Method validation for strobilurin fungicides in cereals and fruit

Strobilurins are a new class of fungicides that are active against a broad spectrum of fungi. In the present work a GC method for analysis of strobilurin fungicides was validated. The method was based on extraction with ethyl acetate/cyclohexane, clean-up by gel permeation chromatography (GPC) and determination of the content by gas chromatography (GC) with electron capture (EC-), nitrogen/phosphorous (NP-), and mass spectrometric (MS-) detection. Three strobilurins, azoxystrobin, kresoxim-methyl and trifloxystrobin were validated on three matrices, wheat, apple and grapes. The validation was based on recovery tests at three or four spiking levels, determined as double determinations and repeated three times (n = 6). The mean recoveries for the three detectors were in the range of 70-114%, and the LODs were between 0.004mg/kg and 0.014mg/kg, for all three strobilurins. The values for repeatability and reproducibility were within the limits for repeatability and reproducibility given by the Horwitz equation. Validation was not accepted for azoxystrobin in grapes on all three detectors and for azoxystrobin in apple for the MS-detector. A comparison of matrix-matched standards versus standards in solvent showed varying differences     

Alpha‐Synuclein Binds to the Inner Membrane of Mitochondria in an α‐Helical Conformation

The human alpha‐Synuclein (αS) protein is of significant interest because of its association with Parkinson's disease and related neurodegenerative disorders. The intrinsically disordered protein (140 amino acids) is characterized by the absence of a well‐defined structure in solution. It displays remarkable conformational flexibility upon macromolecular interactions, and can associate with mitochondrial membranes. Site‐directed spin‐labeling in combination with electron paramagnetic resonance spectroscopy enabled us to study the local binding properties of αS on artificial membranes (mimicking the inner and outer mitochondrial membranes), and to evaluate the importance of cardiolipin in this interaction. With pulsed, twofrequency, double‐electron electron paramagnetic resonance (DEER) approaches, we examined, to the best of our knowledge for the first time, the conformation of αS bound to isolated mitochondria.     

Consolidation by spark plasma sintering (SPS) of polyetheretherketone

The present study deals with the consolidation of an ultra‐high performance polymer, the poly(ether ether ketone) (PEEK), for structural applications, using the powder metallurgy (PM) way, and more precisely the Spark Plasma Sintering (SPS) processing. The effects of SPS parameters such as temperature, pressure, and dwell time on density and mechanical properties of PEEK were investigated via a Design of Experiments (DoE). A temperature of 250 °C, a pressure of 40 MPa, and a dwell time of 20 min have been identified as the optimal SPS process parameters. In these conditions, a density of 1.31 g / cm³ was reached and homogeneous mechanical properties in the volume determined by means of compression tests were found with a compressive modulus of 2.75 GPa, a yield strength of 134 MPa, and a maximum compressive strain of 43%. These results are better than those of commercial products obtained by injection molding. The pressure appears to be a significant parameter on PEEK properties and plays positive or negative roles according to the responses of DoE studied. To our knowledge, it is one of the first studies based on the application of the PM techniques for PEEK consolidation showing the possibility to process below its melting point. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44911.     

Different metabolic and absorption patterns of betaine in response to dietary intake of whole-wheat grain, wheat aleurone or rye aleurone in catheterized pigs

In the present study, a novel method of measuring the uptake of nutrients by 1H NMR spectroscopy was performed to determine dietary effects. Six pigs catheterized in the portal vein and mesenteric artery were fed breads made from whole-wheat grain (WWG), wheat aleurone flour (WAF; 19?% aleurone of bread) or rye aleurone flour (RAF; 15?% aleurone of bread) in a repeated 3?×?3 crossover design. Three meals were provided daily (at 0, 5 and 10?h), and each period comprised of 1?week. Portal and arterial blood samples were collected at fasting (?30?min) on day 4–7, and on day 7, pooled blood samples were collected at 0–2.5, 2.5–5, 5–7.5 and 7.5–10?h after first (0?h) daily meal. Using the arterial-venous difference and ANOVA–simultaneous component analysis, plasma betaine was found to accumulate during the experimental period. On day 7, plasma betaine concentrations was 20–40?% higher than when feeding the WAF diet compared with RAF and WWG (P?=?0.001), whereas the content of betaine in the WAF diet was about twice as high. The arterial-venous difference showed a tendency (P?=?0.078) for the diet–time interaction of betaine absorption in the absorption phases but there was no diet effect (P?=?0.31), which indicates a steady-state absorption has been reached on day 7. Furthermore, high plasma betaine levels correlated with low plasma creatine of endogenous origin. In conclusion, the explorative method revealed that the plasma concentration and absorption of betaine were differentially modified by the diets.     

Mechanistic investigation and selectivity of the grafting onto C60 of macroradicals prepared by cobalt-mediated radical polymerization

The grafting mechanism of poly(vinyl acetate) macroradicals prepared by cobalt-mediated radical polymerization onto C₆₀ is investigated. The experimental conditions directly impact the nature and stability of the PVAc/C₆₀ adducts. In the presence of residual initiating radicals that can compete with PVAc° macroradicals for addition onto C₆₀, mixtures of PVAc/C₆₀ adducts having between one and eight polymer chains per C₆₀ are formed. PVAc/C₆₀ adducts prepared with low [PVAc]:[C₆₀] ratios may contain weak C₆₀–C₆₀ bonds that further dissociate and account for the instability of the products. The formation of such dimers can be lessened by increasing the temperature from 30 °C to 100 °C. The temperature increase also allows a complete dissociation of the PVAc-Co dormant species into PVAc° macroradicals and an almost quantitative grafting of eight PVAc chains onto C₆₀, leading to well-defined C₆₀(PVAc)₈ octa-adducts. These results might shed new light on the grafting onto C₆₀ of macroradicals prepared by other CRP techniques.     

Multicomponent Physical Vapor Deposited Films with Homogeneous Molecular Material Distribution Featuring Improved Resist Sensitivity

Each film preparation technique affects the physical properties of the resulting coating and thus defines its applicability in modern device construction. In this context solvent based spin coated and solvent‐free physical vapor deposited molecular glass photoresist films are systematically investigated for their dissolution behavior, sensitivity, and overall lithographic performance. These investigations demonstrate that the solvent‐free physical vapor deposition leads to a marked increase in sensitivity. This could be explained by the individual molecule by molecule deposition step producing a more homogeneous distribution of the multicomponent resist system, especially the photoacid generator. In addition, this assumption is supported by former published simulations focusing on aggregate formation within thin films. This work demonstrates that the lithographic sensitivity of multicomponent resist system is an intrinsic parameter to investigate molecular material distribution and indicates that the applied film preparation technique is crucial for the corresponding performance and applicability.     

An evidential approach for detection of abnormal behaviour in the presence of unreliable sensors

We address the problem of abnormal behaviour recognition of the inhabitant of a smart home in the presence of unreliable sensors. The corner stone of this work is a two-level architecture sensor fusion based on the Transferable Belief Model (TBM). The novelty of our work lies in the way we detect both unreliable sensors and abnormal behaviour within our architecture by using a temporal analysis of conflict resulting from the fusion of sensors. Detection of abnormal behaviour is based on a prediction/observation process and the influence of the faulty sources is discarded by discounting coefficients. Our architecture is tested in a real-life setting using three heterogeneous sensors enabling the detection of impossible transitions between three possible postures: Sitting, Standing and Lying. The impact of having a faulty sensor management is also tested in the real-life experiment for posture detection.     

Barrier effect of flame retardant systems in poly(methyl methacrylate): Study of the efficiency of the surface treatment by octylsilane of silica nanoparticles in combination with phosphorous fire retardant additives

In this work, flame retardant systems comprising ammonium polyphosphate (AP423) and hydrophilic (A200) or hydrophobic (R805) nanometric silica were incorporated into PMMA. The following techniques were performed to detail the fire behaviour of the composites: mass loss cone calorimetry, pyrolysis‐combustion flow calorimetry, pyrolysis‐gas chromatography–mass spectrometry, thermogravimetric analysis, X‐ray diffraction analysis, Fourier transform infrared spectroscopy and microscopic observations. The best fire behaviour was obtained with the surface‐treated silica in the presence of AP423. The formation of a new crystalline phase from the interactions between AP423 and R805 silica and a strong barrier effect due to a layered residue were the main modes of action of this system. Moreover, we have shown that the difference between the AP423 + R805 and AP423 + A200 systems was due to poor dispersion of the silica into the PMMA matrix in the latter formulation. Copyright © 2011 John Wiley & Sons, Ltd.