Electrochemistry and Spectroscopy of Sulfate and Thiosulfate Complexes of Iron Porphyrins

The electrochemical and spectroscopic properties of the complex formed by the addition of thiosulfate to ferric porphyrins were examined. The NMR spectrum of the thiosulfate–ferric porphyrin complex was consistent with a high-spin ferric complex, while the EPR spectrum at liquid nitrogen temperatures indicated that the complex under these conditions was low-spin. Such behavior has been previously observed for other ferric porphyrin complexes. The visible spectra were characterized by a shift in the Soret band to higher energies, with smaller changes in the longer wavelength region. The complex was reasonably stable in DMF, but slowly reduced over several hours to FeII(TPP) and S4O6 2−. The voltammetric behavior of the thiosulfate complex in DMF consists of two waves, the first of which was irreversible. The ferric/ferrous reduction in the presence of thiosulfate was shifted negatively about 400 mV, compared to the Fe(TPP)(Cl) reduction. The visible, NMR and EPR spectra were most consistent with a Fe–S bonded ferric porphyrin–thiosulfate complex, Fe(P)(SSO3)−. The kinetics of the reduction of ferric porphyrin by thiosulfate in DMSO indicated an autocatalytic mechanism, where the first step is the formation of the catalyst. The identity of the catalyst could not be determined because it must be present at low concentrations, but it is formed from the reaction of the ferric complex with thiosulfate. Coordination of thiosulfate to the porphyrin was not necessary for the reduction to occur, and the reduction of Fe(TPP)(Cl) by thiosulfate was accelerated by the addition of sulfate. Under these conditions, sulfate had replaced thiosulfate as the axial ligand for the ferric porphyrin. In the presence of sulfate, the reduction occurred in a single kinetic pseudo-first order step. The voltammetry, spectroelectrochemistry and kinetics for the reaction of thiosulfate with ferric porphyrins were examined. A rapid reaction between ferric porphyrins and thiosulfate was observed in DMF. The reaction was complex, involving the formation of a catalytic intermediate. Window factor analysis and multivariate curve resolution were used to deconvolute the kinetic data

SAR-Based Vibration Estimation Using the Discrete Fractional Fourier Transform

A vibration estimation method for synthetic aperture radar (SAR) is presented based on a novel application of the discrete fractional Fourier transform (DFRFT). Small vibrations of ground targets introduce phase modulation in the SAR returned signals. With standard preprocessing of the returned signals, followed by the application of the DFRFT, the time-varying accelerations, frequencies, and displacements associated with vibrating objects can be extracted by successively estimating the quasi-instantaneous chirp rate in the phase-modulated signal in each subaperture. The performance of the proposed method is investigated quantitatively, and the measurable vibration frequencies and displacements are determined. Simulation results show that the proposed method can successfully estimate a two-component vibration at practical signal-to-noise levels. Two airborne experiments were also conducted using the Lynx SAR system in conjunction with vibrating ground test targets. The experiments demonstrated the correct estimation of a 1-Hz vibration with an amplitude of 1.5 cm and a 5-Hz vibration with an amplitude of 1.5 mm

Method for defect free keyhole plasma arc welding

A plasma arc welding process for welding metal of increased thickness with one pass includes operating the plasma arc welding apparatus at a selected plasma gas flow rate, travel speed and arc current, to form a weld having a penetration ratio to weld height to weld width, and maintaining the penetration ratio at less than 0.74. Parameters for the plasma gas flow rate, travel speed and arc current are adjusted to a steady state condition during a start up period and maintained during the steady state condition to complete a weld. During a terminal stopping period, the travel speed is stopped and instantaneously replaced by filler wire which adds material to fill the keyhole that had been formed by the welding process. Parameters are subsequently adjusted during the stopping period to terminate the weld in a sound manner

Black hole masses and enrichment of z ~ 6 SDSS quasars

We present sensitive near-infrared spectroscopic observations for a sample of five z ~ 6 quasars. These are amongst the most distant, currently known quasars in the universe. The spectra have been obtained using ISAAC at the VLT and include the CIV, MgII and FeII lines. We measure the FeII/MgII line ratio, as an observational proxy for the Fe/alpha element ratio. We derive a ratio of 2.7+/-0.8 for our sample, which is similar to that found for lower redshift quasars, i.e., we provide additional evidence for the lack of evolution in the FeII/MgII line ratio of quasars up to the highest redshifts. This result demonstrates that the sample quasars must have undergone a major episode of iron enrichment in less than one Gyr and star formation must have commenced at z > 8. The linewidths of the MgII and CIV lines give two estimates for the black hole masses. A third estimate is given by assuming that the quasars emit at their Eddington luminosity. The derived masses using these three methods agree well, implying that the quasars are not likely to be strongly lensed. We derive central black hole masses of 0.3-5.2 10^9 solar masses. We use the difference between the redshift of MgII (a proxy for the systemic redshift of the quasar) and the onset of the Gunn Peterson trough to derive the extent of the ionized Stromgren spheres around our target quasars. The derived physical radii are about five Mpc. Using a simple ionization model, the emission of the central quasars would need of order 10^6-10^8 year to create these cavities in a surrounding intergalactic medium with a neutral fraction between 0.1 and 1.0. As the e-folding time scale for the central accreting black hole is on the order of a few times 10^7 year, it can grow by one e-folding or less within this time span.Comment: Accepted by ApJ, 15 pages, 8 figure

Climate amenities, climate change, and American quality of life

We present a hedonic framework to estimate U.S. households' preferences over local climates, using detailed weather and 2000 Census data. We find that Americans favor an average daily temperature of 65 degrees Fahrenheit, will pay more on the margin to avoid excess heat than cold, and are not substantially more averse to extremes than to temperatures that are merely uncomfortable. These preferences vary by location due to sorting or adaptation. Changes in climate amenities under business-as-usual predictions imply annual welfare losses of 1 to 3 percent of income by 2100, holding technology and preferences constant

On the Use of Quartic Force Fields in Variational Calculations

The use of quartic force fields (QFFs) has been shown to be one of the most effective ways to efficiently compute vibrational frequencies for small molecules. In this paper we outline and discuss how the simple-internal or bond-length bond-angle (BLBA) coordinates can be transformed into Morse-cosine(-sine) coordinates which produce potential energy surfaces from QFFs that possess proper limiting behavior and can effectively describe the vibrational (or rovibrational) energy levels of an arbitrary molecular system. We investigate parameter scaling in the Morse coordinate, symmetry considerations, and examples of transformed QFFs making use of the MULTIMODE, TROVE, and VTET variational vibrational methods. Cases are referenced where variational computations coupled with transformed QFFs produce accuracies compared to experiment for fundamental frequencies on the order of 5 cm(exp 1) and often as good as 1 cm(exp 1)

Direct Measurements of the Stellar Continua and Balmer/4000 Angstrom Breaks of Red z>2 Galaxies: Redshifts and Improved Constraints on Stellar Populations

We use near-infrared (NIR) spectroscopy obtained with GNIRS on Gemini, NIRSPEC on KECK, and ISAAC on the VLT to study the rest-frame optical continua of three `Distant Red Galaxies' (having Js - Ks > 2.3) at z>2. All three galaxy spectra show the Balmer/4000 Angstrom break in the rest-frame optical. The spectra allow us to determine spectroscopic redshifts from the continuum with an estimated accuracy dz/(1+z) ~ 0.001-0.04. These redshifts agree well with the emission line redshifts for the 2 galaxies with Halpha emission. This technique is particularly important for galaxies that are faint in the rest-frame UV, as they are underrepresented in high redshift samples selected in optical surveys and are too faint for optical spectroscopy. Furthermore, we use the break, continuum shape, and equivalent width of Halpha together with evolutionary synthesis models to constrain the age, star formation timescale, dust content, stellar mass and star formation rate of the galaxies. Inclusion of the NIR spectra in the stellar population fits greatly reduces the range of possible solutions for stellar population properties. We find that the stellar populations differ greatly among the three galaxies, ranging from a young dusty starburst with a small break and strong emission lines to an evolved galaxy with a strong break and no detected line emission. The dusty starburst galaxy has an age of 0.3 Gyr and a stellar mass of 1*10^11 Msun. The spectra of the two most evolved galaxies imply ages of 1.3-1.4 Gyr and stellar masses of 4*10^11 Msun. The large range of properties seen in these galaxies strengthens our previous much more uncertain results from broadband photometry. Larger samples are required to determine the relative frequency of dusty starbursts and (nearly) passively evolving galaxies at z~2.5.Comment: Accepted for publication in the Astrophysical Journal. 12 pages, 6 figure