Biogenetic studies in Syringa vulgaris L.: synthesis and bioconversion of deuterium-labeled precursors into lilac aldehydes and lilac alcohols

Syringa vulgaris L. inflorescences were fed with aqueous solutions of regioselectively deuterated compounds assumed to be precursors of lilac aldehyde and lilac alcohol, respectively. Volatiles were extracted by stir bar sorptive extraction (SBSE) and analyzed using enantioselective multidimensional gas chromatography/mass spectrometry (enantio-MDGC/MS); deuterium-labeled lilac aldehydes and lilac alcohols were separated from unlabeled stereoisomers on a fused silica capillary column, coated with heptakis(2,3-di-O-methyl-6-O-tert-butyldimethylsilyl)-beta-cyclodextrin (DIME-beta-CD) (30%) in SE 52 (70%), as the chiral stationary phase. Feeding experiments with [5,5-(2)H(2)]mevalonic acid lactone 22 and [5,5-(2)H(2)]deoxy-d-xylose 23 indicate that the novel mevalonate independent 1-deoxy-d-xylose 5-phosphate/2C-methyl-d-erythritol 4-phosphate pathway is the dominant metabolic route for biosynthesis in lilac flowers. Additionally, bioconversion of deuterium-labeled d(5)-(R/S)-linalool 3, d(6)-(R)-linalool 21, d(5)-(R/S)-8-hydroxylinalool 6, d(5)-(R/S)-8-oxolinalool 7, d(5)-lilac aldehydes 8-11 and d(5)-lilac alcohols 12-15 into lilac during in vivo feeding experiments was investigated and the metabolic pathway is discussed. Incubation of petals with an aqueous solution of deuterated d(5)-(R/S)-linalool 3 indicates an autonomic terpene biosynthesis of lilac flavor compounds in the flower petals of lilac.     

Enantioselective analysis of secondary alcohols and their esters in purple and yellow passion fruits

The enantiomeric compositions of the acetates, butanoates, hexanoates, and octanoates of the secondary alcohols 2-pentanol, 2-heptanol, and 2-nonanol were determined in yellow (Passiflora edulis f. flavicarpa) and purple (Passiflora edulis Sims) passion fruits. The compounds were isolated by means of simultaneous distillation-extraction. Enantiodifferentiation was performed via multidimensional gas chromatography using heptakis(2,3-di-O-methyl-6-O-tert-butyldimethylsilyl)-beta-cyclodextrin as chiral stationary phase. The series of homologous 2-alkyl esters, which are typical constituents of purple passion fruits, were shown to be present as nearly optically pure (R)-enantiomers. The proportions of the (S)-enantiomers varied in different batches and were dependent on the alcohol moieties of the esters. For minor amounts of esters detected in yellow fruits, the (R)-enantiomers were also dominating. However, the enantiomeric excesses were significantly lower than in the purple variety. Enantioselective analysis of the free alcohols revealed that 2-heptanol exhibited opposite configurations in purple and yellow passion fruits. A similar phenomenon was observed for 2-pentanol, which was present in the yellow fruits as a nearly racemic mixture. Data determined in extracts obtained by other techniques (liquid-liquid extraction, vacuum headspace technique) showed that the isolation procedure had no significant impact on the enantiomeric ratios.     

Isolation and structure of whiskey polyphenols produced by oxidation of oak wood ellagitannins

Three new phenolic compounds named whiskey tannins A and B and carboxyl ellagic acid were isolated from commercial Japanese whiskey, along with gallic acid, ellagic acid, brevifolin carboxylic acid, three galloyl glucoses, a galloyl ester of phenolic glucoside, 2,3-(S)-hexahydroxydiphenoylglucose, and castacrenin B. Whiskey tannins A and B were oxidation products of a major oak wood ellagitannin, castalagin, in which the pyrogallol ring at the glucose C-1 position of castalagin was oxidized to a cyclopentenone moiety. These tannins originated from ellagitannins contained in the oak wood used for barrel production; however, the original oak wood ellagitannins were not detected in the whiskey. To examine whether the whiskey tannins were produced during the charring process of barrel production, pyrolysis products of castalagin were investigated. Dehydrocastalagin and a new phenolcarboxylic acid trislactone having an isocoumarin structure were isolated, along with castacrenin F and ellagic acid. However, whiskey tannins were not detected in the products.     

Enantioselective analysis of methyl-branched alcohols and acids in rhubarb (Rheum rhabarbarum L.) stalks

The enantiomeric compositions of 2-methylbutanol (1), 4-methylhexanol (2), 2-methylbutanoic acid (3), and 4-methylhexanoic acid (4) present in rhubarb (Rheum rhabarbarum L.) stalks were determined. Enantiodifferentiation was achieved via multidimensional gas chromatography using heptakis(2,3,6-tri-O-ethyl)-beta-cyclodextrin as a chiral stationary phase. For all compounds the enantiomeric ratios were in favor of the (R)-enantiomers. The alcohols (1 and 2) exhibited generally high excesses of the (R)-enantiomers, the ratios varying slightly from batch to batch. For the acid (3) a rather narrow range averaging 65% (R):35% (S) was observed. The procedure applied to isolate the volatiles (vacuum headspace technique, simultaneous distillation--extraction, liquid--liquid extraction) had no significant impact on the enantiomeric ratios. The study describes for the first time a plant used as food material in which 2-methyl-branched volatiles are not nearly exclusively present as (S)-enantiomers. This information enlarges the current regulatory knowledge regarding the classification of these important flavor compounds as "natural" on the basis of their enantiomeric ratios.     

Influence of temperature, modified atmosphere packaging, and heat treatment on aroma compounds in broccoli

The aroma compounds in broccoli stored in different modified atmospheres were studied. The packaging materials used were oriented polypropylene (OPP), poly(vinyl chloride) (PVC), and low-density polyethylene (LDPE) containing an ethylene-absorbing sachet. All samples were stored for either 1 week at a constant temperature of 10 degrees C or for 3 days at 4 degrees C, followed by 4 days at 10 degrees C. The atmospheres that developed inside the packaging materials differed significantly. The broccoli samples were analyzed raw and after cooking, with regard to volatile compounds, using gas-phase (headspace) extraction followed by gas chromatography-mass spectrometry (GC-MS) and GC-olfactometry. Dimethyl sulfide (DMS), dimethyl disulfide (DMDS), dimethyl trisulfide (DMTS), hexanal, 3-cis-hexen-1-ol, nonanal, ethanol, and a group of thiocyanates were selected for a detailed study because these compounds cause off-odor and can be used as indicators of stress. Significant differences were found in the aroma profiles of the broccoli samples relative to the packaging materials used for storage. Storage in OPP (14% O(2), 10.5% CO(2)) resulted in most of the off-odors, while storage in LDPE (6% O(2), 7% CO(2)) and PVC (17.9% O(2), 4% CO(2)) was found to maintain the concentration of DMS, DMDS, and DMTS during storage. Heat treatment of the broccoli increased the content of aroma compounds as well as the number of compounds containing sulfur.     

Characterization of volatile compounds in chilled cod (Gadus morhua) fillets by gas chromatography and detection of quality indicators by an electronic nose

Volatile compounds in cod fillets packed in Styrofoam boxes were analyzed during chilled storage (0.5 degrees C) by gas chromatography (GC)-mass spectrometry and GC-olfactometry to screen potential quality indicators present in concentrations high enough for detection by an electronic nose. Photobacterium phosphoreum dominated the spoilage bacteria on day 12 when the fillets were rejected by sensory analysis. Ketones, mainly 3-hydroxy-2-butanone, were detected in the highest level (33%) at sensory rejection, followed by amines (TMA) (29%), alcohols (15%), acids (4%), aldehydes (3%), and a low level of esters (<1%). The electronic nose's CO sensor showed an increasing response with storage time coinciding with the production of ethanol and 2-methyl-1-propanol that were produced early in the storage, followed by the production of 3-methyl-1-butanol, 3-methyl-butanal, 2,3-butandiol, and ethyl acetate. Lipid-derived aldehydes, like hexanal and decanal, were detected in similar levels throughout the storage time and contributed to the overall sweet odors of cod fillets in combination with other carbonyls (3-hydroxy-2-butanone, acetaldehyde, 2-butanone, 3-pentanone, and 6-methyl-5-heptene-2-one).     

Sensory activity,chemical structure,and synthesis of Maillard generated bitter-tasting 1-oxo-2,3-dihydro-1H-indolizinium-6-olates

Thermal treatment of aqueous solutions of xylose, rhamnose, and l-alanine led to a rapid development of a bitter taste of the reaction mixture. To characterize the key compounds causing this bitter taste, the recently developed taste dilution analysis (TDA), which is based on the determination of the taste threshold of reaction products in serial dilutions of HPLC fractions, was performed to locate the most intense taste compounds in the complex mixture of Maillard reaction products. By application of this TDA, 26 fractions were obtained, among which seven fractions were evaluated with a high taste impact. LC/MS and NMR spectroscopy as well as synthetic experiments revealed the 1-oxo-2,3-dihydro-1H-indolizinium-6-olates 1-5 as the key compounds contributing the most to the intense bitter taste of the Maillard mixture. Calculation of the taste impact of these compounds based on a dose/activity relationship indicated that these five compounds already accounted for 56.8% of the overall bitterness of the Maillard mixture, thus demonstrating this class of 1-oxo-2,3-dihydro-1H-indolizinium-6-olates as the key bitter compounds. First synthetic studies on the relationship between the chemical structure and the human psychobiological activity of 1-oxo-2,3-dihydro-1H-indolizinium-6-olates revealed that substitution of the furan rings of 1 by 5-methylfuryl moieties (compounds 3-5) or by 5-(hydroxymethyl)furyl groups (compound 6) led to a significant increase of the bitter threshold. In contrast, the substitution of the oxygen atoms in the furan rings of 1 by sulfur atoms induced a significant decrease of the detection threshold of the 1-oxo-2,3-dihydro-1H-indolizinium-6-olate; for example, the thiophene derivative 7 showed the extraordinarily low bitter detection threshold of 6.3 x 10(-5) mmol/kg (water).     

Characterization of the key odorants in raw Italian hazelnuts ( Corylus avellana L. var. Tonda Romana) and roasted hazelnut paste by means of molecular sensory science

The concentrations of 19 odorants, recently characterized by GC-olfactometry and aroma extract dilution analysis as the most odor-active compounds in raw hazelnuts, were quantitated by stable isotope dilution assays (SIDA). Calculation of odor activity values (OAV) on the basis of odor thresholds in oil revealed high OAVs, in particular for linalool, 5-methyl-4-heptanone, 2-methoxy-3,5-dimethylpyrazine, and 4-methylphenol. A model mixture in sunflower oil containing the 13 odorants showing OAVs above 1 in their natural concentrations resulted in a good similarity compared to the overall nut-like, fruity aroma of the raw hazelnuts. Quantitation of the 25 most odor-active compounds in roasted hazelnut paste by SIDA showed clear changes in the concentrations of most odorants, and formation of new odor-active compounds induced by the roasting process was observed. The highest OAVs were calculated for 3-methylbutanal (malty), 2,3-pentanedione (buttery), 2-acetyl-1-pyrroline (popcorn), and (Z)-2-nonenal (fatty), followed by dimethyl trisulfide, 2-furfurylthiol, 2,3-butanedione, and 4-hydroxy-2,5-dimethyl-3(2H)-furanone. The aroma of a model mixture containing the 19 odorants with OAVs above 1 in their actual concentrations in the roasted nut material was judged to elicit a very good similarity to the popcorn-like, coffee-like, and sweet-smoky aroma of the roasted hazelnut paste. New SIDAs were developed for the quantitation of 5-methyl-4-heptanone, 5-methyl-(E)-2-hepten-4-one, 2-thenylthiol, and 3,5,5-trimethyl-2(5H)-furanone.     

Structure elucidation, enantioselective analysis, and biogenesis of nerol oxide in Pelargonium species.

A novel enantioselective synthesis of nerol oxide (3, 6-dihydro-4-methyl-2-(2-methyl-1-propenyl)-2H-pyran) was used for the determination of the absolute configuration at C-2. The order of elution of the enantiomers on octakis-(2, 3-di-O-butyryl-6-O-tert-butyldimethylsilyl)-gamma-cyclodextrin in OV 1701-vi as the chiral stationary phase in enantioselective GC was determined as (2R) before (2S). Enantioselective multidimensional GC/MS (enantio-MDGC/MS) was used for the determination of the enantiomeric ratios of nerol oxide in different geranium oils. As a result, in all investigated oils nerol oxide occurs as a racemate. The biogenesis of nerol oxide in Pelargonium species was investigated by feeding experiments using deuterium-labeled neryl glucoside as the precursor. The Pelargonium plants were able to convert the fed precursor into racemic nerol oxide, which has to be considered as a "natural racemate".     

Instrumental and sensory characterization of heat-induced odorants in aseptically packaged soy milk

Predominant heat-induced odorants generated in soy milk by ultrahigh-temperature (UHT) processing were evaluated by sensory and instrumental techniques. Soy milks processed by UHT (143 degrees C/14 s, 143 degrees C/59 s, 154 degrees C/29 s) were compared to a control soy milk (90 degrees C/10 min) after 0, 1, and 7 days of storage (4.4 +/- 1 degrees C). Dynamic headspace dilution analysis (DHDA) and solvent-assisted flavor evaporation (SAFE) in conjunction with GC-olfactometry (GCO)/aroma extract dilution techniques and GC-MS were used to identify and quantify major aroma-active compounds. Sensory results revealed that intensities of overall aroma and sulfur and sweet aromatic flavors were affected by the processing conditions. Odorants mainly responsible for the changes in sulfur perception were methional, methanethiol, and dimethyl sulfide. Increases in 2-acetyl-1-pyrroline, 2-acetyl-thiazole, and 2-acetyl-2-thiazoline intensities were associated with roasted aromas. A marginal increase in intensity of sweet aromatic flavor could be explained by increases in 2,3-butanedione, 3-hydroxy-2-butanone, beta-damascenone, and 2- and 3-methylbutanal. Predominant lipid-derived odorants, including (E,E)-2,4-nonadienal, (E,E)-2,4-decadienal, (E,Z)-2,4-decadienal, (E)-2-nonenal, (E)-2-octenal, 1-octen-3-one, 1-octen-3-ol, and (E,Z)-2,6-nonadienal, were affected by processing conditions. Intensities of overall aroma and sulfur notes in soy milk decreased during storage, whereas other sensory attributes did not change. Color changes, evaluated by using a Chroma-meter, indicated all UHT heating conditions used in this study generated a more yellow and saturated color in soy milk in comparison to the control soy milk.     

Thermal decomposition of specifically phosphorylated D-glucoses and their role in the control of the Maillard reaction

One of the main shortcomings of the information available on the Maillard reaction is the lack of knowledge to control the different pathways, especially when it is desired to direct the reaction away from the formation of carcinogenic and other toxic substances to more aroma and color generation. The use of specifically phosphorylated sugars may impart some elements of control over the aroma profile generated by the Maillard reaction. Thermal decomposition of 1- and 6-phosphorylated glucoses was studied in the presence and absence of ammonia and selected amino acids through pyrolysis/gas chromatography/mass spectrometry using nonpolar PLOT and medium polar DB-1 columns. The analysis of the data has indicated that glucose-1-phosphate relative to glucose undergoes more extensive phosphate-catalyzed ring opening followed by formation of sugar-derived reactive intermediates as was indicated by a 9-fold increase in the amount of trimethylpyrazine and a 5-fold increase in the amount of 2,3-dimethylpyrazine, when pyrolyzed in the presence of glycine. In addition, glucose-1-phosphate alone generated a 6-fold excess of acetol as compared to glucose. On the other hand, glucose-6-phosphate enhanced retro-aldol reactions initiated from a C-6 hydroxyl group and increased the subsequent formation of furfural and 4-cyclopentene-1,3-dione. Furthermore, it also stabilized 1- and 3-deoxyglucosone intermediates and enhanced the formation of six carbon atom-containing Maillard products derived directly from them through elimination reactions such as 1,6-dimethyl-2,4-dihydroxy-3-(2H)-furanone (acetylformoin), 2-acetylpyrrole, 5-methylfurfural, 5-hydroxymethylfurfural, and 4-hydroxy-2,5-dimethyl-3-(2H)-furanone (Furaneol), due to the enhanced leaving group ability of the phosphate moiety at the C-6 carbon. However, Maillard products generated through the nucleophilic action of the C-6 hydroxyl group such as 2-acetylfuran and 2,3-dihydro-3,5-dihydroxy-4H-pyran-4-one were retarded, due to the blocked nucleophilic atom at C-6.     

Influence of pyrolytic and aqueous-phase reactions on the mechanism of formation of Maillard products

The influence of the reaction phase on the mechanism of formation of Maillard products was studied by comparison of (13)C-label incorporation patterns of the common products formed in model systems consisting of labeled glycine and D-glucoses subjected to both pyrolysis and heating in aqueous solutions. Pyrolysis experiments were performed at 250 degrees C for 20 s, and aqueous model systems were heated in sealed vials for 3 h at 120 degrees C followed by GC/MS analysis. Label incorporation patterns of the following compounds were analyzed: cyclotene, furanmethanol, acetylpyrrole, 5-methyl-pyrrole, trimethylpyrazine, acetic acid, 3-hydroxy-2-butanone, 2,3-butanedione, and 2-methyl-4, 5-dihydro-3(2H)-furanone. Although pyrolysis reaction produced higher number of products, however, the major pathways of formation of variety of important Maillard products followed the same mechanism under both pyrolytic and aqueous systems. Furthermore, contrary to literature speculations, 2-methyl-4, 5-dihydro-3(2H)-furanone was shown to be formed by ring contraction of 2,3-dihydro-3,5-dihydroxy-6-methyl-4(H)-pyran-4-one, through benzilic acid rearrangement, followed by decarboxylation.     

Characterization of the aroma of a meatlike process flavoring from soybean-based enzyme-hydrolyzed vegetable protein

Defatted soybean meal was converted into enzyme-hydrolyzed vegetable protein (E-HVP) using the proteolytic enzyme Flavorzyme. Total free amino acids increased by 40-fold after enzyme hydrolysis, with leucine being the most abundant, followed by phenylalanine, lysine, glutamine/glutamic acid, and alanine. Volatile components from a meatlike process flavoring made from E-HVP were isolated by direct solvent extraction (DSE)-high vacuum transfer (HVT), dynamic headspace sampling and static headspace sampling and analyzed by gas chromatography (GC)-mass spectrometry and GC-olfactometry. Aroma extract dilution analysis was used to establish a flavor dilution chromatogram of the DSE-HVT extract. Results of these complementary techniques indicated the importance of odorants of high (hydrogen sulfide and methanethiol), intermediate (2-methyl-3-furanthiol, 3-mercapto-2-pentanone, 2-furanmethanethiol, and 3-(methylthiol)propanal) and low volatility (maltol and Furaneol) in the overall aroma of the meatlike process flavoring.     

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).     

Aging of whiskey increases the potentiation of GABA(A) receptor response

It is known that the target of most mood-defining compounds such as ethanol is an ionotropic gamma-aminobutyric acid receptor (GABA(A) receptor). The potentiation of the response of these inhibitory neurotransmitter receptors induces anxiolytic, sedative, and anesthetic activities in the human brain. Because both extracts of whiskey by pentane and fragrant components in whiskey potentiate the GABA(A) receptor-mediated response, GABA(A) receptors were expressed in Xenopus oocyte by injecting cRNAs prepared from the cloned cDNA for the alpha(1) and beta(1) subunits of the bovine receptors in order to study the effects of whiskey itself on the GABA(A) receptor-mediated response. Whiskey itself also potentiated the electrical responses of GABA(A) receptors generally more than ethanol at the same concentration as that of the whiskey. The potentiation of the GABA(A) receptor-mediated response increased with the aging period of the whiskey. Inhalation of whiskey to mice increased the sleeping time induced by pentobarbital more than that of the same concentration of ethanol as the whiskey. These results suggest that not only ethanol but also minor components in whiskey play an important role in the potentiation of GABA(A) receptor-mediated response and possibly the sedative effect of whiskey. Although the minor components are present in extremely small quantities compared with ethanol in alcoholic beverages, they may modulate the mood or consciousness of humans through the potentiation of the GABA(A) receptor response after absorption into the brain, because these hydrophobic compounds are easily absorbed into the brain across the blood-brain barrier and are several thousands times as potent as ethanol in the potentiation of the GABA(A) receptor-mediated response.     

Sugar fragmentation in the maillard reaction cascade: isotope labeling studies on the formation of acetic acid by a hydrolytic beta-dicarbonyl cleavage mechanism

The formation of acetic acid was elucidated based on volatile reaction products and related nonvolatile key intermediates. The origin and yield of acetic acid were determined under well-controlled conditions (90-120 degrees C, pH 6-8). Experiments with various 13C-labeled glucose isotopomers in the presence of glycine revealed all six carbon atoms being incorporated into acetic acid: C-1/C-2 ( approximately 70%), C-3/C-4 ( approximately 10%), and C-5/C-6 (approximately 20%). Acetic acid is a good marker of the 2,3-enolization pathway since it is almost exclusively formed from 1-deoxy-2,3-diulose intermediates. Depending on the pH, the acetic acid conversion yield reached 85 mol % when using 1-deoxy-2,3-hexodiulose (1) as a precursor. Hydrolytic beta-dicarbonyl cleavage of 1-deoxy-2,4-hexodiuloses was shown to be the major pathway leading to acetic acid from glucose without the intermediacy of any oxidizing agents. The presence of key intermediates was corroborated for the first time, i.e., tetroses and 2-hydroxy-3-oxobutanal, a tautomer of 1-hydroxy-2,3-butanedione, also referred to as 1-deoxy-2,3-tetrodiulose. The hydrolytic beta-dicarbonyl cleavage represents a general pathway to organic acids, which corresponds to an acyloin cleavage or a retro-Claisen type reaction. Although alternative mechanisms must exist, the frequently reported hydrolytic alpha-dicarbonyl cleavage of 1 can be ruled out as a pathway forming carboxylic acids.     

Isolation, characterization, and antioxidant activity of bromophenols of the marine red alga Rhodomela confervoides

A total of 19 naturally occurring bromophenols, with six new and 13 known structures, were isolated and identified from the methanolic extract of the marine red alga Rhodomela confervoides. The new compounds were identified by spectroscopic methods as 3,4-dibromo-5-((methylsulfonyl)methyl)benzene-1,2-diol (1), 3,4-dibromo-5-((2,3-dihydroxypropoxy)methyl)benzene-1,2-diol (2), 5-(aminomethyl)-3,4-dibromobenzene-1,2-diol (3), 2-(2,3-dibromo-4,5-dihydroxyphenyl)acetic acid (4), 2-methoxy-3-bromo-5-hydroxymethylphenol (5), and (E)-4-(2-bromo-4,5-dihydroxyphenyl)but-3-en-2-one (6). Each compound was evaluated for free radical scavenging activity against DPPH (α,α-diphenyl-β-dipicrylhydrazyl) and ABTS [2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid)diammonium salt] radicals. Most of them exhibited potent activities stronger than or comparable to the positive controls butylated hydroxytoluene (BHT) and ascorbic acid. The results from this study suggest that R. confervoides is an excellent source of natural antioxidants, and inclusion of these antioxidant-rich algal components would likely help prevent the oxidative deterioration of food.     

Activity of 1,4-benzoquinones against formosan subterranean termites (Coptotermes formosanus)

A large number of naturally occurring and synthetic benzoquinones were evaluated for activity against the Formosan subterranean termite, Coptotermes formosanus, with potential use in termite control. Among these bioactive naturally occurring benzoquinones are 2-methyl-5-isopropyl-1,4-benzoquinone, 2-methoxy-6-pentyl-1,4-benzoquinone, 2,3-dimethoxy-5-methyl-6-(3-methyl-2-butenyl)-1,4-benzoquinone, 2,3-dimethoxy-5,6-dimethyl-1,4-benzoquinone, and 2,3-dichloro-5,6-dimethyl-1,4-benzoquinone. All five of these compounds demonstrated 100% mortality against C. formosanus by day 11 at a concentration of 1% (wt/wt) or less. In general, benzoquinones with one or two hydrophobic groups on the 5 and/or 6 positions of the quinone ring along with one or two group(s) on the opposite side of the ring, at the 2 and/or 3 position, led to high rates of mortality against C. formosanus. Quantitative structure-activity relationship (QSAR) studies showed no correlation between lipophilicity (calculated log P) and mortality for the entire group of nonhalogenated benzoquinones. A correlation was observed between C-6 chain length and day 3 percent mortality for 2,3-dimethoxy-5-methyl-6-substituted aliphatic benzoquinones where short chain lengths resulted in higher mortality.     

Role of the solvent glycerol in the Maillard reaction of d-fructose and l-alanine

The volatiles in the headspace above a solution of [(13)C(6)]fructose and alanine in glycerol/water, heated in a closed vial at 130 degrees C for 2 h, were analyzed by solid-phase microextraction in tandem with GC-MS. Carbonyl compounds and pyrazines were among the detected components. The examination of their mass spectra showed that most of the 1-hydroxy-2-propanone and 2,3-pentanedione were (13)C(3)-labeled, the majority of the 2-methylpyrazine and 2-ethyl-3-methylpyrazine were (13)C(5)-labeled, and 2,5-dimethylpyrazine and 3-ethyl-2,5-dimethylpyrazine were mainly (13)C(6)-labeled. This is in agreement with the literature, and corresponds to the incorporation of fructose carbons, and in the case of 2,3-pentanedione, 2-ethyl-3-methylpyrazine, and 3-ethyl-2,5-dimethylpyrazine alanine carbons, into the molecules. However, minority fractions of 1-hydroxy-2-propanone (10%) and 2,3-pentanedione (14%) were found unlabeled, 2-methylpyrazine (10%) and 2-ethyl-3-methylpyrazine (11%) only doubly labeled, and 2,5-dimethylpyrazine (20%) and 3-ethyl-2,5-dimethylpyrazine (27%) only triply labeled, suggesting they contain carbons originating from the solvent glycerol. This could be confirmed by reaction of fructose and alanine in [(13)C(3)]glycerol/water, which produced the same volatiles, with 11-27% existent in their (13)C(3)-labeled form. Hence, glycerol participated not only as a solvent but also as a precursor in the reaction.     

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).