Stereochemistry of Complex Halides of the Transition Metals

The aim of this lecture i& to provide a survey of the stereochemistry of the tetrahalogeno complexes of the metal ions of the first transition series. In particular we wish to consider which non-bonding electron configurations favour the formation of regular tetrahedral complexes but we pass from this to examine the shape of four-coordinate complexes with other non-bonding -electron arrangements. Recent experimental studies dealing with the preparation of various metal complexes having d 2, d 5, d 6 and d 8 non-bonding configurations will be summarised and the results of the investigations of the structures of these complexes are discussed

Stereochemistry of Complex Halides of the Transition Metals

The aim of this lecture i& to provide a survey of the stereochemistry of the tetrahalogeno complexes of the metal ions of the first transition series. In particular we wish to consider which non-bonding electron configurations favour the formation of regular tetrahedral complexes but we pass from this to examine the shape of four-coordinate complexes with other non-bonding -electron arrangements. Recent experimental studies dealing with the preparation of various metal complexes having d 2, d 5, d 6 and d 8 non-bonding configurations will be summarised and the results of the investigations of the structures of these complexes are discussed

Characterizing the Host and Symbiont Proteomes in the Association between the Bobtail Squid, Euprymna scolopes, and the Bacterium, Vibrio fischeri

The beneficial symbiosis between the Hawaiian bobtail squid, Euprymna scolopes, and the bioluminescent bacterium, Vibrio fischeri, provides a unique opportunity to study host/microbe interactions within a natural microenvironment. Colonization of the squid light organ by V. fischeri begins a lifelong association with a regulated daily rhythm. Each morning the host expels an exudate from the light organ consisting of 95% of the symbiont population in addition to host hemocytes and shed epithelial cells. We analyzed the host and symbiont proteomes of adult squid exudate and surrounding light organ epithelial tissue using 1D- and 2D-polyacrylamide gel electrophoresis and multidimensional protein identification technology (MudPIT) in an effort to understand the contribution of both partners to the maintenance of this association. These proteomic analyses putatively identified 1581 unique proteins, 870 proteins originating from the symbiont and 711 from the host. Identified host proteins indicate a role of the innate immune system and reactive oxygen species (ROS) in regulating the symbiosis. Symbiont proteins detected enhance our understanding of the role of quorum sensing, two-component signaling, motility, and detoxification of ROS and reactive nitrogen species (RNS) inside the light organ. This study offers the first proteomic analysis of the symbiotic microenvironment of the adult light organ and provides the identification of proteins important to the regulation of this beneficial association

Core-Level Satellite Excitations of K/Al(100) and K/Al(111)

Alkali-metal-induced satellite peaks associated with the K 3p and Al 2p core levels have been measured with photoemission for K/Al(111) and K/Al(100) under both low- and room-temperature preparation conditions. For low-temperature deposition we observedddd loss peaks in good agreement with electron-energy-loss spectroscopy studies of analogous systems which we assign to the excitation of collective plasmonlike modes in the alkali-metal overlayer. For room-temperature preparation conditions, we observed significant changes in the satellite loss structure which we attribute to a decrease or loss of metallic behavior in the alkali-metal layer. We account for some of our results as a change in bonding configuration of the K atoms from on-top-of surface to substitutional adsorption for low versus room-temperature preparations

On the Universal Law and Humanity Formulas.

This dissertation is a philosophical commentary on the Prussian Enlightenment philosopher Immanuel Kant’s “Universal Law” and “Humanity” formulations of the categorical imperative (i.e. the most basic principle of morality or virtuousness). The former says to choose one’s basic guiding principles (or “maxims”) on the basis of their fitness to serve as universal laws, the latter to always treat the humanity in each person as an end, and never as a means only. Commentators and critics have been puzzled by Kant’s claim that these are two alternative statements of the same basic law, and have raised various objections to Kant’s suggestion that these are the most basic formulas of a fully justified human morality. This dissertation offers new readings of these two formulas, shows how, on these readings, the formulas do indeed turn out being alternative statements of the same basic moral law, and in the process responds to many of the standard objections raised against Kant’s theory. Its first chapter briefly explores the ways in which Kant draws on his philosophical predecessors such as Plato (and especially Plato’s Republic) and Jean-Jacque Rousseau. The second chapter offers a new reading of the relation between the universal law and humanity formulas by relating both of these to a third formula of Kant’s, the “Law of Nature” formula, and also to Kant’s ideas about laws in general and human nature in particular. The third chapter considers and rejects some influential recent attempts to understand Kant’s argument for the humanity formula, and offers an alternative reconstruction instead. Chapter four considers what it is to flourish as a human being in line with Kant’s basic formulas of morality, and argues that the standard readings of the humanity formula cannot properly account for its relation to Kant’s views about the highest human good.PHDPhilosophyUniversity of Michigan, Horace H. Rackham School of Graduate Studieshttp://deepblue.lib.umich.edu/bitstream/2027.42/93978/1/nyholm_1.pd

Metallicity at the explosion sites of interacting transients

Context. Some circumstellar-interacting (CSI) supernovae (SNe) are produced by the explosions of massive stars that have lost mass shortly before the SN explosion. There is evidence that the precursors of some SNe IIn were luminous blue variable (LBV) stars. For a small number of CSI SNe, outbursts have been observed before the SN explosion. Eruptive events of massive stars are named as SN impostors (SN IMs) and whether they herald a forthcoming SN or not is still unclear. The large variety of observational properties of CSI SNe suggests the existence of other progenitors, such as red supergiant (RSG) stars with superwinds. Furthermore, the role of metallicity in the mass loss of CSI SN progenitors is still largely unexplored. Aims. Our goal is to gain insight on the nature of the progenitor stars of CSI SNe by studying their environments, in particular the metallicity at their locations. Methods. We obtain metallicity measurements at the location of 60 transients (including SNe IIn, SNe Ibn, and SN IMs), via emission-line diagnostic on optical spectra obtained at the Nordic Optical Telescope and through public archives. Metallicity values from the literature complement our sample. We compare the metallicity distributions among the different CSI SN subtypes and to those of other core-collapse SN types. We also search for possible correlations between metallicity and CSI SN observational properties. Results. We find that SN IMs tend to occur in environments with lower metallicity than those of SNe IIn. Among SNe IIn, SN IIn-L(1998S-like) SNe show higher metallicities, similar to those of SNe IIL/P, whereas long-lasting SNe IIn (1988Z-like) show lower metallicities, similar to those of SN IMs. The metallicity distribution of SNe IIn can be reproduced by combining the metallicity distributions of SN IMs (that may be produced by major outbursts of massive stars like LBVs) and SNe IIP (produced by RSGs). The same applies to the distributions of the Normalized Cumulative Rank (NCR) values, which quantifies the SN association to H II regions. For SNe IIn, we find larger mass-loss rates and higher CSM velocities at higher metallicities. The luminosity increment in the optical bands during SN IM outbursts tend to be larger at higher metallicity, whereas the SN IM quiescent optical luminosities tend to be lower. Conclusions. The difference in metallicity between SNe IIn and SN IMs suggests that LBVs are only one of the progenitor channels for SNe IIn, with 1988Z-like and 1998S-like SNe possibly arising from LBVs and RSGs, respectively. Finally, even though linedriven winds likely do not primarily drive the late mass-loss of CSI SN progenitors, metallicity has some impact on the observational properties of these transients. Key words. supernovae: general - stars: evolution - galaxies: abundancesComment: Submitted to Astronomy and Astrophysics on 28/02/2015; submitted to arXiv after the 1st referee repor

Understanding the Role of Host Hemocytes in a Squid/Vibrio Symbiosis Using Transcriptomics and Proteomics

The symbiosis between the squid, Euprymna scolopes, and the bacterium, Vibrio fischeri, serves as a model for understanding interactions between beneficial bacteria and animal hosts. The establishment and maintenance of the association is highly specific and depends on the selection of V. fischeri and exclusion of non-symbiotic bacteria from the environment. Current evidence suggests that the host’s cellular innate immune system, in the form of macrophage-like hemocytes, helps to mediate host tolerance of V. fischeri. To begin to understand the role of hemocytes in this association, we analyzed these cells by high-throughput 454 transcriptomic and liquid chromatography/tandem mass spectrometry (LC-MS/MS) proteomic analyses. 454 high-throughput sequencing produced 650, 686 reads totaling 279.9 Mb while LC-MS/MS analyses of circulating hemocytes putatively identified 702 unique proteins. Several receptors involved with the recognition of microbial-associated molecular patterns were identified. Among these was a complete open reading frame to a putative peptidoglycan recognition protein (EsPGRP5) with conserved residues for amidase activity. Assembly of the hemocyte transcriptome showed EsPGRP5 had high coverage, suggesting it is among the 5% most abundant transcripts in circulating hemocytes. Other transcripts and proteins identified included members of the conserved NF-κB signaling pathway, putative members of the complement pathway, the carbohydrate binding protein galectin, and cephalotoxin. Quantitative Real-Time PCR of complement-like genes, cephalotoxin, EsPGRP5, and a nitric oxide synthase showed differential expression in circulating hemocytes from adult squid with colonized light organs compared to those isolated from hosts where the symbionts were removed. These data suggest that the presence of the symbiont influences gene expression of the cellular innate immune system of E. scolopes