Syntheses of Ir 4 (CO) 6 (η 5 -C 5 Me 4 H) 2 and Ir 7 (μ 3 -CO) 3 (CO) 12 (η 5 -C 5 Me 5 ) from Pentametallic Molybdenum-Iridium Cluster Precursors.

Reaction of Mo2Ir3(μ-CO)3(CO)6(η5-C5H5)2(η5-C5Me5) with Ir(CO)2(η5-C5Me4H) afforded the four-valence-electron-deficien

High-nuclearity ruthenium carbonyl cluster chemistry. 9. Ligand substitution at decaruthenium carbonyl clusters

The mono- to tri-substituted decaruthenium cluster anions [Ru10(μ-H)(μ6-C)(CO)24-x(L)x]- [L = P(C6H4Me-4)3, AsPh3, SbPh3, x = 1-3] were prepared as their [PPh4]+ salts in moderate to good yields from reaction of [PPh4][Ru10(μ-H)(μ6-C)(CO)24] with the corresponding group 15 ligands at room temperature in acetone. The tetrakis-substituted cluster Ru10(μ6-C)(μ3-CO)(μ-CO)(CO)19(P(C6H4Me-4)3)4 was obtained in high yield from [PPh4]2[Ru10(μ6-C)(CO)24] and an excess of the phosphine under the same conditions; a single-crystal X-ray diffraction study revealed that the phosphines ligate at the vertices of the "giant tetrahedral" core. Kinetics studies of the formation of [PPh4][Ru10(μ-H)(μ6-C)(AsPh3)2(CO)22] from [PPh4][Ru10(μ-H)(μ6-C)(AsPh3)(CO)23] shows that ligand substitution at these giant tetrahedral clusters proceeds via a strongly associative pathway with the likely intermediacy of a Ru-Ru bond-cleaved intermediat

Mixed-metal cluster chemistry. 39. Syntheses and X-ray structures of Mo 3 Ir 3 (μ 4 -η 2 -CO)(μ 3 -CO)(CO) 10 (η 5 -C 5 H 5 ) 3 and Mo 3 RhIr 3 (μ-CO) 4 (CO) 7 (η 5 -C 5 H 5 ) 3 (η 5 -C 5 Me 5 )

We thank the Australian Research Council (ARC) for support ofthis work. J.F. was the recipient of a China Scholarship Council ANUPostgraduate Scholarship and M.D.R. was the recipient of anAustralian Postgraduate Awar

Mixed-metal cluster chemistry. 37. Syntheses, structural, spectroscopic, electrochemical, and optical power limiting studies of tetranuclear molybdenum–iridium clusters

Tetrahedral Mo2Ir2(μ3-CO)(μ-CO)5(CO)4(η5-C5H5)2 (1) reacted with P(C6H4Me-4)3, P(C6H2Me2-3,5-OMe-4)3, and AsPh3 to afford the substitution products Mo2Ir2(μ-CO)3(CO)6(L)(η5-C5H5)2 [L = P(C6H4Me-4)3 (3), P(C6H2Me2-3,5-OMe-4)3 (4), AsPh3 (5)] in fair to good yields, while reaction of 1 with HC≡CSiPri3 proceeded by insertion into the Mo–Mo bond to give the pseudo-octahedral Mo2Ir2(μ4-η2-HC2SiPri3)(μ-CO)4(CO)4(η5-C5H5)2 (6) in fair yield. While MoIr3(μ-CO)3(CO)7(η5-C5H5) reacted with HC≡CSiMe3 to give a complex mixture of thus-far-uncharacterized products, its phosphine substitution product MoIr3(μ-CO)3(CO)5(PPh3)2(η5-C5H5) reacted with the same alkyne via insertion into a Mo–Ir bond to afford the pseudo-octahedral MoIr3(μ4-η2-HC2SiMe3)(μ-CO)3(CO)4(PPh3)2(η5-C5H5) (8) in good yield. Clusters 4, 5 (two isomers), 6 and 8 have been characterized by single-crystal X-ray diffraction studies. Cyclic voltammetric studies of Mo2Ir2(μ-CO)3(CO)6(PPh3)(η5-C5H5)2 (2), 3–6 and 8 confirmed the tuning of redox potentials upon phosphines/arsine introduction and alkyne modification. IR spectroelectrochemical studies of 2, 6, and 8 suggest decreasing proclivity for bridging carbonyl ligands following oxidation. Variable temperature 31P NMR studies of 3 and 4 revealed interconverting isomers in solution, the structures of which are assigned as analogues of the X-ray diffraction-confirmed isomers of 5. Studies of 2–5 using ns pulses and the open-aperture Z-scan technique revealed that all are optical limiters at wavelengths in the visible region.We thank the Australian Research Council (ARC) for support ofthis work. J.F. is the recipient of a China Scholarship Council ANUPostgraduate Scholarship and M.P.C. holds an ARC AustralianResearch Fellowshi

Equivalence of ELISpot Assays Demonstrated between Major HIV Network Laboratories

The Comprehensive T Cell Vaccine Immune Monitoring Consortium (CTC-VIMC) was created to provide standardized immunogenicity monitoring services for HIV vaccine trials. The ex vivo interferon-gamma (IFN-γ) ELISpot is used extensively as a primary immunogenicity assay to assess T cell-based vaccine candidates in trials for infectious diseases and cancer. Two independent, GCLP-accredited central laboratories of CTC-VIMC routinely use their own standard operating procedures (SOPs) for ELISpot within two major networks of HIV vaccine trials. Studies are imperatively needed to assess the comparability of ELISpot measurements across laboratories to benefit optimal advancement of vaccine candidates.We describe an equivalence study of the two independently qualified IFN-g ELISpot SOPs. The study design, data collection and subsequent analysis were managed by independent statisticians to avoid subjectivity. The equivalence of both response rates and positivity calls to a given stimulus was assessed based on pre-specified acceptance criteria derived from a separate pilot study.Detection of positive responses was found to be equivalent between both laboratories. The 95% C.I. on the difference in response rates, for CMV (-1.5%, 1.5%) and CEF (-0.4%, 7.8%) responses, were both contained in the pre-specified equivalence margin of interval [-15%, 15%]. The lower bound of the 95% C.I. on the proportion of concordant positivity calls for CMV (97.2%) and CEF (89.5%) were both greater than the pre-specified margin of 70%. A third CTC-VIMC central laboratory already using one of the two SOPs also showed comparability when tested in a smaller sub-study.The described study procedure provides a prototypical example for the comparison of bioanalytical methods in HIV vaccine and other disease fields. This study also provides valuable and unprecedented information for future vaccine candidate evaluations on the comparison and pooling of ELISpot results generated by the CTC-VIMC central core laboratories

Markets, the Organisation of Exchanges and « Instituted economic process » - An Analytical Perspective

[fre] Ce papier développe une analyse de l'organisation des processus d'échange. En limitant l'analyse à des caractéristiques institutionnelles spécifiquement économiques, l'intention est à la fois d'approfondir la sociologie économique des marchés, et de situer l'organisation institutionnelle des processus d'échange dans un champ beaucoup plus large que celui des seuls échanges de marché. Le papier développe une procédure pour analyser la variété et la dynamique des processus d'échange en identifiant certains paramètres sous-jacents clefs. La constitution séparée de catégories d'acteurs économiques entre lesquels les échanges se produisent; les nœuds d'interdépendance entre les agents économiques et les processus d'échange, marché et hors marché; les interactions à travers les processus d'échanges entre les vendeurs et les acheteurs dont dépendent les processus d'achange sont analysés de manière à comprendre les différences et variations systématiques à la fois entre et à l'intérieur des marchés du travail, des produits et du capital. [eng] This paper develops an analysis of the organisation of exchange processes. By limiting analysis to specifically economic instituted characteristics, the intention is both deepen the economic sociology of markets, and to situate instituted organisation of exhange processes in a much broader field than market exchanges. The paper develops a procedure for analysing the variety and dynamics of exchange processes by identifying some key underlying parameters. The separation and formation of classes of economic agent between which exchange occurs;the interdependant nexus of economic agents and exchange processes, market and non-market; and interaction accross the exchange process between sellers and buyers upon which exchange processes depend are analysed as way of understanding systematic differences and variations both between and within labour, product and capital markets.

Ignorance not racism : the ethical implications of cultural schema theory within policing

Communication between cultures that do not share similar norms, values, beliefs, experiences, attitudes and practices has long proven to be a difficult exercise (Balsmeier & Heck, 1994). These difficulties can have serious consequences when the miscommunication happens in the justice system; the innocent can be convicted and witnesses undermined. Much work has been carried out on the need for better communication in the courtroom (Eades, 1993; Lauchs, 2010; Supreme Court of Queensland, 2010; Supreme Court of Western Australia, 2008) but far less on language and interactions between police and indigenous Australians (Powell, 2000). It is ethically necessary that officers of the law be made aware of linguistic issues to ensure they conduct their investigations in a fair and effective manner. Despite years of awareness raising issues still arise. Issues of clashes between police and indigenous peoples are still prevalent (Heath, 2012; Remeikis, 2012). This paper will attempt to explain the reason for this discrepancy and, in doing so, suggest some solutions to the problem. \ud \ud This paper draws on cultural schema theory in an attempt to determine if cultural difference in language could be negatively affecting communication between Aboriginal people and the police of South East Queensland. Findings from this research are significant in determining if miscommunication is adding to the already unequal standing of Aboriginal people within the Criminal Justice system, and encouraging the already volatile relationship between Aboriginal people and police