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.     

Development of a Two-Phase Cosolvent Washing-Fungal Biosorption Process for the Remediation of DDT-Contaminated Soil

A bench scale, two-phase soil washing-biosorption process was developed for the remediation of p,p′-DDT-contaminated soil (containing 990 and 7750 mg kg^-1 of p,p′-DDT). Removal of p,p′-DDT from contaminated soil was achieved by washing the soil with low molecular weight primary alcohols (ethanol or 1-propanol). An improved efficiency of p,p′-DDT removal was observed with increasing C-chain length of the cosolvent and by increasing the cosolvent volume fraction. When 40 or 80% 1-propanol were used, greater than 93% of p,p′-DDT was desorbed from the respective soils. p,p′-DDT was partitioned from the cosolvent solutions using biomass of Cladosporium sp. strain AJR³18,501 as the sorptivematrix. When studies were conducted using a cosolvent-recycling regime (with 80% 1-propanol) greater than 95% of p,p′-DDT was removed from Soil A (990 mg kg^-1 p,p′-DDT) and Soil B (7750 mg kg^-1 p,p′-DDT) with the majority of the desorbed organochlorine repartitioning onto the fungal biomass. Less than 2.4 μg mL^-1 p,p′-DDT was detected in the cosolvent wash solution of Soil A after 80 hr: potentially the cosolvent could be further reused to treat other soil. A higher concentration of p,p′-DDT was detected in the cosolvent wash solution of soil B after 120 hr (13.3 μg mL^-1) indicating that the p,p′-DDT sorption sites on the fungal biomass were fully saturated.     

In vivo investigation of changes in biomarkers of oxidative stress induced by plant food rich diets

It is well established that vegetables and fruit (VF) contain antioxidant phytochemicals. Consequently, it is expected that individuals who consume diets with a high content of VF should be better protected against oxidative cellular damage than individuals who do not, but not all data support this assumption. The objective of this study was to identify possible explanations for this conundrum. The effects of two diets that differed in VF content on markers of oxidative damage were studied. Sixty-four women participated in a 14-day dietary intervention. Subjects consumed on average either 3.6 or 12.1 servings of VF per day. The primary end points assessed were 8-hydroxy-2-deoxyguanosine (8-oxo-dG) in peripheral lymphocyte DNA and 8-isoprostaglandin F-2alpha (8-iso-PGF2alpha) excreted in urine. Subjects consuming the high versus low VF diet had lower concentrations of 8-oxo-dG (p < 0.01) and of 8-iso-PGF2alpha (p < 0.01). However, the reduction in oxidative end points by high VF was not uniform. Rather, an antioxidant effect was observed primarily in individuals whose oxidative end points at baseline were above the median for the study population. Using change in plasma carotenoids (end point minus baseline measurements) as an index of phytochemical intake, the reduction in oxidative markers was inversely proportional to change in plasma carotenoids; this effect was stronger for lipid peroxidation (p < 0.01) than DNA oxidation (p < 0.05). These findings imply that increasing exogenous antioxidant exposure may primarily benefit individuals with elevated levels of oxidative stress. Null findings do not necessarily indicate that an antioxidant compound lacks in vivo activity.     

Observations on under-the-row subsoiling after conventional tillage

A technique of subsoiling directly under the row to be planted has been found to be beneficial, because barriers to root development are pierced in a location that is difficult to recompact. Over a 15-year period, average yields increased substantially in the southeastern United States when this system was practiced. However, the increases were not consistent, and some reasons for those variations are analyzed.     

Performance characteristics of methods of analysis used for regulatory purposes. I. Drug dosage forms. C. Automated methods

For analysis of drug dosage forms, precision measures of AOAC approved automated methods, usually containing a spectrophotometric or fluorometric measurement step, were recalculated on a consistent statistical basis, using a computer program "FDACHEMIST." Ten collaborative studies of 14 compounds in 38 materials, consisting of various dosage forms, usually in 10 replications by an average of 7 laboratories, with a total of 2461 determinations, were reviewed. The average relative standard deviations within-laboratory (RSDo) and among-laboratories (RSDx) were 1.1 and 1.9%, respectively, and the ratio of RSDo/RSDx was 0.57, with an average outlier rate of 0.57% of the reported values. The line of best fit for RSDx plotted against - log concentration increases slightly with decreasing concentration, extending from an RSDx of about 1.6% at 100% concentration to an RSDx of 2.2% at 0.1% concentration, a change in RSDx of about 0.2% for a 10-fold decrease in concentration, independent of analyte and matrix.     

Mechanism of wine lactone formation: demonstration of stereoselective cyclization and 1,3-hydride shift

The cyclization mechanism of (E)-2,6-dimethyl-6-hydroxyocta-2,7-dienoic acid to wine lactone under acidic aqueous conditions was investigated using the two stereoselectively deuterium-labeled precursors (2E,6R,7Z)-[8-2H]-2,6-dimethyl-6-hydroxyocta-2,7-dienoic acid and (2E,7E)-(+/-)-[8-2H]-2,6-dimethyl-6-hydroxyocta-2,7-dienoic acid. A detailed analysis of the generated wine lactone isomers by enantioselective multidimensional gas chromatography (MDGC)/ion trap tandem mass spectrometry demonstrates that the formation of wine lactone proceeds via a nonenzymatic stereoselective cationic cyclization cascade that includes a 1,3-hydride shift. Usually, such mechanisms are features of cyclization reactions that are catalyzed by terpene cyclases. This nonenzymatic conversion of an acyclic precursor to a bicyclic monoterpene under relevant cationic cyclization conditions has rarely been observed and confirms recent suggestions that the precursor itself can provide the chemical functionality required for specific steps in the cyclization cascade.     

Flavonoids of zoysiagrass (Zoysia spp.) cultivars varying in fall armyworm (Spodoptera frugiperda) resistance

Flavonoid profiles of 12 zoysiagrass (Zoysia spp.) cultivars sampled six times in 1998 were correlated to fall armyworm (Spodoptera frugiperda J. E. Smith) larval weights and survival on replicated field-grown plant material and analyzed to determine genetic and seasonal variations of flavonoids among zoysiagrass cultivars. From multiple regression analyses and correlations, flavonoid peak 10 (luteolin-glucoside) had the greatest positive association with average fall armyworm weight; however, resistance appeared to be correlated with a number of other flavonoids. The flavonoid profiles of cultivars subjected to clustering procedures showed consistent genetic variability for five of six samplings and was used to genotype 23 cultivars. The dendrogram supported the results of the FASTCLUS procedure in clustering certain genotypes such as fall armyworm-resistant Cavalier and Zeon together, as well as J-36 and Meyer. Flavonoid evaluations measure genetic relatedness among cultivars and could be used for selective breeding of resistance to fall armyworm.     

Conventional analyses of data from dietary validation studies may misestimate reporting accuracy: illustration from a study of the effect of interview modality on children's reporting accuracy

OBJECTIVE: To compare two approaches to analysing energy- and nutrient-converted data from dietary validation (and relative validation) studies - conventional analyses, in which the accuracy of reported items is not ascertained, and reporting-error-sensitive analyses, in which reported items are classified as matches (items actually eaten) or intrusions (items not actually eaten), and reported amounts are classified as corresponding or overreported. DESIGN: Subjects were observed eating school breakfast and lunch, and interviewed that evening about that day's intake. For conventional analyses, reference and reported information were converted to energy and macronutrients; then t-tests, correlation coefficients and report rates (reported/reference) were calculated. For reporting error-sensitive analyses, reported items were classified as matches or intrusions, reported amounts were classified as corresponding or overreported, and correspondence rates (corresponding amount/reference amount) and inflation ratios (overreported amount/reference amount) were calculated. SUBJECTS: Sixty-nine fourth-grade children (35 girls) from 10 elementary schools in Georgia (USA). RESULTS: For energy and each macronutrient, conventional analyses found that reported amounts were significantly less than reference amounts (every P < 0.021; paired t-tests); correlations between reported and reference amounts exceeded 0.52 (every P < 0.001); and median report rates ranged from 76% to 95%. Analyses sensitive to reporting errors found median correspondence rates between 67% and 79%, and that median inflation ratios, which ranged from 7% to 17%, differed significantly from 0 (every P < 0.0001; sign tests). CONCLUSIONS: Conventional analyses of energy and nutrient data from dietary reporting validation (and relative validation) studies may overestimate accuracy and mask the complexity of dietary reporting error.     

Räumliche Spannungsmessungen mit dem Stress State Transducer (SST) in ungesättigten aggregierten Böden - theoretische Betrachtungen und erste Ergebnisse

Stress measurements in undisturbed unsaturated soils with a Stress State Transducer (SST) - theory and first results A method to quantify the spatial stress distribution will be introduced and first results will be discussed. This method allows the detailed analysis of principal and shear stresses as well as the determination of the direction angle of principal stresses and the octahedral shear stress angle. The described Stress State Transducer (SST) is composed of six single strain gage sensors that enable the accurate and reproducable recording of stresses in six directions in a wide load range. Their data form the base for calculation of spatial stress distribution. Some first results show that in a luvisol derived from loess wheeling at a wheel load of 4.0 Mg induces high shear stresses in a depth of 30 cm. This probably causes plastic soil deformation.     

Defining output-based standards to achieve and maintain tuberculosis freedom in farmed deer, with reference to member states of the European Union

Within the European Union (EU), detailed legislation has been developed for cattle, but not deer, to minimise disease risks associated with trade in animals and animal products. This legislation is expressed as input-based standards, providing a detailed outline of the activity required (for example, testing of animals and application of defined control measures), on the expectation that an adequate output (for example, confidence in freedom) will be achieved. Input-based standards are at odds with the increasing shift towards output-based standards, particularly in OIE rules governing international trade. In this paper, we define output-based standards to achieve and maintain freedom from tuberculosis (TB) in farmed deer, with reference to EU member states. After considering the probability of freedom achieved for cattle under existing EU legislation, we defined a ‘free farmed deer holding’ as one with a probability of freedom from infection of at least 99%. We then developed an epidemiological model of TB surveillance systems for deer holdings, incorporating different surveillance strategies, including combinations of diagnostic tests, and a variety of different scenarios relating to the potential for introduction of infection. A range of surveillance strategies were identified to achieve and maintain a free farmed deer holding, and worked examples are presented. The surveillance system sensitivity for varying combinations of screening and confirmatory tests in live animals, animals at slaughter and on-farm deaths is also presented. Using a single test at a single point in time, none of the TB tests routinely used in farmed deer is able to achieve an acceptable probability of TB freedom. If repeat testing were undertaken, an acceptable probability of TB freedom could be achieved, with differing combinations of the surveillance system sensitivity, frequency of testing and risk of introduction. The probability of introduction of infection through the importation of infected deer was influenced by the use of a pre-movement test (assumed 90% test sensitivity and negative test results), the TB prevalence in the source herd and the number of animals imported. A surveillance system sensitivity of at least 81% was achieved with different combinations of annual live animal surveillance and surveillance of animals at slaughter or on-farm deaths. This methodology has broad applicability and could also be extended to other diseases in both deer and other species with relevance to trade in animals and animal products.