Distribution of lutein,zeaxanthin, and related geometrical isomers in fruit,vegetables, wheat,and pasta products

Quantitative data with regard to dietary (3R,3'R,6'R)-lutein, (3R,3'R)-zeaxanthin, and their (E/Z)-geometrical isomers are scarce, and in most cases, only the combined concentrations of these two carotenoids in foods are reported. Lutein and zeaxanthin accumulate in the human macula and have been implicated in the prevention of age-related macular degeneration (AMD). The qualitative and quantitative distributions of lutein, zeaxanthin, and their (E/Z)-isomers in the extracts from some of the most commonly consumed fruits, vegetables, and pasta products were determined by HPLC employing a silica-based nitrile-bonded column. Green vegetables had the highest concentration of lutein (L) and zeaxanthin (Z), and the ratios of these carotenoids (L/Z) were in the range 12-63. The yellow-orange fruits and vegetables, with the exception of squash (butternut variety), had much lower levels of lutein in comparison to greens but contained a higher concentration of zeaxanthin. The ratio of lutein to zeaxanthin (L/Z) in two North American bread varieties of wheat (Pioneer, Catoctin) was 11 and 7.6, respectively, while in a green-harvested wheat (Freekeh) imported from Australia, the ratio was 2.5. Between the two pasta products examined, lasagne and egg noodles, the latter had a much higher concentration of lutein and zeaxanthin. The levels of the (E/Z)-geometrical isomers of lutein and zeaxanthin in these foods were also determined.     

Carotenoids from guava (Psidium guajava l.): isolation and structure elucidation

Sixteen carotenoids were isolated from the flesh of Brazilian red guavas (Psidium guajava L.). Their structures were established by means of UV-visible, 400 and 500 MHz (1)H NMR, 120 and 125 MHz (13)C NMR, mass, and circular dichroism spectra. The carotenoids were identified as phytofluene, (all-E)-, (9Z)-, (13Z)-, and (15Z)-beta-carotene, (all-E)-gamma-carotene, (all-E)-, (9Z)-, (13Z)-, and (15Z)-lycopene, (all-E,3R)-beta-cryptoxanthin, (all-E, 3R)-rubixanthin, (all-E,3S,5R,8S)-cryptoflavin, (all-E,3R,3'R, 6'R)-lutein, (all-E,3S,5R,6R,3'S,5'R,8'R)-, and (all-E,3S,5R,6R,3'S, 5'R,8'S)-neochrome. Thirteen of the carotenoids identified are reported as guava carotenoids for the first time.     

Phenolic, flavonoid, and lutein ester content and antioxidant activity of 11 cultivars of chinese marigold

This study analyzed 11 Chinese cultivars of marigold to determine their major phytochemical contents and antioxidant activities. Dried marigold flowers were extracted with ethanol, ethyl acetate, and n-hexane and the extracts were analyzed by high-performance liquid chromatography-mass spectrometry and chemical methods to determine their lutein esters, phenolic and flavonoid contents, and antioxidant activity, respectively. The different cultivars of marigold showed considerable variations in their lutein ester contents, ranging from 161.0 to 611.0 mg/100 g of flower (dry basis). The lutein esters in marigolds consisted predominantly of six all trans-diesters, but small amounts of cis isomers of the respective diesters were also present. The different cultivars of marigold also showed marked variations in total phenols and flavonoids, as well as antioxidant and radical-scavenging activities. Ethanol was confirmed to be the best solvent for extracting both phenols and flavonoids from marigold flowers, while n-hexane was the worst. The ethanolic extracts also exhibited the highest antioxidant and radical-scavenging activities. The cultivar Xinhong had the highest phenolic and flavonoid contents and radical-scavenging activity, as well as one of the highest lutein contents and antioxidant activities.     

Differentiation between lutein monoester regioisomers and detection of lutein diesters from marigold flowers (Tagetes erecta L.) and several fruits by liquid chromatography-mass spectrometry.

Liquid chromatography-atmospheric pressure chemical ionization mass spectrometry (LC-APCIMS) was employed for the identification of eight lutein monoesters, formed by incomplete enzymatic saponification of lutein diesters of marigold (Tagetes erecta L.) by Candida rugosa lipase. Additionally, the main lutein diesters naturally occurring in marigold oleoresin were chromatographically separated and identified. The LC-MS method allows for characterization of lutein diesters occurring as minor components in several fruits; this was demonstrated by analysis of extracts of cape gooseberry (Physalis peruviana L.), kiwano (Cucumis metuliferus E. Mey. ex Naud.), and pumpkin (Cucurbita pepo L.). The assignment of the regioisomers of lutein monoesters is based on the characteristic fragmentation pattern: the most intense daughter ion generally results from the loss of the substituent (fatty acid or hydroxyl group) bound to the epsilon-ionone ring, yielding an allylic cation. The limit of detection was estimated at 0.5 microg/mL with lutein dimyristate as reference compound. This method provides a useful tool to obtain further insight into the biochemical reactions leading to lutein ester formation in plants.     

Nitrocapsanthin and nitrofucoxanthin, respective products of capsanthin and fucoxanthin reaction with peroxynitrite

The in vitro reactivity of capsanthin (1) and fucoxanthin (2) with peroxynitrite was investigated, and the reaction products produced by scavenging with peroxynitrite were analyzed. (14'Z)-Nitrocapsanthin (3) and 12-nitrocapsanthin (4) were isolated from the products of the reaction of capsanthin with peroxynitrite. Similarly, (14Z)-15-nitrofucoxanthin (5), (11Z)-11-nitrofucoxanthin (6), and (14Z,9'Z)-15-nitrofucoxanthin (7) were obtained from the reaction of peroxynitrite reaction with fucoxanthin. Capsanthin and fucoxanthin inhibited the nitration of tyrosine by peroxynitrite. Furthermore, nitrocapsanthins (3 and 4) and nitrofucoxanthins (5 and 6) exhibited an inhibitory effect on Epstein-Barr virus early antigen activation in Raji cells and an antiproliferative effect on human pancreatic carcinoma. Moreover, nitrocapsanthins (3 and 4) inhibited carcinogensis of mouse skin tumors initiated by 7,12-dimethylbenz[a]anthracene (DMBN).     

Isotopic labeling and LC-APCI-MS quantification for investigating absorption of carotenoids and phylloquinone from kale (Brassica oleracea)

The ability to study bioavailability of nutrients from foods is an important step in determining the health impact of those nutrients. This work describes a method for studying the bioavailability of nutrients from kale (Brassica oleracea var. Acephala) by labeling the nutrients with carbon-13, feeding the kale to an adult volunteer, and analyzing plasma samples for labeled nutrients. Results showed that conditions for producing atmospheric intrinsically labeled kale had no detrimental effect on plant growth. Lutein, beta-carotene, retinol, and phylloquinone were analyzed using liquid chromatography-atmospheric pressure chemical ionization mass spectrometry. Analysis of plasma samples showed that labeled lutein peaked in plasma at 11 h (0.23 microM), beta-carotene peaked at 8 (0.058 microM) and 24 h (0.062 microM), retinol peaked at 24 h (0.10 microM), and phylloquinone peaked at 7 h (3.0 nM). This method of labeling kale with (13)C was successful for producing clearly defined kinetic curves for (13)C-lutein,(13)C-beta-carotene, (13)C-retinol, and (13)C-phylloquinone.     

Kale carotenoids are unaffected by, whereas biomass production, elemental concentrations, and selenium accumulation respond to, changes in selenium fertility

Selenium (Se) is a micronutrient in mammalian nutrition and is accumulated in kale (Brassica oleracea L. var. acephala), which has high levels of lutein and beta-carotene. Selenium, lutein, and beta-carotene have important human health benefits and possess strong antioxidant properties. The objectives of this study were to determine the influence of different Se [as sodium selenate (Na(2)SeO(4)) and sodium selenite (Na(2)SeO(3))] fertility levels on (1) biomass accumulation, (2) the accumulation patterns of carotenoid pigments, and (3) elemental accumulation in the leaves of kale. Winterbor kale was greenhouse-grown using nutrient solution culture with Se treatment concentrations of 0.0, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, and 3.5 mg Se/L as Na(2)SeO(4) and 0.0, 0.5, 1.0, 1.5, 2.0, 2.5, and 3.0 mg Se/L as Na(2)SeO(3). Increases in either selenate (SeO(4)(-)(2)) or selenite (SeO(3)(-)(2)) resulted in decreases in kale leaf tissue biomass. Neither of the Se treatments had an effect on the accumulation of lutein or beta-carotene in leaf tissues. Increasing SeO(4)(-)(2) significantly increased the accumulation of kale leaf Se; however, leaf tissue Se did not significantly change over the SeO(3)(-)(2) treatments. Increases in SeO(4)(-)(2) affected the leaf tissue concentrations of P, K, Ca, Mg, S, B, Cu, Mn, and Mo, whereas SeO(3)(-)(2) only affected B and S. Growing kale in the presence of SeO(4)(-)(2) would result in the accumulation of high levels of tissue Se without affecting carotenoid concentrations.     

Simple saponification method for the quantitative determination of carotenoids in green vegetables

A simple, reliable, and gentle saponification method for the quantitative determination of carotenoids in green vegetables was developed. The method involves an extraction procedure with acetone and the selective removal of the chlorophylls and esterified fatty acids from the organic phase using a strongly basic resin (Ambersep 900 OH). Extracts from common green vegetables (beans, broccoli, green bell pepper, chive, lettuce, parsley, peas, and spinach) were analyzed by high-performance liquid chromatography (HPLC) for their content of major carotenoids before and after action of Ambersep 900 OH. The mean recovery percentages for most carotenoids [(all-E)-violaxanthin, (all-E)-lutein epoxide, (all-E)-lutein, neolutein A, and (all-E)-beta-carotene] after saponification of the vegetable extracts with Ambersep 900 OH were close to 100% (99-104%), while the mean recovery percentages of (9'Z)-neoxanthin increased to 119% and that of (all-E)-neoxanthin and neolutein B decreased to 90% and 72%, respectively.     

Glycosidic conjugates of C13 norisoprenoids, monoterpenoids, and cucurbates in Boronia megastigma (Nees)

Analysis of a methanolic extract of marc from Boronia megastigma (Nees) using LC-MS (APCI, nominal mass) provided strong evidence for the presence of both glycosides and malonyl glycosides of methyl cucurbates, C13 norisoprenoids including megastigmanes, and monoterpene alcohols. Subsequent fractionation of an extract from the marc using XAD-2 and LH 20 chromatography followed by LC-UV/MS-SPE-NMR and accurate mass LC-MS resulted in the isolation and identification of (1R,4R,5R)-3,3,5-trimethyl-4-[(1E)-3-oxobut-1-en-1-yl]cyclohexyl β-D-glucopyranoside (3-hydroxy-5,6-dihydro-β-ionone-β-D-glucopyranoside); 3,7-dimethylocta-1,5-diene-3,7-diol-3-O-β-D-glucopyranoside; and a methyl {(1R)-3-(β-D-glucopyranosyloxy)-2-[(2Z)-pent-2-en-1-yl]cyclopentyl}acetate stereoisomer (a methyl cucurbate-β-D-glucopyranoside); and provided evidence for 3,7-dimethylocta-1,5-diene-3,7-diol-3-O-(6'-O-malonyl)-β-D-glucopyranoside in boronia flowers.     

Phenolic antioxidants (hydrolyzable tannins, flavonols, and anthocyanins) identified by LC-ESI-MS and MALDI-QIT-TOF MS from Rosa chinensis flowers

Rosa chinensis (Yuejihua) is a well-known ornamental plant, and its flowers are commonly used in traditional Chinese medicine. Methanolic crude extracts of dried R. chinensis flowers were used for simultaneous determination of phenolic constituents by liquid chromatography-mass spectrometry (LC-MS) and matrix-assisted laser desorption/ionization quadrupole ion trap time-of-flight mass spectrometry (MALDI-QIT-TOF MS). A total of 36 known and unknown phenolics were identified as hydrolyzable tannins, flavonols, and anthocyanins, mainly including gallotannins (mono-, di-, or trigalloylglucopyranosides), ellagitannins, quercetin, quercetin/kaempferol mono- and diglycosides, and cyanidin/pelargonidin diglycosides. MALDI-QIT-TOF MS was applied not only to verify most phenolics isolated and identified by LC-MS but also to tentatively identify two ellagitannins (rugosins B and C) not isolated and unidentified by LC-MS. This study is the first to demonstrate the rapid and successful use of MALDI-QIT-TOF MS and LC-MS to directly and simultaneously identify phenolics in the crude extracts of R. chinensis flowers without any purification. The antioxidant activity of the crude extracts from R. chinensis flowers was also measured with three assay methods. The results showed that the phenolic antioxidants from R. chinensis flowers exhibited very strong radical scavenging effect and antioxidant power. High levels of flavonols and hydrolyzable tannins might be important bioactive principles in the dried R. chinensis flowers.     

Comparative study on antioxidant activity of lycopene (Z)-isomers in different assays

Several studies have implicated the potent antioxidant properties of lycopene. However, most of the studies used only the (all-E)-isomer. (Z)-Isomers of lycopene were found in substantial amounts in processed foods and in human tissues. In the present study, we investigated in vitro the antioxidant activity of (5Z)-, (9Z)-, and (13Z)-lycopene compared to the (all-E)-isomer. Additionally, prolycopene, the (7Z,9Z,7'Z,9'Z)-isomer found in tangerine tomatoes, was analyzed. No significant differences were found between the isomers in ferric reducing antioxidant power assay and in bleaching the radical cation of 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS), both based on ET mechanisms. In contrast, scavenging activity against peroxyl radicals generated by thermal degradation of 2,2'-azobis(2-amidinopropane) (AAPH) was higher in the (Z)-isomers. (5Z)-Lycopene was most antioxidant in scavenging lipid peroxyl radicals, evaluated by analyzing the inhibition of MbFe(III) lipid peroxidation of linoleic acid in mildly acidic conditions (pH 5.8) in a micellar environment, modeling a possible antioxidant action in the gastric compartment.     

Analysis of a model reaction system containing cysteine and (E)-2-methyl-2-butenal, (E)-2-hexenal, or mesityl oxide

Cysteine conjugates, resulting from the addition of cysteine to alpha,beta-unsaturated carbonyl compounds, are important precursors of odorant sulfur compounds in food flavors. The aim of this work was to better understand this chemistry in the light of the unexpected double addition of cysteine to two unsaturated aldehydes. These reactions were studied as a function of pH. When (E)-2-methyl-2-butenal (tiglic aldehyde, 4) was treated with cysteine in water at pH 8, the major product formed was the new compound (4R)-2-(2-[[(2R)-2-amino-2-carboxyethyl]thio]methylpropyl)-1,3-thiazolidine-4-carboxylic acid (6). Under acidic conditions (pH 1), we also observed a double addition, but the second cysteine was linked by a vinylic sulfide bond to form the previously unreported major product, (2R,2'R,E)-S,S'-(2,3-dimethyl-1-propene-1,3-diyl)bis-cysteine (7). When (E)-2-hexenal (12) was treated with cysteine under acidic conditions, the major product was the novel (4R,2' 'R)-2-[2'-(2' '-amino-2' '-carboxyethylthio)pentyl]-1,3-thiazolidine-4-carboxylic acid (13), and the formation of an vinylic sulfide compound analogous to 7 was not observed. Reduction of the acidic crude reaction mixture with NaBH(4) afforded 13 and the cysteine derivative (R)-S-[1-(2-hydroxyethyl)butyl]cysteine (14) in 14% yield. Treating (E)-2-hexenal with cysteine at pH 8 followed by NaBH(4) reduction yielded the new product (3R)-7-propylhexahydro-1,4-thiazepine-3-carboxylic acid (15). Addition of cysteine to mesityl oxide (16), at pH 8, followed by reduction with NaBH(4) furnished (R)-S-(3-hydroxy-1,1-dimethylbutyl)cysteine (3) and the new compound (3R)-hexahydro-5,7,7-trimethyl-1,4-thiazepine-3-carboxylic acid (18).     

3-Methylthiopropionic acid ethyl ester, isolated from Katsura-uri (Japanese pickling melon, Cucumis melo var. conomon), enhanced differentiation in human colon cancer cells

The fully ripened fruit of Katsura-uri Japanese pickling melon ( Cucumis melo var. conomon) has rarely been used for food because the midripened fruit is utilized for making pickles, but the fully ripened fruit is no longer valuable for pickles due to the fruit body being too soft. We have considered the utilization of the fully ripened Katsura-uri fruit that may be used for nonpickling products, particularly if the fully ripened fruit demonstrated health benefits such as anticarcinogenic properties. The phytochemical extract from the fully ripened fruit of Katsura-uri Japanese pickling melon was purified via a bioassay-guided fractionation scheme, which was based on the induction of differentiation in a RCM-1 human colon cancer cell line. On the criteria of two differentiation markers (duct formation and alkaline phosphatase activity), the most potent fraction contained a compound identified as 3-methylthiopropionic acid ethyl ester, based on GC retention time, EI-MS, (1)H NMR, and (13)C NMR spectra. Previously, the role of 3-methylthiopropionic acid ethyl ester was considered as an odor producing compound in many fruits, but this study indicates potential medical benefits of this compound.     

Enzymatic dehydrogenative polymerization of urushiols in fresh exudates from the lacquer tree, Rhus vernicifera DC

Fresh exudates from the lacquer tree, Rhus vernicifera DC, were extracted with acetone and the solution was chromatographed to isolate monomer, dimer, trimer, and oligomer fractions of urushiols. Constituents of the monomeric and dimeric fractions were then identified by two-dimensional (2D) 1H-13C heteronuclear multiple quantum coherence (HMQC) and heteronuclear multiple bond coherence (HMBC) NMR spectroscopic techniques. The results showed that the monomeric fraction contained 3-[8'Z,11'E,13'Z-pentadecatrienyl]catechol (1), 3-[8'Z,11'Z,14'-pentadecatrienyl]catechol (2), and 3-pentadecanyl]catechol (3), which was verified by HPLC analysis. The dimeric fraction contained 8'-(3' ',4' '-dihydroxy-5' '-alkenyl)phenyl-3-[9'E,11'E,13'Z-pentadecatrienyl]catechol (4), 14'-(3' ',4' '-dihydroxy-5' '-alkenyl)phenyl-3-[8'Z,10'E,12'E-pentadecatrienyl]catechol (5), 2-hydroxyl-3- or -6-alkenylphenyl ethyl ether (6), 14'-(3' ',4' '-dihydroxy-2' '-alkenyl)phenyl-3-[8'Z,10'E,12'E-pentadeca-trienyl]catechol (7), 15'-(2' '-hydroxy-3' '- or -6' '-alkenyl)phenyloxy-3-[8'Z,11'Z,13'E)-pentadecatrienyl]catechol (8), 14'-(2' ',3' '-dihydroxy-4' '-alkenyl)phenyl-3-[8'Z,10'E,12'E-pentadecantrienyl]catechol (9), 1,1',2,2'-tetrahydroxy-6,6'-dialkenyl-4,3'-biphenyl (10), 1,1',2,2'-tetrahydroxy-6,6'-dialkenyl-4,4'-biphenyl (11), 1,1',2,2'-tetrahydroxy-6,6'-dialkenyl-5,4'-biphenyl (12), and 1,2,1'-trihydroxy-6,6'-dialkenyldibenzofuran (13) as constituents. In addition, dimeric ethers and peroxides, such as compounds 14 and 15, were produced by autoxidation of monomeric urushiols in atmospheric air. The possible reaction mechanisms for the dehydrogenative polymerization of urushiols by Rhus laccase present in the fresh raw exudates under the atmospheric oxygen are discussed on the basis of structures identified. This is of primary importance because the use of the urushi exudates as coating materials does not involve organic solvents and is an environmentally friendly process.     

Nickel peroxide induced oxidation of canthaxanthin.

Treatment of canthaxanthin (beta,beta-carotene-4,4'-dione) (1) with nickel peroxide in dichloromethane yielded a series of cleavage products, i.e., 4-oxo-beta-ionone (2), (7E, 9E)-4-oxo-beta-apo-11-carotenal (3a), (7E, 9Z)-4-oxo-beta-apo-11-carotenal (3b), 4-oxo-beta-apo-13-carotenone (4), 4-oxo-beta-apo-14'-carotenal (5), 4-oxo-beta-apo-12'-carotenal (6), and 4-oxo-beta-apo-10'-carotenal (7). In addition, oxidized canthaxanthin derivatives, i.e., isomeric ketols all-trans-9, 10-dihydro-9-hydroxy-10-oxo-canthaxanthin (8a), (9'Z)-9, 10-dihydro-9-hydroxy-10-oxo-canthaxanthin (8b), and (13'Z)-9, 10-dihydro-9-hydroxy-10-oxo-canthaxanthin (8c) were obtained together with the tentatively identified (9'Z)-canthaxanthin-20-al (9). Structure elucidation of the reaction products was achieved by mass spectrometry and two-dimensional NMR spectroscopy.     

Ent-2'-epi-Orobanchol and its acetate, as germination stimulants for Striga gesnerioides seeds isolated from cowpea and red clover

Striga gesnerioides is a root parasitic weed of economic significance to cowpea (Vigna unguiculata) crops in Western Africa. Seeds of the parasite germinate in response to cowpea root exudates. Germination stimulants for the seeds were isolated from the hydroponic culture filtrate of cowpea, and their structures were unambiguously determined as (-)-(3aR,4R,8bR,2'R)-ent-2'-epi-orobanchol and (+)-(3aR,4R,8bR,2'R)-ent-2'-epi-orobanchyl acetate, on the basis of mass, CD, and (1)H NMR spectra; optical rotatory power; and chromatographic behavior on HPLC. The alcohol was first isolated and identified from the cowpea root exudates, and the acetate may be the same compound that had been previously isolated from the exudates and designated as alectrol. Identity of the stimulants produced by cowpea to those produced by red clover (Trifolium pratense) was confirmed.     

Carotenoid, chlorophyll, and chlorophyll-derived compounds in grapes and port wines

Carotenoids and chlorophyll-derived compounds in grapes and Port wines were investigated by HPLC-DAD and HPLC-DAD-MS (ESP+) analysis. A total of 13 carotenoid and chlorophyll-derived compounds are formally reported in grapes, 3 are identified for the first time, pheophytins a and b and (13Z)-beta-carotene, and 3 others remain unknown. In Port wines 19 compounds with carotenoid or chlorophyll-like structures are present, 8 still unidentified. The young wines showed higher total carotenoid content and chlorophyll-like compounds compared to aged Ports, with lutein and beta-carotene as major carotenoids. Among samples analyzed of monovarietal Vitis vinifera L. cultivar wines produced with the five most important Douro varieties, Tinta Roriz contained the highest levels of carotenoids and Touriga Franca the lowest. The forced-aging study indicated that lutein was more sensitive to temperature than beta-carotene. Additionally, aged wines showed higher ratios of beta-carotene/lutein concentrations compared to new Ports. Rates of degradation of chlorophyll derivative compounds were higher than those for carotene and lutein.     

HPLC determination of chlorophyll and carotenoid pigments in processed green pea cultivars (Pisum sativum L.)

Chlorophyll and carotenoid pigments from six cultivars of processed green peas (Avola, Tristar, Rampart, Turon, Bella, and Greenshaft) were extracted with 100% acetone and analyzed by reversed-phase HPLC. A total of 17 pigments were identified in the pea cultivars including 8 xanthophylls ((all-E)-neoxanthin, (9'Z)-neoxanthin, (all-E)-violaxanthin, neochrome, (all-E)-lutein epoxide, (all-E)-lutein, neolutein B, neolutein A), 4 chlorophyll b related compounds (chlorophyll b derivative, chlorophyll b, chlorophyll b', and pheophytin b), 4 chlorophyll a related compounds (chlorophyll a derivative, chlorophyll a, chlorophyll a', and pheophytin a), and (all-E)-beta-carotene. The efficiency of different extraction procedures using 100% acetone showed that initial extraction followed by three reextractions without holding time between gave a higher extraction yield than no reextraction and 30 or 60 min holding time. All six cultivars contained the same pigments, but the concentration of each pigment varied significantly. On average of the two years, the chlorophyll a concentration varied from 4800 to 7300 microg/100 g fresh weight, the chlorophyll b concentration from 2100 to 2800 microg/100 g fresh weight, the (all-E)-lutein concentration from 1200 to 1900 microg/100 g fresh weight, and the (all-E)-beta-carotene concentration from 300 to 490 microg/100 g fresh weight in the processed pea cultivars. These differences in pigment concentration between the investigated cultivars are discussed in relation to maturity, product color and nutritional quality.     

Chromatographic separation and in vitro activity of sorgoleone congeners from the roots of sorghum bicolor

Sorgoleone, 2-hydroxy-5-methoxy-3-[(8'Z,11'Z)-8',11',14'-pentadecatriene]-p-benzoquinone (1), and its corresponding hydroquinone are the major components of the root exudate of Sorghum bicolor. The name sorgoleone includes minor analogues differing in the length or degree of unsaturation of the 3-alkyl side chain. These compounds are known to be phytotoxic, probably through inhibition of photosystem II (PSII) driven oxygen evolution, as previously demonstrated for 1. Isolation of these sorgoleone congeners was achieved by C(8) column chromatography and argentation thin-layer chromatography, and the purified compounds were structurally characterized. The abilities of the minor sorgoleones to inhibit PSII were similar to that of the major compound, suggesting that all of these sorgoleone congeners contribute to the overall allelopathy of sorghum.     

Volatile constituents and key odorants in leaves, buds, flowers, and fruits of Laurus nobilis L

The volatiles of fresh leaves, buds, flowers, and fruits from bay (Laurus nolilis L.) were isolated by solvent extraction and analyzed by capillary gas chromatography-mass spectrometry. Their odor quality was characterized by gas chomatography-olfactometry-mass spectrometry (HRGC-O-MS) and aroma extract dilution analysis (AEDA). In fresh bay leaves 1,8-cineole was the major component, together with alpha-terpinyl acetate, sabinene, alpha-pinene, beta-pinene, beta-elemene, alpha-terpineol, linalool, and eugenol. Besides 1,8-cineole and the pinenes, the main components in flowers were alpha-eudesmol, beta-elemene, and beta-caryophyllene, in fruits (E)-beta-ocimene and biclyclogermacrene, and in buds (E)-beta-ocimene and germacrene D. The aliphatic ocimenes and farnesenes were absent in leaves. By using HRGC-O-MS 21 odor compounds were identified in fresh leaves. Application of AEDA revealed (Z)-3-hexenal (fresh green), 1,8-cineole (eucalyptus), linalool (flowery), eugenol (clove), (E)-isoeugenol (flowery), and an unidentified compound (black pepper) with the highest flavor dilution factors. Differences between buds, flowers, fruits, and leaves with regard to the identified odor compounds are presented.