Behavior of Humic Acid as a Micellar Phase in Micellar Electrokinetic Chromatography (MEKC)

The possibility of humic acids acting as micellar phase in micellar electrokinetic chromatography was evaluated. We investigated the separation of naphthalene in capillary electrophoresis using various samples of humic acids as micellar phase under different pH conditions, concentrations of humic acid, and temperature. The humic acid samples studied were from different origins including peat, vermicompost and a commercial sample acquired from Aldrich. Methanol was used as a marker for the electroosmotic flow. The results indicate that the formation of micelle depends on the number and nature of the hydrophobic association sites in an aqueous humic acid solution and on the origin and concentration of the humic acid at a defined pH. At lower pH values, the possibility of the humic acid molecule forming pseudomicelles increases due to a combination of neutralized and dissociated charged sites.     

Antioxidant activity of aryltetralone lignans and derivatives from Virola sebifera (Aubl.)

Aryltetralone lignans bearing methylenedioxy groups (1a-b; 2a-b) were isolated from seeds of Virola sebifera. Their antioxidant activities were evaluated by inhibition of lipid peroxidation as indicated by TBARS and chemiluminescence emission (CL) assays. The lignan 1c, 'having a 2'-hydroxy-4',5'-methylenedioxyphenyl group, was the most active compound with TBARS/CL Q 1/2 values of 0.89 and 0.10 microg/mL, respectively. The catechol derivatives 3 and 4, obtained by demethylenation of lignans 1a and 2a, were of similar activity to 1c, and all were much more effective as antioxidants than alpha-tocopherol.     

Reduction of Weed Growth under the Influence of Extracts and Metabolites Isolated from Miconia spp.

Weeds pose a problem, infesting areas and imposing competition and harvesting difficulties in agricultural systems. Studies that provide the use of alternative methods for weed control, in order to minimize negative impacts on the environment, have intensified. Native flora represents a source of unexplored metabolites with multiple applications, such as bioherbicides. Therefore, we aimed to carry out a preliminary phytochemical analysis of crude extracts and fractions of Miconia auricoma and M. ligustroides and to evaluate these and the isolated metabolites phytotoxicity on the growth of the target species. The growth bioassays were conducted with Petri dishes with lettuce, morning glory, and sourgrass seeds incubated in germination chambers. Phytochemical analysis revealed the presence of flavonoids, isolated myricetin, and a mixture of quercetin and myricetin. The results showed that seedling growth was affected in a dose-dependent manner, with the root most affected and the seedlings of the lettuce, morning glory, and sourgrass as the most sensitive species, respectively. Chloroform fractions and myricetin were the most inhibitory bioassays evaluated. The seedlings showed structural changes, such as yellowing, nonexpanded cotyledons, and less branched roots. These results indicate the phytotoxic potential of Miconia allelochemicals, since there was the appearance of abnormal seedlings and growth reduction.     

Enzymatic synthesis of medium chain monoglycerides in a solvent-free system

The synthesis of monocaprin, monolaurin, and monomyristin in a solvent-free system was conducted by mixing a commercial immobilized lipase with the organic reactants (glycerol and fatty acids) in a 20-mL batch reactor with constant stirring. The effects of temperature, fatty acid/glycerol molar ratio, and enzyme concentration on the reaction conversion were determined. The addition of molecular sieves in the assays of monomyristin synthesis was also evaluated. The reactions were carried out for 5 to 6 h and the nonpolar phase was analyzed by gas chromatography. The best results in terms of selectivity and conversion (defined as the percentage of fatty acid consumed) were achieved when the stoichiometric amount of reagents (molar ratio=1) and 9% (w/w) commercial enzyme were used and the reaction was performed at 60°C. The addition of molecular sieves did not improve the synthesis of monomyristin. Conversions as high as 80%, with monoglycerides being the major products, were attained. After 5 h of reaction, the concentration of monoglyceride was about twice that of diglyceride, and only trace amounts of triglyceride were found. The results illustrate the technical possibility of producing medium chain monoglycerides in a solvent-free medium using a simple batch reactor.     

Electrospray ionization mass spectrometric fragmentation of hydroquinone derivatives

The fragmentation patterns of nine di-, tri- and tetracyclic hydroquinones with potential antitumor activity were rationalized by invoking competing mechanisms that included sterically accelerated homolytic cleavage, Meerwein-type rearrangements and dehydrations through elimination or intramolecular nucleophilic substitution.     

Characterization of Cellulolytic Extract from <Emphasis Type="Italic">Pycnoporus sanguineus</Emphasis> PF-2 and Its Application in Biomass Saccharification

The aim of this work was to evaluate the biochemical features of the white-rot fungi Pycnoporus sanguineus cellulolytic complex and its utilization to sugarcane bagasse hydrolysis. When cultivated under submerged fermentation using corn cobs as carbon source, P. sanguineus produced high FPase, endoglucanase, β-glucosidase, xylanase, mannanase, α-galactosidase, α-arabinofuranosidase, and polygalacturonase activities. Cellulase activities were characterized in relation to pH and temperature. β-Glucosidase and FPase activities were higher at 55 °C, pH 4.5, and endoglucanase activity was higher at 60 °C, in a pH range of 3.5–4.0. All cellulase activities were highly stable at 40 and 50 °C through 48 h of pre-incubation. Crude enzymatic extract from P. sanguineus was applied in a saccharification experiment using acid-treated and alkali-treated sugarcane bagasse as substrate, and the hydrolysis yields were compared to that obtained by a commercial cellulase preparation. Reducing sugar yields of 60.4% and 64.0% were reached when alkali-treated bagasse was hydrolyzed by P. sanguineus extract and commercial cellulase, respectively. Considering the glucose production, it was observed that P. sanguineus extract and commercial cellulase ensured yields of 22.6% and 36.5%, respectively. The saccharification of acid-treated bagasse was lower than that of alkali-treated bagasse regardless of the cellulolytic extract. The present work showed that P. sanguineus has a great potential as an enzyme producer for biomass saccharification.     

Biosynthesis and antioxidant activity of 4NRC β-glycoside

This Letter describes glycosylation of 4-Nerolidylcatechol (4-NRC) the major secondary metabolite from Pothomorphe peltata and Pothomorphe umbellata showing remarkable antioxidant, antimalarial, anti-inflammatory, and anti-HIV activities. One step biosynthesis was catalyzed by Cunninghamella echinulata ATCC 9245 and the reaction was undertaken in PDSM medium at 27 °C, 200 rpm for 96 h. After purification by silica gel flash column chromatography the 4-NRC β-glycoside was identified by ultrahigh resolution mass spectrometry and ¹H NMR. The antioxidant activity was evaluated by differential pulse voltammetry.     

Substituent electrophilicities in the NMR spectra of barbituric derivatives

Comparison of the ¹H and ¹³ C NMR spectra of a series of substituted 5‐benzylidene‐N,N′‐dimethylbarbituric acids (1) revealed chemical‐shift variations of different centers that correlated with the theoretical electrophilicities or with the substituent electrophilic constant σ_ω , in an example of the usefulness of these DFT‐based indices. Copyright © 2012 John Wiley & Sons, Ltd.     

Surface properties of sensors based on aminophenol-polymerized film

In this work, carbon electrodes modified with aminophenols were developed for the production of pesticides biosensors based on acetylcholinesterase. The polymers were potentiodynamically deposited on a graphite electrode surface by the oxidation of monomers, 2-aminophenol, 3-aminophenol and 4-aminophenol. The electrochemical behaviour and surface analysis of the electrodes modified by polyaminophenols non-immobilized and immobilized on acetylcholinesterase were studied by cyclic voltammetry, electrochemical impedance spectroscopy and atomic force microscopy. Roughness values obtained for graphite electrodes modified with poly(4-aminophenol) and poly(4-aminophenol)/acetylcholinesterase were 174 and 86 nm, respectively. The acetylcholinesterase enzyme was immobilized on a graphite and a graphite modified with poly(4-aminophenol), and these electrodes were coupled in the flow system. Potentiometric response due to hydrogen ions generated by an enzymatic system in the presence of acetylcholine chloride substrate was evaluated. The results showed that the graphite/poly(4-aminhophenol) sensor presents high sensitivity to hydrogen ions when compared with other graphite/polyaminophenols sensors. The biosensor coupled in a continuous flow system was employed for the detection of dichlorvos. The detection and quantification limits were 0.8 and 2.4 μmol L⁻¹ dichlorvos, respectively. This sensor reveals an efficient and promising material for biomolecules immobilization.