Bioactive and luminescent indole and isatin based gold(i) derivatives

A series of luminescent monometallic [AuL(PPh 3 )] (1-3) and bimetallic [Au 2 (µ-dppe)L 2 ] (4, 6, 8) and [Au 2 (µ-dppp)L 2 ] (5, 7, 9) complexes, where L is either 4-cyano-indole, isatin, or 5, 7-dimethyl-isatin, and dppe and dppp are 1, 2-bis(diphenylphosphino)ethane and 1, 3-bis(diphenylphosphino)propane, respectively, have been synthesised. X-ray diffraction confirmed the tendency to establish aurophillic interations for those complexes containing dppe. Luminescence studies and theoretical calculations revealed a different origin for both families, i.e. indole and isatin species. Thus, indole derivatives presented a ligand-to-ligand-charge-transfer transition (LLCT) from the indole to the PPh 3 fragment, whereas for the isatin derivatives an intraligand-charge-transfer transition (ILCT) within the isatin fragment is proposed. In both cases, the gold centre was slightly implicated as a ligand-to-metal-charge transfer transition (LMCT) (from the indole/isatin to Au(i)). Cell antiproliferative assays in lung cancer cells (A549), leukemia Jurkat-pLVTHM and Jurkat-shBak cells (cisplatin sensitive and resistant, respectively) showed excellent cytotoxic values (10.11-0.28 µM), showing the leukemia cells to be the most sensitive and the bimetallic species to be the most active agents. Preliminary studies associated the cytotoxicity with a combination of different factors, the metallic fragment being mainly responsible. Remarkably, these complexes are able to inhibit the cellular growth of cisplatin resistant Jurkat-shBak cells highlighting their promising future as an alternative anticancer agent

Materiality and Indigenous Agency: Limits to the Colonial Order (Argentinean Patagonia, Eighteenth–Nineteenth Centuries)

This paper highlights the agency of indigenous peoples in the manipulation, alteration, and/or definition of limits to the colonial order established in Patagonia by the end of the eighteenth century. Hence, it rests on the ideas of the ambivalence of power and intercultural relations. Interethnic relationships are explored in two case studies from the same colonizing project: “Nueva Colonia y Fuerte de Floridablanca” (San Julián Bay, Santa Cruz province) and “Fuerte San José” (Valdés peninsula, Chubut province). Social practices, material conditions of the colonial settlements, and particularly, the indigenous perceptions of the colonial posts are thoroughly considered. This information is thus intended to discuss the divergent trajectories of interethnic relationships, as well as to approach colonialism in Patagonia from the natives’ logics.Fil: Buscaglia, Silvana. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Saavedra 15. Instituto Multidisciplinario de Historia y Ciencias Humanas; Argentin