Cationic Ruthenium Complexes in Catalysis: The Activation of Propargylic Alcohols Through Electronically Tuned Complexes

With increasing complexity of metal complexes, it is of worthwhile interest to pursue systematic examinations of ligand modifications to study their impact on the reactivity of a catalyst. To that end, this study aimed to understand the effect electron-withdrawing ligands conveyed to catalytic activity in the etherification of propargylic alcohols and related reactions. A number of half-sandwich ruthenium complexes bearing ligands with varying electron–withdrawing properties were synthesized and structurally characterized. Their electronic and structural properties were investigated utilizing X-ray crystallography, revealing that the series of complexes did not vary significantly in structure. The complexes were studied electronically with cyclic voltammetry, which discovered that the coordinated electron-withdrawing ligands resulted in complexes that were more difficult to oxidize and with possibly decreased electron density at the ruthenium center. All complexes showed catalytic activity in the etherification of propargylic alcohols and in the formation of oxygen-containing heterocycles from propargylic alcohols and diketones. Thermal instability offers an explanation as to why some catalyst systems do not perform very well at elevated temperatures. In a separate study, a more stable tridentate ligand was employed as an architecture for further study in this electronic fine-tuning methodology. A new ruthenium complex bearing a tridendate diacetylpyridine ligand was synthesized, characterized, and employed as catalyst in the coupling of carboxylic acids to terminal alkynes to form enol esters with good regioselectivity. Iron offers a number of advantages in transition metal catalysis, as it is inexpensive and relatively non-toxic. Based on preliminary findings from the Bauer laboratory, an in situ catalyst formed through oxidation of ferrocene boronic acid was found to be catalytically active in the etherification of propargylic acetates. Most interestingly, and opposed to all catalytic reactions performed for this study, the ferrocenium cation does not require elevated temperatures and performs well at room temperature

Keck Spectroscopy of 3<z<7 Faint Lyman Break Galaxies: The Importance of Nebular Emission in Understanding the Specific Star Formation Rate and Stellar Mass Density

The physical properties inferred from the SEDs of z>3 galaxies have been influential in shaping our understanding of early galaxy formation and the role galaxies may play in cosmic reionization. Of particular importance is the stellar mass density at early times which represents the integral of earlier star formation. An important puzzle arising from the measurements so far reported is that the specific star formation rates (sSFR) evolve far less rapidly than expected in most theoretical models. Yet the observations underpinning these results remain very uncertain, owing in part to the possible contamination of rest-optical broadband light from strong nebular emission lines. To quantify the contribution of nebular emission to broad-band fluxes, we investigate the SEDs of 92 spectroscopically-confirmed galaxies in the redshift range 3.8<z<5.0 chosen because the H-alpha line lies within the Spitzer/IRAC 3.6 um filter. We demonstrate that the 3.6 um flux is systematically in excess of that expected from stellar continuum, which we derive by fitting the SED with population synthesis models. No such excess is seen in a control sample at 3.1<z<3.6 in which there is no nebular contamination in the IRAC filters. From the distribution of our 3.6 um flux excesses, we derive an H-alpha equivalent width (EW) distribution. The mean rest-frame H-alpha EW we infer at 3.8<z<5.0 (270 A) indicates that nebular emission contributes at least 30% of the 3.6 um flux. Via our empirically-derived EW distribution we correct the available stellar mass densities and show that the sSFR evolves more rapidly at z>4 than previously thought, supporting up to a 5x increase between z~2 and 7. Such a trend is much closer to theoretical expectations. Given our findings, we discuss the prospects for verifying quantitatively the nebular emission line strengths prior to the launch of the James Webb Space Telescope.Comment: 16 pages, 9 figures, submitted to Ap

The Baryon Content of Cosmic Structures

We make an inventory of the baryonic and gravitating mass in structures ranging from the smallest galaxies to rich clusters of galaxies. We find that the fraction of baryons converted to stars reaches a maximum between M500 = 1E12 and 1E13 Msun, suggesting that star formation is most efficient in bright galaxies in groups. The fraction of baryons detected in all forms deviates monotonically from the cosmic baryon fraction as a function of mass. On the largest scales of clusters, most of the expected baryons are detected, while in the smallest dwarf galaxies, fewer than 1% are detected. Where these missing baryons reside is unclear.Comment: ApJ Letters, in pres

New Constraints on Cosmic Reionization from the 2012 Hubble Ultra Deep Field Campaign

Understanding cosmic reionization requires the identification and characterization of early sources of hydrogen-ionizing photons. The 2012 Hubble Ultra Deep Field (UDF12) campaign has acquired the deepest infrared images with the Wide Field Camera 3 aboard Hubble Space Telescope and, for the first time, systematically explored the galaxy population deep into the era when cosmic microwave background (CMB) data indicates reionization was underway. The UDF12 campaign thus provides the best constraints to date on the abundance, luminosity distribution, and spectral properties of early star-forming galaxies. We synthesize the new UDF12 results with the most recent constraints from CMB observations to infer redshift-dependent ultraviolet (UV) luminosity densities, reionization histories, and electron scattering optical depth evolution consistent with the available data. Under reasonable assumptions about the escape fraction of hydrogen ionizing photons and the intergalactic medium clumping factor, we find that to fully reionize the universe by redshift z~6 the population of star-forming galaxies at redshifts z~7-9 likely must extend in luminosity below the UDF12 limits to absolute UV magnitudes of M_UV\sim -13 or fainter. Moreover, low levels of star formation extending to redshifts z~15-25, as suggested by the normal UV colors of z\simeq7-8 galaxies and the smooth decline in abundance with redshift observed by UDF12 to z\simeq10, are additionally likely required to reproduce the optical depth to electron scattering inferred from CMB observations.Comment: Version accepted by ApJ (originally submitted Jan 5, 2013). The UDF12 website can be found at http://udf12.arizona.ed

Paediatric extracranial germ-cell tumours.

Management of paediatric extracranial germ-cell tumours carries a unique set of challenges. Germ-cell tumours are a heterogeneous group of neoplasms that present across a wide age range and vary in site, histology, and clinical behaviour. Patients with germ-cell tumours are managed by a diverse array of specialists. Thus, staging, risk stratification, and treatment approaches for germ-cell tumours have evolved disparately along several trajectories. Paediatric germ-cell tumours differ from the adolescent and adult disease in many ways, leading to complexities in applying age-appropriate, evidence-based care. Suboptimal outcomes remain for several groups of patients, including adolescents, and patients with extragonadal tumours, high tumour markers at diagnosis, or platinum-resistant disease. Survivors have significant long-term toxicities. The challenge moving forward will be to translate new insights from molecular studies and collaborative clinical data into improved patient outcomes. Future trials will be characterised by improved risk-stratification systems, biomarkers for response and toxic effects, rational reduction of therapy for low-risk patients and novel approaches for poor-risk patients, and improved international collaboration across paediatric and adult cooperative research groups.This is the author accepted manuscript. The final version is available from Elsevier via http://dx.doi.org/10.1016/S1470-2045(15)00545-

Expanding the search for galaxies at z ~7-10 with new NICMOS Parallel Fields

We have carried out a search for galaxies at z ~ 7-10 in ~14.4 sq. arcmin of new NICMOS parallel imaging taken in the Great Observatories Origins Deep Survey (GOODS, 5.9 sq. arcmin), the Cosmic Origins Survey (COSMOS, 7.2 sq. arcmin), and SSA22 (1.3 sq. arcmin). These images reach 5 sigma sensitivities of J110 = 26.0-27.5 (AB), and combined they increase the amount of deep near-infrared data by more than 60% in fields where the investment in deep optical data has already been made. We find no z>7 candidates in our survey area, consistent with the Bouwens et al. (2008) measurements at z~7 and 9 (over 23 sq. arcmin), which predict 0.7 galaxies at z~7 and <0.03 galaxies at z~9. We estimate that 10-20% of z>7 galaxies are missed by this survey, due to incompleteness from foreground contamination by faint sources. For the case of luminosity evolution, assuming a Schecter parameterization with a typical phi* = 10^-3 Mpc^-3, we find M* > -20.0 for z~7 and M* > -20.7 for z~9 (68% confidence). This suggests that the downward luminosity evolution of LBGs continues to z~7, although our result is marginally consistent with the z~6 LF of Bouwens et al.(2006, 2007). In addition we present newly-acquired deep MMT/Megacam imaging of the z~9 candidate JD2325+1433, first presented in Henry et al. (2008). The resulting weak but significant detection at i' indicates that this galaxy is most likely an interloper at z~2.7.Comment: Accepted to ApJ. Replacement includes updated discussion of incompleteness from foreground contaminatio

Comparison of carboplatin versus cisplatin in the treatment of paediatric extracranial malignant germ cell tumours: A report of the Malignant Germ Cell International Consortium.

PURPOSE: To compare the outcomes of paediatric and adolescent extracranial malignant germ cell tumour (GCT) patients treated with either carboplatin or cisplatin on clinical trials conducted by the Children's Oncology Group (COG) and the Children's Cancer and Leukaemia Group (CCLG). METHODS: The Malignant Germ Cell International Consortium (MaGIC) has created a database of the GCT clinical trials conducted since 1983 by COG (United States, Canada and Australia), which used cisplatin-based regimens, and by CCLG (United Kingdom), which used carboplatin-based regimens. Using the parametric cure model, this study compared the overall 4-year event-free survival (EFS), stratified by age, stage, site and the a-priori defined MaGIC 'risk' groups: standard risk ((SR) 1 (EFS >80%; age 80%, age ≥ 11y) and poor risk (PR) (EFS ≤ 70%, age ≥ 11y). RESULTS: Cisplatin-based therapy was used in 620 patients; carboplatin was used in 163 patients. In the overall multivariate cure model, the two regimens did not differ significantly (cisplatin: 4-year EFS 86%; 95% confidence interval (CI) 83-89% versus carboplatin 4-year EFS 86%; 95% CI 79-90%; p = 0.87). No significant differences were noted in stratified analyses by site, stage, age and MaGIC risk groups: SR1 (p = 0.20), SR2 (p = 0.55) or PR (p = 0.72) patients. CONCLUSIONS: In these trials conducted contemporaneously, there is no significant difference in outcome observed overall, or any subset of patients, who were treated with regimens containing cisplatin versus carboplatin These results suggested sufficient equipoise to justify a randomised trial to evaluate the effectiveness of carboplatin versus cisplatin in the treatment of children, adolescents and young adults with standard risk GCT, which is currently underway

A Lyman Break Galaxy Candidate at z~9

We report the discovery of a z~9 Lyman Break Galaxy (LBG) candidate, selected from the NICMOS Parallel Imaging Survey as a J-dropout with J110 - H160 = 1.7. Spitzer/IRAC photometry reveals that the galaxy has a blue H160 - 3.6 um color, and a spectral break between 3.6 and 4.5 um. We interpret this break as the Balmer break, and derive a best-fit photometric redshift of z~9. We use Monte Carlo simulations to test the significance of this photometric redshift, and show a 96% probability of z>7. We estimate a lower limit to the comoving number density of such galaxies at z~9 of phi > 3.8 x 10^{-6} Mpc^{-3}. If the high redshift of this galaxy is confirmed, this will indicate that the luminous end of the rest-frame UV luminosity function has not evolved substantially from z~ 9 to z~3. Still, some small degeneracy remains between this z~9 model and models at z~2-3; deep optical imaging (reaching I ~ 29 AB) can rule out the lower-z models.Comment: Accepted to ApJ Letter

High star formation rates as the origin of turbulence in early and modern disk galaxies

High spatial and spectral resolution observations of star formation and kinematics in early galaxies have shown that two-thirds are massive rotating disk galaxies with the remainder being less massive non-rotating objects. The line of sight averaged velocity dispersions are typically five times higher than in today's disk galaxies. This has suggested that gravitationally-unstable, gas-rich disks in the early Universe are fuelled by cold, dense accreting gas flowing along cosmic filaments and penetrating hot galactic gas halos. However these accreting flows have not been observed, and cosmic accretion cannot power the observed level of turbulence. Here we report on a new sample of rare high-velocity-dispersion disk galaxies we have discovered in the nearby Universe where cold accretion is unlikely to drive their high star-formation rates. We find that the velocity dispersion is most fundamentally correlated with their star-formation rates, and not their mass nor gas fraction, which leads to a new picture where star formation itself is the energetic driver of galaxy disk turbulence at all cosmic epochs.Comment: 9 pages, 2 figures, Supplimentary Info available at: http://pulsar.swin.edu.au/~agreen/nature/sigma_mean_arXiv.pdf. Accepted for publication in Natur