Phenolic compounds in NaOH extracts of UK soils and their contribution to antioxidant capacity

Antioxidants are released during the NaOH extraction of soils, and this also releases phenolic compounds from plant and soil material. We hypothesized that phenolics would be important contributors to the antioxidant capacity (AOC) of soils. The concentrations of 12 phenolic compounds and the AOCs in 4 m ‐NaOH extracts of a range of UK soil types were measured. Samples of both surface and subsurface horizons were taken from 24 sites representing the major soil types (brown soils, gleys, podzols, peats and lithomorphic soils). The land use/vegetation varied from deciduous woodland through heather moorland to agricultural crops. The internal standards method was used to quantify the phenolics, which were detected by gas chromatography. The AOCs of the extracts and of standards of the individual phenolic compounds were measured using the TEAC (Trolox Equivalent Antioxidant Capacity) method. There were differences in the phenolic distributions extracted from soils with different land uses/plant inputs, as well as differences between surface and subsurface samples. A statistically significant linear relationship was found between the AOCs of the extracts and the sum of the phenolic compounds, as both these variables were positively correlated with the organic matter content of the soils. The AOCs of the individual phenols were used to calculate their contribution to the overall AOC of the extracts, and this was found to be small (approximately 1% of the total AOC). We concluded that the measured phenolic compounds were not important contributors to the AOCs of the soil extracts, and therefore that other unidentified antioxidant compounds were probably present.     

Inheritance of grain fill rate in barley

Grain fill rate is an important characteristic influencing productivity of barley (Hordeum vulgare L.) in northern areas of production. This study was conducted to determine the inheritance of grain fill rate and its relationship to other agronomic traits. Thirty‐three doubled haploid lines and parents from two crosses were evaluated for three years at Palmer, Alaska. The distribution of lines for grain fill rate in the progenies was approximately normal. Heritability of grain fill rate was 89.6% in one cross and 90.0% in the other. Rapid grain fill rate was associated with shorter effective grain fill period, longer time to heading, and higher grain yield, but not with time to maturity. Rapid grain fill rate appears to provide a means of improving grain yield without increasing time to maturity.     

Modeling production of antifungal compounds and their role in biocontrol product inhibitory activity

Partial least squares (PLS) regression modeling was used to relate the antifungal activity of Bacillus subtilis solid-state fermentation extracts to the individual high-performance liquid chromatography (HPLC) peaks from those extracts. A model was developed that predicted bioassay inhibition based on the extract HPLC profile (R(2) = 0.99). Concentrations of the members of the antifungal lipopeptide families iturin A and fengycin were found to correlate positively with extract inhibition, but a peak with unidentified chemical composition (designated as peak 48) showed the strongest correlation with extract inhibition. HPLC data were used to construct models for the production of iturin A, fengycin, and peak 48 as a function of the substrate moisture content, incubator temperature, and aeration rate in the solid-state bioreactors. Maximum production of all compounds occurred at the highest moisture content (1.7 g/g dry basis) and lowest incubator temperature (19 degrees C) tested. Optimal aeration rates for the production of the two known lipopeptides and peak 48 were 0.1 and 1.5 L/min, respectively.     

Genotypic variation in Fe concentration of barley grain

Abstract

Iron deficiency in humans is the most prevalent micronutrient deficiency worldwide. To screen for high Fe cultivar, genotypic variation in Fe concentration of barley grain was investigated in two collections of barley: 274 standard varieties selected at the Barley Germplasm Center of the Research Institute for Bioresources, Okayama University (SV) and 135 varieties from the Barley Core Collection of Americas (BCCAM). The Fe concentration of barley grain showed large variation, ranging from 24.6 to 63.3 mg kg^?1 in SV, from 21.0 to 83.0 mg kg^?1 in BCCAM barleys. The Fe concentration was not affected by the key characters of barley varieties, kernel row types, and hulled or hull-less. The Fe concentration was also not related to the place of origin of the barley variety. About 90% of total Fe was localized in the grain without hull. These results provide fundamental data for breeding Fe-rich cultivars and for studying the mechanisms involved in genotypic variation in Fe concentration.     

Phenolic compounds in Spanish olive oils.

Phenolic compounds in Spanish virgin olive oils were characterized by HPLC. Simple phenols such as hydroxytyrosol, tyrosol, vanillic acid, p-coumaric acid, ferulic acid, and vanillin were found in most of the oils. The flavonoids apigenin and luteolin were also found in most of the oils. The dialdehydic form of elenolic acid linked to tyrosol and hydroxytyrosol was also detected, as were oleuropein and ligstroside aglycons. The structure of a new compound was elucidated by MS and NMR as being that of 4-(acetoxyethyl)-1,2-dihydroxybenzene. Changes of phenolic compounds in virgin olive oils with maturation of fruits were also studied. Hydroxytyrosol, tyrosol, and luteolin increased their concentration in oils with maturation of fruits. On the contrary, glucoside aglycons diminished their concentration with maturation. No clear tendency was observed for the rest of the phenolic compounds identified.     

Phenolic compounds from the leaf extract of artichoke (Cynara scolymus L.) and their antimicrobial activities

A preliminary antimicrobial disk assay of chloroform, ethyl acetate, and n-butanol extracts of artichoke (Cynara scolymus L.) leaf extracts showed that the n-butanol fraction exhibited the most significant antimicrobial activities against seven bacteria species, four yeasts, and four molds. Eight phenolic compounds were isolated from the n-butanol soluble fraction of artichoke leaf extracts. On the basis of high-performance liquid chromatography/electrospray ionization mass spectrometry, tandem mass spectrometry, and nuclear magnetic resonance techniques, the structures of the isolated compounds were determined as the four caffeoylquinic acid derivatives, chlorogenic acid (1), cynarin (2), 3,5-di-O-caffeoylquinic acid (3), and 4,5-di-O-caffeoylquinic acid (4), and the four flavonoids, luteolin-7-rutinoside (5), cynaroside (6), apigenin-7-rutinoside (7), and apigenin-7-O-beta-D-glucopyranoside (8), respectively. The isolated compounds were examined for their antimicrobial activities on the above microorganisms, indicating that all eight phenolic compounds showed activity against most of the tested organisms. Among them, chlorogenic acid, cynarin, luteolin-7-rutinoside, and cynaroside exhibited a relatively higher activity than other compounds; in addition, they were more effective against fungi than bacteria. The minimum inhibitory concentrations of these compounds were between 50 and 200 microg/mL.     

Phenolic compounds and antioxidant capacity of Georgia-grown blueberries and blackberries

Blueberries and blackberries grown at various locations in Georgia were collected and analyzed for flavonoids, total anthocyanins, total polyphenols, and Trolox-equivalent antioxidant capacity (TEAC). Each sample was analyzed for phenolic acids (gallic acid, p-hydroxybenzoic acid, caffeic acid, ferulic acid, and ellagic acid) and flavonoids (catechin, epicatechin, myricetin, quercetin, and kaempferol). A high-performance liquid chromatographic (HPLC) method with photodiode array detection was used for analysis. Compounds were analyzed as aglycons after acid hydrolysis with 1.2 M HCl. Identification of each compound was based on retention time and UV spectra by comparison with pure commercial standards. Phenolic acids ranged from 0.19 to 258.90 mg/100 g fresh weight (FW), and flavonoids ranged from 2.50 to 387.48 mg/100 g FW. Total polyphenols ranged from 261.95 to 929.62 mg/100 g FW, and total anthocyanins ranged from 12.70 to 197.34 mg/100 g FW. TEAC values varied from 8.11 to a maximum of 38.29 microM/g FW. A linear relationship was observed between TEAC values and total polyphenols or total anthocyanins. The data indicate that blueberries and blackberries are rich sources of antioxidants.     

Phenolic compounds profile of cornicabra virgin olive oil

This study presents the phenolic compounds profile of commercial Cornicabra virgin olive oils from five successive crop seasons (1995/1996 to 1999/2000; n = 97), determined by solid phase extraction reversed phase high-performance liquid chromatography (SPE RP-HPLC), and its relationship with oxidative stability, processing conditions, and a preliminary study on variety classification. The median of total phenols content was 38 ppm (as syringic acid), although a wide range was observed, from 11 to 76 ppm. The main phenols found were the dialdehydic form of elenolic acid linked to tyrosol (p-HPEA-EDA; 9 +/- 7 ppm, as median and interquartile range), oleuropein aglycon (8 +/- 6 ppm), and the dialdehydic form of elenolic acid linked to hydroxytyrosol (3,4-DHPEA-EDA; 5 +/- 8 ppm). In many cases the correlation with oxidative stability was higher when the sum of the dialdehydic form of elenolic acid linked to hydroxytyrosol (3,4-DHPEA-EDA) and oleuropein aglycon (r (2) = 0.91-0.96) or the sum of these two and hydroxytyrosol (r (2) = 0.90-0.97) was considered than was observed with HPLC total phenols (r (2)= 0.91-0.95) and especially with colorimetric determination of total polyphenols and o-diphenols (r (2) = 0.77-0.95 and 0.78-0.92, respectively). 3,4-DHPEA-EDA, p-HPEA-EDA, the aglycons of oleuropein and ligstroside, and HPLC total phenols content presented highly significant differences (p = 0.001-0.010) with respect to the dual- and triple-phase extraction systems used, whereas colorimetric total polyphenols content did not (p = 0.348) and o-diphenols showed a much lower significant difference (p = 0.031). The five variables that most satisfactorily classified the principal commercial Spanish virgin olive oil varieties were 1-acetoxypinoresinol, 4-(acetoxyethyl)-1,2-dihydroxybenzene (3,4-DHPEA-AC), ligstroside aglycon, p-HPEA-EDA, and RT 43.3 contents.     

Oxygen deficiency in barley (Hordeum vulgare) grain during malting

The steep water is generally aerated in industrial barley malting. However, it is questionable whether oxygen actually reaches the embryo, which remains entrapped under the husk, testa, and pericarp until chitting occurs. The aim of our study was to investigate whether barley embryos experience oxygen deficiency during steeping, and whether various steeping conditions affect the oxygen deficiency. Alcohol dehydrogenase Adh2 was induced in all steeping conditions studied. Therefore, oxygen deficiency occurred regardless of the steeping conditions. However, steeping conditions affected the rate of recovery from oxygen deficiency, germination rate, and onset of alpha-amylase production. When barley was subjected to oxygen deficiency by applying N(2) gas during steeping, the timing of the treatment determined its effects. The importance of aeration increased as the process proceeded. Oxygen deprivation at the beginning of the process had little effect on malt quality. Therefore, the timing of aeration is important in the optimization of germination during the steeping stage of malting.     

Phenolic compounds and antioxidant activity of sorghum grains of varying genotypes

The effects of plant color, pericarp thickness, pigmented testa, and spreader genes on phenols and antioxidant activity levels of 13 sorghum genotypes were evaluated. Total phenols, condensed tannins, flavan-4-ols, and anthocyanins were measured. Antioxidant activity levels using the 2,2'-azinobis(3-ethyl-benzothiazoline-6-sulfonic acid) and 2,2-diphenyl-1-picrylhydrazyl assays were evaluated. Sorghums with a pigmented testa and spreader genes (B(1)()B(2)()S) had the highest levels of phenols and antioxidant activity. In addition, sorghums with purple/red plants (PQ) and thick pericarp (z) genes had increased levels of phenols and antioxidant activity. Sorghums with a black pericarp had higher levels of flavan-4-ols and anthocyanins than the other varieties. This suggests that genes for plant color, pericarp thickness, presence of a pigmented testa, and spreader genes increase phenols and antioxidant activity levels. This information can be useful in the production of sorghums with increased phenols and antioxidant activity levels.     

冬大麦花后穗部氮素积累及转移的研究

在大田条件下,以扬饲麦3、扬饲麦1、苏啤2号和扬农啤2号等4个品种为供试材料,在07、5、1502、25.kg/hm24个氮肥处理水平下,研究了大麦花后穗部氮积累及转移的规律。结果表明,在扬饲麦3、扬饲麦1、苏啤2号和扬农啤2号4个品种各氮肥处理的平均值中,开花期绿叶的含氮量依次为2.64%、2.76%、2.63%和2.45%,穗部含氮量依次为1.43%、1.83%、1.69%和1.51%。成熟期子粒含氮量分别为2.65%、2.63%、2.48%和2.14%。氮的花前积累量(NABF)依次为17.68、15.27、19.80和14.85.mg/plant,总积累量(NTA)分别为33.75、25.51、54.24和28.83mg/plant,花后积累量(NAAF)依次为16.061、0.25、34.45和13.98.mg/plant,转移量(NT)依次为12.60、10.551、3.48和9.54.mg/plant,转移效率(NTE)分别为71.49%、69.84%、68.42%和64.97%。收获指数(NHI)分别为84.91%、81.95%、88.47%和81.90%;随着施氮水平的提高,各品种的花前氮积累量、总积累量、花后积累量和氮转移量均呈上升趋势,而氮转移效率、氮转移对子粒的贡献(NCR)率则成下降趋势;大麦花后穗部氮积累过程可以用Richards方程W=A/(1+be-kt)m来描述,通径分析方程各特征参数与氮积累和转移的关系表明,影响大麦穗部氮积累和转移的主要因素是最大积累速率,其次是起始积累势,最大积累速率越高,起始积累势越小,越有利于氮的积累和转移。同时,积累中期和前期的积累速率和积累量对大麦穗部氮积累和转移的影响也较大。     

Study of the reactions between (+)-catechin and furfural derivatives in the presence or absence of anthocyanins and their implication in food color change

(+)-catechin was separately incubated with furfural or with 5-(hydroxymethyl)furfural, and the formation of new oligomeric bridged compounds having flavanol units linked by furfuryl or 5-hydroxymethylfurfuryl groups was observed. LC/ESI-MS analyses detected four dimeric adducts along with intermediate adducts in each solution, and reaction was faster with furfural than with hydroxymethylfurfural. In addition, new compounds exhibiting the same UV--visible spectra as xanthylium salts with absorption maxima around 440 nm were also detected. When malvidin 3-O-glucoside or cyanidin 3-O-glucoside was added to the mixtures, new oligomeric colorless and colored pigments involving both (+)-catechin and anthocyanin moieties were detected, showing thus that the two polyphenols competed in the condensation process. Among the obtained colored pigment adducts, two dimeric compounds in which the flavanol was bridged to the anthocyanin were observed. Their UV-visible spectra were similar to the spectrum of malvidin 3-O-glucoside, but their maximum in the visible region was bathochromically shifted.     

Phenolic compounds and browning in sherry wines subjected to oxidative and biological aging

The composition in hydroxybenzoic and hydroxycinnamic acids, hydroxycinnamic esters, tyrosol, syringaldehyde, and flavan-3-ol derivatives of three different types of sherry wine obtained by aging of the same starting wine under different conditions was studied. So-called "fino" wine was obtained by biological aging under flor yeasts, "oloroso" wine by oxidative aging, and "amontillado" wine by a first stage of biological aging followed by a second oxidative step. On the basis of the results, the wines subjected to oxidative aging exhibited higher phenol contents, in addition to scarcely polar compounds absorbing at 420 nm that were absent in the wines obtained by biological aging. Taking into account that flavan-3-ol derivatives play an important role in wine browning, a model catechin solution was inoculated with flor yeast which, contrary to the findings of other authors in the absence of yeasts, formed no colored compounds. This different behavior may account for the resistance to browning of pale sherry wines in the presence of flor yeasts.     

New phenolic compounds formed by evolution of (+)-catechin and glyoxylic acid in hydroalcoholic solution and their implication in color changes of grape-derived foods

The reaction between (+)-catechin and glyoxylic acid in model solution system was investigated by LC/DAD and LC/ESI-MS analyses. The formation of phenolic compounds exhibiting absorption maxima near 300 nm and presenting a shoulder around 350 nm was observed. Their structures consisted of a (+)-catechin unit with one or two aldehyde groups linked at positions 6, 8 or 6 and 8 of the A ring. In addition, new yellow pigments exhibiting UV-visible spectra similar to those of xanthylium salts with absorption maxima at 450 and 280 nm were also detected. The major yellow compound was isolated and identified by ESI-MS and 1D and 2D NMR spectroscopy. The implication of these compounds in color change and browning observed during aging of grape-derived beverages is also discussed.     

Nutritionally relevant parameters in low-phytate barley (hordeumvulgare L.) grain mutants

Nutritionally relevant parameters in barley low-phytate mutant grains were analyzed in order to assess the potential value of these lines for future feeding trials. Phytate (myo-inositol 1,2,3,4,5,6-hexakisphosphate) levels in grains from A- and B-type low-phytate mutants corresponded to 25% and 66% of those of the parent line content, respectively. These relative decreases in phytate were accompanied by proportional increases of inorganic phosphate amounts. Apart from phytate, A-type grains also contained substantial quantities of myo-inositol 1,3,4,5-tetrakisphosphate. Phytate levels in straw and root material from mutants were similar to parent line controls, indicating that low-phytate mutations were grain specific. Analysis of K, Mg, Ca, and Zn revealed normal or slightly increased mineral cation levels in grains from all low-phytate lines, suggesting that mutationally impaired phytate accumulation did not affect mineral storage capacity. Other nutritionally important parameters such as starch and protein contents were similar to parent line controls. Finally, dynamic changes in the phosphorus composition during kernel development suggested that A-type mutations directly affected phytate synthesis, whereas B-type mutations seemed to act on regulation of synthesis.     

Phenolic compounds contribute to dark bran pigmentation in hard white wheat

Unacceptably dark bran color has prevented the white-kernelled variety Argent from meeting grain color marketing standards for hard white wheats (Triticum aestivum L.). The objective of this research was to identify phenolic compounds that negatively affect bran color in white wheat using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) and vanillin-HCl and NaOH staining methods. In mature bran, FT-ICR-MS detected derivatives of the flavonol quercetin in varieties Argent and RL4137 (red-kernelled wheat) but not in W98616, a white wheat variety with acceptable grain color. Derivatives of the isoflavone formononetin were more abundant in W98616 relative to RL4137 and Argent. Vanillin-HCl staining indicated that RL4137 sequestered high levels of proanthocyanidin (PA) throughout its entire seed coat, whereas white wheats sequestered PAs as discrete speckles. Argent possessed abundant speckles over its entire seed coat, whereas speckles were almost undetectable in W98616. In mature kernels, flavonoids throughout the seed coat of RL4137 reacted with NaOH, but only the speckles appeared to react in white wheats. W98616 consistently had lighter grain than Argent before and after NaOH treatment. Free and bound phenolic differences in bran samples confirmed that the darker seed coat color of Argent, relative to W98616, was likely due to higher total phenolic acid content. Although isoflavones accumulated in Argent and RL4137, it appears that the majority of the flux through the flavonoid pathway ultimately accumulates quercetin derivatives and PAs. In W98616, PAs accumulate, but it appears that flavonoid biosynthesis ultimately accumulates isoflavones. Argent, compared to W98616, generally accumulated higher levels of total phenolics (flavonols, stilbenes, and PAs) within its darker pigmented bran.     

Phenolic compounds and chromatographic profiles of pear skins (Pyrus spp.)

A standardized profiling method based on liquid chromatography with diode array and electrospray ionization/mass spectrometric detection (LC-DAD-ESI/MS) was used to analyze the phenolic compounds in the skins of 16 pears (Pyrus spp.). Thirty-four flavonoids and 19 hydroxycinnamates were identified. The main phenolic compounds (based on peak area) in all of the pear skins were arbutin and chlorogenic acid. The remaining phenolics varied widely in area and allowed the pears to be divided into four groups. Group 1, composed of four Asian pears (Asian, Asian brown, Korean, and Korean Shinko), contained only trace quantities of the remaining phenolics. Yali pear (group 2) contained significant amounts of dicaffeoylquinic acids. Fragrant pear (group 3) contained significant quantities of quercetin glycosides and lesser quantities of isorhamnetin glycosides and the glycosides of luteolin, apigenin, and chrysoeriol. The remaining 10 pears (group 4) (Bartlett, Beurre, Bosc, Comice, D'Anjou, Forelle, Peckham, Red, Red D'Anjou, and Seckel) contained significant quantities of isorhamnetin glycosides and their malonates and lesser quantities of quercetin glycosides. Red D'Anjou, D'Anjou, and Seckel pears also contained cyanidin 3-O-glucoside. Thirty-two phenolic compounds are reported in pear skins for the first time.     

Phenolic contents and antioxidant activities in covered whole-grain flours of Norwegian barley varieties and in fractions obtained after pearling

Abstract

Phenolic contents and corresponding antioxidant activities were studied in covered whole-grain flours of Norwegian barley varieties and in two different pearling fractions. In covered whole-grain flours the summarized amount of phenolics (Σ-P) ranged from 481–676 mg gallic acid equivalent (GAE)/100 g dry matter (DM) and the corresponding total antioxidant activities (Σ-FRAP) between 6.1–8.7 mmol Fe^{3 +}/100 g DM. About 50% of the phenolics in these samples were easily extractable (free). Upon pearling a general decrease in both Σ-P and Σ-FRAP was seen in the pearled samples, while the ratio between free and bound phenolics was similar or increased to those in the covered whole-grain samples. The hulls had the highest Σ-P and Σ-FRAP and were dominated by bound phenolics. Despite accounting for only 10–20% of the total grain weight, the hulls typically contributed to 45% of the total antioxidant capacity measured in the covered whole-grain flours. Pearling makes it possible to obtain barley fractions with different amounts of phenolics, different ratios of free and bound phenolics, and thus different antioxidant activities.