Evidence Favoring Molybdenum−Carbon Bond Formation in Xanthine Oxidase Action: \u3csup\u3e17\u3c/sup\u3eO- and \u3csup\u3e13\u3c/sup\u3eC-ENDOR and Kinetic Studies

The reaction mechanism of the molybdoenzyme xanthine oxidase has been further investigated by 13C and 17O ENDOR of molybdenum(V) species and by kinetic studies of exchange of oxygen isotopes. Three EPR signal-giving species were studied:  (i) Very Rapid, a transient intermediate in substrate turnover, (ii) Inhibited, the product of an inhibitory side reaction with aldehyde substrates, and (iii) Alloxanthine, a species formed by reaction of reduced enzyme with the inhibitor, alloxanthine. The Very Rapid signal was developed either with [8-13C]xanthine or with 2-oxo-6-methylpurine using enzyme equilibrated with [17O]H2O. The Inhibited signal was developed with 2H13C2HO and the Alloxanthine signal by using [17O]H2O. Estimates of Mo−C distances were made, from the anisotropic components of the 13C-couplings, by corrected dipolar coupling calculations and by back-calculation from assumed possible structures. Estimated distances in the Inhibited and Very Rapid species were about 1.9 and less than 2.4 Å, respectively. A Mo−C bond in the Inhibited species is very strongly suggested, presumably associated with side-on bonding to molybdenum of the carbonyl of the aldehyde substrate. For the Very Rapid species, a Mo−C bond is highly likely. Coupling from a strongly coupled 17O, not in the form of an oxo group, and no coupling from other oxygens was detected in the Very Rapid species. No coupled oxygens were detected in the Alloxanthine species. That the coupled oxygen of the Very Rapid species is the one that appears in the product uric acid molecule was confirmed by new kinetic data. It is concluded that this oxygen of the Very Rapid species does not, as frequently assumed, originate from the oxo group of the oxidized enzyme. A new turnover mechanism is proposed, not involving direct participation of the oxo ligand group, and based on that of Coucouvanis et al. [Coucouvanis, D., Toupadakis, A., Lane, J. D., Koo, S. M., Kim, C. G., Hadjikyriacou, A. (1991) J. Am. Chem. Soc. 113, 5271−5282]. It involves formal addition of the elements of the substrate (e.g., xanthine) across the MoS double bond, to give a Mo(VI) species. This is followed by attack of a “buried” water molecule (in the vicinity of molybdenum and perhaps a ligand of it) on the bound substrate carbon, to give an intermediate that on intramolecular one-electron oxidation gives the Very Rapid species. The latter, in keeping with the 13C, 17O, and 33S couplings, is presumed to have the 8-CO group of the uric acid product molecule bonded side-on to molybdenum, with the sulfido molybdenum ligand retained, as in the oxidized enzyme

Three‐Dimensional Sonographic Measurement of Blood Volume Flow in the Umbilical Cord

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/135361/1/jum201231121927.pd

Spectroscopic Target Selection in the Sloan Digital Sky Survey: The Quasar Sample

We describe the algorithm for selecting quasar candidates for optical spectroscopy in the Sloan Digital Sky Survey. Quasar candidates are selected via their non-stellar colors in "ugriz" broad-band photometry, and by matching unresolved sources to the FIRST radio catalogs. The automated algorithm is sensitive to quasars at all redshifts lower than z=5.8. Extended sources are also targeted as low-redshift quasar candidates in order to investigate the evolution of Active Galactic Nuclei (AGN) at the faint end of the luminosity function. Nearly 95% of previously known quasars are recovered (based on 1540 quasars in 446 square degrees). The overall completeness, estimated from simulated quasars, is expected to be over 90%, whereas the overall efficiency (quasars:quasar candidates) is better than 65%. The selection algorithm targets ultraviolet excess quasars to i^*=19.1 and higher-redshift (z>3) quasars to i^*=20.2, yielding approximately 18 candidates per square degree. In addition to selecting ``normal'' quasars, the design of the algorithm makes it sensitive to atypical AGN such as Broad Absorption Line quasars and heavily reddened quasars.Comment: 62 pages, 15 figures (8 color), 8 tables. Accepted by AJ. For a version with higher quality color figures, see http://archive.stsci.edu/sdss/quasartarget/RichardsGT_qsotarget.preprint.p

Fluorescence lifetime imaging microscopy: in vivo application to diagnosis of oral carcinoma

A compact clinically compatible fluorescence lifetime imaging microscopy (FLIM) system was designed and built for intraoperative disease diagnosis and validated in vivo in a hamster oral carcinogenesis model. This apparatus allows for the remote image collection via a flexible imaging probe consisting of a gradient index objective lens and a fiber bundle. Tissue autofluorescence (337 nm excitation) was imaged using an intensified CCD with a gate width down to 0.2 ns. We demonstrate a significant contrast in fluorescence lifetime between tumor (1.77±0.26 ns) and normal (2.50±0.36 ns) tissues at 450 nm and an over 80% intensity decrease at 390 nm emission in tumor versus normal areas. The time-resolved images were minimally affected by tissue morphology, endogenous absorbers, and illumination. These results demonstrate the potential of FLIM as an intraoperative diagnostic technique

Spectral Variability of Quasars in the Sloan Digital Sky Survey. I: Wavelength Dependence

Sloan Digital Sky Survey (SDSS) repeat spectroscopic observations have resulted in multiple-epoch spectroscopy for roughly 2500 quasars observed more than 50 days apart. From this sample, we identify 315 quasars that have varied significantly between observations. We create an ensemble difference spectrum (bright phase minus faint phase) covering rest-frame wavelengths from 1000 to 6000 Angstroms. This average difference spectrum is bluer than the average single-epoch quasar spectrum; a power-law fit to the difference spectrum yields a spectral index alpha_lambda = -2.00, compared to an index of alpha_lambda = -1.35 for the single-epoch spectrum. The strongest emission lines vary only 30% as much as the continuum. Due to the lack of variability of the lines, measured photometric color is not always bluer in brighter phases, but depends on redshift and the filters used. Lastly, the difference spectrum is bluer than the ensemble quasar spectrum only for lambda_rest < 2500 Angstroms, indicating that the variability cannot result from a simple scaling of the average quasar spectrum.Comment: 47 pages, 14 figures, 3 tables, accepted for publication in Ap

Colors of 2625 Quasars at 0<z<5 Measured in the Sloan Digital Sky Survey Photometric System

We present an empirical investigation of the colors of quasars in the Sloan Digital Sky Survey (SDSS) photometric system. The sample studied includes 2625 quasars with SDSS photometry. The quasars are distributed in a 2.5 degree wide stripe centered on the Celestial Equator covering $\sim529$ square degrees. Positions and SDSS magnitudes are given for the 898 quasars known prior to SDSS spectroscopic commissioning. New SDSS quasars represent an increase of over 200% in the number of known quasars in this area of the sky. The ensemble average of the observed colors of quasars in the SDSS passbands are well represented by a power-law continuum with $\alpha_{\nu} = -0.5$ ($f_{\nu} \propto \nu^{\alpha}$). However, the contributions of the $3000 {\rm \AA}$ bump and other strong emission lines have a significant effect upon the colors. The color-redshift relation exhibits considerable structure, which may be of use in determining photometric redshifts for quasars. The range of colors can be accounted for by a range in the optical spectral index with a distribution $\alpha_{\nu}=-0.5\pm0.65$ (95% confidence), but there is a red tail in the distribution. This tail may be a sign of internal reddening. Finally, we show that there is a continuum of properties between quasars and Seyfert galaxies and we test the validity of the traditional division between the two classes of AGN.Comment: 66 pages, 15 figures (3 color), accepted by A

The Ensemble Photometric Variability of ~25000 Quasars in the Sloan Digital Sky Survey

Using a sample of over 25000 spectroscopically confirmed quasars from the Sloan Digital Sky Survey, we show how quasar variability in the rest frame optical/UV regime depends upon rest frame time lag, luminosity, rest wavelength, redshift, the presence of radio and X-ray emission, and the presence of broad absorption line systems. The time dependence of variability (the structure function) is well-fit by a single power law on timescales from days to years. There is an anti-correlation of variability amplitude with rest wavelength, and quasars are systematically bluer when brighter at all redshifts. There is a strong anti-correlation of variability with quasar luminosity. There is also a significant positive correlation of variability amplitude with redshift, indicating evolution of the quasar population or the variability mechanism. We parameterize all of these relationships. Quasars with RASS X-ray detections are significantly more variable (at optical/UV wavelengths) than those without, and radio loud quasars are marginally more variable than their radio weak counterparts. We find no significant difference in the variability of quasars with and without broad absorption line troughs. Models involving multiple discrete events or gravitational microlensing are unlikely by themselves to account for the data. So-called accretion disk instability models are promising, but more quantitative predictions are needed.Comment: 41 pages, 21 figures, AASTeX, Accepted for publication in Ap

NOMINAL VALUES FOR SELECTED SOLAR AND PLANETARY QUANTITIES: IAU 2015 RESOLUTION B3

In this brief communication we provide the rationale for and the outcome of the International Astronomical Union (IAU) resolution vote at the XXIXth General Assembly in Honolulu, Hawaii, in 2015, on recommended nominal conversion constants for selected solar and planetary properties. The problem addressed by the resolution is a lack of established conversion constants between solar and planetary values and SI units: a missing standard has caused a proliferation of solar values (e.g., solar radius, solar irradiance, solar luminosity, solar effective temperature, and solar mass parameter) in the literature, with cited solar values typically based on best estimates at the time of paper writing. As precision of observations increases, a set of consistent values becomes increasingly important. To address this, an IAU Working Group on Nominal Units for Stellar and Planetary Astronomy formed in 2011, uniting experts from the solar, stellar, planetary, exoplanetary, and fundamental astronomy, as well as from general standards fields to converge on optimal values for nominal conversion constants. The effort resulted in the IAU 2015 Resolution B3, passed at the IAU General Assembly by a large majority. The resolution recommends the use of nominal solar and planetary values, which are by definition exact and are expressed in SI units. These nominal values should be understood as conversion factors only, not as the true solar/planetary properties or current best estimates. Authors and journal editors are urged to join in using the standard values set forth by this resolution in future work and publications to help minimize further confusion