Thermodynamic Studies of [H_(2)Rh(diphosphine)_2]^+ and [HRh(diphosphine)_(2)(CH_(3)CN)]^(2+) Complexes in Acetonitrile

Thermodynamic studies of a series of [H_(2)Rh(PP)_2]^+ and [HRh(PP)_(2)(CH_(3)CN)]^(2+) complexes have been carried out in acetonitrile. Seven different diphosphine (PP) ligands were selected to allow variation of the electronic properties of the ligand substituents, the cone angles, and the natural bite angles (NBAs). Oxidative addition of H_2 to [Rh(PP)_2]^+ complexes is favored by diphosphine ligands with large NBAs, small cone angles, and electron donating substituents, with the NBA being the dominant factor. Large pK_a values for [HRh(PP)_(2)(CH_(3)CN)]^(2+) complexes are favored by small ligand cone angles, small NBAs, and electron donating substituents with the cone angles playing a major role. The hydride donor abilities of [H_(2)Rh(PP)_2]^+ complexes increase as the NBAs decrease, the cone angles decrease, and the electron donor abilities of the substituents increase. These results indicate that if solvent coordination is involved in hydride transfer or proton transfer reactions, the observed trends can be understood in terms of a combination of two different steric effects, NBAs and cone angles, and electron-donor effects of the ligand substituents

Is the PAMELA Positron Excess Winos?

Recently the PAMELA satellite-based experiment reported an excess of galactic positrons that could be a signal of annihilating dark matter. The PAMELA data may admit an interpretation as a signal from a wino-like LSP of mass about 200 GeV, normalized to the local relic density, and annihilating mainly into W-bosons. This possibility requires the current conventional estimate for the energy loss rate of positrons be too large by roughly a factor of five. Data from anti-protons and gamma rays also provide tension with this interpretation, but there are significant astrophysical uncertainties associated with their propagation. It is not unreasonable to take this well-motivated candidate seriously, at present, in part because it can be tested in several ways soon. The forthcoming PAMELA data on higher energy positrons and the FGST (formerly GLAST) data, should provide important clues as to whether this scenario is correct. If correct, the wino interpretation implies a cosmological history in which the dark matter does not originate in thermal equilibrium.Comment: 7 pages, 4 figue

Dolphin-Assisted Therapy: Claims versus Evidence

The purpose of this paper is to review and critique studies that have been conducted on dolphin-assisted therapy for children with various disorders. Studies have been released claiming swimming with dolphins is therapeutic and beneficial for children with autism, attention deficit hyperactivity disorder, physical disabilities, and other psychological disorders. The majority of the studies conducted supporting the effectiveness of dolphin-assisted therapy have been found to have major methodological concerns making it impossible to draw valid conclusions. Readers will be informed of the history of, theory behind, and variations of dolphin-assisted therapy along with a review and critique of studies published which purportedly support its use

Activation of the Listeria monocytogenes Virulence Program by a Reducing Environment.

Upon entry into the host cell cytosol, the facultative intracellular pathogen Listeria monocytogenes coordinates the expression of numerous essential virulence factors by allosteric binding of glutathione (GSH) to the Crp-Fnr family transcriptional regulator PrfA. Here, we report that robust virulence gene expression can be recapitulated by growing bacteria in a synthetic medium containing GSH or other chemical reducing agents. Bacteria grown under these conditions were 45-fold more virulent in an acute murine infection model and conferred greater immunity to a subsequent lethal challenge than bacteria grown in conventional media. During cultivation in vitro, PrfA activation was completely dependent on the intracellular levels of GSH, as a glutathione synthase mutant (ΔgshF) was activated by exogenous GSH but not reducing agents. PrfA activation was repressed in a synthetic medium supplemented with oligopeptides, but the repression was relieved by stimulation of the stringent response. These data suggest that cytosolic L. monocytogenes interprets a combination of metabolic and redox cues as a signal to initiate robust virulence gene expression in vivoIMPORTANCE Intracellular pathogens are responsible for much of the worldwide morbidity and mortality from infectious diseases. These pathogens have evolved various strategies to proliferate within individual cells of the host and avoid the host immune response. Through cellular invasion or the use of specialized secretion machinery, all intracellular pathogens must access the host cell cytosol to establish their replicative niches. Determining how these pathogens sense and respond to the intracellular compartment to establish a successful infection is critical to our basic understanding of the pathogenesis of each organism and for the rational design of therapeutic interventions. Listeria monocytogenes is a model intracellular pathogen with robust in vitro and in vivo infection models. Studies of the host-sensing and downstream signaling mechanisms evolved by L. monocytogenes often describe themes of pathogenesis that are broadly applicable to less tractable pathogens. Here, we describe how bacteria use external redox states as a cue to activate virulence

Non-local nuclear spin quieting in quantum dot molecules: Optically-induced extended two-electron spin coherence time

We demonstrate the extension of coherence between all four two-electron spin ground states of an InAs quantum dot molecule (QDM) via non-local suppression of nuclear spin fluctuations in both constituent quantum dots (QDs), while optically addressing only the upper QD transitions. Long coherence times are revealed through dark-state spectroscopy as resulting from nuclear spin locking mediated by the exchange interaction between the QDs. Lineshape analysis provides the first measurement of the quieting of the Overhauser field distribution correlating with reduced nuclear spin fluctuations.Comment: Supplementary materials can be found on the publication page of our website. http://research.physics.lsa.umich.edu/dst/Publications.htm

Mini-chromosome maintenance complexes form a filament to remodel DNA structure and topology.

Deregulation of mini-chromosome maintenance (MCM) proteins is associated with genomic instability and cancer. MCM complexes are recruited to replication origins for genome duplication. Paradoxically, MCM proteins are in excess than the number of origins and are associated with chromatin regions away from the origins during G1 and S phases. Here, we report an unusually wide left-handed filament structure for an archaeal MCM, as determined by X-ray and electron microscopy. The crystal structure reveals that an α-helix bundle formed between two neighboring subunits plays a critical role in filament formation. The filament has a remarkably strong electro-positive surface spiraling along the inner filament channel for DNA binding. We show that this MCM filament binding to DNA causes dramatic DNA topology change. This newly identified function of MCM to change DNA topology may imply a wider functional role for MCM in DNA metabolisms beyond helicase function. Finally, using yeast genetics, we show that the inter-subunit interactions, important for MCM filament formation, play a role for cell growth and survival

PRIMUS: The Effect of Physical Scale on the Luminosity-Dependence of Galaxy Clustering via Cross-Correlations

We report small-scale clustering measurements from the PRIMUS spectroscopic redshift survey as a function of color and luminosity. We measure the real-space cross-correlations between 62,106 primary galaxies with PRIMUS redshifts and a tracer population of 545,000 photometric galaxies over redshifts from z=0.2 to z=1. We separately fit a power-law model in redshift and luminosity to each of three independent color-selected samples of galaxies. We report clustering amplitudes at fiducial values of z=0.5 and L=1.5 L*. The clustering of the red galaxies is ~3 times as strong as that of the blue galaxies and ~1.5 as strong as that of the green galaxies. We also find that the luminosity dependence of the clustering is strongly dependent on physical scale, with greater luminosity dependence being found between r=0.0625 Mpc/h and r=0.25 Mpc/h, compared to the r=0.5 Mpc/h to r=2 Mpc/h range. Moreover, over a range of two orders of magnitude in luminosity, a single power-law fit to the luminosity dependence is not sufficient to explain the increase in clustering at both the bright and faint ends at the smaller scales. We argue that luminosity-dependent clustering at small scales is a necessary component of galaxy-halo occupation models for blue, star-forming galaxies as well as for red, quenched galaxies.Comment: 13 pages, 6 figures, 5 tables; published in ApJ (revised to match published version

Lineage dynamics of murine pancreatic development at single-cell resolution.

Organogenesis requires the complex interactions of multiple cell lineages that coordinate their expansion, differentiation, and maturation over time. Here, we profile the cell types within the epithelial and mesenchymal compartments of the murine pancreas across developmental time using a combination of single-cell RNA sequencing, immunofluorescence, in situ hybridization, and genetic lineage tracing. We identify previously underappreciated cellular heterogeneity of the developing mesenchyme and reconstruct potential lineage relationships among the pancreatic mesothelium and mesenchymal cell types. Within the epithelium, we find a previously undescribed endocrine progenitor population, as well as an analogous population in both human fetal tissue and human embryonic stem cells differentiating toward a pancreatic beta cell fate. Further, we identify candidate transcriptional regulators along the differentiation trajectory of this population toward the alpha or beta cell lineages. This work establishes a roadmap of pancreatic development and demonstrates the broad utility of this approach for understanding lineage dynamics in developing organs