Ag(I)(Et(2)PCH(2)CH(2)PPh(2))(2)]NO(3): An Antimitochondrial Silver Complex

The silver(I) complex [Ag(eppe)(2)]NO(3) (eppe = Et(2)PCH(2)CH(2)PPh(2)) is shown by X-ray crystallography to be tetrahedral with Ag - PEt(2) and Ag - P Ph(2) bond lengths of 2.482 and 2.518 A, respectively. The complex is selectively antimitochondrial and inhibits the growth of a number of yeast strains in non-fermentable media at concentrations as low as 2.5 muMu and induces the mitochondrial mutation petite The effect is largely reversed by the presence of aspirin. The complex is shown to be stable in the cell culture media and in the presence of glutathione, but readily reacts with disulfides of oxidized glutathione and serum albumin. Surprisingly, neither [Au(eppe)(2)]Cl nor [Au(eppe)(2)]Cl (dppe = Ph(2)PCH(2)CH(2)PPh(2)) showed any mitochondrial selectivity in the same screening protocol.     

Different coordination modes of a tripod phosphine in gold(i) and silver(i) complexes

The following gold(I) and silver(I) complexes of the tritertiary phosphine 1,1,1- tris(diphenylphosphinomethyl)ethane, tripod , have been synthesised: Au(3)(tripod)X(3) [X = Cl(1), Br(2), I(3)]; [Au(3)(tripod)(2)Cl(2)]Cl (4); Au(tripod)X [X = Br(5), I(6)]; Ag(3)(tripod) (NO(3))(4) (7), Ag(tripod)NO(3) (8). They were characterized by X-ray diffraction (complexes 2, 3 and 4), (31)P NMR spectroscopy, electrospray and FAB mass spectrometry and infrared spectroscopy. Complexes 2 and 3 show a linear coordination geometry for Au(I), with relatively short Au-P bond distances. Complex 3 has a Au***Au intramolecular distance of 3.326 A degrees , while complex 2 had a short Au***Au intermolecular interaction of 3.048 A degrees . Complexes 4-6 were found by (31)P NMR spectroscopy studies to contain a mixture of species in solution, one of which crystallised as [Au(3)(tripod|)(2)Cl(2)]Cl which was shown by X-ray diffraction to contain both tetrahedral and linear Au(I), the first example of a Au(I) complex containing such a mixture of geometries. The reaction of [Au(3) (tripod)Cl(3)] (1) with tripod led successfully to the formation of [Au(3)(tripod|)(2)Cl(2)](+) and [Au(3)(tripod)(2)Cl(3)](+) and [Au(3)(tripod|)(3)Cl](2+). The silver(I) complexes, 7 and 8 appear to contain linear and tetrahedral Ag(I), respectively.     

Impurities in vegetable oil refining soapstock

Summary The nature of the impurities in vegetable oil foots renders them resistant to treatment by acids as in normal acidulation. Strong caustic was found to attack the gums and make them at least partially soluble in a 5 to 10% aqueous caustic solution. At this concentration a soap phase of 45–60% TFA could be centrifugally separated, and the majority of the impurities or their degraded products were discharged in the lye. The ratio of Oxidized Acids and Insoluble Impurities to the TFA was much lower in the soap than in the raw soapstock; the Oxidized Acids/Black Acids ratio could generally be reduced to 5% or less. This reduction in impurities was found to improve laboratory still yields markedly without the necessity of Twitchell- or pressure- splitting the black acids from treated stocks. Distillate yields of 86–89% were obtained from treated stocks, compared to 69–70% from untreated stocks.     

Ultra-wideband analog-to-digital conversion via signal expansion

We consider analog to digital (A/D) conversion, based on the quantization of coefficients obtained via the projection of a continuous time signal over a set of basis functions. The framework presented here for A/D conversion is motivated by the sampling of an input signal in domains which may lead to significantly less demanding A/D conversion characteristics, i.e., lower sampling rates and lower bit resolution requirements. We show that the proposed system efficiently parallelizes the analog to digital converter (ADC), which lowers the sampling rate requirements by increasing the number of basis functions on which the continuous time signal is projected, leading to a tradeoff between sampling rate reduction and system complexity. Additionally, the A/D conversion resolution requirements can be reduced by optimally assigning the available number of bits according to the variance distribution of the coefficients obtained from the signal projection over the new A/D conversion domain. In particular, we study A/D conversion in the frequency domain, where samples of the continuous signal spectrum are taken such that no time aliasing occurs in the discrete time version of the signal. We show that the frequency domain ADC overcomes some of the difficulties encountered in conventional time-domain methods for A/D conversion of signals with very large bandwidths, such as ultra-wideband (UWB) signals. The proposed A/D conversion method is compared with conventional ADCs based on pulse code modulation (PCM). Fundamental figures of merit in A/D conversion and system tradeoffs are discussed for the proposed ADC. The signal-to-noise and distortion ratios of the frequency domain ADC are presented, which quantify the impact of the most critical impairments of the proposed ADC technique. We also consider application to communications receivers, and provide a design example of a multi-carrier UWB receiver.     

Stress corrosion cracking of a low alloy steel in high purity steam

The catastrophic failure of a steam turbine at Hinkley Point “A” Nuclear Power Station resulted from stress corrosion cracking of the discs on the low pressure (L.P.) turbine rotor. This paper describes investigations carried out within the South Western Region of the C.E.G.B. to determine the mechanism and the environment responsible for cracking.The results show that stress corrosion cracks can be initiated and propagated during normal turbine operation and furthermore they suggest that cracking is due to the action of wet, high purity steam on stressed metal. The chemical quality of the steam was found to be very high, the impurities were well within the normal range associated with power plant operation.The results are in agreement with the recent findings of more widespread cracking at Hinkley Point and elsewhere. It is considered that as the steam is inherently aggressive then the measures currently being taken by C.E.G.B., i.e. the removal of the highly stressed keyways, limiting steam access to regions of high stress and the use of improved alloys, should prevent further failures of this type.     

Quantitative assessment of surface-enhanced resonance Raman scattering for the analysis of dyes on colloidal silver

Factors that affect quantitative analysis by surface-enhanced resonance Raman scattering (SERRS) have been investigated using azobenzotriazol and reactive dyes. Preaggregation of the silver colloid was the most effective method to obtain repeatable and reproducible scattering. Aggregation by poly(l-lysine) or spermine provided better precision than aggregation by sodium chloride or nitric acid. Repeatable quantitative analysis was achieved with the azobenzotriazol dyes. A linear calibration graph was obtained over different concentration ranges below 10(-)(8) M, depending on the nature of the colloid. Calculations estimate that 10(-)(8) M is the concentration at which monolayer coverage of the dye on the silver colloid is achieved. Above 10(-)(8) M, there was only a minor increase in the scattering intensity from the azobenzotriazol dyes. In contrast, the reactive dyes did not give a response proportional to concentration over the range studied. The different responses obtained for the two types of dye are believed to be caused by differences in the nature of the interaction of the molecules with the silver surface. The conclusion reached is that control of the colloid preparation, aggregation process, and surface chemistry are essential for successful quantitative analysis of dyes on colloidal silver by SERRS.     

EPECUR setup for the search for narrow baryon resonances in pion-proton scattering

The EPECUR experimental setup has been designed to search for narrow resonant states by precisely measuring differential and total reaction cross sections for pion-nucleon interactions with 1-MeV pion energy steps. Over the 5 years that passed from the submission of the idea of the experiment to the start of data taking in April 2009, a non-magnetic spectrometer with a liquid hydrogen target based on the large-aperture multiwire drift chambers with a hexagonal structure has been built at the universal beamline 322 of the U-10 proton synchrotron at the Alikhanov Institute for Theoretical and Experimental Physics. Owing to the unique properties of the beamline, the beam particle momentum can be measured with an accuracy of 0.1% or better using 1-mm-pitch proportional chambers located at the first focus of the beamline. The design of numerous subsystems of the setup is based on modern electronic components including microprocessors and field programmable gate arrays. All the subsystems have been tuned and tested both individually and as parts of the whole setup. The distributed data acquisition system is based on the widely spread USB and Ethernet protocols, which help achieve high performance characteristics and take full advantage of the industrial solutions.     

Effect of soluble ash components on the viscosity of lignite-water mixtures

The removal of multivalent cations from lignite-water mixtures (LWM) was shown to lower mixture apparent viscosity by a factor of about 40, for example, at 100 s^?1 by reducing both the yield stress and plastic viscosity. The cations Ca⁺⁺, Mg⁺⁺, Al⁺⁺⁺, K⁺, and Na⁺, among others, were found to be present in the aqueous phase of the LWM in concentrations ranging from 546 ppm to 8 ppm. The primary anions present were CI^? and SO₄⁼. The degree to which the cations affected viscosity were of order trivalent > divalent > monovalent. The nature of the anion was found to be relatively unimportant. A process utilizing ion-exchange resins for removing multivalent cations to produce low viscosity lignite-water or coal-water mixtures is described.     

Unsaturated polyester resins for thermoset applications using renewable isosorbide as a component for property improvement

Unsaturated polyester (UPE) resins are used in a variety of thermosetting applications due to the reduced cost when compared to epoxy resins; however, UPE resins also have reduced thermomechanical performance. Investigating avenues to improve the performance of UPEs has led to the use of bio‐based starting materials as structural components of the synthesized prepolymers as a result of their advantageous structural features. Isosorbide, a compound derived from renewable feedstocks, has been utilized to provide additional stiffness from the diol component for novel unsaturated polyesters resins. These resins have been shown to possess T_g's (32?72°C) and storage moduli (540?2200 MPa) that are in the desired range for composite materials with viscosities (1.2?25 Pa s) amenable to a variety of liquid molding techniques. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42315.