Rhodium Pyrazolate Complexes as Potential CVD Precursors

Reaction of 3,5-(CF3)(2)PzLi with [Rh(mu-Cl)(eta(2)-C2H4)(2)](2) or [Rh(mu-Cl)(PMe3)(2)](2) in Et2O gave the dinuclear complexes [Rh(eta(2)-C2H4)(2)(mu-3,5-(CF3)(2)-Pz)](2) (1) and [Rh-2(mu-Cl)(mu-3,5-(CF3)(2)-Pz) (PMe3)(4)] (2) respectively (3,5-(CF3)(2)Pz = bis-trifluoromethyl pyrazolate). Reaction of PMe3 with [Rh(COD)(mu-3,5-(CF3)(2)-Pz)](2) in toluene gave [Rh(3,5-(CF3)(2)-Pz)(PMe3)(3)] (3). Reaction of 1 and 3 in toluene (1 : 4) gave moderate yields of the dinuclear complex [Rh(PMe3)(2)(mu-3,5-(CF3)(2)-Pz)](2) (4). Reaction of 3,5-(CF3)(2)PzLi with [Rh(PMe3)(4)]Cl in Et2O gave the ionic complex [Rh(PMe3)(4)][3,5-(CF3)(2)-Pz] (5). Two of the complexes, 1 and 3, were studied for use as CVD precursors. Polycrystalline thin films of rhodium (fcc-Rh) and metastable-amorphous films of rhodium phosphide (Rh2P) were grown from 1 and 3 respectively at 170 and 130 degrees C, 0.3 mmHg in a hot wall reactor using Ar as the carrier gas (5 cc min(-1)). Thin films of amorphous rhodium and rhodium phosphide (Rh2P) were grown from 1 and 3 at 170 and 130 degrees C respectively at 0.3 mmHg in a hot wall reactor using H-2 as the carrier gas (7 cc min(-1)).Welch Foundation F-816Petroleum Research Fund 47014-ACSNSF 0741973Chemistr

Probing Fine-Scale Ionospheric Structure with the Very Large Array Radio Telescope

High resolution (~1 arcminute) astronomical imaging at low frequency (below 150 MHz) has only recently become practical with the development of new calibration algorithms for removing ionospheric distortions. In addition to opening a new window in observational astronomy, the process of calibrating the ionospheric distortions also probes ionospheric structure in an unprecedented way. Here we explore one aspect of this new type of ionospheric measurement, the differential refraction of celestial source pairs as a function of their angular separation. This measurement probes variations in the spatial gradient of the line-of-sight total electron content (TEC) to 0.001 TECU/km accuracy over spatial scales of under 10 km to over 100 km. We use data from the VLA Low-frequency Sky Survey (VLSS; Cohen et al. 2007, AJ 134, 1245), a nearly complete 74 MHz survey of the entire sky visible to the Very Large Array (VLA) telescope in Socorro, New Mexico. These data comprise over 500 hours of observations, all calibrated in a standard way. While ionospheric spatial structure varies greatly from one observation to the next, when analyzed over hundreds of hours, statistical patterns become apparent. We present a detailed characterization of how the median differential refraction depends on source pair separation, elevation and time of day. We find that elevation effects are large, but geometrically predictable and can be "removed" analytically using a "thin-shell" model of the ionosphere. We find significantly greater ionospheric spatial variations during the day than at night. These diurnal variations appear to affect the larger angular scales to a greater degree indicating that they come from disturbances on relatively larger spatial scales (100s of km, rather than 10s of km).Comment: Accepted for publication by The Astronomical Journa

Virological response without CD4 recovery

The objective of antiretroviral therapy (ART) is to suppress viral replication so that immune restoration can occur. Failure of immune restoration is usually associated with poor virological suppression. In children a good immunological and clinical response to ART is often achieved despite incomplete viral suppression. However, we have recently managed a number of children in whom immune restoration did not occur despite excellent virological suppression. We present a case, discuss possible causes and speculate on the appropriate course of action. Southern African Journal of HIV Medicine Vol. 7 (3) 2006: pp. 45-4

Paediatric ART outcomes in a decentralised model of care in Cape Town, South Africa

Background. Although subSaharan Africa faces the world’s largest paediatric HIV epidemic, only 1 in 4 children has access to combination antiretroviral therapy (ART). A decentralised approach to HIV care is  advocated, but programmes in resourcelimited settings encounter many challenges to community-initiated paediatric ART implementation.Methods. A retrospective cohort analysis of 613 children receiving ART between 2004 and 2009 was performed in seven physician-run primary healthcare (PHC) clinics in Cape Town. Baseline characteristics, serial CD4+, viral load (VL) levels and status at study closure were collected.Results. Two subgroups were identified: children who were initiated on ART in a PHC clinic (n=343) and children who were down-referred from tertiary hospitals (n=270). The numbers of children initiated on ART in PHC increased sevenfold over the study period. Down-referred children were severely ill at ART initiation, with higher VLs, lower CD4+ counts and higher rates of tuberculosis co-infection (25.3% v. 16.9%; p=0.01). Median time to virological suppression was 29 weeks in PHC-ART initiates and 44 weeks in children down-referred (p<0.0001). Children down-referred to PHC either maintained or gained virological suppression. Longitudinal cohort analysis demonstrated sustained VL suppression >80%, high rates of immune reconstitution and low mortality.Conclusions. Increasing numbers of children are initiated on ART in PHC settings and achieve comparable immunological, virological and survival outcomes, suggesting successful decentralisation of paediatric HIV care. Down-referral of children with adherence-related virological failure may  assist with attainment of virological suppression and sparing use of  second-line medications

Compact Radio Sources within 30" of Sgr A*: Proper Motions, Stellar Winds and the Accretion Rate onto Sgr A*

Recent broad-band 34 and 44 GHz radio continuum observations of the Galactic center have revealed 41 massive stars identified with near-IR counterparts, as well as 44 proplyd candidates within 30" of Sgr A*. Radio observations obtained in 2011 and 2014 have been used to derive proper motions of eight young stars near Sgr A*. The accuracy of proper motion estimates based on near-IR observations by Lu et al. and Paumard et al. have been investigated by using their proper motions to predict the 2014 epoch positions of near-IR stars and comparing the predicted positions with those of radio counterparts in the 2014 radio observations. Predicted positions from Lu et al. show an rms scatter of 6 mas relative to the radio positions, while those from Paumard et al. show rms residuals of 20 mas, which is mainly due to uncertainties in the IR-based proper motions. Under the assumption of homogeneous ionized winds, we also determine the mass-loss rates of 11 radio stars, finding rates that are on average $\sim$2 times smaller than those determined from model atmosphere calculations and near-IR data. Clumpiness of ionized winds would reduce the mass loss rate of WR and O stars by additional factors of 3 and 10, respectively. One important implication of this is a reduction in the expected mass accretion rate onto Sgr A* from stellar winds by nearly an order of magnitude to a value of few$\times10^{-7}$ \msol\ yr$^{-1}$. Finally, we present the positions of 318 compact 34.5 GHz radio sources within 30\arcs\ of Sgr A*. At least 45 of these have stellar counterparts in the near-IR $K_s$ (2.18 $\mu$m) and $L'$ (3.8$\mu$m) bands.Comment: 30 pages, 4 figures, ApJ (in press

The Variability of Polarized Radiation from Sgr A*

Sgr A* is variable at radio and submillimeter wavelengths on hourly time scales showing time delays between the peaks of flare emission as well as linearly polarized emission at millimeter and sub-mm wavelengths. To determine the polarization characteristics of this variable source at radio frequencies, we present VLA observations of Sgr A* and report the detection of polarized emission at a level of 0.77\pm0.01% and 0.2\pm0.01% at 43 and 22 GHz, respectively. The change in the time averaged polarization angle between 22 and 43 GHz corresponds to a RM of -2.5\pm0.6 x10^3 rad m{-2} with no phase wrapping (or \sim 5x10^4 rad m^2 with 2\pi phase wrap). We also note a rise and fall time scale of 1.5 -- 2 hours in the total polarized intensity. The light curves of the degree of linearly polarized emission suggests a a correlation with the variability of the total intensity at 43 GHz. The available polarization data at radio and sub-mm wavelengths suggest that the rotation measure decreases with decreasing frequency. This frequency dependence, and observed changes in polarization angle during flare events, may be caused by the reduction in rotation measure associated with the expansion of synchrotron-emitting blobs.Comment: 11 pages, 3 figures, ApJL (in press

Reduced efficacy of praziquantel against Schistosoma mansoni associated with multiple-rounds of mass drug administration

The efficacy of praziquantel against Schistosoma mansoni was significantly lower in Ugandan schools that had received more prior rounds of mass drug administration, as determined by fitting a statistical model to parasite egg counts before and after treatment

Multifrequency observations of the jets in the radio galaxy NGC 315

We present images of the jets in the nearby radio galaxy NGC 315 made with the VLA at five frequencies between 1.365 and 5 GHz with resolutions between 1.5 and 45 arcsec FWHM. Within 15 arcsec of the nucleus, the spectral index of the jets is 0.61. Further from the nucleus, the spectrum is flatter, with significant transverse structure. Between 15 and 70 arcsec from the nucleus, the spectral index varies from 0.55 on-axis to 0.44 at the edge. This spectral structure suggests a change of dominant particle acceleration mechanism with distance from the nucleus and the transverse gradient may be associated with shear in the jet velocity field. Further from the nucleus, the spectral index has a constant value of 0.47. We derive the distribution of Faraday rotation over the inner +/-400 arcsec of the radio source and show that it has three components: a constant term, a linear gradient (both probably due to our Galaxy) and residual fluctuations at the level of 1 - 2 rad/m^2. These residual fluctuations are smaller in the brighter (approaching) jet, consistent with the idea that they are produced by magnetic fields in a halo of hot plasma that surrounds the radio source. We model this halo, deriving a core radius of approximately 225 arcsec and constraining its central density and magnetic-field strength. We also image the apparent magnetic-field structure over the first +/-200 arcsec from the nucleus.Comment: 20 pages, 17 figures, accepted for publication in MNRAS. Minor corrections to match published version, including a short note on emission from the background galaxy FGC011