Assessment of the antioxidant potential of scotch whiskeys by electron spin resonance spectroscopy: relationship to hydroxyl-containing aromatic components.

Electron spin resonance (ESR) spectroscopy has been used to assess the antioxidant capacity of eight Scotch whiskeys by measuring the extent by which the original spirits, or pyridine solutions of their residues, reduced Fremy's radical or galvinoxyl radical. All whiskeys displayed antioxidant activity greater than that of a 0.2 mM solution of Trolox in the Fremy's assay and of a 0.1 mM solution of quercetin in the galvinoxyl assay. The relative antioxidant capacities determined according to the two assays were highly correlated and strongly related to the total phenol content as determined by using the Folin-Ciocalteu method. Activity was a consequence of maturation in oak casks with the "newmake" spirit showing no effect. Of 10 aromatic constituents analyzed, activity was most strongly correlated with ellagic acid and gallic acid in both assays. The reductive capacities of four major phenolics were determined, which, in summation, accounted for 31-53% of the total antioxidant activity of the whiskeys. There was no evidence for synergistic interaction between the phenols investigated.     

Lupine induced "crooked calf disease" in Washington and Oregon: identification of the alkaloid profiles in Lupinus sulfureus, Lupinus leucophyllus, and Lupinus sericeus

Several lupines (Lupinus spp.) present on western U.S. rangelands contain alkaloids that are teratogenic to livestock and cause congenital birth defects in calves (crooked calf disease). Periodically, large losses of calves due to lupine-induced "crooked calf disease" occur in northern Oregon and eastern Washington state. Five lupine populations from this area representing three species (L. leucophyllus, L. sulfureus, and L. sericeus) were evaluated taxonomically and by gas chromatography/mass spectrometry, and the major alkaloids in each lupine species were identified. The teratogenic alkaloid anagyrine was present in both of the lupine species responsible for the high outbreaks in east-central Washington and northeastern Oregon. However, the alkaloid profiles of the two lupines identified as L. leucophyllus were dissimilar, as were the alkaloid profiles of the two lupines identified as L. sulfureus. Botanical classification is not sufficient to determine potential teratogenicity, and it must be followed by chemical characterization to determine risk to livestock.     

Purification and identification of linoleic acid hydroperoxides generated by soybean seed lipoxygenases 2 and 3

It has been known that lipoxygenase (LOX) isozymes exhibit differences in product formation, but most product information to date is for LOX 1 among soybean (Glycine max) LOX isozymes. In this study, LOXs 2 and 3 were purified and used to generate hydroperoxide (HPOD) products in an in vitro system using linoleic acid as a substrate in the presence of either air or O2. The products were analyzed to determine their stereoisomeric characteristics. The control (no enzyme) showed only low levels of hydroperoxide production and no stereoisomeric specificity. LOX 2 shows high specificity in product formation, producing roughly 4 times more 13-HPOD than 9-HPOD, nearly all of which was 13-S(Z,E)-HPOD. LOX 3 produced more 9-HPOD than 13-HPOD at approximately a 2:1 ratio. No single stereoisomer was predominant among LOX 3 products. These results demonstrate that different isozymes of LOX have characteristic product profiles in in vitro reactions.     

Composition, stability, and bioavailability of garlic products used in a clinical trial

In support of a new clinical trial designed to compare the effects of crushed fresh garlic and two types of garlic supplement tablets (enteric-coated dried fresh garlic and dried aged garlic extract) on serum lipids, the three garlic products have been characterized for (a) composition (14 sulfur and 2 non-sulfur compounds), (b) stability of suspected active compounds, and (c) availability of allyl thiosulfinates (mainly allicin) under both simulated gastrointestinal (tablet dissolution) conditions and in vivo. The allyl thiosulfinates of blended fresh garlic were stable for at least 2 years when stored at -80 degrees C. The dissolution release of thiosulfinates from the enteric-coated garlic tablets was found to be >95%. The bioavailability of allyl thiosulfinates from these tablets, measured as breath allyl methyl sulfide, was found to be complete and equivalent to that of crushed fresh garlic. S-Allylcysteine was stable for 12 months at ambient temperature. The stability of the suspected active compounds under the conditions of the study and the bioavailability of allyl thiosulfinates from the dried garlic supplement have validated the use of these preparations for comparison in a clinical trial.     

Kinetic and stoichiometric assessment of the antioxidant activity of flavonoids by electron spin resonance spectroscopy

There is current interest in the use of naturally occurring flavonoids as antioxidants for the preservation of foods and the prevention of diseases such as atherosclerosis and cancers. To establish the molecular characteristics required for maximum antioxidant activity, electron spin resonance (ESR) spectroscopy has been used to determine the stoichiometry and kinetics of the hydrogen-donating ability of 15 flavonoids and d-alpha-tocopherol to galvinoxyl, a resonance-stabilized, sterically protected aryloxyl radical. The second-order reaction rates, which will be governed by O-H bond dissociation energies, were myricetin > morin > quercetin > fisetin approximately catechin > kaempferol approximately luteolin > rutin > d-alpha-tocopherol > taxifolin > tamarixetin > myricetin 3',4',5'-trimethyl ether > datiscetin > galangin > hesperitin approximately apigenin. Reactivity is highly dependant on the configuration of OH groups on the flavonoid B and C rings, there being little contribution from the A ring to antioxidant effectiveness. Highest reaction rates and stoichiometries were observed with flavonols capable of being oxidized to orthoquinones or extended paraquinones. However, rates and stoichiometries did not always correlate and the data suggest that kinetic factors may be of greater importance within a biological context.     

Ellagitannins,flavonoids, and other phenolics in red raspberries and their contribution to antioxidant capacity and vasorelaxation properties

Analysis of extracts of Glen Ample raspberries (Rubus idaeus L.) by gradient, reverse phase HPLC with diode array and tandem mass spectrometry identified eleven anthocyanins, including cyanidin-3-sophoroside, cyanidin-3-(2(G)-glucosylrutinoside), cyanidin-3-glucoside, cyanidin-3-rutinoside, pelargonidin-3-sophoroside, pelargonidin-3-(2(G)-glucosylrutinoside), and pelargonidin-3-glucoside. Significant quantities of an ellagitannin, sanguiin H-6, with an M(r) of 1870 were detected along with lower levels of a second ellagitannin, lambertianin C, which has an M(r) of 2804. Other phenolic compounds that were detected included trace levels of ellagic acid and its sugar conjugates along with one kaempferol- and four quercetin-based flavonol conjugates. Fractionation by preparative HPLC revealed that sanguiin H-6 was a major contributor to the antioxidant capacity of raspberries together with vitamin C and the anthocyanins. Vasodilation activity was restricted to fractions containing lambertianin C and sanguiin H-6.     

Nutrient losses from rain‐fed bench terraced cultivation systems in high rainfall areas of the mid‐hills of Nepal

Between the elevations of 1000 and 2000 m in the mid‐hills of Nepal, over 12 million people subsist on land‐holdings of less than 0·5 ha. These farmers have limited access to commercial inputs such as fertilisers and are reliant on organic manures for soil fertility maintenance. Participatory research was conducted with farmers on bari land (upper slope rain‐fed crop terraces) in the hill community of Landruk (bench terraces 0–5° slope, 3000–3500 mm annual rainfall, which aimed to develop soil and water management interventions that controlled erosion without resulting in high leaching, and so were effective in minimising total nutrient losses. Interventions tested were the control of water movement through diversion of run‐on and planting fodder grasses on terrace risers on bench terraces. The interventions were effective in reducing soil loss from the bari land in comparison with existing farmer practices, but no effect was observed on nutrient losses in solution form through runoff and leaching. Losses of NO₃‐N in leachate ranged from 17·3 to 99·7 kg ha⁻¹ yr⁻¹, but only 0·7 to 5·6 kg ha⁻¹ yr⁻¹ in runoff. The overall nutrient balance suggests that the system is not sustainable. Fertility is heavily dependent on livestock inputs and if the current trends of declining livestock numbers due to labour constraints continue, further losses in productivity can be expected. However, farmers are interested in interventions that tie ecosystem services with productivity enhancement and farmers' priorities should be used as entry points for promoting interventions that are system compatible and harness niche opportunities. Copyright © 2007 John Wiley & Sons, Ltd.     

How pristine are tropical forests? An ecological perspective on the pre-Columbian human footprint in Amazonia and implications for contemporary conservation

Archeologists, paleoecologists and anthropologists argue that ecologists need to give greater consideration to the pre-historical influence of humans in shaping the current structure and composition of tropical forests. We examine these arguments within the context of Amazonia, and assess the extent to which (i) the concepts of “pristine forests” and “cultural parklands” are mutually exclusive, (ii) the aggregated distribution of some plants necessarily indicates enrichment planting, (iii) pre-Columbian human disturbance has increased forest biodiversity, (iv) pre-Columbian indigenous practices were always sustainable, and (v) if indeed, the ecological impacts of pre-Columbian peoples are relevant for modern biodiversity conservation. Overall, we reject the notion that “the pristine myth has been thoroughly debunked” by archeological evidence, and suggest that the environmental impacts of historical peoples occurred along gradients, with high-impacts in settlements and patches of Amazonian Dark Earth (ADE), lesser impacts where occasional enrichment planting took place in forests surrounding agricultural plots, and a very low influence (in terms of light hunting pressure and other types of resource extraction) across vast areas of Amazonia that may always have been far from permanent settlements and navigable rivers. We suggest that the spatial distribution of pre-Columbian finds is given more attention, and urge caution before case studies are extrapolated to the entire Basin. Above all, we feel that debates over “naturalness” and environmental impacts of pre-Columbian humans are of limited relevance to present and future biodiversity conservation, and can detract from the major challenges facing Amazonia and other tropical forest regions today.     

Bayesian estimation of cluster-level test accuracy based on different sampling schemes

We develop Bayesian models to estimate cluster-level test characteristics, sensitivity, specificity, prevalence, and predictive values, based on four different sampling schemes: a single test case and three sequential test cases. The corresponding cluster-level characteristics are calculated and compared for different sample sizes, sampling schemes, individual-level sensitivities, specificities, and cut-off values. We compared posterior estimates of individual-level and cluster-level characteristics for these four sampling schemes with simulated data. Two illustrations, one for Johne’s disease in cattle and another for Salmonella in pig herds, are used to demonstrate application of the methods.