Interaction of metal ions with nucleic acids and related compounds. II. Studies on Au(III)-nucleic acid system

The nature of interaction of Au(III) with nucleic acids was studied by using methods such as uv and ir spectrophotometry, viscometry, pH titrations, and melting-temperature measurements. Au(III) is found to interact slowly with nucleic acids over a period of several hours. The uv spectra of native calf-thymus DNA 9pH 5.6 acetate buffer containing (0.01M NaCIO4) showed a shift in λ max to high wavelengths and an increase in optical density at 260 nm. There was a fourfold decrease in viscosity (expressed as ηsp/c). The reaction was faster at pH 4.0 and also with denatured DNA (pH 5.6) and whole yeast RNA (pH 5.6). The order of preference of Au(III) (as deduced from the time of completion of reaction) for the nucleic acids in RNA > denatured DNA > DNA. The reaction was found to be completely reversible with respect KCN. Infrared spectra of DNA-Au(III) complexes showed binding to both the phosphate and bases of DNA. The same conclusions were also arrived at by melting-temperature studies of Au(III)-DNA system. pH titrations showed liberation of two hydroxylions at r = 0.12 [r = moles of HAuCl4 added per mole of DNA-(P)] and one hydrogen ion at r = 0.5. The probable binding sites could be N(1)/N(7) of adenine, N(7) and/or C(6)O of guanine, N(3) of cytosine and N(3) of thymine. DNAs differing in their (G = C)-contents [Clostridium perfingens DNA(G = C, 29%), salmon sperm DNA (G + C, 42%) and Micrococcus lysodeikticus DNA(G + C, 29%), salmon sperm DNA (G = C, 72%)] behaved differently toward Au(III). The hyperchromicity observed for DNAs differing in (G + C)-content and cyanide reversal titrations indicate selectivity toward ( A + T)-rich DNA at lw values of r. Chemical analysis and job's continuous variation studies indicated the existence of possible complexes above and below r = 1. The results indicate that Au(III) ions probably bind to hte phosphate group in the initial stages of the reaction, particularly at low values of r, and participation of the base interaction also increases. Cross-linking of the two strands by Au(III) may take place, but a complete collapse of the doulbe helix is not envisaged. It is probable that tilting of the bases or rotaiton of the bases around the glucosidic bond, resulting in a significant distrotion of the double helix, might take place due to binding of Au(III) to DNA.

Simultaneous measurement of multiple parameters using a single fiber Bragg grating

A novel approach for simultaneous measurement of chirp (any parameter that can induce strain gradient on FBG) and temperature using a single FBG is proposed. Change in reflectivity at central wavelength of FBG reflection & Bragg wavelength shifts induced due to temperature were used for chirp & temperature measurements respectively. Theoretical resolution limit for chirp and temperature using an Optical Spectrum Analyzer (OSA) with 1pm wavelength resolution and >58dB dynamic range are 12.8fm and 1/13 degrees C respectively.

Large negative magnetoresistance and metal-insulator transition observed in MnO/C composite coatings grown on ceramic alumina by metalorganic chemical vapor deposition

MnO/C composite coatings were grown by the metalorganic chemical vapor deposition process on ceramic alumina in argon ambient. Characterization by various techniques confirms that these coatings are homogeneous composites comprising nanometer-sized MnO particles embedded in a matrix of nanometer-sized graphite. Components of the MnO/C composite coating crystalline disordered, but are electrically quite conductive. Resistance vs. temperature measurements show that coating resistance increases exponentially from a few hundred ohms at room temperature to a few megaohms at 30 K. Logarithmic plots of reduced activation energy vs. temperature show that the coating material undergoes a metal-insulator transition. The reduced activation energy exponent for the film under zero magnetic field was 2.1, which is unusually high, implying that conduction is suppressed at much faster rate than the Mott or the Efros-Shklovskii hopping mechanism. Magnetoconductance us. magnetic field plots obtained at various temperatures show a high magnetoconductance (similar to 28.8%) at 100 K, which is unusually large for a disordered system, wherein magnetoresistance is attributed typically to weak localization. A plausible explanation for the unusual behavior observed in the carbonaceous disordered composite material is proposed. (C) 2010 Elsevier Ltd. All rights reserved.

Microstructural evolution and giant magnetoresistance in melt spun and annealed Cu-85(FeCo)(15) alloy

Granular alloys of Cu with FeCo were prepared by the melt-spinning technique. The alloy was characterized by x-ray, transmission electron microscopy, vibrating sample magnetometer, and magnetoresistance measurements. The alloys were heat treated for different temperatures to optimize the magnetoresistance properties. Structural characterization reveals that the FeCo phase initially precipitates out as fcc and later transforms to the bcc structure by martensitic transformation. It is seen that the trend in the magnetoresistance properties is different for the measurements carried out at room temperature and 4.2 K. This has been attributed to the transformation of fine fcc precipitates to the bcc structure during the low temperature measurements. It is seen that the presence of fine particles causes an increase in the field for saturation and is not suitable for applications where moderate field giant magnetoresistance is required. (C) 1999 American Institute of Physics. [S0021-8979(99)08317-6].

Standard Gibbs energy of formation of Pb2Ru2O6.5

Lead ruthenate is used as a bifunctional electrocatalyst for both oxygen evolution and reduction and as a conducting component in thick-film resistors. It also has potential applications in supercapacitors and solid oxide fuel cells. However, thermodynamic properties of the compound have not been reported in the literature. The standard Gibbs energy of formation has now been determined in the temperature range from 873 to 1123 K using a solid-state cell incorporating yttria-stabilized zirconia (YSZ) as the electrolyte, a mixture of PbO + Pb2Ru2O6.5 + Ru as the measuring electrode, and Ru + RuO2 as the reference. The design of the measuring electrode is based on a study of phase relations in the ternary system Pb–Ru–O at 1123 K. For the reaction,S0884291400095625_eqnU1 the standard enthalpy of formation and standard entropy at 298.15 K are estimated from the high-temperature measurements. An oxygen potential diagram for the system Pb–Ru–O is composed based on data obtained in this study and auxiliary information from the literature

Identification and optimization of ammonia reactors through hybrid simulation

A hybrid simulation technique for identification and steady state optimization of a tubular reactor used in ammonia synthesis is presented. The parameter identification program finds the catalyst activity factor and certain heat transfer coefficients that minimize the sum of squares of deviation from simulated and actual temperature measurements obtained from an operating plant. The optimization program finds the values of three flows to the reactor to maximize the ammonia yield using the estimated parameter values. Powell's direct method of optimization is used in both cases. The results obtained here are compared with the plant data.

Oceanographic and meteorological observations for project Little Window: March 1970

ENGLISH: Project Little Window was planned to provide some answers to the important scientific question of whether or not the HRIR (high resolution infrared radiometer) sensors aboard NASA and NOAA satellites can provide useful data for much of the oceanographic community. The sensors aboard these satellites were designed in response to the initial needs of meteorologists for temperature measurements integrated over a distance of 5-10 nautical miles and extending over a range from 30°C to about -75°C (i2-4°C). To this end the sensors have been a very powerful tool to the meteorologist in preparing daily weather advisories and in carrying out research. SPANISH: El proyecto Little Window fue planeado para suministrar algunas respuestas al importante tema científico sobre si los captadores (ltsensors") infrarrojos de alta resoluci6n (IRAR) a bordo de los satélites NASA y NOAA, pueden o no proveer datos útiles para la mayor1a de los oceanógrafos. Los captadores a bordo de estos satélites fueron concebidos en respuesta a las necesidades iniciales de los meteor6logos para obtener mediciones de temperatura integradas sobre una distancia de 5-10 millas náuticas, y entre 30°c y aproximadamente -75°C (~2-4°C). Con este fin los captadores han sido un instrumento poderoso para el meteor6logo en la preparaci6n de las informaciones diarias de tiempo y en la realizaci6n de las investigaciones. (PDF contains 171 pages.)

An experimental investigation of the heat transfer from a buoyant gas plume to a horizontal unobstructed ceiling

This thesis presents an experimental investigation of the axisymmetric heat transfer from a small scale fire and resulting buoyant plume to a horizontal, unobstructed ceiling during the initial stages of development. A propane-air burner yielding a heat source strength between 1.0 kW and 1.6 kW was used to simulate the fire, and measurements proved that this heat source did satisfactorily represent a source of buoyancy only. The ceiling consisted of a 1/16" steel plate of 0.91 m. diameter, insulated on the upper side. The ceiling height was adjustable between 0.5 m and 0.91 m. Temperature measurements were carried out in the plume, ceiling jet, and on the ceiling.

Heat transfer data were obtained by using the transient method and applying corrections for the radial conduction along the ceiling and losses through the insulation material. The ceiling heat transfer coefficient was based on the adiabatic ceiling jet temperature (recovery temperature) reached after a long time. A parameter involving the source strength Q and ceiling height H was found to correlate measurements of this temperature and its radial variation. A similar parameter for estimating the ceiling heat transfer coefficient was confirmed by the experimental results.

This investigation therefore provides reasonable estimates for the heat transfer from a buoyant gas plume to a ceiling in the axisymmetric case, for the stagnation region where such heat transfer is a maximum and for the ceiling jet region (r/H ≤ 0.7). A comparison with data from experiments which involved larger heat sources indicates that the predicted scaling of temperatures and heat transfer rates for larger scale fires is adequate.

Análisis del proceso de Friction Drilling: Análisis de la calidad de la junta atornillada

[ES]En el presente trabajo, se pretende optimizar la unión atornillada de chapas de dos materiales disimilares (acero y aluminio) mediante un proceso no convencional, el taladrado por fricción. Dicho proceso está orientado a la calderería fina, sector en el cual tiene gran número de aplicaciones. Se comenzará con una serie de ensayos iníciales y se procederá a realizar pruebas sistemáticas. Se realizarán mediciones de temperaturas, momentos torsores y fuerzas, y se analizaran las tolerancias dimensionales generadas por el proceso para la elección de los parámetros óptimos. El documento se centrará en analizar de forma teórica el comportamiento mecánico de la unión y de los ensayos de tracción correspondientes. Esto servirá para realizar los futuros ensayos de calidad y posteriormente comparar los resultados con los de las uniones convencionales.

Electronic structure in five-coordinate complexes of nickel(II) with heavy-donor ligands

I.

Various studies designed to elucidate the electronic structure of the arsenic donor ligand, o-phenylenebisdimethylarsine (diarsine), have been carried out. The electronic spectrum of diarsine has been measured at 300 and 77˚K. Electronic spectra of the molecular complexes of various substituted organoarsines and phosphines with tetracyanoethylene have been measured and used to estimate the relative ionization potentials of these molecules.

Uv photolysis of arsines in frozen solution (96˚K) has yielded thermally labile, paramagnetic products. These include the molecular cations of the photolyzed compounds. The species (diars)⁺ exhibits hyper-fine splitting due to two equivalent ⁷⁵As(I=3/2) nuclei. Resonances due to secondary products are reported and assignments discussed.

Evidence is presented for the involvement of d-orbitals in the bonding of arsines. In (diars)⁺ there is mixing of arsenic “lone-pair” orbitals with benzene ring π-orbitals.

II.

Detailed electronic spectral measurements at 300 and 77˚K have been carried out on five-coordinate complexes of low-spin nickel(II), including complexes of both trigonal bipyramidal (TBP) and square pyramidal (SPY) geometry. TBP complexes are of the form NiLX⁺ (X=halide or cyanide,

L = Qƭ(CH₂)₃As(CH₃)₂]₃ or

P [hexagon - Q'CH₃] , Q = P, As,

Q’=S, Se).

The electronic spectra of these compounds exhibit a novel feature at low temperature. The first ligand field band, which is asymmetric in the room temperature solution spectrum, is considerably more symmetrical at 77˚K. This effect is interpreted in terms of changes in the structure of the complex.

The SPY complexes are of the form Ni(diars)₂X^z (X=CL, Br, CNS, CN, thiourea, NO₂, As). On the basis of the spectral results, the d-level ordering is concluded to be xy ˂ xz, yz ˂ z² ˂˂ x² - y². Central to this interpretation is identification of the symmetry-allowed ¹A₁ → ¹E (xz, yz → x² - y²) transition. This assignment was facilitated by the low temperature measurements.

An assignment of the charge-transfer spectra of the five-coordinate complexes is reported, and electronic spectral criteria for distinguishing the two limiting geometries are discussed.

Occurrence of whale sharks in coastal waters in the Indian Ocean: an interesting coincidence

Salinity, temperature and pressure are parameters which govern the oceanographic state of a marine water body and together they make up density of seawater. In this contribution we will focus our interest on one of these parameters, the salinity: accuracy in relation to different purposes as well as observation technique and instrumentation. We will also discuss the definition of salinity. For example most of the Indian Ocean waters are within the salinity range from 34.60-34.80, which emphasize the importance of careful observations and clear definitions of salinity, in such a way that it is possible to define water masses and predict their movements. In coastal waters the salinity usually features much larger variation in time and space and thus less accuracy is sometimes needed. Salinity has been measured and defined in several ways over the past century. While early measurements were based on the amount of salt in a sea water sample, today the salinity of seawater is most often determined from its conductivity. As conductivity is a function of salinity and temperature, determination involves also measurement of the density of seawater is now more precisely estimated and thus the temperature. As a result of this method the Practical Salinity Scale (PSS) was developed. The best determination of salinity from conductivity and the temperature measurements gives salinity with resolution of 0.001 psu, while the accuracy of titration method was about ± 0.02‰. Because of that, even calculation of movements in the ocean is also improved.

The prediction of hot streak migration in a high-pressure turbine

Accurate predictions of combustor hot streak migration enable the turbine designer to identify high-temperature regions that can limit component life. It is therefore important that these predictions are achieved within the short time scales of a design process. This article compares temperature measurements of a circular hot streak through a turning duct and a research turbine with predictions using a three-dimensional Reynolds-averaged Navier-Stokes solver. It was found that the mixing length turbulence model did not predict the hot streak dissipation accurately. However, implementation of a very simple model of the free stream turbulence (FST) significantly improved the exit temperature predictions on both the duct and research turbine. One advantage of the simple FST model described over more complex alternatives is that no additional equations are solved. This makes the method attractive for design purposes, as it is not associated with any increase in computational time.

Improved infrared thermal imaging of a CMOS MEMS device

We report a technique which can be used to improve the accuracy of infrared (IR) surface temperature measurements made on MEMS (Micro-Electro-Mechanical- Systems) devices. The technique was used to thermally characterize a SOI (Silicon-On-Insulator) CMOS (Complementary Metal Oxide Semiconductor) MEMS thermal flow sensor. Conventional IR temperature measurements made on the sensor were shown to give significant surface temperature errors, due to the optical transparency of the SiO 2 membrane layers and low emissivity/high reflectivity of the metal. By making IR measurements on radiative carbon micro-particles placed in isothermal contact with the device, the accuracy of the surface temperature measurement was significantly improved. © 2010 EDA Publishing/THERMINIC.

An advanced multi-configuration stator well cooling test facility

Optimisation of cooling systems within gas turbine engines is of great interest to engine manufacturers seeking gains in performance, efficiency and component life. The effectiveness of coolant delivery is governed by complex flows within the stator wells and the interaction of main annulus and cooling air in the vicinity of the rim seals. This paper reports the development of a test facility which allows the interaction of cooling air and main gas paths to be measured at conditions representative of those found in modern gas turbine engines. The test facility features a two stage turbine with an overall pressure ratio of approximately 2.6:1. Hot air is supplied to the main annulus using a Rolls-Royce Dart compressor driven by an aero-derivative engine plant. Cooling air can be delivered to the stator wells at multiple locations and at a range of flow rates which cover bulk ingestion through to bulk egress. The facility has been designed with adaptable geometry to enable rapid changes of cooling air path configuration. The coolant delivery system allows swift and accurate changes to the flow settings such that thermal transients may be performed. Particular attention has been focused on obtaining high accuracy data, using a radio telemetry system, as well as thorough through-calibration practices. Temperature measurements can now be made on both rotating and stationary discs with a long term uncertainty in the region of 0.3 K. A gas concentration measurement system has also been developed to obtain direct measurement of re-ingestion and rim seal exchange flows. High resolution displacement sensors have been installed in order to measure hot running geometry. This paper documents the commissioning of a test facility which is unique in terms of rapid configuration changes, non-dimensional engine matching and the instrumentation density and resolution. Example data for each of the measurement systems is presented. This includes the effect of coolant flow rate on the metal temperatures within the upstream cavity of the turbine stator well, the axial displacement of the rotor assembly during a commissioning test, and the effect of coolant flow rate on mixing in the downstream cavity of the stator well. Copyright © 2010 by ASME.

Finite element analysis of compressor disc heat transfer using the transient conduction method with sparse boundary collocation points

Surface temperature measurements from two discs of a gas turbine compressor rig are used as boundary conditions for the transient conduction solution (inverse heat transfer analysis). The disc geometry is complex, and so the finite element method is used. There are often large radial temperature gradients on the discs, and the equations are therefore solved taking into account the dependence of thermal conductivity on temperature. The solution technique also makes use of a multigrid algorithm to reduce the solution time. This is particularly important since a large amount of data must be analyzed to obtain correlations of the heat transfer. The finite element grid is also used for a network analysis to calculate the radiant heat transfer in the cavity formed between the two compressor discs. The work discussed here proved particularly challenging as the disc temperatures were only measured at four different radial locations. Four methods of surface temperature interpolation are examined, together with their effect on the local heat fluxes. It is found that the choice of interpolation method depends on the available number of data points. Bessel interpolation gives the best results for four data points, whereas cubic splines are preferred when there are considerably more data points. The results from the analysis of the compressor rig data show that the heat transfer near the disc inner radius appears to be influenced by the central throughflow. However, for larger radii, the heat transfer from the discs and peripheral shroud is found to be consistent with that of a buoyancy-induced flow.