Combinatorial synthesis and high-throughput photopotential and photocurrent screening of mixed-metal oxides for photoelectrochemical water splitting

A high-throughput method has been developed using a commercial piezoelectric inkjet printer for synthesis and characterization of mixed-metal oxide photoelectrode materials for water splitting. The printer was used to deposit metal nitrate solutions onto a conductive glass substrate. The deposited metal nitrate solutions were then pyrolyzed to yield mixed-metal oxides that contained up to eight distinct metals. The stoichiometry of the metal oxides was controlled quantitatively, allowing for the creation of vast libraries of novel materials. Automated methods were developed to measure the open-circuit potentials (Eoc), short-circuit photocurrent densities (Jsc), and current density vs. applied potential (J–E) behavior under visible light irradiation. The high-throughput measurement of Eoc is particularly significant because open-circuit potential measurements allow the interfacial energetics to be probed regardless of whether the band edges of the materials of concern are above, close to, or below the values needed to sustain water electrolysis under standard conditions. The Eoc measurements allow high-throughput compilation of a suite of data that can be associated with the composition of the various materials in the library, to thereby aid in the development of additional screens and to form a basis for development of theoretical guidance in the prediction of additional potentially promising photoelectrode compositions

Testing the Influence of Community Characteristics on School Misconduct

This study examines the effect of dynamic and structural community characteristics on school misconduct. Data include over 45,000 students in the eighth, tenth, or twelfth grade in 237 schools. Hierarchical linear models tested the direct and interactive effects of community measures, while accounting for student and school characteristics. Community substance abuse norms as well as perceptions of community crime and disorder mediated the influence of concentrated disadvantage on school misconduct. Interaction effects demonstrated that community substance abuse norms were more influential for students enrolled in schools that had a less positive school climate although individual and school characteristics remained robust predictors of school misconduct. School misconduct is influenced by the characteristics of the surrounding community and school context, as well as the interaction between those contexts. Research relying on census data measures of community characteristics may underestimate community influence on school misconduct, and omit proximal community influences on school misconduct

A Deep Search For Faint Galaxies Associated With Very Low-redshift C IV Absorbers: III. The Mass- and Environment-dependent Circumgalactic Medium

Using Hubble Space Telescope Cosmic Origins Spectrograph observations of 89 QSO sightlines through the Sloan Digital Sky Survey footprint, we study the relationships between C IV absorption systems and the properties of nearby galaxies as well as large-scale environment. To maintain sensitivity to very faint galaxies, we restrict our sample to 0.0015 < z < 0.015, which defines a complete galaxy survey to L > 0.01 L* or stellar mass log M_* > 8 Msun. We report two principal findings. First, for galaxies with impact parameter rho < 1 rvir, C IV detection strongly depends on the luminosity/stellar mass of the nearby galaxy. C IV is preferentially associated with galaxies with log M_* > 9.5 Msun; lower mass galaxies rarely exhibit significant C IV absorption (covering fraction f = 9 +12-6% for 11 galaxies with log M_* < 9.5 Msun). Second, C IV detection within the log M_* > 9.5 Msun population depends on environment. Using a fixed-aperture environmental density metric for galaxies with rho < 160 kpc at z < 0.055, we find that 57+/-12% (8/14) of galaxies in low-density regions (regions with fewer than seven L > 0.15 L* galaxies within 1.5 Mpc) have affiliated C IV absorption; however, none (0/7) of the galaxies in denser regions show C IV. Similarly, the C IV detection rate is lower for galaxies residing in groups with dark-matter halo masses of log Mhalo > 12.5 Msun. In contrast to C IV, H I is pervasive in the CGM without regard to mass or environment. These results indicate that C IV absorbers with log N(C IV) > 13.5 cm^-2 trace the halos of log M_* > 9.5 Msun galaxies but also reflect larger scale environmental conditions.Comment: 26 pages, 13 figures. ApJ, in pres

The Mass-Loss Induced Eccentric Kozai Mechanism: A New Channel for the Production of Close Compact Object-Stellar Binaries

Over a broad range of initial inclinations and eccentricities an appreciable fraction of hierarchical triple star systems with similar masses are essentially unaffected by the Kozai-Lidov mechanism (KM) until the primary in the central binary evolves into a compact object. Once it does, it may be much less massive than the other components in the ternary, enabling the "eccentric Kozai mechanism (EKM):" the mutual inclination between the inner and outer binary can flip signs driving the inner binary to very high eccentricity, leading to a close binary or collision. We demonstrate this "Mass-loss Induced Eccentric Kozai" (MIEK) mechanism by considering an example system and defining an ad-hoc minimal separation between the inner two members at which tidal affects become important. For fixed initial masses and semi-major axes, but uniform distributions of eccentricity and cosine of the mutual inclination, ~10% of systems interact tidally or collide while the primary is on the MS due to the KM or EKM. Those affected by the EKM are not captured by earlier quadrupole-order secular calculations. We show that fully ~30% of systems interact tidally or collide for the first time as the primary swells to AU scales, mostly as a result of the KM. Finally, ~2% of systems interact tidally or collide for the first time after the primary sheds most of its mass and becomes a WD, mostly as a result of the MIEK mechanism. These findings motivate a more detailed study of mass-loss in triple systems and the formation of close NS/WD-MS and NS/WD-NS/WD binaries without an initial common envelope phase.Comment: 12 pages, 6 figures, 1 table. Accepted for publication in ApJ. For a brief video explaining this paper, see http://youtu.be/4CdTOF17q5

Effect of Baseline Subretinal Fluid on Treatment Outcomes in VIVID-DME and VISTA-DME Studies

Purpose To evaluate the effect of baseline subretinal fluid (SRF) on treatment outcomes with intravitreal aflibercept injection (IAI) versus laser treatment in patients with diabetic macular edema (DME) in the VIVID and VISTA studies. Design Post hoc analysis of 2 randomized controlled trials. Participants Eight hundred seventy-two patients with DME. Methods We randomized patients to receive IAI 2 mg every 4 weeks (2q4), IAI 2 mg every 8 weeks after 5 monthly doses (2q8), or laser. Main Outcome Measures Effect of presence or absence of baseline SRF on visual outcomes in the integrated dataset at weeks 52 and 100. Results Mean best-corrected visual acuity (BCVA) gains in the 2q4, 2q8, and laser arms at week 52 were +14.5, +11.0, and –2.3 letters, respectively, (those with baseline SRF) and +10.3, +10.6, and +2.5 letters, respectively, (those without). At week 100, mean gains were +13.5, +10.9, and −2.3 letters (those with baseline SRF) and +10.6, +10.0, and +2.7 letters (those without). The treatment effect for IAI versus laser from baseline to week 52 of 100 was greater for patients with baseline SRF versus those without (nominal P Conclusions This post hoc analysis demonstrated the visual outcome benefits of IAI over laser, regardless of baseline SRF status. A greater treatment effect of IAI was observed in patients with baseline SRF versus those without; however, no meaningful impact of baseline SRF status on treatment outcomes with IAI was demonstrated, indicating that the differential effects of laser might have been the driving force behind the different treatment outcomes in both groups

The COS-Dwarfs Survey: The Carbon Reservoir Around sub-L* Galaxies

We report new observations of circumgalactic gas from the COS-Dwarfs survey, a systematic investigation of the gaseous halos around 43 low-mass z $\leq$ 0.1 galaxies using background QSOs observed with the Cosmic Origins Spectrograph. From the projected 1D and 2D distribution of C IV absorption, we find that C IV absorption is detected out to ~ 0.5 R$_{vir}$ of the host galaxies. The C IV absorption strength falls off radially as a power law and beyond 0.5 R$_{vir}$, no C IV absorption is detected above our sensitivity limit of ~ 50-100 m$\AA$. We find a tentative correlation between detected C IV absorption strength and star formation, paralleling the strong correlation seen in highly ionized oxygen for L~L* galaxies by the COS-Halos survey. The data imply a large carbon reservoir in the CGM of these galaxies, corresponding to a minimum carbon mass of $\gtrsim$ 1.2$\times 10^6$ $M_\odot$ out to ~ 110 kpc. This mass is comparable to the carbon mass in the ISM and more than the carbon mass currently in stars of these galaxies. The C IV absorption seen around these sub-L* galaxies can account for almost two-thirds of all $W_r$> 100 m$\AA$ C IV absorption detected at low z. Comparing the C IV covering fraction with hydrodynamical simulations, we find that an energy-driven wind model is consistent with the observations whereas a wind model of constant velocity fails to reproduce the CGM or the galaxy properties.Comment: 18 Pages, 11 Figures, ApJ 796 13

The COS Absorption Survey of Baryon Harbors (CASBaH): Warm-hot Circumgalactic Gas Reservoirs Traced by Ne VIII Absorption

We survey the highly ionized circumgalactic media (CGM) of 29 blindly selected galaxies at 0.49 < z_(gal) < 1.44 based on high-S/N ultraviolet spectra of z > 1 QSOs and the galaxy database from the COS Absorption Survey of Baryon Harbors (CASBaH). We detect the Ne VIII doublet in nine of the galaxies, and for gas with N(Ne VIII) > 10^13.3 cm^-2 (> 10^13.5 cm^-2), we derive a Ne VIII covering fraction f_c = 75 +15/-25% (44 +22/-20%) within impact parameter (rho) < 200 kpc of M_* = 10^(9.5-11.5) Msol galaxies and f_c = 70 +16/-22% (f_c = 42 +20/-17%) within rho < 1.5 virial radii. We estimate the mass in Ne VIII-traced gas to be M_gas(Ne VIII) > 10^9.5 Msol (Z/Zsol)^-1, or 6-20% of the expected baryonic mass if the Ne VIII absorbers have solar metallicity. Ionizing Ne VII to Ne VIII requires 207 eV, and photons with this energy are scarce in the CGM. However, for the median halo mass and redshift of our sample, the virial temperature is close to the peak temperature for the Ne VIII ion, and the Ne VIII-bearing gas is plausibly collisionally ionized near this temperature. Moreover, we find that photoionized Ne VIII requires cool and low-density clouds that would be highly underpressured (by approximately two orders of magnitude) relative to the putative, ambient virialized medium, complicating scenarios where such clouds could survive. Thus, more complex (e.g., non-equilibrium) models may be required; this first statistical sample of Ne VIII absorber/galaxy systems will provide stringent constraints for future CGM studies.Comment: Published in ApJL, Volume 877, Issue 2, Article L2

ASASSN-15pz: Revealing Significant Photometric Diversity among 2009dc-like, Peculiar SNe Ia

We report comprehensive multi-wavelength observations of a peculiar Type Ia-like supernova ("SN Ia-pec") ASASSN-15pz. ASASSN-15pz is a spectroscopic "twin" of SN 2009dc, a so-called "Super-Chandrasekhar-mass" SN, throughout its evolution, but it has a peak luminosity M_B,peak = -19.69 +/- 0.12 mag that is \approx 0.6 mag dimmer and comparable to the SN 1991T sub-class of SNe Ia at the luminous end of the normal width-luminosity relation. The synthesized Ni56 mass of M_Ni56 = 1.13 +/- 0.14 M_sun is also substantially less than that found for several 2009dc-like SNe. Previous well-studied 2009dc-like SNe have generally suffered from large and uncertain amounts of host-galaxy extinction, which is negligible for ASASSN-15pz. Based on the color of ASASSN-15pz, we estimate a host extinction for SN 2009dc of E(B-V)_host=0.12 mag and confirm its high luminosity (M_B, peak[2009dc] \approx -20.3 mag). The 2009dc-like SN population, which represents ~1% of SNe Ia, exhibits a range of peak luminosities, and do not fit onto the tight width-luminosity relation. Their optical light curves also show significant diversity of late-time (>~ 50 days) decline rates. The nebular-phase spectra provide powerful diagnostics to identify the 2009dc-like events as a distinct class of SNe Ia. We suggest referring to these sources using the phenomenology-based "2009dc-like SN Ia-pec" instead of "Super-Chandrasekhar SN Ia," which is based on an uncertain theoretical interpretation.Comment: 21 pages, 16 figures, accepted for publication in Ap

LC-MS/MS Method for the determination of carbamathione in human plasma

Liquid chromatography-tandem mass spectrometry methodology is described for the determination of S-(N,N-diethylcarbamoyl)glutathione (carbamathione) in human plasma samples. Sample preparation consisted of a straightforward perchloric acid medicated protein precipitation, with the resulting supernatant containing the carbamathione (recovery ∼98%). For optimized chromatography/mass spec detection a carbamathione analog, S-(N,N-di-i-propylcarbamoyl)glutathione, was synthesized and used as the internal standard. Carbamathione was found to be stable over the pH 1-8 region over the timeframe necessary for the various operations of the analytical method. Separation was accomplished via reversed-phase gradient elution chromatography with analyte elution and re-equilibration accomplished within 8 minutes. Calibration was established and validated over the concentration range of 0.5-50 nM, which is adequate to support clinical investigations. Intra- and inter-day accuracy and precision determined and found to be < 4% and < 10%, respectively. The methodology was utilized to demonstrate the carbamathione plasma-time profile of a human volunteer dosed with disulfiram (250 mg/d). Interestingly, an unknown but apparently related metabolite was observed with each human plasma sample analyzed