An approach to the synthesis of dimeric resveratrol natural products via a palladium-catalyzed domino reaction

A route for the rapid assembly of the carbon framework of several resveratrol natural products is presented. A palladium-catalyzed domino reaction of bromostilbene derivative 6 and tolane 7, involving two sequential Heck coupling reactions, provides access to the benzofulvene-based core of various resveratrol-derived natural products. The carbon skeleton of pallidol and its congeners is achieved by a Lewis acid-induced Nazarov-type oxidative cyclization of 9.     

EccA1, a component of the Mycobacterium marinum ESX-1 protein virulence factor secretion pathway, regulates mycolic acid lipid synthesis

Pathogenic mycobacteria, which cause multiple diseases including tuberculosis, secrete factors essential for disease via the ESX-1 protein export system and are partially protected from host defenses by their lipid-rich cell envelopes. These pathogenic features of mycobacterial biology are believed to act independently of each other. Key ESX-1 components include three ATPases, and EccA1 (Mycobacterium marinum MMAR_5443; M.?tuberculosis Rv3868) is the least characterized. Here we show that M.?marinum EccA1's ATPase activity is required for ESX-1-mediated protein secretion, and surprisingly for the optimal synthesis of mycolic acids, integral cell-envelope lipids. Increased mycolic acid synthesis defects, observed when an EccA1-ATPase mutant is expressed in an eccA1-null strain, correlate with decreased in?vivo virulence and intracellular growth. These data suggest that two mycobacterial virulence hallmarks, ESX-1-dependent protein secretion and mycolic acid synthesis, are critically linked via EccA1.     

Immunocytochemical Analysis of P2X2 in Rat Circumvallate Taste Buds

ABSTRACT: BACKGROUND: Our laboratory has shown that classical synapses and synaptic proteins are associated with Type III cells. Yet it is generally accepted that Type II cells transduce bitter, sweet and umami stimuli. No classical synapses, however, have been found associated with Type II cells. Recent studies indicate that ionotropic purinergic receptors P2X2/P2X3 are present in rodent taste buds. Taste nerve processes express the ionotropic purinergic receptors (P2X2/P2X3). P2X2/P2X3Dbl/ mice are not responsive to sweet, umami and bitter stimuli, and it has been proposed that ATP acts as a neurotransmitter in taste buds. The goal of the present study is to learn more about the nature of purinergic contacts in rat circumvallate taste buds by examining immunoreactivity to antisera directed against the purinergic receptor P2X2. RESULTS: P2X2-like immunoreactivity is present in intragemmal nerve processes in rat circumvallate taste buds. Intense immunoreactivity can also be seen in the subgemmal nerve plexuses located below the basal lamina. The P2X2 immunoreactive nerve processes also display syntaxin-1-LIR. The immunoreactive nerves are in close contact with the IP3R3-LIR Type II cells and syntaxin-1-LIR and/or 5-HT-LIR Type III cells. Taste cell synapses are observed only from Type III taste cells onto P2X2-LIR nerve processes. Unusually large, "atypical" mitochondria in the Type II taste cells are found only at the close appositions with P2X2-LIR nerve processes. P2X2 immunogold particles are concentrated at the membranes of nerve processes at the close appositions with taste cells. CONCLUSIONS: Based on our fluorescence and immunoelectron microscopical studies we believe that both perigemmal and most all intragemmal nerve processes display P2X2-LIR. Moreover, colloidal gold immunoelectron microscopy indicates that P2X2-LIR in nerve processes is concentrated at sites of close apposition with Type II cells. This supports the hypothesis that ATP may be a key neurotransmitter in taste transduction and that Type II cells release ATP, activating P2X2 receptors in nerve processes.     

The influence of ball-milling on structural and magnetic properties of Co-based powders

The melt-spun Co- and Fe-based amorphous alloys have been investigated extensively for applications in magnetic devices, which require magnetically soft materials. Although these alloys exhibit excellent soft magnetic properties, their thin sheet shape, which is a consequence of the low glass forming ability, limits significantly their engineering applications. A powder metallurgy is thus an alternative way of producing bulk and, at the same time, soft magnetic materials, having desired shape. In our case, Co₅₆Fe₁₆Zr₈B₂₀ and Co_70.3Fe_4.7Si₁₀B₁₅ amorphous ribbons have been ball-milled for a short time and subsequently compacted (by hot pressing) into disc-shaped specimens with the aim to achieve samll values of resulting coercivity. This work is focused only on the first preparation step i.e. on structural and magnetic properties of ball-milled powders obtained by ball-milling of Co-based melt-spun ribbons at different conditions. Two different ways of milling were employed in order to obtain a powder form of the material: the ribbons were either continuously ball-milled for up to 12 hours or, after each half an hour of ball-milling, the vials were cooled in liquid nitrogen bath for half an hour. Mössbauer spectroscopy, X-ray diffraction and differential scanning calorimetry were employed to compare and to present the differences between these two different ways of milling.     

Municipal Solid Waste Landfill Leachate Treatment and Electricity Production Using Microbial Fuel Cells

Microbial fuel cells were designed and operated to treat landfill leachate while simultaneously producing electricity. Two designs were tested in batch cycles using landfill leachate as a substrate without inoculation (908 to 3,200 mg/L chemical oxygen demand (COD)): Circle (934 mL) and large-scale microbial fuel cells (MFC) (18.3 L). A total of seven cycles were completed for the Circle MFC and two cycles for the larger-scale MFC. Maximum power densities of 24 to 31 mW/m² (653 to 824 mW/m³) were achieved using the Circle MFC, and a maximum voltage of 635 mV was produced using the larger-scale MFC. In the Circle MFC, COD, biological oxygen demand (BOD), total organic carbon (TOC), and ammonia were removed at an average of 16%, 62%, 23%, and 20%, respectively. The larger-scale MFC achieved an average of 74% BOD removal, 27% TOC removal, and 25% ammonia reduction while operating over 52 days. Analysis of the microbial characteristics of the leachate indicates that there might be both supportive and inhibiting bacteria in landfill leachate for operation of an MFC. Issues related to scale-up and heterogeneity of a mixed substrate remain.     

Challenges and successes in using inductively coupled plasma mass spectrometry for measurements of tungsten in environmental water and soil samples

Military small arms ranges in the United States have been used for munitions training with tungsten rounds, which are comprised of powdered tungsten (W) pressed together with polymeric binders. As a result, W has been introduced into surface soils. The environmental and human health effects of W remain open questions. The US Army Corps of Engineers is responsible for environmental monitoring, site assessments, and cleanup of small arms ranges. This work requires routine measurements of tungsten in natural waters and soils. However, the existing sample preparation and analytical procedures were not specifically developed with W in mind for environmental analysis. Our work suggests modification of existing metal sample preparation and analytical procedures are necessary to accurately quantify W in environmental media. Our group has been actively conducting W measurements using inductively coupled plasma mass spectrometry (ICPMS), both with quadrupole and sector field ICPMS systems. We have used heavy rare earth elements and iridium as internal standards. For soils, the great majority of the W from small arms can be dissolved using acid leaching with HNO₃–H₃PO₄ mixtures; more rigorous preparations with fusion or HF digestions can also be used. In ICPMS analysis, the largest challenge involves dealing with the significant carry-over and memory of W in sample introduction systems. This ultimately limits measurement capabilities, particularly at sub-µg L^?1 levels. With careful attention to the sample and standards’ matrix constituents, and proper washout time, successful analysis is possible and ICPMS is clearly the preferred technique. A commercially available fluoropolymer sample introduction system exhibits significantly improved memory characteristics.     

Properties of surface dielectric barrier discharge plasma generator for fabrication of nanomaterials

This paper presents surface dielectric barrier discharge plasma generators as an efficient source of low-energy ions. Either positive or negative ions can be extracted from a plasma cloud with an external DC field created by the third electrode. Three different cross-section geometries of DBD generators were analyzed, simulated and fabricated. Currents of ions extracted from the plasma cloud were measured and the results were discussed. It was demonstrated that if the third electrode consists of liquid–gas interface, the presented arrangement can be used as a versatile reactor for nanomaterial synthesis (on the example of the synthesis of silver nanoparticles).     

Reduction of magnetic field fluctuations in powered magnets for NMR using inductive measurements and sampled-data feedback control

Resistive and hybrid (resistive/superconducting) magnets provide substantially higher magnetic fields than those available in low-temperature superconducting magnets, but their relatively low spatial homogeneity and temporal field fluctuations are unacceptable for high resolution NMR. While several techniques for reducing temporal fluctuations have demonstrated varying degrees of success, this paper restricts attention to methods that utilize inductive measurements and feedback control to actively cancel the temporal fluctuations. In comparison to earlier studies using analog proportional control, this paper shows that shaping the controller frequency response results in significantly higher reductions in temporal fluctuations. Measurements of temporal fluctuation spectra and the frequency response of the instrumentation that cancels the temporal fluctuations guide the controller design. In particular, we describe a sampled-data phase-lead-lag controller that utilizes the internal model principle to selectively attenuate magnetic field fluctuations caused by the power supply ripple. We present a quantitative comparison of the attenuation in temporal fluctuations afforded by the new design and a proportional control design. Metrics for comparison include measurements of the temporal fluctuations using Faraday induction and observations of the effect that the fluctuations have on nuclear resonance measurements.