Biobased composites from glyoxal-phenolic resins and sisal fibers

Lignocellulosic materials can significantly contribute to the development of biobased composites. In this work, glyoxal-phenolic resins for composites were prepared using glyoxal, which is a dialdehyde obtained from several natural resources. The resins were characterized by (1)H, (13)C, (2)D, and (31)P NMR spectroscopies. Resorcinol (10%) was used as an accelerator for curing the glyoxal-phenol resins in order to obtain the thermosets. The impact-strength measurement showed that regardless of the cure cycle used, the reinforcement of thermosets by 30% (w/w) sisal fibers improved the impact strength by one order of magnitude. Curing with cycle 1 (150 degrees C) induced a high diffusion coefficient for water absorption in composites, due to less interaction between the sisal fibers and water. The composites cured with cycle 2 (180 degrees C) had less glyoxal resin coverage of the cellulosic fibers, as observed by images of the fractured interface observed by SEM. This study shows that biobased composites with good properties can be prepared using a high proportion of materials obtained from natural resources. (C) 2009 Elsevier Ltd. All rights reserved.

Sisal Fibers Treated with NaOH and Benzophenonetetracarboxylic Dianhydride as Reinforcement of Phenolic Matrix

In this work, composites based on a phenolic matrix and untreated- and treated sisal fibers were prepared. The treated sisal fibers used were those reacted with NaOH 2% solution and esterified using benzophenonetetracarboxylic dianhydride (BTDA). These treated fibers were modified with the objective of improving the adhesion of the fiber-matrix interface, which in turn influences the properties of the composites. BTDA was chosen as the esterifying agent to take advantage of the possibility of introducing; the polar and aromatic groups that are also present in the matrix structure into the surface of the fiber, which could then intensify the interactions occurring in the fiber-matrix interface. The fibers were then analyzed by SEM and FTIR to ascertain their chemical composition. The results showed that the fibers had been successfully modified. The composites (reinforced with 15%, w/w of 3.0 cm length sisal fiber randomly distributed) were characterized by SEM, impact strength, and water absorption capacity. In the tests conducted, the response of the composites was affected both by properties of the matrix and the fibers, besides the interfacial properties of the fiber-matrix. Overall, the results showed that the fiber treatment resulted in a composite that was less hygroscopic although with somewhat lower impact strength, when compared with the composite reinforced with untreated sisal fibers. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 115: 269-276, 2010

Phenolic matrices and sisal fibers modified with hydroxy terminated polybutadiene rubber: Impact strength, water absorption, and morphological aspects of thermosets and composites

The aim of the present work was to investigate the toughening of phenolic thermoset and its composites reinforced with sisal fibers, using hydroxyl-terminated polybutadiene rubber (HTPB) as both impact modifier and coupling agent. Substantial increase in the impact strength of the thermoset was achieved by the addition 10% of HTPB. Scanning electron microscopy (SEM) images of the material with 15% HTPB content revealed the formation of some rubber aggregates that reduced the efficiency of the toughening mechanism. In composites, the toughening effect was observed only when 2.5% of HTPB was added. The rubber aggregates were found located mainly at the matrix-fiber interface suggesting that HTPB could be used as coupling agent between the sisal fibers and the phenolic matrix. A composite reinforced with sisal fibers pre-impregnated with HTPB was then prepared; its SEM images showed the formation of a thin coating of HTPB on the surface of the fibers. The ability of HTBP as coupling agent between sisal fibers and phenolic matrix was then investigated by preparing a composite reinforced with sisal fibers pre-treated with HTPB. As revealed by its SEM images, the HTPB pre-treatment of the fibers resulted on the formation of a thin coating of HTPB on the surface of the fibers, which provided better compatibility between the fibers and the matrix at their interface, resulting in a material with low water absorption capacity and no loss of impact strength. (C) 2009 Elsevier B.V. All rights reserved.

Amino acids profile of sugar cane spirit (cachaca), rum, and whisky

An analytical procedure for the separation and quantification of 20 amino acids in cachacas has been developed involving C18 solid phase cleanup, derivatization with o-phthalaldehyde/2-mercaptoethanol, and reverse phase liquid chromatography with fluorescence detection. The detection limit was between 0.0050 (Cys) and 0.25 (Ser) mg L-1, whereas the recovery index varies from 69.5 (Lys) to 100 (Tyr)%. Relative standard deviations vary from 1.39 (Trp) to 13.4 (Glu)% and from 3.08 (Glu) to 13.5 (His) for the repeatability and intermediate precision, respectively. From the quantitative profile of amino acids in 41 cachacas, 5 turns, and 12 whisky samples, the following order of amino acids in significant quantities is observed: Gly = Ser < Cys < Ile < His < Pro = Asp < Asn < Tyr for cachaca; Phe < Glu = Gln = Val = Ala < His = Gly Thr = Arg = Tyr < Asn Ser = Lys = Pro < Cys = Asp for rum; and Ala = Asn < Trp < Gln = His = Met = Ile = Cys < Thr < Asp Leu < Phe = Lys < Ser = Gly = Tyr = Val < Glu = Pro < Arg for whisky samples. (C) 2007 Elsevier Ltd. All rights reserved.

Determination of amino acids by capillary electrophoresis-electrospray ionization-mass spectrometry: An evaluation of different protein hydrolysis procedures

In this work, a CE equipment, online hyphenated to an IT MS analyzer by a linear sheath liquid interface promoting ESI, was used to develop a method for quantitative determination of amino acids. Under appropriate conditions (BGE composition, 0.8% HCOOH, 20% CH(3)OH; sheath liquid composition, 0.8% HCOOH, 60% methanol; V(ESI), +4.50 W), analytical curves of all amino acids from 3 to 80 mg/L were recorded presenting acceptable linearity (r > 0.99). LODs in the range of 16-172 mu mol/L were obtained. BSA, a model protein, was submitted to different hydrolysis procedures (classical acid and basic, and catalyzed by the H(+) form of a cation exchanger resin) and its amino acid profiles determined. In general, the resin-mediated hydrolysis yields were overall similar or better than those obtained by classical acid or basic hydrolysis. The resulting experimental-to-theoretical BSA concentration ratios served as correction factors for the quantitation of amino acids in Brazil nut resin generated hydrolysates.

Reactivity of Beer Bitter Acids Toward the 1-Hydroxyethyl Radical as Probed by Spin-Trapping Electron Paramagnetic Resonance (EPR) and Electrospray Ionization-Tandem Mass Spectrometry (ESI-MS/MS)

The iso-alpha-acids or isohumulones are the major contributors to the bitter taste of beer, and it is well-recognized that they are degraded during beer aging. In particular, the trans-isohumulones seem to be less stable than the cis-isohumulones. The major radical identified in beer is the 1-hydroxyethyl radical; however, the reactivity between this radical and the isohumulones has not been reported until now. Therefore, we studied the reactivity of isohumulones toward the 1-hydroxyethyl radical through a competitive kinetic approach. It was observed that both cis- and trans-isohumulones and dihydroisohumulones are decomposed in the presence of 1-hydroxyethyl radicals, while the reactivities are comparable. On the other hand, the tetrahydroisohumulones did not react with 1-hydroxyethyl radicals. The apparent second-order rate constants for the reactions between the 1-hydroxyethyl radical and these compounds were determined by electron paramagnetic resonance (EPR) spectroscopy and electrospray ionization-tandem mass spectrometry [ESI(+)-MS/MS]. It follows that degradation of beer bitter acids is highly influenced by the presence of 1-hydroxyethyl radicals. The reaction products were detected by liquid chromatography electrospray ionization-ion trap-tandem mass spectrometry (LC-ESI-IT-MS/MS), and the formation of oxidized derivatives of the isohumulones was confirmed. These data help to understand the mechanism of beer degradation upon aging.

An insight into the beginning stage of the aqueous ring opening metathesis polymerization of exo,exo-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid with Ru(III) compounds: the consumption of Ru(III) species in the presence of carboxylic acids monitored by ESR spectroscopy

The presence of paramagnetic species in the aqueous ring opening metathesis polymerizations of the exo,exo-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid monomer with RuCl(3) and K(2)[RuCl(5)H(2)O] compounds was studied using ESR techniques. It was observed that the intensities of the Ru(III) signals in the ESR spectra decrease on the time scale of the induction period so that the ROMP can take place. The intensity of the Ru(III) signal almost disappeared 50 min after reacting with K(2)[RuCl(5)H(2)O] and after 100 mm in the case of RuCl(3). Reactions of the cis-[Ru(NH(3))(4)(H(2)O)(2)](tfms)(3) and [Ru(NH(3))(5)H(2)O](tfms)(3) complexes with the monomer and different organic compounds representing the organic functions in the monomer (furan, norbornene, but-2-ene-1,4-diol and formic, acetic, oxalic and maleic acids) were also monitored by ESR and UV/vis spectra. It was deduced that the organic acids provide the disappearance of the Ru(III) signal. The proton NMR relaxation times of the residual water in D(2)O for reactions with oxalic acid suggested that the presence of paramagnetic ions in the solution decreases along with

Coumarins and phenolic fingerprints of oak and Brazilian woods extracted by sugarcane spirit

A total of 25 sugarcane spirit extracts of six different Brazilian woods and oak, commonly used by cooperage industries for aging cachaca, were analyzed for the presence of 14 phenolic compounds (ellagic acid, gallic acid, vanillin, syringaldehyde, synapaldehyde, coniferaldehyde, vanillic acid, syringic acid, quercetin, trans-resveratrol, catechin, epicatechin, eugenol, and myricetin) and two coumarins (scopoletin and coumarin) by HPLC-DAD-fluorescence and HPLC-ESI-MS(n). Furthermore, an HPLC-DAD chromatographic fingerprint was build-up using chemometric analysis based on the chromatographic elution profiles of the extracts monitored at 280 nm. Major components identified and quantified in Brazilian wood extracts were coumarin, ellagic acid, and catechin, whereas oak extracts shown a major contribution of catechin, vanillic acid, and syringaldehyde. The main difference observed among oak and Brazilian woods remains in the concentration of coumarin, catechin, syringaldehyde, and coniferaldehyde. The chemometric analysis of the quantitative profile of the 14 phenolic compounds and two coumarins in the wood extracts provides a differentiation between the Brazilian wood and oak extracts. The chromatographic fingerprint treated by multivariate analysis revealed significant differences among Brazilian woods themselves and oak, clearly defining six groups of wood extracts: (i) oak extracts, (ii) jatoba extracts, (iii) cabreuva-parda extracts, (iv) amendoim extracts, (v) canela-sassafras extracts and (vi) pequi extracts.

The origin of the molecular interaction between amino acids and gold nanoparticles: A theoretical and experimental investigation

This study describes the synthesis of novel biological hybrid materials, where 3D structures were obtained using gold nanoparticles (AuNps) and methionine (Met) in a one-step procedure in aqueous media. The type of nanostructure can be controlled by tuning the intermolecular interactions between Met and AuNp, which strongly depends on the pH used for the synthesis. Computational simulation using the density-functional theory (DFT) showed that the AuNp - Met 3D structures are formed upon reorientation of Met molecules so that the backbone amine groups interact via H-bonds. These findings were experimentally confirmed using FTIR and UV-vis spectroscopy. Crown Copyright (C) 2008 Published by Elsevier B. V. All rights reserved.

Relationship between antioxidant capacity and total phenolic content of red, rosé and white wines

Phenolic compounds are one of the most important quality parameters of wines, since they contribute to wine organoleptic characteristics such as colour, astringency, and bitterness. Furthermore, several studies have pointed out that many show biological properties of interest, related to their antioxidant capacity. This antioxidant activity has been thoroughly studied and a wide variety of methods have been developed to evaluate it. In this study, the antioxidant activity of commercial Terras Madeirenses Portuguese wines (Madeira Island) was measured by three different analytical methods: [1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging assay, 2,2′-azino-bis-(3-ethylbenzothiazoline-6-sulfonic acid (ABTSradical dot+)) radical cation decolourisation, and ferric reducing/antioxidant power (FRAP) for the evaluation of reducing power (PR) and correlate them with the total phenolic content determined with the Folin–Ciocalteu’s reagent using gallic acid as a standard. The total polyphenol concentration was found to vary from 252 to 1936 mg/l gallic acid equivalents (GAE). The antiradical activity varied from 0.042 to 0.715 mM Trolox equivalents and the antioxidant capacity varied from 344 to 1105 mg/l gallic acid equivalents (GAE). For the reduction power we obtained 3.45–3.86 mM quercetin equivalents.

An improved and fast UHPLC-PDA methodology for determination of L-ascorbic and dehydroascorbic acids in fruits and vegetables: evaluation of degradation rate during storage

This study provides a versatile validated method to determine the total vitamin C content, as the sum of the contents of L-ascorbic acid (L-AA) and dehydroascorbic acid (DHAA), in several fruits and vegetables and its degradability with storage time. Seven horticultural crops from two different origins were analyzed using an ultrahigh-performance liquid chromatographic–photodiode array (UHPLC-PDA) system, equipped with a new trifunctional high strength silica (100% silica particle) analytical column (100 mm×2.1 mm, 1.7 μm particle size) using 0.1% (v/v) formic acid as mobile phase, in isocratic mode. This new stationary phase, specially designed for polar compounds, overcomes the problems normally encountered in HPLC and is suitable for the analysis of large batches of samples without L-AA degradation. In addition, it proves to be an excellent alternative to conventional C18 columns for the determination of L-AA in fruits and vegetables. The method was fully validated in terms of linearity, detection (LOD) and quantification (LOQ) limits, accuracy, and inter/intraday precision. Validation experiments revealed very good recovery rate of 96.6±4.4% for L-AA and 103.1±4.8 % for total vitamin C, good linearity with r2-values >0.999 within the established concentration range, excellent repeatability (0.5%), and reproducibility (1.6%) values. The LOD of the method was 22 ng/mL whereas the LOQ was 67 ng/mL. It was possible to demonstrate that L-AA and DHAA concentrations in the different horticulture products varied oppositely with time of storage not always affecting the total amount of vitamin C during shelf-life. Locally produced fruits have higher concentrations of vitamin C, compared with imported ones, but vegetables showed the opposite trend. Moreover, this UHPLC-PDA methodology proves to be an improved, simple, and fast approach for determining the total content of vitamin C in various food commodities, with high sensitivity, selectivity, and resolving power within 3 min of run analysis.

A fast method using a new hydrophilic–lipophilic balanced sorbent in combination with ultra-high performance liquid chromatography for quantification of significant bioactive metabolites in wines

This manuscript describes the development and validation of an ultra-fast, efficient, and high throughput analytical method based on ultra-high performance liquid chromatography (UHPLC) equipped with a photodiode array (PDA) detection system, for the simultaneous analysis of fifteen bioactive metabolites: gallic acid, protocatechuic acid, (−)-catechin, gentisic acid, (−)-epicatechin, syringic acid, p-coumaric acid, ferulic acid, m-coumaric acid, rutin, trans-resveratrol, myricetin, quercetin, cinnamic acid and kaempferol, in wines. A 50-mm column packed with 1.7-μm particles operating at elevated pressure (UHPLC strategy) was selected to attain ultra-fast analysis and highly efficient separations. In order to reduce the complexity of wine extract and improve the recovery efficiency, a reverse-phase solid-phase extraction (SPE) procedure using as sorbent a new macroporous copolymer made from a balanced ratio of two monomers, the lipophilic divinylbenzene and the hydrophilic N-vinylpyrrolidone (Oasis™ HLB), was performed prior to UHPLC–PDA analysis. The calibration curves of bioactive metabolites showed good linearity within the established range. Limits of detection (LOD) and quantification (LOQ) ranged from 0.006 μg mL−1 to 0.58 μg mL−1, and from 0.019 μg mL−1 to 1.94 μg mL−1, for gallic and gentisic acids, respectively. The average recoveries ± SD for the three levels of concentration tested (n = 9) in red and white wines were, respectively, 89 ± 3% and 90 ± 2%. The repeatability expressed as relative standard deviation (RSD) was below 10% for all the metabolites assayed. The validated method was then applied to red and white wines from different geographical origins (Azores, Canary and Madeira Islands). The most abundant component in the analysed red wines was (−)-epicatechin followed by (−)-catechin and rutin, whereas in white wines syringic and p-coumaric acids were found the major phenolic metabolites. The method was completely validated, providing a sensitive analysis for bioactive phenolic metabolites detection and showing satisfactory data for all the parameters tested. Moreover, was revealed as an ultra-fast approach allowing the separation of the fifteen bioactive metabolites investigated with high resolution power within 5 min.

Quantification of polyphenols with potential antioxidant properties in wines using reverse phase HPLC

A RP-HPLC method with photodiode array detection (DAD) was developed to separate, identify and quantify simultaneously the most representative phenolic compounds present in Madeira and Canary Islands wines. The optimized chromatographic method was carefully validated in terms of linearity, precision, accuracy and sensitivity. A high repeatability and a good stability of phenolics retention times (a3%) were obtained, as well as relative peak area. Also high recoveries were achieved, over 80.3%. Polyphenols calibration curves showed a good linearity (r2 A0.994) within test ranges. Detection limits ranged between 0.03 and 11.5 lg/mL for the different polyphenols. A good repeatability was obtained, with intra-day variations less than 7.9%. The described method was successfully applied to quantify several polyphenols in 26 samples of different kinds of wine (red, ros and white wines) from Madeira and Canary Islands. Gallic acid was by far the most predominant acid. It represents more than 65% of all phenolics, followed by p-coumaric and caffeic acids. The major flavonoid found in Madeira wines was trans-resveratrol. In some wines, (–)-epicatechin was also found in highest amount. Canary wines were shown to be rich in gallic, caffeic and p-coumaric acids and quercetin.

Simultaneous analysis of free amino acids and biogenic amines in honey and wine samples using in loop orthophthalaldeyde derivatization procedure

This work presents a RP-HPLC method for the simultaneous quantification of free amino acids and biogenic amines in liquid food matrices and the results of the application to honey and wine samples obtained from different production processes and geographic origins. The developed methodology is based on a pre-column derivatization with o-phthaldialdehyde carried out in the sample injection loop. The compounds were separated in a Nova-Pack RP-C18 column (150 mm × 3.9 mm, 4 μm) at 35 °C. The mobile phase used was a mixture of phase A: 10 mM sodium phosphate buffer (pH 7.3), methanol and tetrahydrofuran (91:8:1); and phase B: methanol and phosphate buffer (80:20), with a flow rate of 1.0 ml/min. Fluorescence detection was used at an excitation wavelength of 335 nm and an emission wavelength of 440 nm. The separation and quantification of 19 amino acids and 6 amines was carried out in a single run as their OPA/MCE derivatives elute within 80 min, ensuring a reproducible quantification. The method showed to be adequate for the purpose, with an average RSD of 2% for the different amino acids; detection limits varying between 0.71 mg/l (Asn) and 8.26 mg/l (Lys) and recovery rates between 63.0% (Cad) and 98.0% (Asp). The amino acids present at the highest concentration in honey and wine samples were phenylalanine and arginine, respectively. Only residual levels of biogenic amines were detected in the analysed samples.