characterizations conclude that the Lewis-acid sites are determinant for higher conversion rather than surface area. AmNO has better activity also in the reflux system at 70 ºC, against 170 ºC for Nb2O5, reaching above 70% conversion. In addition, reactions in ultrasound-assisted systems are also appealing due to the lower time and temperature, with conversion rates above 40%. Both catalysts showed interesting results under milder conditions than those in the literature.

The conventional biodiesel process, although it reaches high conversion yields and productivity, faces problems related to the use of homogeneous catalysts. This work aims to study mixtures of calcium oxide (CaO) and niobium oxide (Nb2O5) as the heterogeneous catalyst. It was used a full 23 factorial design with four central points to analyze how the mass percentage of the oxides, the molar ratio of reactants, and the reaction temperature affect the conversion yield to methyl esters. The best conversion yield was found near to 89% using 1.8% of catalyst, a 1:36 oil to methanol ratio and at 77 ºC as reaction temperature. Finally, it was performed a simplified simulation to compare the heterogeneous catalyst process with the conventional process, and an algorithm to compare the effects of the exit streams of each process would have on the environment. The simulations results display a better performance for the heterogeneous catalyst process studied.

RESUMO Este trabalho objetivou avaliar os custos envolvidos na construção de modelos de biodigestores (indiano, chinês e canadense) no município de Cascavel – PR. Determinaram-se os custos de produção de energia a partir do biogás produzido por dejetos de caprinos, bovinos e suínos, para sistemas de semiconfinamento. Foram utilizadas propriedades rurais com 20; 40; 60; 80 e 100 animais de cada um dos três grupos avaliados. A partir do volume de dejetos produzidos por animal, foram dimensionados os biodigestores e calculados os custos para a construção e a implantação de cada modelo, e o custo total da produção anual de energia em função do número de animais. O biodigestor modelo canadense apresentou o menor custo de construção e de implantação, variando de R$ 2.104,00 a R$ 7.266,00. A geração de energia com dejetos de suínos apresentou o menor custo, variando de 0,015 a 0,050 R$/KWh em biodigestor modelo canadense. A maior produção anual de energia foi verificada para bovinos, variando de 24.090 kWh/ano a 120.450 kWh/ano, para os três modelos de biodigestor em estudo.

ABSTRACT This study aimed at assessing the costs incurred in building different biodigester models (Indian, Chinese, and Canadian) in Cascavél – PR, Brazil. We also determined costs related to biogas production from goat, bovine, and swine dungs in semi-confinement systems. For this purpose, we evaluated farms with herds of 20, 40, 60, 80, and 100 animals of each group. The biodigesters’ volume were based on each animal amount of excrement and, then, we calculated the costs for building and implementing each model, as well as costs associated to annual energy production on the number of animals used. The lowest cost was observed for Canadian biodigester with respect to both building and implementation, ranging from R$ 2,104.00 to R$ 7,266.00. Power generation using swine waste had the lowest costs varying 0.015 to 0.050 R$/ kWh with Canadian model. The largest annual energy production was recorded for bovine dung, varying 24,090 to 120,450 kWh/ year for the 3 studied models.

In this study, we report the preparation of a new tetra-substituted epoxide aldehyde cyclopentane, which acts as a starting material for the synthesis of plinol, from (R)-(+)-epoxy-limonene. The synthesis was performed in three steps and resulted in a good yield. The structural determination was performed by 1H and 13C NMR, and the relative stereochemistry was defined by nuclear Overhauser effect (NOE) experiments with computer calculations of molecular modeling, particularly with respect to indirect coupling constant calculations.

A esterificação direta de naftoquinonas mostrou-se uma tarefa difícil. Metodologias mais comuns envolvem a aplicação de cloretos de acila em piridina ou anidridos, entretanto, quando ácidos de cadeia longa são utilizados tais metodologias se mostram ineficientes devido aos baixos rendimentos obtidos. Apresentamos uma nova síntese de ésteres de cadeia longa de juglona baseado na esterificação de Steglich utilizando um ácido de Lewis barato como cocatalisador. Rendimentos obtidos são consideravelmente maiores do que os reportados previamente. Química computacional foi utilizada para avaliar os efeitos do CeCl3 como cocatalisador. Os compostos preparados foram testados como inibidores de deposição de parafinas em petróleo. Éster palmítico da juglona foi capaz de reduzir 4 ºC na temperatura de início de aparecimento de cristais (WAT) do óleo estudado, representando uma redução de 1,5% m/m de parafinas normais precipitadas.

Direct esterification on naphthoquinone presented itself as a hard task. Usual methodologies apply acyl chloride in pyridine or anhydrides but with long-chain esters this procedure proved to be ineffective because of the low yields obtained. We present a new synthesis of long-chain esters of juglone based on Steglich esterification using a cheap Lewis acid as cocatalyst. Yields obtained are considerably better than those found previously. Computational chemistry was used to evaluate the effects of CeCl3 as cocatalyst. Prepared compounds were tested as wax deposition inhibitors in crude oil. Palmitic ester of juglone was able to lower 4 ºC on the wax appearance temperature (WAT) of the studied oil, representing a reduction of precipitated normal paraffin of 1.5% m/m.

De acordo com a literatura, a reação de Diels-Alder de furano sem uso de catalisador pode durar várias semanas e apresenta baixo rendimento devido à baixa reatividade do dieno. O uso de catalisadores ácidos de Lewis ou de altas pressões são descritos como métodos eficazes para melhorar o rendimento da reação. Este trabalho descreve nosso estudo recente sobre a utilização de pentacloreto de nióbio, como catalisador em reações de Diels-Alder entre furano e alguns dienófilos reativos, entre os quais o acrilato de metila apresentou bons rendimentos, especialmente sob temperaturas mais baixas. Outros dienófilos apresentaram rendimentos mais baixos devido a problemas, tais como a formação de produtos secundários e de elevado caráter de reversibilidade da reação.

According to the relevant literature, the Diels-Alder reaction of furan without a catalyst can last several weeks and shows a low yield due to the diene's low reactivity. The use of Lewis acid catalysts or high pressures is described as an effective method for improving the reaction yields. This paper describes our recent study on the use of niobium pentachloride as the catalyst in Diels-Alder reactions between furan and several reactive dienophiles, among which methyl acrylate showed good yields, especially at lower temperatures. Other dienophiles have shown lower yields because of problems such as byproduct formation and the high reversibility of the reaction.

To choose among the variety of oleaginous plants for biodiesel production, the oil content of several matrices was determined through different low-field ¹H nuclear magnetic resonance (NMR) experiments with varied pulse sequences, namely single-pulse, spin-echo, CPMG, and CWFP. The experiments that involved the first three sequences showed high correlation with each other and with the solvent extraction method. The quality of the vegetable oils was also evaluated on the basis of the existing correlation between the T2 values of the oils and their properties, such as viscosity, iodine index, and cetane index. These analyses were performed using HCA and PCA chemometric tools. The results were sufficiently significant to allow separation of the oleaginous matrices according to their quality. Thus, the low-field ¹H NMR technique was confirmed as an important tool to aid in the selection of oleaginous matrices for biodiesel production.

Homo and heterotrinuclear acetates are unique compounds having μ3-oxo bridge and many interesting properties of such compounds are derived from this structure. Some undergraduate inorganic textbooks discuss several aspects of these compounds and we present here an undergraduate experiment for the high-yield synthesis of [Fe2MO(CH3CO2)6(H 2O)3], with M = Fe3+, Co2+ and Ni2+, as well as their characterization using infrared spectroscopy and cyclic voltametry. The proposed experiment gives the opportunity to discuss several concepts of coordination chemistry that follow the characterization techniques, such as: types of acetate coordination, reversibility of electrochemical processes, quelate and trans effects and lability.

Banana, mamão e abacaxi são as frutas tropicais mais consumidas no mundo, sendo o Brasil um dos principais produtores. Os fungos Colletotrichum musae, Colletotrichum gloeosporioides e Fusarium subglutinans f.sp ananas são os principais causadores de doenças e perdas em pós-colheita de frutas. A proposta deste estudo foi avaliar a eficácia de cinco monoterpenos em inibir o crescimento micelial e a germinação dos conídios destes três fitopatógenos. Os monoterpenos citral, citronelal, L-carvona, isopulegol e a-pineno foram diluídos em etanol à concentração final de 0,2 a 1%. Todos os monoterpenos testados inibiram os três fungos estudados de maneira dose-dependente. Citral foi o mais efetivo dos óleos testados e apresentou uma potente atividade fungicida em concentrações acima de 0,5%. Mais ainda, avaliação in vivo com estas frutas tropicais demonstrou a eficácia de citral como inibidor do crescimento fúngico. Estes resultados indicam o uso em potencial de citral como um pesticida natural no controle das doenças em pós-colheita de frutas tropicais.

Banana, papaya and pineapple are the most consumed tropical fruits in the world, being Brazil one of the main producers. Fungi Colletotrichum musae, Colletotrichum gloeosporioides and Fusarium subglutinans f.sp. ananas cause severe post harvest diseases and losses in fruits quality. The aim of this work was to evaluate the effectiveness of five monoterpenes to inhibit the mycelial growth and conidia germination of these three phytopathogens. The monoterpenes citral, citronellal, L-carvone, isopullegol and a-pinene were diluted in ethanol to final concentrations from 0.2 to 1%. All monoterpenes were found to inhibit the growth of the three studies fungi in a dose-dependent manner. Citral was the most effective of the oils tested and showed potent fungicidal activity at concentrations above 0.5%. Also, in vivo evaluation with these tropical fruits demonstrated the efficiency of citral to inhibit fungal growth. These results indicate the potential use of citral as a natural pesticide control of post-harvest fruit diseases.

O sucesso no uso de Trichogramma como agente de controle biológico depende de sua produção em laboratório que é etapa fundamental, entre outras, em qualquer programa de controle biológico. Este trabalho investigou a capacidade de parasitismo de Trichogramma pratissolii Querino & Zuchi, uma nova espécie encontrada, parasitando ovos de Anagasta kuehniella (Zeller) e Corcyra cephalonica (Stainton) (Lepidoptera: Pyralidae) submetidos a 15, 18, 21, 24, 27, 30 e 33ºC. Ovos desses hospedeiros foram oferecidos para fêmeas recém-emergidas por 24h. Esse procedimento foi repetido para cada fêmea e temperatura até a morte das fêmeas do parasitóide, para estimar o parasitismo diário, acumulado e a longevidade das fêmeas. Em ambos hospedeiros, o parasitismo diário decresceu em função da idade da fêmea. Em todas as temperaturas estudadas e ambos hospedeiros, o maior parasitismo ocorreu durante as primeiras 24h e, atingiu 80% do total no quarto e terceiro dias quando parasitou A. kuehniella e C. cephalonica, respectivamente. Para ambos os hospedeiros os maiores índices de parasitismo foram observados entre 21ºC e 27ºC. A longevidade média de fêmeas de T. pratissolii sem alimento e provenientes de ovos de A. kuehniella e C. cephalonica sobreviveram de 1,0 a 8,9 dias, quando criadas a 15ºC e 33ºC, respectivamente. Os resultados encontrados indicam que ovos de A. kuehniella e C. cephalonica e temperaturas de 21ºC a 27ºC foram apropriados para criação de T. pratissolii.

The successful use of Trichogramma as biocontrol agent depends on its mass production in laboratory, a fundamental step for any biological control program among other factors. This work investigated the parasitism capacity of Trichogramma pratissolii Querino & Zuchi (Hymenoptera: Trichogrammatidae), a new recorded Trichogramma species, parasitizing eggs of Anagasta kuehniella (Zeller) and Corcyra cephalonica (Stainton) (Lepidoptera: Pyralidae) under the temperatures of 15, 18, 21, 24, 27, 30 and 33ºC. Eggs of these hosts were offered to newly emerged females during 24h. This procedure was repeated daily for each female and each temperature up to female death, in order to estimate daily and accumulated parasitism, and female longevity. On both hosts, the daily parasitism decreased as function of the female age. Under all temperatures studied and both hosts the highest rate of parasitism was observed during the first 24h of host exposure, and reached 80% of total parasitism in the 4th and 3rd days when parasitizing A. kuehniella and C. cephalonica, respectively. On both hosts, the highest parasitism rate was observed under temperatures from 21ºC to 27ºC. Average longevities of T. pratissolii females deprived of food emerging from A. kuehniella and C. cephalonica lived for 1.0 and 8.9 days when reared at 15ºC e 33ºC, respectively. The results indicate that eggs of A. kuehniella and C. cephalonica and temperatures from 21ºC to 27ºC were appropriate to rear T. pratissolii.

Inseticidas químicos são amplamente usados para o controle da traça-das-crucíferas, Plutella xylostella (L.). Esta é considerada a principal praga das crucíferas em todo o mundo e o surgimento de resistência de P. xylostella tem sido freqüentemente relatado. Este trabalho investigou as diferentes interações dos fungos Metarhizium anisopliae (Metsch.) Sorok. e Beauveria bassiana (Bals.) Vuill. com o parasitóide de larva-pupa Oomyzus sokolowskii (Kurdjumov) sobre larvas de P. xylostella. O experimento foi conduzido à temperatura de 26 ± 1°C, UR de 75 ± 5% e fotofase de 12h, empregando-se delineamento inteiramente casualizado, constando de oito tratamentos com seis repetições cada. Foram utilizados os isolados E9 de M. anisopliae e ESALQ 447 de B. bassiana, na concentração de 10(7) conídios ml-1. Os resultados mostram que M. anisopliae e B. bassiana reduziram o parasitismo de P. xylostella por O. sokolowskii . Por outro lado, efeitos aditivos no controle de P. xylostella foram evidenciados nas diferentes combinações dos fungos com o parasitóide, exceto para B. bassiana quando pulverizado 24h antes da exposição a O. sokolowskii. Os fungos M. anisopliae e B. bassiana foram mais eficientes quando aplicados após a exposição das larvas ao parasitóide, e a eficiência de O. sokolowskii foi influenciada negativamente pela presença dos fungos independente da combinação. A associação dos fungos com o parasitóide apresentam potencial para serem testados em campo, objetivando o controle de P. xylostella bem como favorecer economicamente o sistema produtivo das brássicas.

Chemical insecticides are broadly applied to control diamondback moth, Plutella xylostella (L.). Diamondback moth is a major pest of cruciferous worldwide, and resistance of this pest to insecticide has been often reported. Thus, this research investigated the interactions among the fungi Metarhizium anisopliae (Metsch.) Sorok., Beauveria bassiana (Bals.) Vuill., and the larval-pupal parasitoid Oomyzus sokolowskii (Kurdjumov) before and after application of the fungi on DBM larvae offered to the parasitoid. The experiment was carried out at 26 ± 1ºC, 75 ± 5% RH and 12h photophase using a completely randomized design, with eight treatments with six replications each. The isolates E9 of M. anisopliae and ESALQ 447 of B. bassiana, were used at the concentration of 10(7) conidia ml-1. The results showed that M. anisopliae and B. bassiana reduced the parasitism of P. xylostella by O. sokolowskii. Additive effects were found on the mortality of P. xylostella with the different combinations among the fungi and parasitoid, except for the treatment B. bassiana inoculated 24h before exposition of the larvae to O. sokolowskii. The isolates were more efficacious when applied after exposition of the larvae to the parasitoid. The efficiency of O. sokolowskii was negatively influenced by the presence of the fungi, mainly when the fungi were applied 24h before diamondback's larvae were exposed to the parasitoid. The association of the fungi with the parasitoid presents potential to be tested in field. The use of these natural enemies in the integrated management of P. xylostella may economically improve the cabbage productive system, especially for organic farming.