Characterization and quantification of anthocyanins and polyphenolics in bluehHoneysuckle (Lonicera caerulea L.)

Anthocyanins and phenolics of 10 blue honeysuckle (Lonicera caerulea L.) genotypes were characterized and quantified by HPLC-DAD. Peak assignments were confirmed by low-resolution electrospray mass spectrometry. Six anthocyanins were detected with the major peak identified as cyanidin 3-glucoside. Five additional anthocyanins were characterized as cyanidin 3,5-diglucoside, cyanidin 3-rutinoside, pelargonidin 3-glucoside, peonidin 3-glucoside, and peonidin 3-rutinoside. Four polyphenolics were identified as chlorogenic acid, neochlorogenic acid, quercetin 3-rutinoside, and quercetin 3-glucoside. Two additional unidentified phenolics were characterized as flavonol and hydroxycinnamic derivatives based on UV-vis spectra. Hydroxycinnamate levels ranged from 30.4 to 156.2 mg/100 g, whereas the flavonol content ranged from 12.6 to 32.8 mg/100 g. The L. caerulea subspecies boczkarnikovae contained the highest amounts of hydroxycinnamic derivatives and flavonols.     

Effect of black raspberry ( Rubus occidentalis L.) extract variation conditioned by cultivar, production site, and fruit maturity stage on colon cancer cell proliferation

Black raspberries have been shown to inhibit multiple stages of oral, esophageal, and colon cancer. The objective of this study was to evaluate how black raspberry extract variability conditioned by horticultural factors affected the antiproliferative activity of 75 black raspberry extracts using an in vitro colon cancer cell model. HT-29 cells grown in 96-well plates were treated with freeze-dried extracts at 0.6 and 1.2 mg of extract/mL of medium. Percent cell growth inhibition for each concentration of the extracts was determined using the sulforhodamine B assay. All extracts significantly inhibited the growth of HT-29 colon cancer cells in a dose-dependent manner. Cell proliferation was significantly influenced by cultivar, production site, and stage of maturity. The lack of correlation between growth inhibition and extract total phenolic and total monomeric anthocyanin assays suggested horticultural parameters influence bioactivity in a complex manner.     

Processing and storage effects on monomeric anthocyanins, percent polymeric color, and antioxidant capacity of processed blackberry products

Blackberries are a rich source of polyphenolics, particularly anthocyanins, that may contribute to the reduced risk of chronic disease; however, as with most berries, the fresh fruit are only seasonally available. With most of the blackberries consumed as frozen or in thermally processed forms after long-term storage, the purpose of this study was to evaluate the effects of processing and 6 months of storage on the anthocyanins and antioxidant capacity of blackberries that were individually quick-frozen (IQF), canned-in-syrup, canned-in-water, pureed, and juiced (clarified and nonclarified). Monomeric anthocyanins, percent polymeric color, and antioxidant capacity by oxygen radical absorbance capacity (ORAC FL) and photochemiluminescence (PCL) were determined postprocessing (1 day) and after 1, 3, and 6 months of storage. Processing resulted in increases in polymeric color values (up to 7%) and losses in monomeric anthocyanins (up to 65%). For most products, processing also resulted in losses in antioxidant capacity (by ORAC FL and PCL). Storage at 25 degrees C of all processed products resulted in dramatic losses in monomeric anthocyanins with as much as 75% losses of anthocyanins throughout storage, which coincided with marked increases of percent polymeric color values of these products over 6 months of storage. There were no changes in ORAC FL or PCL for processed products throughout long-term storage. No significant changes in antioxidant capacity or anthocyanin content were observed in IQF fruit during long-term storage at -20 degrees C.     

Urinary excretion of black raspberry (Rubus occidentalis) anthocyanins and their metabolites

Anthocyanins are the most abundant phenolic compounds, widely distributed in fruits and vegetables, and exhibit potent antioxidant capacity. Humans ingest a significant amount of anthocyanins in the daily diet. The objective of the current study was to examine human absorption and metabolism of black raspberry anthocyanins when administered at high doses (2.69 +/- 0.085 g/day). Ten healthy men consumed 45 g of freeze-dried black raspberries daily for 1 week. Urine samples were collected over a 12 h period in 4 h intervals at day 1 and day 7. Urinary anthocyanins were analyzed by high-performance liquid chromatography coupled to a photodiode array detector and a tandem mass spectrometer using precursor ion and product ion analyses. Anthocyanins were excreted in intact forms and metabolized into methylated derivatives in human urine. The urinary excretion of anthocyanins reached a maximum concentration (1091.8 +/- 1081.3 pmol/L, n = 10) during the 4-8 h period after black raspberry ingestion. As compared to the anthocyanin distribution in black raspberries, urinary cyanidin 3-xylosylrutinoside was detected at a higher concentration than that of cyanidin-3-rutinoside.     

Influence of cultivar and germination on bioactive amines in soybeans (Glycine max L. Merril)

The levels of amines in soybeans as affected by cultivar in two consecutive years and by germination were investigated. Spermidine, spermine, putrescine, agmatine, and cadaverine were detected, whereas tyramine, histamine, tryptamine, serotonine, and phenylethylamine were not. Spermidine was the predominant amine followed by spermine. High concentrations of these amines confirmed soybean as a rich source. Cadaverine was confirmed to be inherent to soybean. The percent contribution of spermidine and spermine to total levels was not affected by cultivar in either years. However, amine levels were affected by cultivars in different ways in the consecutive years. Cadaverine was affected more by the cultivar, whereas spermidine, spermine, and agmatine were affected by harvest year. During germination the levels of amines from soybean increased significantly, except for agmatine. Spermidine and spermine accumulated in the cotyledon, whereas cadaverine and putrescine accumulated in the radicle and hypocotyl.     

Influence of cultivar and fruit ripening on olive (Olea europaea) fruit protein content, composition, and antioxidant activity

Proteins of olive fruit mesocarp are not very well-known at present. However, they have been shown to pass, at least partially, to the olive oil during its elaboration and therefore might be contributing to some of the special characteristics of this vegetable oil. In this study, protein content and composition were determined in olive fruits, cv. Arbequina and Picual, at three stages of ripening: green, spotted, and purple. Mesocarp proteins constituted 1.3-1.8% of the dry weight of the olive fruit, and cultivar and fruit ripening did not produce important changes in mesocarp protein content or composition. In addition, this composition was also similar to the amino acid composition of a 4.6-kDa polypeptide, which is the major protein component of olive oils and of oil bodies of olive fruit mesocarp, suggesting that this polypeptide is likely to be a major component of mesocarp proteins. There was, also, a relationship between the oil content of the olive fruit and the protein content determined, suggesting a stabilizing function of these proteins in the oil bodies of the olive fruit, analogously to the role suggested for oleosins. This stabilizing function does not seem to be extended to olive oils because when the polypeptides isolated were added at 20 ppm to soybean oil, the stability of the oil increased only slightly, suggesting that if these compounds play some role in the stability of the oils, this should be mostly a consequence of the possible interactions among these protein components and other olive oil antioxidant constituents.     

Impact of growing environment on chickasaw blackberry (Rubus L.) aroma evaluated by gas chromatography olfactometry dilution analysis

The aroma extract of Chickasaw blackberry (Rubus L.) was separated with silica gel normal phase chromatography into six fractions. Gas chromatography-olfactometry (GCO) was performed on each fraction to identify aroma active compounds. Aroma extraction dilution analysis (AEDA) was employed to characterize the aroma profile of Chickasaw blackberries from two growing regions of the United States: Oregon and Arkansas. Comparative AEDA analysis showed that the berries grown in the two regions had similar aroma compositions; however, those odorants had various aroma impacts in each region. The compounds with high flavor dilution factors in Oregon's Chickasaw were ethyl butanoate, linalool, methional, trans,cis-2,6-nonadienal, cis-1,5-octadien-3-one, and 2,5-dimethyl-4-hydroxy-3(2H)-furanone, whereas in the Chickasaw grown in Arkansas, they were ethyl butanoate, linalool, methional, ethyl 2-methylbutanoate, beta-damascenone, and geraniol.     

Phenolic compounds, carotenoids, anthocyanins, and antioxidant capacity of colored maize (Zea mays L.) kernels

In this study, the contents of total phenolics, flavonoids, anthocyanins, β-carotene, and lutein as well as free, conjugated, and insoluble bound phenolic acids were determined in whole kernels of 10 different colored maize genotypes. In addition, the antioxidant activity was evaluated as radical scavenging activity with ABTS (2,2-azino-bis/3-ethil-benothiazoline-6-sulfonic acid) and DPPH (2,2-diphenyl-1-picrylhydrazyl) reagents. Generally, considerable differences in phytochemical contents and antioxidant capacity were observed between the genotypes. The β-carotene and lutein contents ranged from 0 to 2.42 mg/kg d.m. and from 0 to 13.89 mg/kg d.m., respectively, whereas the total anthocyanin contents of anthocyanin-rich colored maize genotypes ranged from 2.50 to 696.07 mg CGE/kg d.m. (cyanidin 3-glucoside equivalent) with cyanidin 3-glucoside (Cy-3-Glu) as the most dominant form. The light blue ZPP-2 selfed maize genotype has a higher content of total phenolics, flavonoids, and ferulic acid as compared to other tested maize and the highest ABTS radical scavenging activity.     

Thermal degradation of anthocyanins from purple potato (cv. Purple Majesty) and impact on antioxidant capacity

Degradation parameters of purified anthocyanins from purple-fleshed potato (cv. Purple Majesty) heated at high temperatures (100-150 °C) were determined. Purified anthocyanins, prepared by removing salts, sugars, and colorless nonanthocyanin phenolics from the crude extract, were monitored and quantified using HPLC and spectrophotometry for heat-induced degradation products. Separation of colorless phenolics from the anthocyanins was confirmed using HPLC at two wavelengths, 280 and 520 nm. The degradation kinetics of purified anthocyanins followed a first-order reaction with reaction rate constants (k values) of 0.0262-0.2855 min(-1), an activation energy of 72.89 kJ/mol, thermal death times (D values) of 8.06-8789 min, and a z value of 47.84 °C over the temperature range of 100-150 °C. The enthalpy and entropy of activation were 59.97 kJ/mol and -116.46 J/mol·K, respectively. The antioxidant capacity in the purified anthocyanins, measured by DPPH and ABTS assays, was increased after the thermal treatment, indicating antioxidant activities of degradation products in the samples.     

Influence of vine vigor on grape (Vitis vinifera L. Cv. Pinot Noir) anthocyanins. 1. Anthocyanin concentration and composition in fruit

The relationships between grapevine (Vitis vinifera) vigor variation and resulting fruit anthocyanin accumulation and composition were investigated. The study was conducted in a commercial vineyard consisting of the same clone, rootstock, age, and vineyard management practices. The experimental design involved assigning vigor zones in two vineyard sites based upon differences in vine growth. Fruits and wines were analyzed by HPLC from designated vigor zones in 2003 and 2004. Average berry weight (grams), average dry skin weight (milligrams), degrees Brix, and pH were higher and titratable acidity (grams per liter) was lower in 2003 compared to 2004. In 2003, only the highest and lowest vigor zones had differences in berry weight, whereas there were no differences in 2004. In both years, high vigor zones had lower degrees Brix and higher titratable acidity (milligrams per liter). Accumulation of anthocyanins (milligrams per berry) was greater in 2003 compared to 2004. There was a trend for lower anthocyanin concentration (milligrams per berry) in high vigor zones in both years. In 2004 compared to 2003, there was a higher proportion of malvidin-3-O-glucoside and lower proportions of the other four anthocyanins (delphinidin-, cyanidin-, petunidin-, and peonidin-3-O-glucosides) found in Pinot Noir. In both years, site A had proportionally higher peonidin-3-O-glucoside and lower malvidin-3-O-glucoside than site B. Some of these differences may be related to the higher exposure and temperatures found in site B compared to site A and also in the low vigor zones.     

Influence of vine vigor on grape (Vitis vinifera L. Cv. Pinot Noir) anthocyanins. 2. Anthocyanins and pigmented polymers in wine

The relationships between grapevine (Vitis vinifera) vigor variation and resulting wine anthocyanin concentration and composition and pigmented polymer formation were investigated. The study was conducted in a commercial vineyard consisting of the same clone, rootstock, age, and vineyard management practices. Vine vigor parameters were used to designate vigor zones within two vineyard sites (A and B) to produce research wines (2003 and 2004) and conduct a model extraction experiment (2004 only) to investigate the vine-fruit-wine continuum. Wines and model extracts were analyzed by HPLC and UV-vis spectrophotometry. For the model extractions, there were no differences between sites for pomace weight, whereas juice volume was higher for site A. This was not related to a larger berry size. Site A had a higher anthocyanin concentration (milligrams per liter) in the model extracts than site B specifically for the medium- and low-vigor zones. For anthocyanin composition in the model extraction, site B had a greater proportion of malvidin-3-O-glucoside and less of the remaining anthocyanin glucosides (delphinidin, cyanidin, petunidin, and peonidin) compared to site A. In the wines, there was a vintage effect, with the 2003 wines having a higher anthocyanin concentration (milligrams per liter) than the 2004 wines. This appears to have been primarily due to a greater accumulation of anthocyanins in the fruit. In general, the medium-vigor zone wines had higher anthocyanin concentrations than either the high- or low-vigor zone wines. There was also vintage variation related to anthocyanin composition, with the 2003 wines having a higher proportion of delphinidin and petunidin glucosides and lower malvidin-3-O-glucoside compared to 2004. In both years, there were higher proportions of delphinidin and petunidin glucosides in wines made from low-vigor-zone fruit. Wines made from low-vigor zones showed a greater propensity to form vitisin A as well as pigmented polymers. Low-vigor-zone wines had a approximately 2-fold increase in pigmented polymer concentration (milligrams per liter) over high-vigor-zones wines. There was a strong positive relationship between pigmented polymer concentration, bisulfite bleaching resistant pigments, proanthocyanidin concentration, and color density in wines. Overall, differences found in the wines magnified variation in the fruit.     

Influence of cultivar and processing on cherry (Prunus avium) allergenicity

Oral allergy syndrome is an immediate food allergic event that affects lips, mouth, and pharynx, is often triggered by fruits and vegetables, and may be associated with pollinosis. Here, we report on the allergenic pattern of different varieties of cherry (Prunus avium) and results obtained by applying several technological processes to the selected varieties. Whole cherries were submitted to chemical peeling, thermal treatment, and syruping processes, and the relative protein extracts were analyzed by in vitro (sodium dodecyl sulfate-polyacrylamide gel electrophoresis and immunoblotting analysis) and in vivo tests (skin prick test). Electrophoretic analyses demonstrated that there was no marked difference among cherry cultivars. Chemical peeling successfully removed Pru av 3, a lipid transfer protein (LTP) responsible for oral allergy syndrome in patients without pollinosis, leading to the industrial production of cherry hypoallergenic derivatives. Furthermore, the syruping process removed almost all allergenic proteins to whom patients with pollinosis are responsive. In vivo tests confirmed electrophoretic results.     

Antimicrobial and antioxidant properties of rosemary and sage (Rosmarinus officinalis L. and Salvia officinalis L., Lamiaceae) essential oils

The essential oils of rosemary ( Rosmarinus officinalis L.) and sage ( Salvia officinalis L.) were analyzed by means of gas chromatography-mass spectrometry and assayed for their antimicrobial and antioxidant activities. Antimicrobial activity was tested against 13 bacterial strains and 6 fungi, including Candida albicans and 5 dermatomycetes. The most important antibacterial activity of both essential oils was expressed on Escherichia coli, Salmonella typhi, S. enteritidis, and Shigella sonei. A significant rate of antifungal activity, especially of essential oil of rosemary, was also exhibited. Antioxidant activity was evaluated as a free radical scavenging capacity (RSC), together with the effect on lipid peroxidation (LP). RSC was assessed by measuring the scavenging activity of essential oils on 2,2-diphenyl-1-picrylhydrazil (DPPH) and hydroxyl radicals. Effects on LP were evaluated following the activities of essential oils in Fe(2+)/ascorbate and Fe(2+)/H2O2 systems of induction. Investigated essential oils reduced the DPPH radical formation (IC50 = 3.82 microg/mL for rosemary and 1.78 microg/mL for sage) in a dose-dependent manner. Strong inhibition of LP in both systems of induction was especially observed for the essential oil of rosemary.     

Effect of high-oxygen atmospheres on blueberry phenolics, anthocyanins, and antioxidant capacity

The influence of high oxygen concentrations on total phenolic, total anthocyanin, individual phenolic compounds, and antioxidant capacity (measured as oxygen radical absorbance capacity, ORAC) in highbush blueberry fruit (Vaccinium corymbosum L. cv. Duke) was investigated. Freshly harvested blueberries were placed in jars ventilated continuously with air or with 40, 60, 80, or 100% O(2) at 5 degrees C for up to 35 days. Samples were taken initially and at 7-day intervals during storage. Whereas the quality parameters of titratable acidity, total soluble solids, and surface color were only slightly affected by the superatmospheric O(2) treatments, the antioxidant levels were markedly increased by 60-100% O(2) treatments as compared with 40% O(2) treatment or air control during 35 days of storage. Elevated O(2) between 60 and 100% also promoted increases of total phenolics and total anthocyanins as well as the individual phenolic compounds analyzed by HPLC. Fruit treated with O(2) concentrations of >/=60% also exhibited significantly less decay. Data obtained in this study suggest that high-oxygen treatments may improve the antioxidant capacity of blueberry fruit. Furthermore, antioxidant capacity may be correlated with total phenolic and anthocyanin contents in blueberries.     

Effect of soil zinc,pH, and cultivar on cadmium uptake in leaf lettuce (Lactuca sativa L. var. crispa)

Abstract

Six noncrisphead lettuce cultivars (Lactuca sativa L.) were grown in pots, using soil from field plots that had been amended annually with 90 MT/ha of an industrial sludge as part of a continuous study initiated in 1981. Two greenhouse experiments (each replicated 6 times) were completed—one in the spring and one in the fall. Variables included 6 cultivars, 2 soil pH levels and 2 soil Zn levels. All variables appeared to influence Cd accumulation in the leaf tissue. Uptake of Cd and Zn increased with decreasing soil pH for all cultivars. ‘Grand Rapids’ accumulated the least leaf Cd and ‘Summer Bibb’ the most. A positive correlation between leaf Zn and leaf Cd was observed, but the correlation between soil Zn and leaf Cd was variable.     

Analysis of phenolic compounds in two blackberry species (Rubus glaucus and Rubus adenotrichus) by high-performance liquid chromatography with diode array detection and electrospray ion trap mass spectrometry

High-performance liquid chromatography with diode array (LC-DAD) and electrospray ionization mass spectrometric detection (ESI-MS) was used to analyze phenolic compounds of two blackberry species ( Rubus glaucus Benth. and Rubus adenotrichus Schlech.) growing in South America. UV-visible spectrophotometry was a valuable tool for identifying the class of phenolic compound, whereas MS and MS ( n ) fragmentation data were useful for their structural characterization. Ellagitannins were the major compounds, with sanguiin H-6 and lambertianin C being the predominant ones. The anthocyanin composition as well as the presence or absence of kaempferol glycosides can be used to distinguish the Rubus species studied. Flavonol hexoside-malonates were identified in both berries. Hydroxycinnamic acids were minor compounds and found as ferulic, caffeic, and p-coumaric acid esters. Similar contents were obtained by analysis of soluble ellagitannins and ellagic acid glycosides as ellagic acid equivalents and by analysis of ellagic acid equivalents released after acid hydrolysis.     

Nonvolatile S-alk(en)ylthio-L-cysteine derivatives in fresh onion (Allium cepa L. cultivar)

The L-cysteine derivatives (R)-2-amino-3-(methyldisulfanyl)propanoic acid (S-methylthio-L-cysteine), (R)-2-amino-3-(propyldisulfanyl)propanoic acid (S-propylthio-L-cysteine), (R)-2-amino-3-(1-propenyldisulfanyl)propanoic acid (S-(1-propenylthio)-L-cysteine), and (R)-2-amino-3-(2-propenyldisulfanyl)propanoic acid (S-allylthio-L-cysteine) were prepared from 3-[(methoxycarbonyl)dithio]-L-alanine, obtained from the reaction of L-cysteine with methoxycarbonylsulfenyl chloride. The occurrence of these S-(+)-alk(en)ylthio-L-cysteine derivatives in onion (Allium cepa L.) was proven by using UPLC-MS-ESI(+) in SRM mode. Their concentrations in fresh onion were estimated to be 0.19 mg/kg S-methylthio-L-cysteine, 0.01 mg/kg S-propylthio-L-cysteine, and 0.56 mg/kg (S-(1-propenyllthio)-L-cysteine, concentrations that are about 3000 times lower than that of isoalliin (S-(1-propenyl-S-oxo-L-cysteine). These compounds were treated with Fusobacterium nucleatum, a microorganism responsible for the formation of mouth malodor. These L-cysteine disulfides were demonstrated to predominantly produce tri- and tetrasulfides. Isoalliin is almost entirely consumed by the plant enzyme alliin lyase (EC 4.4.1.4 S-alk(en)yl-S-oxo-L-cysteine lyase) in a few seconds, but it is not transformed by F. nucleatum. This example of flavor modulation shows that the plant produces different precursors, leading to the formation of the same types of volatile sulfur compounds. Whereas the plant enzyme efficiently transforms S-alk(en)yl-S-oxo-L-cysteine, mouth bacteria are responsible for the transformation of S-alk(en)ylthio-L-cysteine.     

How to improve bayberry (Myrica rubra Sieb. et Zucc.) juice color quality: effect of juice processing on bayberry anthocyanins and polyphenolics

Fresh bayberries (Myrica rubra Sieb. et Zucc.) were processed into juice at an industrialized scale with four treatments: control, SO2 addition, pasteurization of the crushed pulp, and blanching before fruit crushing. Changes in anthocyanin pigments and polyphenolics (hydrobenzoic acids and flavonol glycosides) were monitored during processing. Centrifuged juice yield ranged from 73 to 78% (w/w), but only 12-27% of the anthocyanins and 20-32% of the polyphenolics were recovered in the ultrahigh-temperature (UHT) juices. Fifty-two to 58% of anthocyanins and 30-35% of polyphenolics were present in the centrifuged cakes. The initial processing steps of blanching, crushing, pasteurization, and depectinization caused a great loss of total and individual polyphenolics. Total monomeric anthocyanins were significantly higher (p < 0.05) in pasteurization- and blanching-treated samples than those in the SO2 treated samples, whereas those in the SO2-treated sample were significantly higher (p < 0.05) than those in the control juice. Overall polyphenolic levels were significantly higher (p < 0.05) in pasteurization- and blanching-treated samples than in the SO2-treated and control samples after each processing step. Important changes occurred in the polyphenolic profile with a 50-150% of hydroxybenzoic acids increase due to the free gallic acid from the flavonol glycoside-gallates during the initial processing steps. Flavonol deoxyhexosides were more stable than the flavonol hexosides during bayberry juice processing.     

Influence of cultivar,cooking, and storage on cell-wall polysaccharide composition of winter squash (Cucurbita maxima)

Changes in the cell-wall polysaccharides (CWP) of the edible tissues of four winter squash cultivars during storage and after cooking were investigated. A procedure for isolating cell walls of tissues containing high levels of starch was used. The starch-free CWP were sequentially fractionated using CDTA, dilute Na(2)CO(3), and 4 M KOH. Cellulose made up 40-42% of the total CWP for three cultivars (Delica, CF 2, and CF 4) at harvest but was 35% in the softer Red Warren. The pectic polysaccharides of Delica, CF 2, and CF 4 cell walls are more branched than those from Red Warren squash. The higher proportion of uronic acid in the pectic polysaccharides of Red Warren squash correlates with its lower firmness. Cooking resulted in an increase in the water-soluble pectins and a decrease in the pectins associated with cellulose. The total CWP content of the squash cultivars remained unchanged for up to 2 months of storage and then markedly decreased between 2 and 3 months of storage. The galactose content of Delica and Red Warren cell walls remained relatively constant from harvest to 2 months of storage and then decreased markedly during 2-3 months of storage.