Sorption behavior of volatile phenols at the oak wood/wine interface in a model system

The sorption in a model system of aroma compounds of enological interest (mixture of the eight derivatives from guaiacol, 4-ethylphenol, and whiskylactone) onto wood was investigated to assess the influence of wood on the concentration of these volatiles during the aging of wine. To evaluate the influence of the solubility of aroma compounds in sorption phenomena, this parameter was determined for each volatile compound in model wine at 10 and 25 degrees C. The solubility is significantly higher in the model wine than in water and remains constant in the range of temperatures studied, except for guaiacol and vanillin. Kinetic and equilibrium sorptions were investigated. Sorption kinetics showed that the sorption equilibrium for all aroma compounds was reached after 6-7 days. From the study of the individual sorption isotherms, two distinct kinds of sorption behavior were observed depending on the presence or not of an ethylenic para substituent conjugated to the phenyl ring. K(ww) partition coefficients between the wood and the model wine were determined, which exhibited an unusual positive variation with temperature.     

Tissue distribution, elimination, and metabolism of sodium [36Cl]perchlorate in lactating goats

Perchlorate has contaminated water sources throughout the United States but particularly in the arid Southwest, an area containing large numbers of people and few water sources. Recent studies have demonstrated that perchlorate is present in alfalfa and that perchlorate is secreted into the milk of cows. Studies in lactating cows have indicated that only a small portion of a perchlorate dose could be accounted for by elimination in milk, feces, or urine. It was hypothesized that the remainder of the perchlorate dose was excreted as chloride ion. The purpose of this study was to determine the fate and disposition of (36)Cl-perchlorate in lactating dairy goats. Two goats (60 kg) were each orally administered 3.5 mg (16.5 muCi) of (36)Cl-perchlorate, a dose selected to approximate environmental perchlorate exposure but that would allow for adequate detection of radioactive residues after a 72 h withdrawal period. Blood, milk, urine, and feces were collected incrementally until slaughter at 72 h. Total radioactive residue (TRR) and perchlorate concentrations were measured using radiochemical techniques and liquid chromatography mass spectrometry (LC-MS-MS). Peak blood levels of TRR occurred at 12 h ( approximately 195 ppb) postdose; peak levels of parent perchlorate, however, occurred after only 2 h, suggesting that perchlorate metabolism occurred rapidly in the rumen. The serum half-life of perchlorate was estimated to be 2.3 h. After 24 h, perchlorate was not detectable in blood serum but TRR remained elevated (160 ppb) through 72 h. Milk perchlorate levels peaked at 12 h (155 ppb) and were no longer detectable by 36 h, even though TRRs were readily detected through 72 h. Perchlorate was not detectable in skeletal muscle or liver at slaughter (72 h). Chlorite and chlorate were not detected in any matrix. The only radioactive residues observed were perchlorate and chloride ion. Bioavailability of perchlorate was poor in lactating goats, but the perchlorate that was absorbed intact was rapidly eliminated in milk and urine.     

Accumulation and extractability of grape skin tannins and anthocyanins at different advanced physiological stages

Quantitative and qualitative modifications of tannins and anthocyanins in grape skin were investigated at different dates of harvest, from berries sorted on the basis of their density. Free anthocyanins accumulated until 170 g/L of sugars in pulp before undergoing a slight decrease. Changes in anthocyanin composition were observed with increasing sugar levels in the pulp that reflected structural differences between classes of anthocyanins. The proportion of methoxylated anthocyanins continued to increase in the skin as sugar accumulated while the proportion of coumaroylated anthocyanins initially increased (up to 200 g/L of sugars in the pulp) and then rapidly decreased. In comparison, no major quantitative nor qualitative change was observed for tannins, except for a slight increase of the mean degree of polymerization. Whatever the physiological stage of the pulp, the extraction yield of skin phenolics into hydroalcoholic solution for 5 h was lower than 77% for anthocyanins and 38% for proanthocyanidins. For both classes of compounds, no clear evolution in these extraction yields could be observed as sugars accumulated in pulp (from 162.6 to 275.0 g/L). Nevertheless, some structural features within each family of compounds significantly influenced extractability, for example, a lower extraction yield for coumaroylated anthocyanins and for tannins with a high degree of polymerization. Finally, no direct relationship could be found in extraction media between the amounts of all red pigments (measured in acidic conditions) and the color intensity at 520 nm (measured in wine-like model solutions).     

Difference in folate content of green and red sweet peppers (Capsicum annuum) determined by liquid chromatography-mass spectrometry

Folic acid (pteroylmonoglutamic acid) is used in enriched foods; however, very little folic acid occurs naturally in fruits and vegetables. For the U.S. Department of Agriculture's National Food and Nutrient Analysis Program, a number of fruits and vegetables have been assayed for endogenous folates, by a liquid chromatography-mass spectrometry method, to evaluate the accuracy of existing data for total folate determined by standard microbiological analysis. Folate in red and green sweet peppers (Capsicum annuum) differed notably (70.2 and 20.7 microg/100 g, respectively) and exceeded existing values determined by microbiological assay (18 and 11 microg/100 g, respectively). 5-Methyltetrahydrofolate was the predominant vitamer, but a significant amount of 5-formyltetrahydrolfolate and some 10-formylfolate were present. These findings may assist in making dietary recommendations or developing research diets related to folate. The data from this study have been used to update the folate values in release 19 of the USDA Nutrient Database for Standard Reference.     

Metabolic profiling of turmeric (Curcuma longa L.) plants derived from in vitro micropropagation and conventional greenhouse cultivation

Turmeric (Curcuma longa) was considered only a culinary spice in many parts of the world until the notable anti-inflammation curcuminoids were discovered from this herb. Because it is a sterile triploid and is propagated vegetatively by rhizome division, turmeric is susceptible to pathogens that accumulate and are transmitted from generation to generation, and amplification of particularly useful stocks is a slow process. An in vitro propagation method has been developed to alleviate these problems. Metabolic profiling, using GC-MS and LC-ESI-MS, was used to determine if chemical differences existed between greenhouse-grown and in vitro micropropagation derived plants. The major chemical constituent curcuminoids, a group of diarylheptanoid compounds, as well as major mono- and sesquiterpenoids were identified and quantified. Principal component analysis and hierarchical cluster analysis revealed chemical differences between lines (T3C turmeric vs Hawaiian red turmeric) and tissues (rhizome, root, leaf, and shoot). However, this analysis indicated that no significant differences existed between growth treatments (conventional greenhouse-grown vs in vitro propagation derived plants).     

Protection of lipids from oxidation by epicatechin, trans-resveratrol, and gallic and caffeic acids in intestinal model systems

Consumption of polyphenols is associated with health promotion through diet, although many are poorly absorbed in animals and humans alike. Lipid peroxides may reach the intestine and initiate deleterious oxidation. Here we measured inhibition of the oxidation of linoleic acid (LA) in authentic fluid from rat small intestine (RIF) by two dietary polyphenols, a flavonoid, epicatechin (EC), and a stilbene, resveratrol (RV), and by gallic (GA) and caffeic (CA) acids, and their partition coefficients. Both polyphenols inhibited 80%, and CA inhibited 65%, of the production of hexanal. GA was the weakest antioxidant in this assay. Interestingly, measuring peroxides production in RIF showed that only epicatechin inhibited the first stage of oxidation. The oxidizing agent, the antioxidant comound, the solution pH and lipophilicity are known to affect the total antioxidative activity. We suggest that the mechanism of this activity changes in accord with the environment: i.e., RV may act as a free radial scavenger, but here, in protecting lipids in intestinal fluid from oxidation, it acts as a hydrogen atom donor. Since the concentration of phenolics is much higher in the intestinal fluid than is ever achieved in plasma or other body tissues, it is suggested that their antioxidant activity could be exerted in the gastrointestinal tract (GIT), breaking the propagation of lipid peroxides oxidation and production of toxic compounds.     

Efficient and sensitive method for quantitative analysis of alkaloids in hardinggrass (Phalaris aquatica L.)

An efficient high-performance thin-layer chromatography (HPTLC) method for the analysis of alkaloids in hardinggrass (Phalaris aquatica L.) was developed. The method employed HPTLC glass plates precoated with silica gel 60F-254 as the stationary phase. The solvent system consisted of ethyl acetate/chloroform/7 N NH4OH in methanol (8:2:1, v/v/v). Using unidimensional double-development, bands were well separated for 10 alkaloid standards as well as alkaloids observed in hardinggrass plant extracts. Identities of compounds observed using HPTLC were validated by high-performance liquid chromatography-mass spectrometry (HPLC-MS). Software was used to quantify individual alkaloids in plant samples based on HPTLC retention factors and intensities relative to standards of known concentration. Correlation coefficients of 0.99 were obtained between estimated and actual concentrations for four standards (methyltyramine, hordenine, gramine, and 5-methoxydimethyltryptamine), with linearity in the range of 120-3840 ng/spot. The HPTLC method is repeatable and specific for beta-carboline, tryptamine, gramine, and tyramine type alkaloids in mixed standard and plant extracts. Initial results indicate substantial variation in alkaloid composition among and within hardinggrass populations.     

Interpreting the dependence of soil respiration on soil temperature and water content in a boreal aspen stand

Continuous half-hourly measurements of soil CO₂ efflux made between January and December 2001 in a mature trembling aspen stand located at the southern edge of the boreal forest in Canada were used to investigate the seasonal and diurnal dependence of soil respiration (R_s) on soil temperature (T_s) and water content (θ). Daily mean R_s varied from a minimum of 0.1 μmol m⁻² s⁻¹ in February to a maximum of 9.2 μmol m⁻² s⁻¹ in mid-July. Daily mean T_s at the 2-cm depth was the primary variable accounting for the temporal variation of R_s and no differences between Arrhenius and Q₁₀ response functions were found to describe the seasonal relationship. R_s at 10 °C (R_s10) and the temperature sensitivity of R_s (Q_10Rs) calculated at the seasonal time scale were 3.8 μmol m⁻² s⁻¹ and 3.8, respectively. Temperature normalization of daily mean R_s (R_sN) revealed that θ in the 0–15 cm soil layer was the secondary variable accounting for the temporal variation of R_s during the growing season. Daily R_sN showed two distinctive phases with respect to soil water field capacity in the 0–15 cm layer (θ_fc, 0.30 m³ m⁻³): (1) R_sN was strongly reduced when θ decreased below θ_fc, which reflected a reduction in microbial decomposition, and (2) R_sN slightly decreased when θ increased above θ_fc, which reflected a restriction of CO₂ or O₂ transport in the soil profile.Diurnal variations of half-hourly R_s were usually out of phase with T_s at the 2-cm depth, which resulted in strong diurnal hysteresis between the two variables. Daily nighttime R_s10 and Q_10Rs parameters calculated from half-hourly nighttime measurements of R_s and T_s at the 2-cm depth (when there was steady cooling of the soil) varied greatly during the growing season and ranged from 6.8 to 1.6 μmol m⁻² s⁻¹ and 5.5 to 1.3, respectively. On average, daily nighttime R_s10 (4.5 μmol m⁻² s⁻¹) and Q_10Rs (2.8) were higher and lower, respectively, than the values obtained from the seasonal relationship. Seasonal variations of these daily parameters were highly correlated with variations of θ in the 0–15 cm soil layer, with a tendency of low R_s10 and Q_10Rs values at low θ. Overall, the use of seasonal R_s10 and Q_10Rs parameters led to an overestimation of daily ranges of half-hourly R_s (ΔR_s) during drought conditions, which supported findings that the short-term temperature sensitivity of R_s was lower during periods of low θ. The use of daily nighttime R_s10 and Q_10Rs parameters greatly helped at simulating ΔR_s during these periods but did not improve the estimation of half-hourly R_s throughout the year as it could not account for the diurnal hysteresis effect.