Otimização das condições de produção de ésteres etílicos a partir de óleo de peixe com elevado teor de ácidos graxos ômega-3

The production of ethyl esters by alcoholysis is an alternative for splitting triacylglycerols due to the possibility of using low temperatures, which results in oxidative protection of the polyunsaturated fatty acids. Ethyl esters produced under mild conditions of temperature could be used as substrate for obtaining structured lipids. The reaction parameters of production of ethyl esters from fish oil with high content of omega-3 fatty acids by alcoholysis were optimized using response surface methodology. An experimental design (2³) (with levels +1 and -1, six axial points with levels -alpha and +alpha and three central points) was applied. The variables investigated were concentration of catalyst, amount of ethyl alcohol and temperature. Ethyl ester conversion was monitored by high performance size exclusion chromatography (HPSEC) and the best result obtained was 95% conversion rate. The optimal conditions were 40 °C, 1% of NaOH and 36% of ethanol.

Alquilbenzeno sulfonato linear: uma abordagem ambiental e analítica

The environmental impact of detergents and other consumer products is behind the continued interest in the chemistry of the surfactants used. Of these, linear alkylbenzene sulfonates (LASs) are most widely employed in detergent formulations. The precursors to LASs are linear alkylbenzenes (LABs). There is also interest in the chemistry of these hydrocarbons, because they are usually present in commercial LASs (due to incomplete sulfonation), or form as one of their degradation products. Additionally, they may be employed as molecular tracers of domestic waste in the aquatic environment. The following aspects are covered in the present review: The chemistry of surfactants, in particular LAS; environmental impact of the production of LAS; environmental and toxicological effects of LAS; mechanisms of removal of LAS in the environment, and methods for monitoring LAS and LAB, the latter in domestic wastes. Classical and novel analytical methods employed for the determination of LAS and LAB are discussed in detail, and a brief comment on detergents in Brazil is given.

Biossensor enzimático para detecção de fungicidas ditiocarbamatos: estudo cinético da enzima aldeído desidrogenase e otimização do biossensor

Initially, all major factors that affect the rate of the AldH-catalyzed reaction (enzyme concentration, substrate concentration, temperature and pH) were investigated. Optimal activity was observed between pH values of 7.5 and 9.5 in the temperature range of 25 to 50 ºC. Kinetic parameters, such as Km (2.92 µmol L-1) and Vmax (1.33 10-2 µmol min-1) demonstrate a strong enzyme-substrate affinity. The sensors were based on screen-printed electrodes modified with the Meldola Blue-Reinecke salt (MBRS) combination. Operational conditions (NAD+ and substrate contents, enzyme loading and response time) were optimized. Also, two enzyme immobilization procedures were tested: entrapment in poly(vinyl alcohol) bearing styrylpyridinium groups (PVA-SbQ) and crosslinking with glutaraldehyde. Chronoamperometry was employed to observe the biosensor responses during enzymatic hydrolysis of propionaldehyde and also to construct inhibition curves with maneb and zineb fungicides. Best results were found with the following conditions: [NAD+] = 0.25 mmol L-1; [propionaldehyde] = 80 µmol L-1; enzyme loading = 0.8 U per electrode; response time = 10 min, and inhibition time = 10 min. Current intensities around 103 ± 13 nA with the sensors and good stability was obtained for both immobilization procedures. Detection limits, calculated using 10% inhibition were 31.5 µg L-1 and 35 µg L-1 for maneb and zineb, respectively. Results obtained with other MBRS-modified electrodes consisting of mono and bi-enzymic sensors were compared. The ability to catalyze NADH oxidation by MB was also highlighted.

Otimização do banho eletrolítico da liga Fe-W-B resistente à corrosão

A study on optimization of bath parameters for electrodeposition of Fe-W-B alloys from plating baths containing ammonia and citrate is reported. A 2³ full factorial design was successfully employed for experimental design analysis of the results. The corrosion resistance and amorphous character were evaluated. The bath conditions obtained for depositing the alloy with good corrosion resistance were: 0.01 M iron sulfate, 0.10 M sodium tungstate and 0.60 M ammonium citrate. The alloy was deposited at 12% current efficiency. The alloy obtained had Ecorr -0.841 V and Rp 1.463 x 10(4) Ohm cm². The deposit obtained under these conditions had an amorphous character and no microcracks were observed on its surface. Besides this, the bath conditions obtained for depositing the alloy with the highest deposition efficiency were: 0.09 M iron sulfate, 0.30 M sodium tungstate and 0.50 M ammonium citrate. The alloy was deposited at 50% current efficiency, with an average composition of 34 wt% W, 66 wt% Fe and traces of boron. The alloy obtained had Ecorr -0.800 V and Rp 1.895 x 10³ Ohm cm². Electrochemical corrosion tests verified that the Fe-W-B alloy deposited under both conditions had better corrosion resistance than Fe-Mo-B.

Otimização e validação da técnica de extração líquido-líquido com partição em baixa temperatura (ELL-PBT) para piretróides em água e análise por CG

The liquid-liquid extraction with the low temperature partition technique was developed for the analysis of four pyrethroids in water by CG. Using a factorial design the extraction technique was optimised evaluating the effect of the variables ionic strength, contact time and proportion between sample and solvent volumes. The validation parameters sensitivity, precision, accuracy and detection and quantification limits were evaluated. The LOD and LOQ of the method varied from 1.1 to 3.2 µg L-1 and 2.7 to 9.5 µg L-1, respectively.

Planejamento estatístico de experimentos como uma ferramenta para otimização das condições de biossorção de Cu(II) em batelada utilizando-se casca de nozes pecã como biossorvente

In order to reduce the total number of experiments for achieving the highest amount of adsorbed Cu2+ (qmax) using pecan nutshells (Carya illinoensis) as biosorbent, a full 2(4) factorial design with two central points was carried out (mass of biosorbent- m, pH, initial metallic ion concentration- C0, time of contact- t). In order to continue the optimization of the system, a central composite surface analysis design with two factors and five central points was carried out. The maximum amount of Cu2+ taken up by the pecan nutshells was 20 mg g-1. These results were confirmed by determining a Cu2+ isotherm using the best conditions attained by the statistical design of experiments.

Utilização do índice de retenção linear para caracterização de compostos voláteis em café solúvel utilizando GC-MS e coluna HP-Innowax

Gas chromatography coupled with mass spectrometry (GC-MS) is widely used for the characterization of volatile compounds. However, due to the complexity of the soluble coffee matrix, a complete identification of the components should not be based on mass spectra interpretation only. The linear index of retention (LRI) is frequently used to give support to mass spectra. The aim of this work is to investigate the characterization of the volatile compounds in soluble coffee samples by GC-MS using LRI values found with a HP-INNOWAX column. The method used allows a significant increase of the reliability of identifying compounds.

Otimização de metodologia para derivação de desoxinivalenol através de planejamento experimental

The objective of this work was to optimize the derivatization reaction for determining deoxynivalenol (DON) by gas chromatography employing an experimental planning procedure. The factors were: temperature, reaction time, catalyst and trifluoroacetic anhydride concentration. The relative peak areas were used to evaluated the effects. The best conditions for DON derivatization were 200 µL TFAA and 18 mg sodium bicarbonate for 6 min at 74 ºC for 7 to 21 µg of DON. Under these conditions, the detection limit was 1.4 µg of DON.

Determinação simultânea de As, Cd e Pb em amostras de água purificada para hemodiálise por espectrometria de absorção atômica com forno de grafite, após otimização multivariada baseada no uso de planejamento experimental

This paper reports the development of a methodology for simultaneously determining As, Cd and Pb, employing GF AAS with polarized Zeeman-effect background correction. In order to make the procedure applicable, the influence of pyrolysis and atomization temperatures and the amount of chemical modifiers were studied. Factorial and central composite designs were used to optimize these variables. Precision and accuracy of the method were investigated using Natural Water Reference material, Nist SRM 1640. Results are in agreement with certified values at the 95% confidence limit when the Student t-test is used. This methodology was used for quality control of purified water for hemodialysis.

Aplicação da metodologia de planejamento fatorial e análise de superfícies de resposta para otimização da fermentação alcoólica

In the present work, the influence of the amount of nitrogen and phosphorus and degrees Brix on the yield and productivity of alcoholic fermentation has been evaluated. The methodology used was factorial design and response surface analysis. Within the range studied only for phosphorus a statistically significant effect was observed. The broth of sugar cane of the CB 453 variety already possessed enough nitrogen for the fermentation. The mathematical and empirical model was validated for productivity and not for yield. The concentration of alcohol produced in the fermentation was not enough to cause cellular growth inhibition.

Otimização de método para determinação de flavonóis e flavonas em frutas por cromatografia líquida de alta eficiência utilizando delineamento estatístico e análise de superfície de resposta

This work optimized the HPLC conditions for the simultaneous determination of luteolin, apigenin, myricetin, quercetin and kaempferol in aglycone form, as well defined the best conditions for hydrolysis/extraction of these flavonoids in fruits, using the statistical central composite design and response surface analysis. A reverse phase method was developed using a gradient of methanol/water acidified with 0.3% formic acid as mobile phase and a photodiode array detector. The samples were extracted with methanol/water (50:50 v/v) at 90 ºC. The optimum time and HCl concentration varied for the different fruits investigated, demonstrating the necessity of optimizing these conditions for each fruit analyzed. Good recovery (87.1 to 96.3%), repeatability and linearity were obtained.

Otimização dos parâmetros de produção de hidrolisados protéicos enzimáticos utilizando pescado de baixo valor comercial

The enzymatic modification of proteins has been widely studied with the aim of add value to low commercial value fish. The objective of this work was to evaluate and optimize the parameters involved in the production process of an enzymatic protein hydrolyzed with high protein content. The results showed that for Alcalase the most significant parameters were temperature, pH and substrate concentration and for Flavourzyme were pH, substrate concentration and enzyme concentration. It was obtained for Alcalase a predictive model for the recovered nitrogen and for Flavourzyme a predictive model for the hydrolysis degree.

Efeito da acidez e de modificadores orgânicos na determinação de metilxantinas: um experimento de cromatografia liquida de alta eficiência (CLAE) empregando otimização uni e multivariada

In this work a new experiment using HPLC is proposed in order to explore the role of acidity and the organic modifiers in the determination of methylxanthines in tea and coffee. Multivariate and univariate optimizations of the experimental conditions were used.

Otimização e validação intralaboratorial de método para análise de resíduos de cloranfenicol em leite caprino por cromatografia gasosa com detecção por captura de elétrons (CG/DCE)

The presence of chloramphenicol residues in goat milk can cause toxic effects in the population. The present work consists of the optimization and validation of analytical methodology for determination of chloramphenicol residues in goat milk by GC/ECD. The extraction was made with ethyl acetate and the clean-up with SPE-C18. The identification was made by comparison of retention time and GC/MS, and the quantification by external standard. The method was selective, linearity (0.998), precise (5.8-13.4%), exact (69.87-73.71%) and robust. The LOD and LOQ of method were 0.030 and 0.10 μg/kg, respectively. The method was efficiently for analysis of chloramphenicol in goat milk.

Otimização de metodologia analítica para o doseamento de flavonoides de Bauhinia cheilantha (Bongard) Steudel

The present study examined the optimization of stabilization and extraction processes of the flavonoids of Bauhinia cheilantha (Bongard) Steudel. Four drying temperatures (room temperature, 40, 60 and 80 ºC) and seven extraction systems (distilled water, 100% methanol, 80% methanol, 100% ethanol, 80% ethanol, 80% acetone and 60% acetone) were examined. The results demonstrated a reduction in flavonoid levels with increasing drying temperatures; and 80% acetone, 80% ethanol, and methanol p.a extraction systems were found to be most efficient and its weren't differents statisticaly (p<0.05).