Determination of antioxidant power of red and white wines by a new electrochemical method and its correlation with polyphenolic content

A new method for measuring the antioxidant power of wine has been developed based on the accelerated electrochemical oxidation of 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS). The calibration (R = 0.9922) and repeatability study (RSD = 7%) have provided good statistical parameters. The method is easy and quick to apply and gives reliable results, requiring only the monitoring of time and absorbance. It has been applied to various red and white wines of different origins. The results have been compared with those obtained by the total antioxidant status (TAS) method. Both methods reveal that the more antioxidant wines are those with higher polyphenolic content. From the HPLC study of the polyphenolic content of the same samples, it is confirmed that there is a positive correlation between the resveratrol content of a wine and its antioxidant power.     

Optimization of headspace solid-phase Microextraction (SPME) for the odor analysis of surface-ripened cheese

Fifty volatile compounds of surface smear-ripened cheese were detected and identified using headspace solid-phase microextraction (HS-SPME) and vacuum distillation coupled to gas chromatography-mass spectrometry. Changes in the headspace of aroma compounds were monitored over the whole packaging period (47 days) using the HS-SPME method. Initially, the concentration of methanethiol increased before reaching a plateau. This evolution could be linked to the growth of Brevibacterium linens. During the shelf life of cheese, levels of acetic acid and 3-methylbutanoic acid remained constant, whereas butane-2,3-dione, 3-hydroxybutan-2-one, and hydroxypropan-2-one levels gradually declined and acetone and 3-methylbutanol levels dropped sharply to a plateau. Changes in odor could be related to changes of the rind, which behaved as a barrier, strongly influencing the distribution of volatile compounds in the headspace. Using a gas chromatography-olfactometry technique without separation, it was shown that the SPME extract was representative of the cheese odor.     

Role of aldehydic derivatives in the condensation of phenolic compounds with emphasis on the sensorial properties of fruit-derived foods

The reactions between (epi)catechin, mavidin 3-O-glucoside, and some aldehydes were investigated by LC/DAD and LC/ESI-MS analysis. The obtained results showed that the acetaldehyde-mediated condensation occurred more generally and glyoxylic acid, furfural, and 5-(hydroxymethyl)furfural (HMF) react in the same way in the first stages of the reactions. In terms of reactivity, reactions were faster with acetaldehyde than with glyoxylic acid, furfural, or HMF, where the reactions were slower. In the case of acetaldehyde, the obtained purple derivatives were more predominant and stable than the colorless adducts and no xanthylium salt was detected. Interactions involving glyoxylic acid yield purple adducts, which were obtained in small amount compared to the colorless ones. The latter were shown to proceed to more polymerized and yellowish derivatives. Finally, in the case of furfural and HMF, purple compounds involving flavanol and anthocyanin units were detected, and colorless compounds were shown to be predominant and to yield yellowish xanthylium salts.     

Synthesis and stable isotope dilution assay of ethanethiol and diethyl disulfide in wine using solid phase microextraction. Effect of aging on their levels in wine

Ethanethiol and diethyl disulfide (DEDS) most often occurred at levels above their olfactive threshold in wines with nauseous sulfur-linked smells. As ethanethiol is very oxidizable and chemically reactive, a stable isotopic dilution analysis of both ethanethiol and its disulfide in wines using solid phase microextraction and GC-MS was developed. The latter involved the determination of the proportion of DEDS formed by oxidation of the thiol during the analysis conditions, which was obtained by the use of two differently labeled disulfide standards. An original synthesis of labeled ethanethiol standards in conditions minimizing oxidation was developed, and the corresponding labeled diethyl disulfides were obtained from these thiols. This analytical method was used to follow the levels of these sulfur compounds during aging in a young red wine spiked with ethanethiol and added with enological tannins, with or without oxygen addition. The total levels of these two sulfur compounds were shown to decrease steadily after 60 days of aging, up to 83%. The effect of oxygen sped this decrease, but the effect of enological tannins was very slight. Residual ethanethiol was detected in its disulfide form from approximately 36% in the nonoxygenated wines to 69% in the oxygenated samples.     

Heavy Metal Contamination in Sediments of Lake Nahuel Huapi,Nahuel Huapi National Park,Northern Patagonia,Argentina

Trace metals (Sb, As, Br, Cs, Co, Cr, Ag and Hg), rare earth elements (Ce, Eu, La, Lu, Sm, Tb and Yb), and Sc. were analysed in suspended load and in two sediment cores from Lake Nahuel Huapi, Nahuel Huapi National Park, Patagonia, Argentina, by using Instrumental Neutron Activation Analysis. The core activity profiles of ²¹⁰Pb and ¹³⁷Cs were measured to estimate the age of the sediments. Silver was enriched in the upper layers of both cores, and correlated with the strong growthof the population of Bariloche City in the last 50 yr. Concentrations are higher in the core sampled near Bariloche, andindicate some transport in the water body. Silver concentrationsmeasured in the suspended load were 4.58±0.36 and 3.46±0.40 μg g^-1 in the southern margin of the lake, near San Carlos de Bariloche City, whereas in the northern margin the concentrations were 1.68±0.18 and 1.88±0.23 μg g^-1. Concentration ratio for silver in suspended load and upper core layers were equal in both sampling points. These facts suggest that Ag contents correspond to inputs associated with human activities. Bromine concentrations show a strong increase abovebase line values, similar to silver. In contrast, caesium, chromium, and cobalt concentrations do not differ from base linevalues. The metalloids antimony and arsenic show little variationwith regard to base line concentration. Noticeable, the mercurycontents found in the suspended load.     

Comparison between phenetic characterisation using RAPD and ISSR markers and phenotypic data of cultivated chestnut (Castanea sativa Mill.)

Patterns of phenotypic and phenetic variability in sixPortuguese cultivars of chestnut (Castanea sativa Mill.) are evaluated. Morphological characterisationwas based on the quantification of seventeen traits. Varianceanalysis showed significant differences among cultivars, and cultivar× year for all the traits studied, and trees within cultivarsshowed also some significant differences for some of themorphological variables. A significant correlation was obtainedbetween length of the leaf blade and the percentage of unisexual andandrogynic inflorescence with the effective thermal index,accumulated rainfall from April to October and from July to October,or the accumulated temperature below seven during the dormant period.Principal Component and cluster analysis were performed to group thecultivars, according to their similarity coefficients. For molecularcharacterisation, 125 RAPD and 157 ISSR polymorphic markers wereamplified using 28 and 7 primers respectively. High level ofcongruence among the two marker systems (r =90.5%) was obtained from comparison of pheneticsimilarities based on the percentage of shared fragments. ISSRmarkers revealed important advantages over RAPDs, due to a higheffective multiplex ratio (12.5 for ISSR compared with 2.2 forRAPD analysis) and reproducibility. Although morphological andmolecular results are comparable, slight differences are showed incluster analysis UPGMA dendrograms. Molecular analysis explainedhomonym situations among 'Martainha' and'Longal' cultivars in Portugal.     

Genetic differentiation in the olive complex (Olea europaea) revealed by RAPDs and RFLPs in the rRNA genes

We assessed the genetic differentiation of the Mediterranean olive from its wild relatives found in different geographic areas (Mediterranean, Asia, Africa) using eighty RAPDs revealed with eight primers. Variance analysis (AMOVA) enabled us to estimate the overall genetic differentiation parameters between wild populations. Oleasters from the Near East and Turkey were discriminated from the other Mediterranean populations. Olea laperrinei, O. maroccana and O. cerasiformis were the taxa the most related to the Mediterranean olive. In contrast, O. africana was shown to be the most genetically distant taxa from the Mediterranean olive. However, we characterised hybrid trees between these two taxa. Significant trends between genetic and geographic distances were met within the subspecies cuspidata and within the Mediterranean olive. A genetic diversity gradient was observed in both subspecies europaea and cuspidata. These results are in agreement with a mechanism of differentiation by distance in the O. europaea complex, but another non-exclusive mechanism could also be gene flow between differentiated taxa. Furthermore, we characterised the discriminating power of each RAPD to recognise the different taxa using intraclass correlation coefficients. Lastly, IGS-RFLPs enabled us to assess rDNA polymorphisms on a sub-sample of individuals. On the basis of these data, a low interspecifc differentiation was found. This suggests a recent genetic divergence between the different taxa of the O. europaea complex or the occurrence of gene flow during favourable periods or because human displacements. All the olive cultivars were genetically related to the oleaster populations supporting that Mediterranean is the olive domestication area.     

Supercritical CO(2) and subcritical propane extraction of pungent paprika and quantification of carotenoids, tocopherols, and capsaicinoids.

Ground paprika (Capsicum annuum L.) was extracted with supercritical carbon dioxide (SC-CO(2)) and subcritical propane at different conditions of pressure and temperature to estimate the yield and variation in carotenoid, tocopherol, and capsaicinoid contents and composition. The yield of paprika extract was found to be affected by the extraction conditions with SC-CO(2) but fairly constant at different conditions with subcritical propane. The maximum yields of oleoresin were 7.9 and 8.1% of ground paprika by SC-CO(2) and subcritical propane, respectively. The quantitative distribution of carotenoids, tocopherols, and capsaicinoids between paprika extract and powder was influenced by extraction conditions. SC-CO(2) was inefficient in the extraction of diesters of xanthophylls even at 400 bar and 55 degrees C, whereas tocopherols and capsaicinoids were easy to extract at these conditions. Under mild conditions subcritical propane was superior to SC-CO(2) in the extraction of carotenoids and tocopherols but less efficient in the extraction of capsaicinoids.     

Allele mining and haplotype discovery in barley candidate genes for drought tolerance

In the present study, allele mining was conducted on a panel of drought related candidate genes in a set of 96 barley genotypes using EcoTILLING, which is a variant of the targeting induced local lesions in genomes (TILLING) technology. Analyzing approximately 1.5 million basepairs in barley a total number of 94 verified unique haplotypes were identified in 18 amplicons designed for 9 genes. Overall, 185 single nucleotide polymorphisms (SNPs) and 46 insertions/deletions (INDELs) were detected with a mean of 1SNP/92 bp and 1INDEL/372 bp genomic sequence. Based on overlapping haplotype sequences, markers were developed for four candidate genes (HvARH1, HvSRG6, HvDRF1, HVA1), which allows distinguishing between the main haplotypes showing either differences in amino acid sequence or which have larger INDELs in the promoter region. As “proof of concept”, the HvARH1 and HvSRG6 haplotypes were tested for the level of abscisic acid-induced gene expression in subsets of genotypes belonging to different haplotype categories. An integrated database was developed to contain information about the genes, genotypes, and haplotypes analyzed in this study. The database supplies profound information about the natural variation in the tested drought related candidate genes providing a significant asset for further mapping studies dealing with this highly polygenic trait.