Preparation of tetrahydroagathic acid: a serum metabolite of isocupressic acid, a cattle abortifacient in ponderosa pine

Isocupressic acid (1) was used to synthetically prepare a mixture of (8S,13R,S)-labda-15,19-dioic acid (tetrahydroagathic acid) (5) via a two-step oxidation procedure followed by hydrogenation of the double bonds at C13 and C8. Reduction of the C8,17 double bond was stereospecific producing only the 8S isomer and confirmed by the nOe interaction between the resulting C17 and C20 methyl groups. The 13R and 13S isomers of 5 were separated and analyzed by HPLC/MS, and (13S)-tetrahydroagathic acid was isolated and identified by comparison to a standard prepared by hydrogenation of naturally occurring (13S)-dihydroagathic acid (4). (13R,S)-dihydroagathic acid was prepared by selective sodium metal-catalyzed hydrogenation of the C13,14 allylic double bond of agathic acid (3). The prepared compounds were then used as standards to confirm the presence of 4 and 5 and their respective 13R and 13S isomers in bovine serum samples. Tetrahydroagathic acid was shown to be the only metabolite detected in serum samples taken from a suspected cattle abortion case submitted for diagnosis; and, thus, 5 could be a valuable diagnostic marker for pine needle-induced abortions.     

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.     

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.     

Element mass balances for South Carolina Coastal Plain watersheds

Element mass balance estimates for South Carolina Coastal Plain watersheds indicate that fertilizers and liming materials are the major sources for inputs of Ca, Mg, K, Cl, and HCO₃ whereas precipitation is the major input for Na and SO₄. Stream flow is the chief mode of output for all of these elements. A balance between input and output is evident only for Cl. Retentions of 50% or more are shown by Ca, Mg, K, HCO₃ and SO₄ whereas Na shows an apparent net loss. The retention of Ca, Mg and HCO₃ suggests that less than 25% of the dolomitic liming materials applied to the landscape actually dissolve and that the carbonate chemistry of Lower Coastal Plain streams is therefore probably largely controlled by seepage of groundwaters from underlying calcareous aquifers. The retention of K and the loss of Na may be due to cation exchange reactions on soil clays whereas the apparent retention of SO₄ is probably due to reduction to H₂S in floodplain environments and soil adsorption.     

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.     

Winter flocking behaviour of speckled warblers and the Allee effect

The aggregation of individuals into foraging flocks is one behavioural trait that, if disrupted, can cause the Allee effect, which is a slowing in population growth at low density or small population size, and this can greatly increase the risk of extinction. Here, I describe intraspecific flocking behaviour of a colour-banded population of speckled warblers, Chthonicola sagittata, a species that has declined across a large part of its range in the fragmented temperate woodlands of Australia. I make predictions about the context in which the Allee effect might be expressed and the consequences for the viability of populations living in small habitat remnants. Speckled warblers lived in discrete, stable social groups throughout winter, the nucleus of which was the residents from one or more adjacent breeding territories. The timing and mode of flock formation and the size of flocks varied between two winters, apparently in response to the severity of conditions; thus flocking probably facilitates increased foraging efficiency and predator detection, potentially leading to increased survival in harsh conditions. Because flock territories were up to 30 ha each, and larger territories are likely, birds living in remnants smaller than 40 ha may suffer increased mortality if there are too few birds available to form flocks of an appropriate size to facilitate the benefits of grouping when conditions are most extreme. Further, in small remnants where survival is reduced, dominance behaviour and male-male competition may act to compound the Allee effect by reducing reproductive success. Regardless of these predictions, speckled warbler populations may only be viable in remnants that are large enough to support multiple flocks, to enable rapid recruitment to breeding vacancies and thus provide adequate numbers of birds for flocking.     

Epidemiology theory and disturbance spread on landscapes

Abtract Epidemiology models, modified to include landscape pattern, are used to examine the relative importance of landscape geometry and disturbance dynamics in determining the spatial extent of a disturbance, such as a fire. The models indicate that, except for very small values for the probability of spread, a disturbance tends to propagate to all susceptible sites that can be reached. Therefore, spatial pattern, rather than disturbance dynamic, will ordinarily determine the total extent of a single disturbance event. The models also indicate that a single disturbance will seldom become endemic,i.e., always present on the landscape. However, increasing disturbance frequency can lead to a landscape in which the proportion of susceptible, disturbed, and recovering sites are relatively constant. Research supported by Ecological Research Division, Office of Health and Environmental Research, U.S. Department of Energy under contract No. DE-AC05-840R21400 with Martin Marietta Energy Systems, Inc. Contribution No. 10 to the Sevilleta LTER program. Environmental Sciences Division Publication No. 3812, ORNL.