Chemical characterization of lignin and lipophilic fractions from leaf fibers of curaua (Ananas erectifolius)

The chemical composition of leaf fibers of curaua (Ananas erectifolius), an herbaceous plant native of Amazonia, was studied. Special attention was paid to the content and composition of lignin and lipophilic compounds. The analysis of lignin in the curaua fibers was performed in situ by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) and showed a lignin composition with a p-hydroxyphenyl:guaiacyl:syringyl units (H:G:S) molar proportion of 30:29:41 (S/G molar ratio of 1.4). The presence of p-hydroxycinnamic acids (p-coumaric and ferulic acids) in curaua fibers was revealed upon pyrolysis in the presence of tetramethylammonium hydroxide. On the other hand, the main lipophilic compounds, analyzed by GC/MS, were series of long-chain n-fatty acids, n-fatty alcohols, alpha- and omega-hydroxyacids, monoglycerides, sterols, and waxes. Other compounds, such as omega-hydroxy monoesters and omega-hydroxy acylesters of glycerol, were also found in this fiber in high amounts.     

Contribution of malolactic fermentation by Oenococcus oeni and Lactobacillus plantarum to the changes in the nonanthocyanin polyphenolic composition of red wine

The changes in the nonanthocyanin phenolic composition during red wine malolactic fermentation carried out spontaneously and by four different starter cultures of the species Oenococcus oeni and Lactobacillus plantarum were examined to determine whether differences in nonanthocyanin polyphenolic compounds could be attributed to the lactic acid bacteria (LAB) strain that performs this important step of the wine-making process. The polyphenolic compounds were analyzed by high-performance liquid chromatography with photodiode array detection and HPLC with electrospray ionization-mass spectrometry detection. The malolactic cultures selected for this study were indigenous wine LAB strains from the A.O.C. Rioja (Spain). Results showed different malolactic behaviors in relation to wine phenolic compositions for O. oeni and L. plantarum, and also, a diversity was found within each group. The hydroxycinnamic acids and their derivatives, the flavonols and their glycosides, the flavanol monomers and oligomers, and trans-resveratrol and its glucoside were the main compounds modified by the different LAB. The wild LAB population exerted a greater impact in the wine content of some of these phenolic compounds than the inoculated selected monocultures of this study.     

Arabinogalactan proteins are incorporated in negatively charged coffee brew melanoidins

The charge properties of melanoidins in high molecular weight (HMw) coffee brew fractions, isolated by diafiltration and membrane dialysis, were studied. Ion exchange chromatography experiments with the HMw fractions showed that coffee brew melanoidins were negatively charged whereas these molecules did not expose any positive charge at the pH of coffee brew. Fractions with different ionic charges were isolated and subsequently characterized by means of the specific extinction coefficient (K(mix 405nm)), sugar composition, phenolic group content, nitrogen content, and the arabinogalactan protein (AGP) specific Yariv gel-diffusion assay. The isolated fractions were different in composition and AGP was found to be present in one of the HMw fractions. The AGP accounted for 6% of the coffee brew dry matter and had a moderate negative charge, probably caused by the presence of uronic acids. As the fraction that precipitated with Yariv was brown (K(mix 405nm) = 1.2), compared to a white color in the green bean, it was concluded that these AGPs had undergone Maillard reaction resulting in an AGP-melanoidin complex. The presence of mannose (presumably from galactomannan) indicates the incorporation of galactomannans in the AGP-melanoidin complex. As the uronic acid content in the more negatively charged melanoidin-rich, AGP-poor HMw fractions decreased, it was hypothesized that acidic groups are formed or incorporated during melanoidin formation.     

Characterization of plum procyanidins by thiolytic depolymerization

The phenolic compounds of 'Green Gage' (GG) plums ( Prunus domestica L.), "Rainha Claudia Verde", from a 'protected designation of origin' (PDO), in Portugal, were quantified in both flesh and skin tissues of plums collected in two different orchards (GG-V and GG-C). Analyzes of phenolic compounds were also performed on another GG European plum obtained in France (GG-F) and two other French plums, 'Mirabelle' (M) and 'Golden Japan' (GJ). Thiolysis was used for the first time in the analysis of plum phenolic compounds. This methodology showed that the flesh and skin contain a large proportion of flavan-3-ols, which account, respectively, for 92 and 85% in GJ, 61 and 44% in GG-V, 62 and 48% in GG-C, 54 and 27% in M, and 45 and 37% in GG-F. Terminal units of procyanidins observed in plums are mainly (+)-catechin (54-77% of all terminal units in flesh and 57-81% in skin). The GJ plums showed a phenolic composition different from all of the others, with a lower content of chlorogenic acid isomers and the presence of A-type procyanidins as dimers and terminal residues of polymerized forms. The average degree of polymerization (DPn) of plum procyanidins was higher in the flesh (5-9 units) than in the skin (4-6 units). Procyanidin B7 was observed in the flesh of all GG plums and in the skin of the Portuguese ones. Principal component analysis of the phenolic composition of the flesh and skin of these plums obtained after thiolysis allowed their distinction according to the variety and origin, opening the possibility of the use of phenolic composition for variety/origin identification.     

Assessment of antioxidant activity of cane brown sugars by ABTS and DPPH radical scavenging assays: determination of their polyphenolic and volatile constituents

Seven cane brown sugars (four from La Réunion, two from Mauritius, and one from France) were investigated for their polyphenol content and volatile composition in relation to their free radical scavenging capacity determined by ABTS and DPPH assays. The thin layer coated on the sugar crystal was extracted by Soxhlet extractor with dichloromethane. The volatile compounds of brown sugars were studied by GC-MS, and 43 compounds were identified. The total phenolic content of brown sugars was determined according to the Folin-Ciocalteu method. Phenolic compounds were quantified in the brown sugar extracts by LC-UV-ESI-MS. Brown sugar aqueous solutions exhibited weak free radical scavenging activity in the DPPH assay and higher antioxidant activity in the ABTS assay at relatively high concentration. The brown sugar extracts showed interesting free radical scavenging properties despite the low concentration of phenolic and volatile compounds. Sugar is a common foodstuff traditionally used for its sweetening properties, which might be accompanied by antioxidant properties arising from molecules (polyphenols, Maillard products) other than sucrose of the cane brown sugars.     

Volatile constituents from Cinnamomum zeylanicum fruit stalks and their antioxidant activities

Cinnamomum zeylanicum Blume is an important spice and aromatic crop having wide applications in flavoring, perfumery, beverages, and medicines. The steam-distilled volatile oil from cinnamon fruit stalks was analyzed with GC and GC-MS. It showed the presence of hydrocarbons (44.7%) and oxygenated compounds (52.6%). Twenty-seven compounds constituting ca. 95.98% of the volatile oil were characterized. (E)-Cinnamyl acetate (36.59%) and (E)-caryophyllene (22.36%) are found to be major compounds. The volatile oil was screened for its potential as an antioxidant by using in vitro models, such as the beta-carotene-linoleate and phosphomolybdenum complex method. The volatile oil showed 55.94% and 66.9% antioxidant activity at 100 and 200 ppm concentration, respectively. Also, the volatile oil showed good antioxidant capacity, using the formation of the phosphomolybdenum complex. A comparison of the chemical composition of the volatile oil was made with that of buds, flowers, and fruits. This is the first report on the chemical composition of volatile oil of the fruit stalks of this species and its antioxidant activity.     

Genotype and Environment Affect Phytosterol Content and Composition of Wheat

Phytosterols (PS) lower low density lipoprotein (LDL) levels by as much as 10–14% in normal and hypercholesteromic people. High LDL levels in the blood are associated with an increased risk of coronary heart disease. Wheat germ and bran contain significant amounts of PS. The main objective of this study was to evaluate the effect of genotype and environment on PS content and composition in whole wheat grain. Protein and ash contents and mineral composition of the samples were also determined. Grain samples were collected from three cultivars, Jagger, Trego, and Intrada, grown at three locations, Alva, Balko, and Goodwell, OK in 2005. Irrigated and dryland samples were obtained from Goodwell. Total PS content and composition in the grain samples were determined using a gas chromatography system. Whole wheat grain samples varied in PS content from 202 mg/kg to 355 mg/kg. β‐Sitosterol, campesterol, and stigmasterol were the major PS compounds found in all the samples. PS exhibited a significant location‐by‐cultivar random effect (P < 0.048), indicating the presence of genotype‐by‐location interaction. Within each location, a significant cultivar effect was also observed. Protein and ash contents and mineral composition of the samples, except those collected from Goodwell‐dryland, were within the range published in the literature for other wheat cultivars. A fundamental understanding of compositional variation in wheat grain requires multi‐environment testing of genotypes, perhaps over several years. This study is a first step for achieving this goal.     

Cyclic polyalcohols: fingerprints to identify the botanical origin of natural woods used in wine aging

Cyclic polyalcohol composition of 80 natural wood samples from different botanical species, with the majority of them used in the oenology industry for aging purposes, has been studied by gas chromatography-mass spectrometry (GC-MS) after its conversion into their trimethylsilyloxime derivatives. Each botanical species showed a different and specific cyclic polyalcohol profile. Oak wood samples were characterized by the richness in deoxyinositols, especially proto-quercitol. Meanwhile, other botanical species showed a very low content of cyclic polyalcohols. The qualitative and quantitative study of cyclic polyalcohols was a useful tool to characterize and differentiate woods of different botanical origin to guarantee the authenticity of chips used in the wine-aging process. Monosaccharide composition was also analyzed, showing some quantitative differences among species, but cyclic polyalcohols were the compounds that revealed the main differentiation power.     

How heating affects extra virgin olive oil quality indexes and chemical composition

Two monovarietal extra virgin olive oils from Arbequina and Picual cultivars were subjected to heating at 180 degrees C for 36 h. Oxidation progress was monitored by measuring oil quality changes (peroxide value and conjugated dienes and trienes), fatty acid composition, and minor compound content. Tocopherols and polyphenols were the most affected by the thermal treatment and showed the highest degradation rate although their behavior was different for each cultivar. Alpha-tocopherol loss was more important in Arbequina oil whereas, total phenol content loss was greater in Picual oil. The later showed an important decrease in hydroxytyrosol (3,4-DHPEA) and its secoiridoid derivatives (3,4-DHPEA-EDA and 3,4-DHPEA-EA), while lignans decrease was lesser. For Arbequina oil these compounds remained stable, and a lowering tendency was observed for tyrosol (p-HPEA) and its derivatives (p-HPEA-EDA and p-HPEA-EA). In general, flavone content showed a decrease during heating, being higher for Arbequina oil. On the other hand, oleic acid, sterols, squalene, and triterpenic alcohols (erythrodiol and uvaol) and acids (oleanolic and maslinic) were quite constant, exhibiting a high stability against oxidation. From these results, we can conclude that despite the heating conditions, VOO maintained most of its minor compounds and, therefore, most of its nutritional properties.     

On the chemical composition and nutritional value of pleurotus taxa growing on umbelliferous plants (apiaceae)

Unpublished data on the chemical composition and nutritional value of Pleurotus mushrooms, growing on Umbelliferous plants (Apiaceae), are here reported. Cultivated basidiomata of four different Pleurotus taxa were analyzed in order to evaluate the composition in lipids, sugars, nitrogen, water, vitamins, ashes, and energetic values. The results showed that Pleurotus mushrooms are suitable in every type of diet thanks to their low caloric content, gastronomic value, vitamins, and mineral salt contents. The presence of a high content of vitamin B(12) and riboflavin in Pleurotus nebrodensis is noteworthy.     

A comparative study of flavonoid compounds, vitamin C, and antioxidant properties of baby leaf Brassicaceae species

A comparative study of antioxidant compounds, flavonoids and vitamin C, and also antioxidant activity was carried out in four species of Brassicaceae vegetables used for salads: watercress ( Nasturtium officinale R. Br.), mizuna [ Brassica rapa L. subsp. nipposinica (L.H. Bailey) Haneltand], wild rocket [ Diplotaxis tenuifolia (L.) DC.], and salad rocket [ Eruca vesicaria (L.) Cav.]. The characterization of individual phenolic compounds by HPLC-DAD-MS/MS-ESI in watercress and mizuna completes the polyphenol study previously reported for wild rocket and salad rocket. The qualitative study of flavonoids in watercress leaves showed a characteristic glycosylation pattern with rhamnose at the 7 position. Isorhamnetin 3,7-di- O-glucoside was identified in mizuna leaves and may be considered a chemotaxonomical marker in some B. rapa subspecies. Brassicaceae species showed differences in the quantitative study of flavonoids, and the highest content was detected in watercress leaves. Watercress and wild rocket leaves had the highest content of vitamin C. The antioxidant activity evaluated by different methods (ABTS, DPPH, and FRAP assays) showed a high correlation level with the content of polyphenols and vitamin C. In conclusion, the Brassicaceae leaves studied, watercress, mizuna, wild rocket, and salad rocket, presented a large variability in the composition and content of antioxidant compounds. These baby leaf species are good dietary sources of antioxidants with an important variability of bioactive compounds.     

Evaluation of the combined effects of enzymatic treatment and aging on lees on the aroma of wine from Bombino bianco grapes

In this study, two different doses of commercial beta-glucanase enzyme preparation were tested to verify their effect on wines aged on lees. These wines were compared with two samples with no enzymatic treatment. The former was aged on lees (control), and the latter was readily filtered off from the yeast cell biomass (standard). Analysis of variance (one-way ANOVA), the Tukey test, and principal component analysis (PCA) were applied to all of the samples, which were analyzed for aroma composition, along with galacturonic acid, total acidity, pH, and color. Results showed a large number of statistically significant differences among samples. In general, wines treated with beta-glucanase were characterized by higher concentration of many volatile compounds. The presence of lees and even more the exogenous enzymatic action enhanced almost all volatile compounds. Besides the high presence of ethyl esters, it is worth mentioning the behavior of hexanol and trans-3-hexenol, which are strongly enhanced by the presence of lees and by enzymatic treatments.     

石灰性母质对土壤腐殖质组成和性质的影响

本文研究了采自泰安、南京、昆明3地在相近植被类型下的石灰性土壤和非石灰性土壤的腐殖质组成和胡敏酸的结构特征。结果表明,和同一地区的非石灰性土壤相比,石灰性土壤不但胡敏酸/富里酸比值恒较高,活性胡敏酸的相对含量显著较低,且其胡敏酸的芳化度和羧基含量较高,全氮及酰胺态氮的含量较低。看来,土壤呈微碱性反应不仅有利于有机物质腐解过程的进行,而且有利于游离基的形成,从而有利于酚类物质相互之间以及酚类物质与含氮化合物之间的缩聚反应和腐殖酸的脱胺作用的进行。     

Quantitation of nine organic acids in wild mushrooms

The organic acids composition of six wild edible mushroom species (Amanita caesarea, Boletus edulis, Gyroporus castaneus, Lactarius deliciosus, Suillus collinitus, and Xerocomus chrysenteron) was determined by an HPLC-UV detector method. The results showed that all of the samples presented a profile composed of at least five organic acids: citric, ketoglutaric, malic, succinic, and fumaric acids. Several samples also contained oxalic, ascorbic, quinic, and shikimic acids. In a general way, the quantitation of the identified compounds indicated that malic acid, followed by the pair citric plus ketoglutaric acids, were the main compounds in the analyzed species, with the exception of A. caesarea, in which malic and ascorbic acids were the most abundant compounds. The relative amounts and the presence/absence of each identified compound may be useful for the differentiation of the species.     

Free and Bound Phenolic Acids and Total Phenolics in Black,Blue, and Yellow Barley and Their Contribution to Free Radical Scavenging Capacity

Barley is considered a healthy food because of its high content of β‐glucan and phenolic antioxidants. In the current study, 28 black, blue, and yellow barleys were investigated in terms of their composition of free and bound phenolic acids and 2,2‐diphenyl‐1‐picrylhydrazyl radical scavenging capacity. Free phenolics were based on aqueous methanol extraction, whereas bound phenolics were extracted following alkaline hydrolysis. Phenolics were then separated and quantified by liquid chromatography and the Folin–Ciocalteu method. Significant differences were observed between the three barley color groups, and within each color group a wide range of phenolics concentrations existed. Ferulic acid was the predominant phenolic acid in free and bound extracts, followed by p‐coumaric acid in all the barleys investigated. Total phenols content and individual phenolic acids strongly correlated with free radical scavenging capacity of barley. Black and blue barley were found to be related and distinct from yellow barley. The results showed significant variations in phenolics among barleys, with a potential for the development of barley grains with high content of phenolic compounds as antioxidant potential.     

Evaluation of the antioxidant capacity of individual phenolic compounds in virgin olive oil

Virgin olive oil has a high resistance to oxidative deterioration due to its tryacylglycerol composition low in polyunsaturated fatty acids and due to the presence of a group of phenolic antioxidants composed mainly of polyphenols and tocopherols. We isolated several phenolic compounds of extra virgin olive oil (phenyl-ethyl alcohols, lignans, and secoiridoids) by semipreparative high-performance liquid chromatography (HPLC) and identified them using ultraviolet, atmospheric pressure chemical ionization, and electrospray ionization MS detection. The purity of these extracts was confirmed by analytical HPLC using two different gradients. Finally, the antioxidant capacity of the isolated compounds was evaluated by measuring the radical scavenging effect on 1,1-diphenyl-2-picrylhydrazyl radical, by accelerated oxidation in a lipid model system (OSI, oxidative stability instrument), and by an electrochemical method.     

Antioxidant activity of methanol extracts obtained from Plantago species

Antioxidative activities of methanol extracts from five Plantago species (P. afra, P. coronopus, P. lagopus, P. lanceolata, and P. serraria) were characterized by the DPPH scavenging test and the inhibition of Fe2+/ascorbate-induced lipid peroxidation on bovine brain liposomes. All extracts showed antioxidant activity in both methods. Whereas P. serraria exhibited the strongest activity as a DPPH scavenger, P. lanceolata and P. serraria were found to be the most active in the lipid peroxidation inhibition assay. The extracts were investigated regarding their composition by different colorimetric techniques, such as the content of total phenolic compounds by the Folin-Ciocalteu assay, flavonoids by AlCl3 reagent, phenylpropanoid glycosides (PPGs) by Arnow reagent, and iridoids by Trim-Hill assay. A high correlation was found between the scavenging potency and the total phenolic and phenylpropanoid content of the extracts but not between the lipid peroxidation potency and the extract composition. P. serraria is presented as a possible new source of natural antioxidants.     

Impact of oxygen consumption by yeast lees on the autolysis phenomenon during simulation of wine aging on lees

Potential oxygen consumption by lees, more precisely by nonviable yeasts, during wine aging was recently described. Additionally, yeast autolysis is described as the main mechanism of degradation of lees during wine aging. Thus, to understand the effect of oxygen consumption by yeast lees during wine aging, an accelerated wine aging methodology was tested. Wine aging in the presence of yeast lees was studied both in the presence and in the absence of oxygen. Different markers of yeast autolysis were followed to find a relationship between oxygen consumption by yeast lees and changes in the final wine composition after aging. No differences for compounds tested were found in the wine and in the lees except among sterol compounds in lees: in the presence of oxygen, the concentration of ergosterol in lees was significantly lower than that in the absence of oxygen. It was hypothesized that ergosterol could be oxidized under the influence of oxygen, but none of the known products of ergosterol oxidation were recovered in the corresponding yeast lees. In addition, the decrease of ergosterol content in yeast lees cannot account for the total amount of oxygen consumed by yeast lees during such wine aging.     

Contrasting composition of free and mineral-bound organic matter in top- and subsoil horizons of Andosols

Andosols are characterised by high organic matter (OM) content throughout the soil profile, which is mainly due to the stabilisation of soil organic matter (SOM) by mineral interactions. The aim of the study was to examine whether there were differences in the chemical composition of mineral-associated SOM and free OM in the top A horizon and in the subsoil (horizons below the A11 horizon). Our experimental approach included the replicated sampling of a fulvic and an umbic Andosol under pine and laurel forest located on the island of Tenerife with a Mediterranean sub-humid climate. We determined the extent of the organo-mineral interactions by comparing the sizes of the light (free) and heavy (dense) soil fractions obtained by physical separation through flotation in a liquid with a density of 1.9 g cm^–3. We determined the elemental and isotopic composition of both fractions and analysed their chemical composition by analytical pyrolysis. The elemental and isotopic composition showed similar values with depth despite the different vegetation and climatic conditions prevailing at the two sites. Carbon (C) stabilised by mineral interactions increased with depth and represented 80–90% of the total C in the lowest horizons. The heavy fractions mainly released N-containing compounds upon analytical pyrolysis, whereas lignin-derived and alkyl compounds were the principal pyrolysis products released from the light fractions of the top- and subsoil horizons. Principal component analysis showed that the chemical composition of OM stabilised by mineral interaction differs in the different horizons of the soil profile. In the A horizons, the chemical composition of this OM was similar to those of the light fractions, i.e. litter input. There was a gradual change in the bulk molecular composition from a higher contribution of plant-derived molecules in the light and heavy fractions of the A horizon to more microbial-derived molecules as well as black C-derived molecules at depth. We conclude that transport processes in addition to decomposition and possibly in situ ageing affect the chemical composition of mineral-associated OM in subsoils.     

Flavonoids in baby spinach (Spinacia oleracea L.): changes during plant growth and storage

The variation in flavonoid concentration and composition was investigated in baby spinach (Spinacia oleracea L.) cv. Emilia sown on three occasions, each harvested at three growth stages at 6-day intervals. After harvest, leaves were stored in polypropylene bags at 2 or 10 degrees C. Flavonoids were analyzed by reversed phase HPLC. Twelve flavonoid peaks were detected. The main flavonoid, making up on average 43% of the total flavonoid concentration, was identified as 5,3',4'-trihydroxy-3-methoxy-6:7-methylenedioxyflavone-4'-glucuronide. Four other flavonoids each contributed 7-12% of the total flavonoid content. Total flavonoid content was relatively stable during normal retail storage conditions, although some of the individual flavonoid compounds showed considerable variation. The youngest plants had the highest flavonoid concentration, indicating that by harvesting the baby spinach a few days earlier than the current commercial stage of harvest, the flavonoid concentration in the product may be increased and the content of potentially health-promoting compounds enhanced.