Determination of molar absorptivity coefficients for major type-B trichothecenes and certification of calibrators for deoxynivalenol and nivalenol

This paper presents results from the European Commission-funded project Doncalibrant, the objective of which was to produce calibrators with certified mass fractions of the Fusarium toxins deoxynivalenol (DON), 3-acetyldeoxynivalenol (3-Ac-DON), 15-acetyldeoxynivalenol (15-Ac-DON), and nivalenol (NIV), in acetonitrile. The calibrators, available in ampoules, were sufficiently homogeneous, with between-bottle variations (s _bb) of less than 2%. Long-term stability studies performed at four different temperatures between −18 and 40 °C revealed no significant negative trends (at a confidence level of 95%). Molar absorptivity coefficients (in L mol⁻¹ cm⁻¹) were determined for all four toxins (DON: 6805 ± 126, NIV: 6955 ± 205, 3-Ac-DON: 6983 ± 141, 15-Ac-DON: 6935 ± 142) on the basis of a mini-interlaboratory exercise. The overall uncertainty of the calibrators’ target values for DON and NIV were evaluated on the basis of gravimetric preparation data and include uncertainty contributions from possible heterogeneity, storage, and transport. The Doncalibrant project resulted in the production of calibrators for DON (IRMM-315) and NIV (IRMM-316) in acetonitrile with certified mass fractions of 25.1 ± 1.2 μg g⁻¹ and 24.0 ± 1.1 μg g⁻¹, respectively. Both CRMs became commercially available from the Institute for Reference Materials and Measurements (IRMM, Geel, Belgium) at the beginning of 2007.     

Corn stover fractions and bioenergy

Information is presented on structure, composition, and response to enzymes of corn stover related to barriers for bioconversion to ethanol. Aromatic compounds occurred in most tissue cell walls. Ferulic acid esterase treatment before cellulase treatment significantly improved dry weight loss and release of phenolic acids and sugars in most fractions over cellulase alone. Leaf fractions were considerably higher in dry weight loss and released sugars with esterase treatment, but stem pith cells gave up the most phenolic acids. Results help identify plant fractions more appropriate for coproducts and bioconversion and those more suitable as residues for soil erosion control.     

Probing the interaction of solvents with the stationary phase of C18 high-performance liquid chromatographic column material by variable-temperature dependent 129Xe nuclear magnetic resonance spectroscopy

VT (129)Xe NMR was applied to probe the interactions of solvents having different polarity indices with the stationary phase of a RP-C18 HPLC column material. It was observed that the highly polar ethylene glycol molecules do not mix with the alkyl chains of the RP-C18 stationary phase and the solvent is unable to enter the pores and the spaces between the particles. Three phases in this sample are defined as stationary/xenon phase, xenon gas phase (in the pores and the spaces between the particles) and ethylene glycol/xenon phase. In contrast to ethylene glycol, the nonpolar solvent cyclohexane was observed to be well mixed with the RP-C18 stationary phase. The capillary rise effect allows the solvent to enter the pores and the spaces between the particles. Two phases in this sample are defined as stationary/cyclohexane/xenon phase and cyclohexane/xenon phases. The properties of ethyl acetate are between those of ethylene glycol and cyclohexane. The (129)Xe NMR results show that the rational reversed phases should be conditioned from highly solvating to more polar solvents to remove the trapped air. The (129)Xe NMR results also show that pure stationary phase exists only when a highly polar solvent is used in reversed-phase chromatography. For a solvent with lower polarity, a stationary/solvent phase actually forms. This, together with the mobile phase, determines the selective factor for separating mixtures.     

Determination of deoxynivalenol in cereals and cereal products by immunoaffinity column cleanup with liquid chromatography: interlaboratory study

An interlaboratory study was performed on behalf of the UK Food Standards Agency to evaluate the effectiveness of an immunoaffinity column cleanup liquid chromatographic (LC) method for the determination of deoxynivalenol in a variety of cereals and cereal products at proposed European regulatory limits. The test portion was extracted with water. The sample extract was filtered a applied to an immunoaffinity column. After being washed with water, the deoxynivalenol was eluted with acetonitrile or methanol. Deoxynivalenol was quantitated by reversed-phase LC with UV determination. Samples of artificially contaminated wheat-flour, rice flour, oat flour, polenta, and wheat based breakfast cereal, naturally contaminated wheat flour, and blank (very low level) samples of each matrix were sent to 13 collaborators in 7 European countries. Participants were asked to spike test portions of all samples at a range of deoxynivalenol concentrations equivalent to 200-2000 ng/g deoxynivalenol. Average recoveries ranged from 78 to 87%. Based on results for 6 artificially contaminated samples (blind duplicates), the relative standard deviation for repeatability (RSDr) ranged from 3.1 to 14.1%, and the relative standard deviation for reproducibility (RSDR) ranged from 11.5 to 26.3%. The method showed acceptable within-laboratory and between-laboratory precision for all 5 matrixes, as evidenced by HorRat values < 1.3.     

Engineering of a two-step purification strategy for a panel of monoclonal immunoglobulin M directed against undifferentiated human embryonic stem cells

A two-step purification strategy comprising of polyethylene glycol (PEG) precipitation and anion-exchange chromatography was developed for a panel of monoclonal immunoglobulin M (IgM) (pI 5.5–7.7) produced from hybridoma cultures. PEG precipitation was optimized with regards to concentration, pH and mixing. For anion-exchange chromatography, different resins were screened of which Fractogel EMD, a polymer grafted porous resin had the highest capacity. Despite its significantly slower mass transfer, the binding capacity was still higher compared to a convection driven resin (monolith). This purification strategy was successfully demonstrated for all 9 IgMs in the panel. In small scale most antibodies could be purified to >95% purity with the exception of two which gave a lower final purity (46% and 85%). The yield was dependent on the different antibodies ranging from 28% to 84%. Further improvement of recovery and purity was obtained by the digestion of DNA present in the hybridoma supernatant using an endonuclease, benzonase. So far this strategy has been applied for the purification of up to 2 l hybridoma supernatants.     

Comparative study of the effect of various electrode membranes on biofouling and electrochemical measurements

Stability of sensors in biosamples is a critical issue and can be mitigated by membranes. The effect of different membranes (Nafion, cellulose acetate, chitosan, fibronectin, PSS/PL) on the electrochemistry of an outer-sphere redox couple (ruthenium II/III hexaammine) and on the electrocatalytic reduction of dissolved oxygen are described. Biofouling has been induced by albumin solutions. Results demonstrate good performances of fibronectin in all situations investigated. Other membranes do not provide a satisfactory protection from biofouling and some of them, PSS/PL in particular, seriously disturb electrochemical mechanisms.     

Microwave-assisted selenium dioxide mediated selective oxidation of 1-tetralones to 1,2-naphthoquinones

We report an improved procedure for the selective transformation of substituted 1-tetralones to 1,2-naphthoquinones by microwave-assisted selenium dioxide oxidation. The reaction time is effectively reduced from hours to seconds without any loss of yield (40-70%) or selectivity.     

Subjective Aspects of the Art of Decision Analysis: Exploring the Role of Decision Analysis in Decision Structuring,Decision Support and Policy Dialogue

The paper argues that, until very recently, decision analysts have devoted relatively little attention to the processes of problem formulation and subjective judgement in handling ill-structured strategic decision problems. Therefore, following a brief review of existing varieties of decision analysis, a modified policy dialogue' model of decision analysis is presented which integrates decision analysis with decision aids and decision support technology. This model is developed using as an illustration strategic problems drawn from the insurance industry. The paper concludes with some suggestions for the successful application and implementation of decision analysis.     

Isospin-violating dark matter in the Sun

We consider the prospects for studying spin-independent isospin-violating dark matter-nucleon interactions with neutrinos from dark matter annihilation in the Sun, with a focus on IceCube/DeepCore (IC/DC). If dark matter-nucleon interactions are isospin-violating, IC/DC?s reach in the spin-independent cross section may be competitive with current direct detection experiments for a wide range of dark matter masses. We also compare IC/DC?s sensitivity to that of next generation argon, germanium, neon and xenon based detectors.     

Interaction of the general volatile anesthetic Enflurane with bacteriorhodopsin-DPPC proteoliposomes

Thermal decomposition of dried crystalline powder obtained from titanium(IV) bis(acetylacetonate) diisopropoxide (75% solution in 2-propanol) (1) was monitored by simultaneous TG/DTA, EGA-FTIR and EGA-MS measurements and the results were compared with those of amorphous powder obtained by gelling of acetylacetonate-modified titanium(IV) tetra-isopropoxide at molar ratio of 1:2 in boiling 2-methoxyethanol (2). Thermal degradation of 1 in the temperature range of 25–700°C consists of 5 steps with a total mass loss of 62.5%. EGA by FTIR and MS revealed the release of H₂O below 120°C; followed by an intensive evolution of acetylacetone around 245°C. The release of acetone and acetic acid occurs up to 270°C and that of CO and CO₂ up to 530°C.