Comprehensive analysis of vitamin E constituents in human plasma by liquid chromatography-mass spectrometry

The present paper describes the development and validation of a normal-phase liquid chromatography-mass spectrometry (NP-HPLC-MS) method for the screening and quantification of vitamin E constituents in human plasma and food matrixes. Liquid-liquid extraction combined with isotope dilution was applied to extract the lipophilic target analytes. Baseline separation of alpha-tocopherylacetate, alpha-tocopherol, alpha-tocotrienol, alpha-tocopherylquinone, beta-tocopherol, gamma-tocopherol, beta-tocotrienol, gamma-tocotrienol, delta-tocopherol, and delta-tocotrienol was achieved utilizing a normal-phase amine column operated with n-hexane and 1,4-dioxane as solvents. Detection was achieved by positive-ion atmospheric-pressure chemical ionization (APCI). Key features of the method are lower limits of detection, 3-51 nmoles/L; lower limits of quantification, 8-168 nmoles/L; linearity coefficients, 0.9778-0.9989; linear ranges, 0.01-29 micromol/L; recoveries, 53-92%; accuracies, 99-103%; intraday precisions, 2-17%; interday precisions, 5-18%; and suppression values, 0-29%. Fragmentation of tocopherols was studied by tandem mass spectrometry, and a fragmentation scheme for tocotrienols/tocopherols is postulated. Neutral-loss and precursor-ion scan experiments were performed for targeted discovery of oxidation products of tocopherols in human blood and fish oil, the latter being an important food component. The presented data suggest that this method will help to expand the number of quantified/discovered vitamin E constituents detected in food products and analyzed during human/animal trials in order to give a more comprehensive picture to nutritionists about the fate of vitamin E.     

The C-Terminal Domain of LRRK2 with the G2019S Substitution Increases Mutant A53T α-Synuclein Toxicity in Dopaminergic Neurons In Vivo

Alpha-synuclein (α-syn) and leucine-rich repeat kinase 2 (LRRK2) play crucial roles in Parkinson’s disease (PD). They may functionally interact to induce the degeneration of dopaminergic (DA) neurons via mechanisms that are not yet fully understood. We previously showed that the C-terminal portion of LRRK2 (ΔLRRK2) with the G2019S mutation (ΔLRRK2^G2019S) was sufficient to induce neurodegeneration of DA neurons in vivo, suggesting that mutated LRRK2 induces neurotoxicity through mechanisms that are (i) independent of the N-terminal domains and (ii) “cell-autonomous”. Here, we explored whether ΔLRRK2^G2019S could modify α-syn toxicity through these two mechanisms. We used a co-transduction approach in rats with AAV vectors encoding ΔLRRK2^G2019S or its “dead” kinase form, ΔLRRK2^DK, and human α-syn with the A53T mutation (AAV-α-syn^A53T). Behavioral and histological evaluations were performed at 6- and 15-weeks post-injection. Results showed that neither form of ΔLRRK2 alone induced the degeneration of neurons at these post-injection time points. By contrast, injection of AAV-α-syn^A53T alone resulted in motor signs and degeneration of DA neurons. Co-injection of AAV-α-syn^A53T with AAV-ΔLRRK2^G2019S induced DA neuron degeneration that was significantly higher than that induced by AAV-α-syn^A53T alone or with AAV-ΔLRRK2^DK. Thus, mutated α-syn neurotoxicity can be enhanced by the C-terminal domain of LRRK2^G2019 alone^, through cell-autonomous mechanisms.     

Transformation of microporous titanium glycolate nanorods into mesoporous anatase titania nanorods by hot water treatment

High surface area titanium glycolate microporous multi-faceted nanorods were synthesized from the reaction of titanium alkoxides (Ti(OEt)₄, Ti(O ⁱ Pr)₄, or Ti(O ⁿ Bu)₄) with ethylene glycol, using a sol–gel reflux method. The specific surface area of the as-synthesized titanium glycolate nanorods obtained from Ti(OEt)₄ is ~480 m²/g. A hot water treatment at 90 °C for 1 h transformed the titanium glycolate microporous nanorods into mesoporous anatase TiO₂ nanorods. The shape of the nanorods was conserved after hot water treatment and the microporous to mesoporous transformation took place without significant change in the surface area (477 m²/g). Micro Raman spectroscopy, scanning electron microscopy, transmission electron microscopy, X-ray diffraction, solid state NMR, and nitrogen adsorption/desorption were used to characterize the samples. As a demonstration of potential applications, the thus formed mesoporous anatase TiO₂ nanorods were tested for their photocatalytic efficiency in the degradation of crystal violet, and a photodegradation mechanism is proposed.     

Sensitivity variation of doped Fricke gel irradiated with monochromatic synchrotron X rays between 33.5 and 80 keV

An experimental binary radiotherapy proposes the concomitant use of a high-Z compound and synchrotron X rays for enhancing radiation dose selectively in tumours by a photoelectric effect. This study aimed at measuring the resulting dose enhancement in irradiated material. A doped Fricke gel dosemeter model was manufactured with 10 mg ml(-1) of iodine (Telebrix) or barium (Micropaque). Samples were irradiated with a monochromatic synchrotron beam at 33.5, 50, 65 and 80 keV. The ensuing enhancement of the sensitivity of the dosemeter was derived from the nuclear magnetic resonance relaxation rates measured at different X-ray doses. Our results demonstrate (1) the preservation of a linear relationship between relaxation rates and X-ray doses for dosemeters doped with high-Z atoms and (2) a clear energy-dependent sensitivity enhancement for barium-doped Fricke gels. This enhancement was neither reproducible with iodinated compounds nor clearly related to the expected dose enhancement factor. However 1% barium sulphate in the gel could significantly improve the gel's response when it was irradiated by low-energy X rays.     

Poly(4-vinylpyridine) Derivatives with Diphosphine Complexes of Gold(I)

The reaction of poly(4-vinylpyridine), P4VP, with complexes [Au₂(O₂CCF₃)₂{μ-Ph₂P(CH₂) _n PPh₂], n = 1–6, gives the corresponding complexes [(P4VP){Au₂(μ-Ph₂P(CH₂) _n PPh₂)} _x ](CF₃CO₂)_2x . Structural features of the polymers were deduced by study of their powder X-ray diffraction properties, aided by parallel studies of the model t-butylpyridine complexes [Au₂(μ-Ph₂P(CH₂) _n PPh₂)(NC₅H₄-4-t-Bu)₂](CF₃CO₂)₂.     

Relationship between climate, pollen concentrations of Ambrosia and medical consultations for allergic rhinitis in Montreal, 1994-2002

The aim of this study is to evaluate the influence of meteorological factors on Ambrosia pollen concentrations and its impact on medical consultations for allergic rhinitis of residents from various socio-economic levels in Montréal (Québec, Canada) between 1994 and 2002. The study was conducted to recognize the sensitivity of pollen productivity to daily climate variability in order to estimate the consequences on human health vulnerability in the context of global climate change. Information related to medical consultations for allergic rhinitis due to pollen comes from the Quebec Health Insurance Board (Régie de l'assurance-maladie du Québec). Ambrosia pollen concentration was measured by the Aerobiology Research Laboratories (Nepean, Ontario). Daily temperature (maximum, minimum, and mean) and precipitation data were obtained from the Meteorological Service of Canada. Socio-economic data come from the 1996 and 2001 census data of Statistics Canada. Between 1994 and 2002, during the Ambrosia pollen season, 7667 consultations for allergic rhinitis due to pollen were recorded. We found a significant association between the number of medical consultations and pollen levels. Significant associations were detected for over-consultation the day of exposure, 1, 2, 3 and 5 days after exposure to high levels of pollen. The consultation rate is higher from low-income residents (3.10 consultations per 10,000 inhabitants) than for high-income (1.65 consultations per 10,000 inhabitants). Considering the demonstrated impact of pollen levels on health, it has become critical to ensure adequate monitoring of Ambrosia and its meteorological sensivity in the context of the anticipated climate change and its potential consequences on human health.     

Testing for refinement in <Emphasis FontCategory="SansSerif" Type="Italic">Circus</Emphasis>

Circus combines constructs to define complex data operations and interactions; it integrates Z and CSP, and, distinctively, it is a language for refinement that can describe programs as well as specification and design models. The semantics is based on the unifying theories of programming (UTP). Most importantly, Circus is representative of a class of refinement-oriented languages that combines facilities to specify abstract data types in a model-based style and patterns of interaction. What we present here is the Circus testing theory; this work is relevant as a foundation for sound test-generation techniques for a plethora of state-rich reactive languages. To cater for data operations, we define symbolic tests and exhaustive test sets. They are the basis for test-generation techniques that can combine coverage criteria for data and transition models. The notion of correctness is Circus refinement, a UTP-based generalisation of failures-divergences refinement that considers data modelling. Proof of exhaustivity exploits the correspondence between the operational and denotational semantics.     

Friction-induced vibration — with and without external disturbance

The dynamics of friction-induced vibration resulting from a velocity-dependent friction characteristic is studied theoretically and experimentally. The frictional system is further studied in the presence of an external dynamic force. The amplitude of quasi-harmonic vibration is shown to increase with sliding velocity until oscillation ceases at some upper velocity boundary depending on the friction characteristic. The vibration, which can exist at high sliding velocities, may influence the operation of automatic transmissions, brakes and clutches. Introduction of strong damping to the system can reduce or eliminate the induced-vibration. Similar results could be achieved by modifying the friction-velocity characteristic of the fluid and materials at the interface. An external excitation in the transverse direction, with properly chosen frequency and force ratios, can also reduce the amplitude of the friction-induced vibration. The theoretical and experimental results are in good agreement.