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This article describes two of the most common natural sources of red anthraquinones that have been used since antiquity for textile dyeing and as lake pigments, namely cochineal insect and the roots of Rubia and Relbunium plants. Carminic acid is the main component of carmine, the red colorant obtained from cochineal. Alizarin and purpurin are found in the extracts of Rubia roots, but Relbunium roots contain only purpurin. These red anthraquinones have been identified in a variety of cultural heritage objects. High performance liquid chromatography with diode array detection (HPLC-DAD) is described as the most suitable analytical technique for the identification of these dyestuffs, particularly in micro-samples from textiles or pigment layers in paintings and polychrome sculptures. Finally, application of HPLC-DAD analysis to the identification of lake pigments in micro-samples of mural paintings of two eighteenth century Andean churches in Peru is described.

En el presente trabajo se dan a conocer los resultados de estudios químicos de residuos lipídicos recuperados en las matrices cerámicas de contenedores del sitio arqueológico Loma l´Ántigo, un poblado Tardío del valle del Cajón (Catamarca, Argentina). Se analizaron los residuos de 12 muestras arqueológicas por medio de cromatografía gaseosa con detector de ionización de llama (GC-FID) y una olla etnográfica mediante GC-FID y cromatografía gaseosa acoplada a espectrometría de masa (GC-MS), con fines comparativos. La identificación de distintos ésteres metílicos de ácidos grasos (FAMEs) en nueve de las muestras arqueológicas y en la olla etnográfica resulta evidencia del empleo de los contenedores en distintas actividades culinarias, que implicaron la circulación de sustancias de origen vegetal y animal. En la mayoría de estos casos, se identificaron biomarcadores de grasas de rumiantes compatibles con camélidos. La articulación de los estudios químicos con otras fuentes de indagación permitió constatar el empleo de distintos tipos de contenedores en el almacenamiento, elaboración y servicio de comidas y/o bebidas.

In this work, we studied protein binders in micro-samples from mural paintings from two 18th century Colonial Andean churches located in the northernmost region of Chile using a proteomic approach. The protein fraction of the samples was extracted with ammonia following a previously optimized methodology and analyzed by LC–MSMS. We identified collagen as well as egg white and yolk proteins, in accordance with a tempera painting technique. In addition, we detected for the first time the presence of muscle proteins in two of the micro-samples. The collagen and muscle proteins could be ascribed to bovine (Bos taurus) and llama (Vicugna pacos), a domesticated camelid used as food source and for transportation of goods in the Andes since pre-Hispanic times. These findings provide new aspects on the knowledge of old animal glues composition and painting practices in the Andean region with reliable information for restoration and conservation work.

La etnobiología estudia los vínculos de los humanos con el ambiente natural. El eje que guía los estudios es la comprensión de cómo las culturas conceptualizan, clasifican, sienten y utilizan a la naturaleza. La incorporación de información de otros campos de las ciencias exactas y naturales se ha empleado en etnobiología para analizar, por ejemplo, la injerencia que las características materiales tienen en la selección de diferentes materias primas. De igual forma, y aunque poco explorado hasta el momento, la información química permite profundizar la comprensión de distintos procesos, como las formas de elaboración de fermentos, tintes o técnicas de curtiembre. A fin de ejemplificar lo antepuesto, este trabajo analiza el cambio en la elaboración del tinte del fruto de guayacán (Caesalpinia paraguariensis) al seno de la comunidad wichí de Tres Pozos (Formosa, Argentina), desde un enfoque que complementa la información etnobiológica con análisis químicos. Se trata de un tinte que los wichís del Gran Chaco utilizan desde antaño para teñir de negro los hilos de cháguar (Bromelia spp.) y para el cual la forma de elaboración cambió drásticamente a lo largo del tiempo: de mordentado con barro negro a la ausencia de mordentado y, en reemplazo, maceración a tiempos prolongados, técnica de difícil ejecución que las tejedoras describen como “fermentación”. Químicamente, el tinte está compuesto principalmente por taninos hidrolizables de color amarillo-pardo que forman complejos con hierro de coloración negra. Mientras que antaño el hierro provenía del mordiente (barro), en la actualidad es aportado de manera gradual por los recipientes oxidados; de aquí que si se macera a tiempos cortos y/o en recipientes sin óxido en superficie la tinción no resulta del color deseado. La inclusión de información química permitió ampliar la comprensión en torno a las formas de elaboración de este tinte, incluyendo las dificultades actuales de ejecución.

In this paper, we characterized for the first time the painting materials in rock art panels of the Patagonian archaeological locality La Angostura using a methodological approach that combined micro-Raman spectroscopy, attenuated total reflection Fourier Transform infrared spectroscopy, and X-ray fluorescence spectroscopy. In this way, we obtained detailed information on the red, green, and black pigments as well as on accessory minerals present in the paints. Hematite was the chromophore in the red paintings while celadonite and glauconite were identified in the green motifs. A manganese oxide, presumably pyrolusite, was characterized as the black pigment. The pigment compositions were also compared to those of natural sediments collected along the valley of the Chubut River, but the components of the red and green sediment samples differed from those present in the rock art paints. In the red motifs of two of the rock art panels, a relevant finding was the presence of gypsum and anhydrite as a priming layer of the corrugated rock support onto which the red paints were applied. This revealed a different painting technique in comparison to that at the other analyzed panels of La Angostura where paints were applied as thin layers on a smooth surface of the rock support. As far as we know, this is the first report on the identification of gypsum and anhydrite as components of a preparation layer in Patagonian rock art. This result contributes to the open discussion on the origin and function of calcium sulfate in rock art.

In this paper, an interdisciplinary investigation was carried out to study if Santa Maria tricolor style vessels were used as culinary equipment in a 14th century ad domestic cooking space in El Colorado (Yocavil valley, Catamarca, Northwest Argentina) and to question the long-established idea that Santa Maria vessels were exclusively funerary objects. The combined use of gas chromatography (GC-FID), gas chromatography–mass spectrometry (GC-MS), and high-performance liquid chromatography coupled to electrospray ionization and quadrupole time-of-flight mass spectrometry (HPLC-ESI-Q-TOF) to study residual lipids from Santa Maria style vessels provided valuable information on their ancient use. Also, an ordinary striated style ceramic pot with distinct visible soot marks, as well as sediments from the cooking area, was studied for comparative purposes. Fatty acid, sterol, and acylglyceride profiles were characterized, and markers of food sources were searched in the complex mixtures. We identified intact triacylglycerides (TAGs) in the archaeological samples, even unsaturated, indicating exceptional preservation of lipids in the ceramic matrixes. Cholesterol or cholesterol oxidation products were observed in all ceramic containers, as well as plant sterols (stigmasterol, sitosterol) in two containers. Markers for ruminant lipids, such as TAGs that contain odd-chain fatty acids, were found, supported by the identification of odd-chain and branched-chain fatty acids with GC-FID and GC-MS. This evidence contributes to the hypothesis that Santa Maria vessels were used for culinary purposes in this archaeological domestic cooking space., Laboratorio de Etnobotánica y Botánica Aplicada

In this paper, we report the study of proteinaceous binders in samples from a South American Colonial 18th century painting using two complementary mass spectrometry techniques. Before restoration, seven micro-samples were extracted from representative colors of one of the mural paintings located inside the church of Our Lady of Copacabana de Andamarca built in 1723 in Bolivia. Previous analysis by gas chromatography (GC) of the amino acid derivatives of the extracted protein fraction of three of the samples, suggested the presence of animal glue and egg. In this work, we introduce a methodology that combines a protein extraction procedure with a typical treatment for analysis of proteins as tryptic peptides by mass spectrometry. For this study, we applied in the first stage, MALDI-TOF/MS and then, LC-ESI/MS (Orbitrap), an ultrahigh resolution mass spectrometry, to achieve more reliability in the identification of the protein binders. By LC-ESI/MS (Orbitrap), we detected several peptides from egg white proteins, particularly ovalbumin, ovotransferrin and lysozyme, and egg yolk proteins, vitellogenin-2 and apolipoprotein B, with high confidence peptides each. In all the samples, the presence of collagen from animal provenance was established by MALDI-TOF/MS and LC-ESI/MS (Orbitrap). To our knowledge, this is the first time that protein binders in Andean paintings are identified without ambiguity by MALDI-TOF/MS and LC-ESI/MS (Orbitrap) mass spectrometry using a proteomic approach. Fil: Levy, Ivana Karina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina Fil: Neme Tauil, Ricardo Martin. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química Biológica de la Facultad de Ciencias Exactas y Naturales. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química Biológica de la Facultad de Ciencias Exactas y Naturales; Argentina Fil: Valacco, Maria Pia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química Biológica de la Facultad de Ciencias Exactas y Naturales. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química Biológica de la Facultad de Ciencias Exactas y Naturales; Argentina Fil: Moreno, Silvia Margarita. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química Biológica de la Facultad de Ciencias Exactas y Naturales. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química Biológica de la Facultad de Ciencias Exactas y Naturales; Argentina Fil: Siracusano, Gabriela Silvana. Universidad Nacional de Tres de Febrero; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Maier, Marta Silvia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina. Universidad Nacional de Tres de Febrero; Argentina

Santa María and Belén vessels from the Late Intermediate Period (10th–15th centuries AD) in Northwest Argentina are strongly associated to funerary uses as “urns”. However, multiple recent findings of these vessels in domestic non-funerary contexts point towards diverse utilities. In this paper we carried out an exploratory analysis and selected two case studies of Santa María vessels and one of a Belén vessel, all recovered in household floors from three sites in Catamarca, Argentina. In order to enquire into the potential culinary uses of vessels, lipid residues were extracted from the ceramic matrixes and gas chromatography–mass spectrometry (GC–MS) analyses were carried out to explore their origins. In all three vessels lipid residues were recovered and characterized. Two samples showed evidence of plant and animal lipid mixtures, while the third sample only had animal lipids. The culinary utility of these vessels was confirmed, and uses may have included storage or service of liquids or stews. These preliminary results provide insight into an alternative interpretation of Santa María and Belén vessel use. Fil: Lantos, Irene Johanna. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina Fil: Palamarczuk, Valeria. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Saavedra 15. Instituto de las Culturas. Universidad de Buenos Aires. Instituto de las Culturas; Argentina Fil: Orgaz, Martín Alfonso. Universidad Nacional de Catamarca; Argentina Fil: Ratto, Norma Rosa. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Saavedra 15. Instituto de las Culturas. Universidad de Buenos Aires. Instituto de las Culturas; Argentina Fil: Maier, Marta Silvia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina

Liver X receptors (LXRs) are li-gand-dependent transcription factors activated by cholesterol metabolites. These receptors induce a suite of target genes required for de novo synthesis of triglycerides and cholesterol transport in many tissues. Two different isoforms, LXRβ and LXRβ, have been well characterized in liver, adipocytes, macrophages, and intestinal epithelium among others, but their contribution to cholesterol and fatty acid efflux in the lactating mammary epithelium is poorly understood. We hypothesize that LXR regulates lipogenesis during milk fat production in lactation. Global mRNA analysis of mouse mammary epithelial cells (MECs) revealed multiple LXR/RXR targets upregulated sharply early in lactation compared with midpregnancy. LXRβ is the primary isoform, and its protein levels increase throughout lactation in MECs. The LXR agonist GW3965 markedly induced several genes involved in cholesterol transport and lipogenesis and enhanced cytoplasmic lipid droplet accumulation in the HC11 MEC cell line. Importantly, in vivo pharmacological activation of LXR increased the milk cholesterol percentage and induced sterol regulatory element-binding protein 1c (Srebp1c) and ATP-binding cassette transporter a7 (Abca7) expression in MECs. Cumulatively, our findings identify LXRβ as an important regulator of cholesterol incorporation into the milk through key nodes of de novo lipogenesis, suggesting a potential therapeutic target in women with difficulty initiating lactation. Fil: Grinman, Diego Yair. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Fisiología, Biología Molecular y Neurociencias. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Fisiología, Biología Molecular y Neurociencias; Argentina Fil: Careaga Quiroga, Valeria Pilar. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Wellberg, Elizabeth A.. University of Colorado; Estados Unidos Fil: Dansey, Maria Virginia. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Biológica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Kordon, Edith Claudia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Fisiología, Biología Molecular y Neurociencias. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Fisiología, Biología Molecular y Neurociencias; Argentina Fil: Anderson, Steven M.. University of Colorado; Estados Unidos Fil: Maier, Marta Silvia. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Burton, Gerardo. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: MacLean, Paul S.. University of Colorado; Estados Unidos Fil: Rudolph, Michael C.. University of Colorado; Estados Unidos Fil: Pecci, Adali. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Fisiología, Biología Molecular y Neurociencias. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Fisiología, Biología Molecular y Neurociencias; Argentina

When dealing with contemporary art, conservators have to address not only the material aspects of the artwork but also other highly complex issues. The Argentinian artist Leon Ferrari is a representative example. He created avant-garde art installations but also worked with traditional techniques. His works raise dilemmas over concepts such as authorship, authenticity, legitimacy of art. Some of his artworks only interested him as a means to express his opinions and he was not concerned about alterations in their appearance. Therefore, what should be kept in them is not in an area of certainty for conservators. An essential key for achieving a responsible and respectful conservation result, is to understand the ideology involved in each ‘art piece’ created by Ferrari. Fil: Baldomá, Gabriela. Fundación Augusto y León Ferrari; Argentina Fil: Maier, Marta Silvia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina

Las escasas publicaciones que se refieren a los murales de la iglesia de Pachama ofrecen solo analisis parciales de su contenido, por tanto, uno de los principales aportes de este articulo sera ent...

We report the production of the perylenequinone pigment elsinochrome A in aposymbiotic culture of the mycobiont of the crustose epiphytic lichen Graphis elongata Zenker (Lecanoromycetes), collected in Argentina (Buenos Aires). The substance was not detected in the lichenized thallus (using HPLC techniques) and is otherwise only known from one unrelated lichen and a few genera of non-lichenized, plant-pathogenic fungi in the class Dothideomycetes. The phylogenetic affinities of the lichen mycobiont and the cultured fungus were confirmed using DNA sequence data of the mitochondrial small subunit rDNA (mtSSU), which place the lichen fungus into the Allographa clade within Graphidaceae. The mycobiont pigment was purified and characterized by spectroscopic methods. This is the first case where a rare pigment, otherwise known from non-lichenized, plant-pathogenic fungi, is produced in aposymbiotic culture of a lichen mycobiont, while, at the same time, being absent from the lichen thallus itself. Based on this finding, we discuss the previously postulated hypothesis that lichen mycobionts maintain secondary metabolic pathways of non-lichenized ancestors in their genome, while gene expression and production of metabolites is suppressed in the lichenized state due to toxicity to the photobiont. Fil: Fazio, Alejandra Teresa. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Micología y Botánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Micología y Botánica; Argentina Fil: Adler, Monica Teresa. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Micología y Botánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Micología y Botánica; Argentina Fil: Parnmen, Sittiporn. National Institute of Health. Toxicology Center; Tailandia. Associate Researcher at the Field Museum; Estados Unidos Fil: Lücking, Robert. Associate Researcher at the Field Museum; Estados Unidos. Botanic Garden and Botanical Museum; Alemania Fil: Maier, Marta Silvia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina

Scope: Maternal diabetes can program metabolic and cardiovascular diseases in the offspring. The aim of this work was to address whether an olive oil supplemented diet during pregnancy can prevent lipid metabolic alterations in the heart of the offspring of mild diabetic rats. Methods and results: Control and diabetic Wistar rats were fed during pregnancy with either a standard diet or a 6% olive oil supplemented diet. The heart of adult offspring from diabetic rats showed increases in lipid concentrations (triglycerides in males and phospholipids, cholesterol, and free fatty acids in females), which were prevented with the maternal diets enriched in olive oil. Maternal olive oil supplementation increased the content of unsaturated fatty acids in the hearts of both female and male offspring from diabetic rats (possibly due to a reduction in lipoperoxidation), increased the expression of Δ6 desaturase in the heart of male offspring from diabetic rats, and increased the expression of peroxisome proliferator activated receptor α in the hearts of both female and male offspring from diabetic rats. Conclusion: Relevant alterations in cardiac lipid metabolism were evident in the adult offspring of a mild diabetic rat model, and regulated by maternal diets enriched in olive oil. Fil: Capobianco, Evangelina Lorena. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Centro de Estudios Farmacológicos y Botánicos. Universidad de Buenos Aires. Facultad de Medicina. Centro de Estudios Farmacológicos y Botánicos; Argentina Fil: Pelesson, Magalí. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Centro de Estudios Farmacológicos y Botánicos. Universidad de Buenos Aires. Facultad de Medicina. Centro de Estudios Farmacológicos y Botánicos; Argentina Fil: Careaga Quiroga, Valeria Pilar. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina Fil: Fornes, Daiana. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Centro de Estudios Farmacológicos y Botánicos. Universidad de Buenos Aires. Facultad de Medicina. Centro de Estudios Farmacológicos y Botánicos; Argentina Fil: Canosa, Ivana Sofía. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina Fil: Higa, Romina Daniela. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Centro de Estudios Farmacológicos y Botánicos. Universidad de Buenos Aires. Facultad de Medicina. Centro de Estudios Farmacológicos y Botánicos; Argentina Fil: Maier, Marta Silvia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina Fil: Jawerbaum, Alicia Sandra. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Centro de Estudios Farmacológicos y Botánicos. Universidad de Buenos Aires. Facultad de Medicina. Centro de Estudios Farmacológicos y Botánicos; Argentina

Feasting was an important aspect of the domination strategy designed by the Inca Empire in the provinces. Hospitality banquets were the setting for negotiations between Cuzco and the annexed populations. Consumption of food and drink played a fundamental role in these feasts. In this paper we present the first study of organic residues recovered from ceramic vessels from the archaeological site of Fuerte Quemado-Intihuatana (Catamarca, Argentina), an important settlement of the Collasuyu province. Earlier functional studies proposed that these vessels were used to store and serve food and drink in commensal contexts. Results from this preliminary molecular study support this hypothesis because all the containers yielded organic residues. Chemical and isotopic studies suggest that food and different kinds of beers were held in these containers during festive events. Fil: Lantos, Irene Johanna. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina Fil: Orgaz, Martín Alfonso. Universidad Nacional de Catamarca. Escuela de Arqueología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Panarello, Hector Osvaldo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Geocronología y Geología Isotópica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Geocronología y Geología Isotópica; Argentina Fil: Maier, Marta Silvia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina

Fil: Marte, Fernando Daniel. Universidad Nacional de San Martin. Instituto de Investigaciones sobre el Patrimonio Cultural; Argentina

A set of twenty one lupane derivatives (2–22) was prepared from the natural triterpenoid calenduladiol (1) by transformations on the hydroxyl groups at C-3 and C-16, and also on the isopropenyl moiety. The derivatives were tested for their inhibitory activity against acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) and some structure–activity relationships were outlined with the aid of enzyme kinetic studies and docking modelization. The most active compound resulted to be 3,16,30-trioxolup-20(29)-ene (22), with an IC50 value of 21.5 μM for butyrylcholinesterase, which revealed a selective inhibitor profile towards this enzyme. Fil: Castro, Maria Julia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentina Fil: Richmond, Victoria. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina Fil: Romero, Carmen. Universidad de la Laguna. Departamento de Química Orgánica. Instituto Universitario de Bio-Orgánica "Antonio González"; España Fil: Maier, Marta Silvia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina Fil: Estevez Braun, Ana. Universidad de la Laguna. Departamento de Química Orgánica. Instituto Universitario de Bio-Orgánica "Antonio González"; España Fil: Ravelo, Angel G.. Universidad de la Laguna. Departamento de Química Orgánica. Instituto Universitario de Bio-Orgánica "Antonio González"; España Fil: Faraoni, María Belén. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentina Fil: Murray, Ana Paula. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentina

Maternal diabetes impairs fetal lung development. Peroxisome proliferator-activated receptors (PPARs) are ligand-activated transcription factors relevant in lipid homeostasis and lung development. This study aims to evaluate the effect of in vivo activation of PPARs on lipid homeostasis in fetal lungs of diabetic rats. To this end, we studied lipid concentrations, expression of lipid metabolizing enzymes and fatty acid composition in fetal lungs of control and diabetic rats i) after injections of the fetuses with Leukotriene B4 (LTB4, PPARα ligand) or 15deoxyΔ12,14prostaglandin J2 (15dPGJ2, PPARγ ligand) and ii) fed during pregnancy with 6% olive oil- or 6% safflower oil-supplemented diets, enriched with PPAR ligands were studied. Maternal diabetes increased triglyceride concentrations and decreased expression of lipid-oxidizing enzymes in fetal lungs of diabetic rats, an expression further decreased by LTB4 and partially restored by 15dPGJ2 in lungs of male fetuses in the diabetic group. In lungs of female fetuses in the diabetic group, maternal diets enriched with olive oil increased triglyceride concentrations and fatty acid synthase expression, while those enriched with safflower oil increased triglyceride concentrations and fatty acid transporter expression. Both olive oil- and safflower oil-supplemented diets decreased cholesterol and cholesteryl ester concentrations and increased the expression of the reverse cholesterol transporter ATP-binding cassette A1 in fetal lungs of female fetuses of diabetic rats. In fetal lungs of control and diabetic rats, the proportion of polyunsaturated fatty acids increased with the maternal diets enriched with olive and safflower oils. Our results revealed important changes in lipid metabolism in fetal lungs of diabetic rats, and in the ability of PPAR ligands to modulate the composition of lipid species relevant in the lung during the perinatal period. Fil: Kurtz, Melisa Lidia Amelia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Centro de Estudios Farmacológicos y Botánicos; Argentina; Argentina Fil: Capobianco, Evangelina Lorena. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Centro de Estudios Farmacológicos y Botánicos; Argentina; Argentina Fil: Careaga Quiroga, Valeria Pilar. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos Aplicados a la Química Orgánica (i); Argentina; Argentina Fil: Martinez, Nora Alicia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Centro de Estudios Farmacológicos y Botánicos; Argentina; Argentina Fil: Mazzucco, María Belén. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Centro de Estudios Farmacológicos y Botánicos; Argentina; Argentina Fil: Maier, Marta Silvia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos Aplicados a la Química Orgánica (i); Argentina; Argentina Fil: Jawerbaum, Alicia Sandra. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Centro de Estudios Farmacológicos y Botánicos; Argentina; Argentina

Disulfated and trisulfated steroids have been synthesized from cholesterol and their acetylcholinesterase inhibitory activity has been evaluated. In our studies we have found that the activity was not only dependent on the location of the sulfate groups but on their configurations. 2β,3α,6β-trihydroxy-5α-cholestan-6-one trisulfate (18) was the most active steroid with an IC50 value of 15.48 μM comparable to that of 2β,3α-dihydroxy-5α-cholestan-6-one disulfate (1). Both compounds were found to be less active than the reference compound eserine. The butyrylcholinesterase activity of 1 and 18 was one magnitude lower than that against acetylcholinesterase revealing a selective inhibitor profile. Fil: Richmond, Victoria. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos Aplicados A la Química Orgánica (i); Argentina. Universidad de Buenos Aires; Argentina Fil: Murray, Ana Paula. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Bahía Blanca. Instituto de Química del Sur; Argentina. Universidad Nacional del Sur; Argentina Fil: Maier, Marta Silvia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos Aplicados A la Química Orgánica (i); Argentina. Universidad de Buenos Aires; Argentina

Specimens from underwater archaeological excavations have rarely been analysed by Raman spectroscopy probably due to the problems associated with the presence of water and the use of alternative techniques. The discovery of the remains of the Royal Navy warship HMS Swift off the coast of Patagonia, South America, which was wrecked in 1770 while undertaking a survey from its base in the Falkland/Malvinas Islands, has afforded the opportunity for a first-pass Raman spectroscopic study of the contents of several glass jars from a wooden chest, some of which had suffered deterioration of their contents owing to leakage through their stoppers. From the Raman spectroscopic data, it was possible to identify organic compounds such as anthraquinone and copal resin, which were empirically used as materia medica in the eighteenth century to treat shipboard diseases; it seems very likely, therefore, that the wooden chest belonged to the barber-surgeon on the ship. Spectra were obtained from the wet and desiccated samples, but several samples from containers that had leaked were found to contain only minerals, such as aragonite and sediment. Fil: Edwards, Howell G. M.. University of Bradford; Reino Unido Fil: Elkin, Dolores Carolina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Secretaría de Cultura de la Nación. Dirección Nacional de Cultura y Museos. Instituto Nacional de Antropología y Pensamiento Latinoamericano; Argentina Fil: Maier, Marta Silvia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; Argentina

The Raman spectrum of tartrazine has been mistakenly reported as being that of Indian yellow in the literature, which has serious consequences for the identification of this pigment in art works regarding their authentication. Unlike tartrazine, Indian yellow (a natural mixture of the magnesium and calcium salts of euxanthic acid) exhibits in its Raman spectrum a strong fluorescent background when visible excitation is used, however, excitation in the near infrared (1064 nm) permitted the observation of the Raman bands from the raw pigment with the main features placed at 1346, 1368, 1425, 1441 and 1626 cm−1. Indian yellow identification was assured by 1H and 13C Nuclear Magnetic Resonance characterization and the complete assignment of the proton and carbon resonances was accomplished using heteronuclear single quantum correlation (HSQC), heteronuclear multiple bond correlation (HMBC), nuclear overhauser effect spectroscopy (NOESY) and 1H–1H correlation spectroscopy (COSY). Scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) and X-ray fluorescence (XRF) analyzes were also conducted on a genuine sample of this historical pigment. Fil: de Faria, Dalva L.A.. Universidade de Sao Paulo; Brasil Fil: Edwards, Howell G. M.. University of Bradford; Reino Unido Fil: Careaga Quiroga, Valeria Pilar. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina Fil: Walt, Nicholas. L. Cornelissen & Son; Reino Unido Fil: Maier, Marta Silvia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina

The Andean church of Our Lady of Copacabana de Andamarca in Bolivia was built in 1723. Its walls are made of adobe bricks and are decorated with paintings dated from mid 18th century. Before a restoration process involving the governments of Bolivia and the Federal Republic of Germany, seven microsamples were extracted from representative colors of one of the wall paintings inside the church. The aim of our research was to characterize the chromatic palette and investigate the painting technique of this Andean colonial wall painting. To approach these goals, an Integrated investigation comprising Raman and FTIR-ATR spectroscopy, optical microscopy (OM), scanning electron microscopy with X-ray microanalysis (SEM-EDS), gas chromatography (GC), and gas chromatography mass spectrometry (GC-MS) was carried out.The results indicated the use of a mixture of two basic copper sulfates of mineral origin, brochantite and antlerite, as the green pigment, adding relevant information to the palette of green pigments in colonial art. Yellow, orange and red ochre, abundant pigments in the Andean region, were also characterized. Observation by optical microscopy of crosssections of the embedded microsamples and analysis of organic binders by GC and GC-MS pointed to a secco technique and the use of a mixture of egg and vegetable oil (?tempera grassa?) as the pigment binder.In conclusion, our results allowed to establish the pigment palette and offered new insights into the painting technique of Andean wall paintings. Fil: Tomasini, Eugenia Paula. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina Fil: Castellanos Rodriguez, Diana Marcela. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina Fil: Gómez Romero, Blanca Andreina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina Fil: de Faria, Dalva L.A.. Universidade de Sao Paulo; Brasil Fil: Rúa Landa, Carlos. Ministerio de Culturas y Turismo; Bolivia Fil: Siracusano, Gabriela Silvana. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Tres de Febrero; Argentina Fil: Maier, Marta Silvia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina. Universidad Nacional de Tres de Febrero; Argentina

Direct inlet mass spectrometry (DI-MS) was examined for its suitability to quickly identify indigo in mixtures with lipidic and proteinaceous binders, such as those characteristic of paintings and polychromy. The technique was tested on naturally aged reference mixtures of indigo with linseed oil, rabbit skin glue, and whole egg. DI-MS with electron ionization at 70. eV served as an efficient tool for screening indigo in complex matrices and provided, at the same time, a mass spectral fingerprint of the organic binder in just a few minutes. The technique was applied to the identification of indigo in a blue sample from a mural painting dated from the 18th century and housed in an Andean church in Bolivia. At the same time, the acquired data revealed for the first time the use of an egg tempera binding medium in an Andean mural painting. Fil: Gómez Romero, Blanca Andreina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina Fil: Castellanos Rodriguez, Diana Marcela. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina Fil: Careaga Quiroga, Valeria Pilar. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina Fil: Siracusano, Gabriela Silvana. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Tres de Febrero; Argentina Fil: Maier, Marta Silvia. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina. Universidad Nacional de Tres de Febrero; Argentina

A new triterpene glycoside, pseudocnoside A (1), was isolated from the sea cucumber Pseudocnus dubiosus leoninus. The structure of the new compound was established on the basis of extensive NMR spectroscopic analysis (1H and 13C NMR, 1H,1H-COSY, HMBC, HSQC, TOCSY and NOESY), HR-ESI-MS data and chemical transformations. In addition, the cytotoxicity and antiproliferative activities of 1 and structurally related triterpene glycosides isolated from the sea cucumbers Psolus patagonicus and Hemioedema spectabilis were evaluated against cancer cell lines A-549 and HeLa. Fil: Careaga Quiroga, Valeria Pilar. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos Aplicados a la Química Orgánica (i); Argentina Fil: Bueno, Carlos Alberto. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Biológica; Argentina Fil: Muniain, Claudia Cristina. Universidad Nacional de San Martín; Argentina Fil: Alche, Laura Edith. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Biológica; Argentina Fil: Maier, Marta Silvia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos Aplicados a la Química Orgánica (i); Argentina

Carbon-based black pigments are a wide group of dark-colored materials, which are classified according to the starting material used and their method of manufacture. Raman spectroscopy is an ideal technique for the characterization of carbonaceous matter: crystalline carbon materials present well-defined peaks, which can be easily assigned; amorphous carbon materials, on the other hand, show broad bands between 1300 and 1600 cm -1. The aim of this work was the discrimination between carbon-based pigments by micro-Raman spectroscopy. Five carbon-based pigments provided by Zecchi (lampblack, ivory black, bistre, bitumen, and graphite), two humic-earth materials [Van Dyck (Kremer) and Earth of Kassel (Zecchi)], and a commercial wood charcoal were studied. Raman spectra of all the samples showed the characteristic bands at approximately 1580 and 1350 cm -1; however, a clear difference in position, width, and relative intensity could be observed for most of the samples. The resulting analysis showed that micro-Raman spectroscopy allowed the discrimination of most of the reference pigments and allowed the identification of carbon-based black pigments in two South American colonial paintings dated from the early 18th century. Copyright © 2012 John Wiley & Sons, Ltd. Fil: Tomasini, Eugenia Paula. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; Argentina Fil: Halac, Emilia Beatriz. Comisión Nacional de Energía Atómica; Argentina. Universidad Nacional de San Martín. Escuela de Ciencia y Tecnología; Argentina Fil: Reinoso, Maria Elba. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica; Argentina. Universidad Nacional de San Martín. Escuela de Ciencia y Tecnología; Argentina Fil: Di Liscia, Emiliano Javier. Comisión Nacional de Energía Atómica; Argentina Fil: Maier, Marta Silvia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; Argentina

A strain of the lichen mycobiont of Caloplaca erythrantha, isolated from ascospores, was cultured axenically on different solid media. Four of the media employed supported the development of colonies and production of the two major lichen secondary metabolites. These media were: BMYE (mannitol 2%, yeast extract 0·1%, in Bold's basal medium); MEYE (malt extract 2%, yeast extract 0·2%, in distilled water); Hamada's MY10 (malt extract 1%, yeast extract 0·4%, sucrose 10%, in distilled water); and the new BMRM (Bold mannitol rich medium, mannitol 5·3%, malt extract 1%, yeast extract 0·4% in Bold's mineral medium). Percentages refer to final medium volume. The fungal colonies developed well on the four media and produced emodin and 7-chloroemodin, the major secondary compounds of the lichen apothecia. Crystals deposited richly on the external surface of the hyphae, as observed with an optical microscope. The two anthraquinones were purified from the lichen thallus, apothecia and cultured mycelia, and identified by chromatographic (TLC, HPLC) and spectroscopic (NMR, MS) methods. The analysis of lichen apothecia revealed the presence of emodin (0·90% w/w) and 7-chloroemodin (0·56% w/w), whereas colonies cultured for five months generally produced higher percentages than the lichen: 1·72% emodin and 0·30% 7-chloroemodin on BMYE; 0·21% and 0·95% on MEYE; 7·82% and 7·48% on MY10; and 11·70% and 10·80% on BMRM. These results show that the production of both anthraquinones was promoted significantly in mycobiont cultures with high concentrations of the carbon sources sucrose or mannitol, with a higher effect being observed with the latter.

Analytical characterization of reference carbon-based black pigments has been performed using Fourier transform infrared spectroscopy (FTIR) with attenuated total reflectance (ATR) and scanning electron microscopy (SEM) coupled to an energy-dispersive X-ray spectrometer (EDS). The unambiguous identification of these pigments, which are found in paintings, rock art and archeological artifacts, still remains a big challenge due to the variety of sources and manufacturing processes used in their preparation. The analytical results achieved in this study allowed us to discriminate between carbon-based pigments from different sources and detect adulterations. The methodological approach was successfully applied to the identification of vegetable charcoal and bone black in two colonial paintings dated from the eighteenth century. Conclusions regarding the pictorial techniques were drawn from FTIR data. Fil: Tomasini, Eugenia Paula. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; Argentina Fil: Siracusano, Gabriela Silvana. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de San Martín; Argentina Fil: Maier, Marta Silvia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; Argentina

Disodium 2β,3α-dihydroxy-5α-cholestan-6-one disulfate ( 8 ) has been synthesized using cholesterol ( 1 ) as starting material. Sulfation was performed using trimethylamine–sulfur trioxide complex in dimethylformamide as the sulfating agent. The acetylcholinesterase inhibitory activity of compound 8 was evaluated and compared to that of disodium 2β,3α-dihydroxy-5α-cholestane disulfate ( 10 ) and diols 7 and 9 . Compounds 8 and 10 were active with IC 50 values of 14.59 and 59.65 μM, respectively. Diols 7 and 9 showed no inhibitory activity (IC 50 > 500 μM).

This paper gathers the conclusions of a research whose principal aim was to inquire about the knowledge and technological skills possessed by the artisans painters of northern argentinian Patagonia during pre- and postcolumbian times. The study focused on the material properties of the paints that aborigine societies were executing to display their graphic language. The organic and inorganic components were analyzed: pastes, patinas and coloring raw material. It was tried to determine what pigments, binders, additives and fasteners were used and what recipes were applied. During the development of the project, historical and ethnography information were analyzed, which allowed us to design actualistic studies. A multidisciplinary reading from the archaeology, the geology and the chemistry was needed to interpret the corpus of information. Cet article contient les conclusions d’une recherche dont l’objectif principal a consisté à établir quelles étaient les connaissances et les capacités technologiques que possédaient les artisans-peintres de la Patagonie septentrionale argentine lors des périodes pré- et postcolombiennes. L’étude s’est concentrée sur les propriétés matérielles des peintures qu’exécutaient les sociétés indigènes pour déployer leur langage graphique. Les composants inorganiques et organiques des peintures rupestres ont été analysés, ainsi que les crayons, les substances adhérées à des artefacts archéologiques, les supports rocheux, les patines et la matière première colorante. On a cherché à déterminer quels pigments, liants, aditifs et fixateurs étaient employées, et quelles recettes étaient appliquées. Au cours de ce projet, nous avons travaillé à partir d’informations historiques et ethnographiques, qui nous ont à leur tour permis de concevoir les études actuelles. L’interprétation du corpus de données a nécessité de faire appel à une lecture pluridisciplinaire, intégrant l’archéologie, la géologie et la chimie. Fil: Boschin, Maria Teresa. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Centro Nacional Patagónico; Argentina Fil: Maier, Marta Silvia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina Fil: Massaferro, Gabriela Isabel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Centro Nacional Patagónico; Argentina

Pigment samples obtained from a South American Jesuit wooden sculpture housed at the Museum of Natural Sciences in La Plata, Buenos Aires province, Argentina, were characterized using scanning electron microscopy and energy dispersive X-ray microanalysis and infrared spectroscopy. The red pigments were identified as vermilion and minium, while the mineral pigment green earth was identified for the first time in a Colonial artwork, together with calcite as the plaster. Two fungal species, Nigrospora sphaerica (Sac.) Mason and Chaethomium globosum Kunze, were isolated from a sample of wood, which was identified as Cedrela fissilis. Chaetomium is a known soft-rot fungus with the capacity to decay wood, but little is known about the effects of Nigrospora on wood. The presence of the two fungi in decayed areas of the wood suggests a contribution of both of them to the degradation of the sculpture.

Different types of materials found in association with a human skeleton found in an 18th century shipwreck in Patagonia (Argentina) were analyzed by means of OM, SEM–EDX, HPLC, and chemical analysis. Alizarin and purpurin, the main anthraquinones of the dye plant Rubia tinctorum L. (madder) were identified as the coloring matter of a red fabric attached to the skeleton. Metallographic and chemical analysis of one of the dome-shaped buttons associated to the human bones revealed that it was composed of a Pb–Sn–Cu alloy known as pewter. The results obtained support the hypothesis that the remains originally were part of a private marine uniform.

Meliacine (MA), an antiviral principle present in partially purified leaf extracts of Melia azedarach L., prevents the development of herpetic stromal keratitis (HSK) in mice by diminishing the viral load in the eye and the severity of lesions caused by a virus-induced immunopathological reaction. The tetranortriterpenoid 1-cinnamoyl-3,11-dihydroxymeliacarpin (CDM), obtained from MA purification, displays anti-herpetic activity and impedes nuclear factor κB (NF-κB) activation in HSV-1 infected conjunctival cells. To extend our understanding about CDM biological properties, we investigated its anti-HSV-1 activity as well as the effect on NF-κB activation and cytokine secretion induced by viral (HSV-1) and no-viral (LPS) stimuli, in corneal cells and macrophages. CDM exerted a potent anti-HSV-1 effect on corneal cells and inhibited NF-κB translocation to the nucleus, leading to a decrease in IL-6 production. Besides, CDM seemed to modulate IL-6 and TNF-α responses in macrophages, whether they were infected with HSV-1 or stimulated with LPS. However, CDM did not affect NF-κB activation in these cells, suggesting that an alternative NF-κB cell signaling pathway would be involved in the modulation of cytokine production. We conclude that, in addition to its antiviral effect, CDM would be acting as an immunomodulating compound which would be responsible for the improvement of murine HSK already reported. © 2008 Elsevier B.V. All rights reserved. Fil: Bueno, Carlos Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Biológica. Laboratorio de Virología; Argentina Fil: Barquero, Andrea Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Biológica. Laboratorio de Virología; Argentina Fil: Di Cónsoli, Hernan Gabriel. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Biológica. Laboratorio de Virología; Argentina Fil: Maier, Marta Silvia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina Fil: Alche, Laura Edith. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Biológica. Laboratorio de Virología; Argentina

Background: The major triterpene glycoside of the sea cucumber Psolus patagonicus and its desulfated analog were tested for their antiproliferative, cytotoxic and hemolytic activities, and their effect on NF-κB activation. Methods: The antiproliferative action of glycosides 1 and 2 were determined on 3 tumor cell lines. Their effect on the activation of NF-κB was evaluated by indirect immunofluorescence assay staining and the concomitant IκBα degradation was studied by Western blot. Results: Both compounds were able to suppress the growth of 3 tumor cell lines (Hep3B, MDA-MB231 and A549) and induced the activation of NF-κB, a key player linking chronic inflammation and cancer, concomitant with IκBα degradation in the A549 tumor cell line. Compounds 1 and 2 showed hemolytic activity with half maximal inhibitory concentration (IC50) values around 80 μM. Conclusions: Both glycosides showed low cytotoxic activity in A549 tumor cells in comparison with sea cucumber triterpene glycosides containing a linear tetrasaccharide chain. This could be a result of the uncommon presence of two 12α- and 17α-hydroxyl groups and a Δ7 double bond in the aglycone moiety. This aglycone functionalization may be related to their low membranolytic activity. Although glycosides 1 and 2 exert an antiproliferative effect, their mechanisms of action do not involve inhibition of NF-κB. Recently, it has been shown that diverse and new mechanisms of action are responsible for the antitumor and cytotoxic activities of marine compounds. Therefore, more extensive studies are needed to establish a mechanism of action and to deduce a clear structure-activity relationship of sea cucumber triterpene glycosides.

Information on the chemical ecology and bioactivity of chemical compounds present in the sea cucumber Psolus patagonicus is provided through an interdisciplinary approach. The specimens studied were collected from two different and very distant sampling localities: Bridges Islands (Beagle Channel, Ushuaia, 54° 48′57″ S 66° 25′00″ W) at depths of 4 to 10 m by SCUBA diving, and from the scallop beds of Zigochlamys patagonica (39° 27′10″ S 55° 56′76″ W), at depths of 110 m and 115 m (43° 47′84″ S 59° 56′80″ W) by means of non-selective dredge in the South Atlantic Ocean.The secondary metabolites were isolated from complete adults by a combination of chromatographic methods and purified by high-performance liquid chromatography. They were characterized as triterpene glycosides through extensive spectroscopic analyses (nuclear magnetic resonance and fast atom bombardment mass spectroscopy) and chemical methods. A purified fraction containing Patagonicoside A as the main triterpene showed a high level of mortality against the brine shrimp Artemia salina and revealed different antifungal activity of Patagonicoside A and its desulphated glycoside (ds-Patagonicoside A) against the fungi Cladosporium fulvum, Fusarium oxysporum and Monilia sp., compared with a potent commercial antifungal product. Fil: Muniain, Claudia Cristina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Parque Centenario. Museo Argentino de Ciencias Naturales “Bernardino Rivadavia”; Argentina Fil: Centurion, Romina Luisa Sabrina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Parque Centenario. Museo Argentino de Ciencias Naturales “Bernardino Rivadavia”; Argentina Fil: Careaga Quiroga, Valeria Pilar. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Maier, Marta Silvia. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina

Archaeological samples are complex in composition since they generally comprise a mixture of materials submitted to deterioration factors largely dependent on the environmental conditions. Therefore, the integration of analytical tools such as TXRF, FT-IR and GC-MS can maximize the amount of information provided by the sample. Recently, two black rock art samples of camelid figures at Alero Hornillos 2, an archaeological site located near the town of Susques (Jujuy Province, Argentina), were investigated. TXRF, selected for inorganic information, showed the presence of manganese and iron among other elements, consistent with an iron and manganese oxide as the black pigment. Aiming at the detection of any residual organic compounds, the samples were extracted with a chloroform-methanol mixture and the extracts were analyzed by FT-IR, showing the presence of bands attributable to lipids. Analysis by GC-MS of the carboxylic acid methyl esters prepared from the sample extracts, indicated that the main organic constituents were saturated (C(16:0) and C(18:0)) fatty acids in relative abundance characteristic of degraded animal fat. The presence of minor C(15:0) and C(17:0) fatty acids and branched-chain iso-C(16:0) pointed to a ruminant animal source.

The skeletal remains of seven individuals were excavated in a secondary burial context in the site of Cima de los Huesos, in the San Matías Gulf (Río Negro, Argentina). AMS dating of two samples for this site to 1173 ± 45 and 1225 ± 47 years BP make it one of the earliest burials of its kind uncovered so far in the Patagonian region. Among the findings, the skeleton of a male painted with parallel lines alternating red and black colors was uncovered. SEM-EDS elemental analysis of microsamples removed from the red and the black pigments showed the presence of Mn and Fe as the main components, respectively. Raman microspectroscopy combined with micro-X-ray diffraction analysis showed that the red pigment contains hematite and that the black pigment is composed of members of the pyroxene mineral group, ferrosilite (FeSiO3) and enstatite (MgSiO3) along with kanoite (MnMgSi2O6). This is, to our knowledge, the first report on the use of pyroxenes as black pigments to decorate human remains or archeological artifacts in South America. No organic compounds that could have been used as binders for the paints were detected by FTIR-ATR. Contamination due to quartz and aluminosilicates, mainly microcline and albite, from the burial environment did not allow determining whether clay minerals were used in the paints as binders and/or extenders. The multitechnique approach used was crucial to overcome the limitations of the individual techniques to firmly identify Mn-containing black pigments. Fil: Tomasini, Eugenia Paula. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina Fil: Favier Dubois, Cristian Mario. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tandil. Investigaciones Arqueológicas y Paleontológicas del Cuaternario Pampeano. Universidad Nacional del Centro de la Provincia de Buenos Aires. Investigaciones Arqueológicas y Paleontológicas del Cuaternario Pampeano; Argentina Fil: Little, Nicole C.. Smithsonian Institution; Estados Unidos Fil: Centeno, Silvia A.. The Metropolitan Museum of Art; Estados Unidos Fil: Maier, Marta Silvia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina

Pre-Hispanic Andean societies depended economically on the cultivation of maize (Zea mays), the main staple food crop in the region after its introduction from highland Mexico. Here we report new data from residue analysis of potsherds recovered in archaeological sites in western Tinogasta, Catamarca province, Argentina, ca. 3rd to 16th centuries AD. Molecular and isotopic (δ13C values) compositions of fatty acids and microscopically identified maize starch granules from organic residues absorbed in archaeological potsherds were compared with Andean ingredients and food residues obtained from experimental replica pots, where traditional recipes were cooked. Complex mixtures of lipids and starch remains observed in archaeological cooking pots indicated combinations of Andean ingredients such as llama, beans, algarroba, and maize, and suggest continuity in the domestic foodways through time. The distribution and δ13C values of lipids preserved in vessels used for alcoholic beverage preparation, storage and transport in Inka sites suggested the possible consumption of two drinks with distinct patterns: traditional Andean maize beer (chicha) and a local fermented drink made from algarroba flour (aloja). This is potential evidence for consumption practices in festive contexts sponsored by the Inka state. Fil: Lantos, Irene Johanna. Universidad de Buenos Aires. Facultad de Filosofía y Letras. Museo Etnográfico "Juan B. Ambrosetti"; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Spangenberg, J. E.. Universite de Lausanne; Suiza Fil: Giovannetti, Marco Antonio. Universidad Nacional de La Plata. Facultad de Ciencias Naturales y Museo. División Arqueologia; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Ratto, N.. Universidad de Buenos Aires. Facultad de Filosofía y Letras. Museo Etnográfico "Juan B. Ambrosetti"; Argentina Fil: Maier, Marta Silvia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina

The starfish Heliaster helianthus contains Thornasteroside A (1) and Helianthoside (2) and its isomer (3) as the major sulfated steroidal glycosides. Saponin containing fractions obtained by purification of extracts of H. helianthus induced escape reactions and mortality in the limpets Siphonaria lessoni and Fissurella radiosa. ESI-MS and ESI-MS/MS were successfully applied to the rapid screening of two cytotoxic fractions obtained by purification of the ethanolic extracts of arms and central disks dissected from H. helianthus. Three major compounds were identified, together with minor sulfated steroidal mono- and diglycosides of polyhydroxysteroids. Fil: Maier, Marta Silvia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; Argentina Fil: Centurion, Romina Luisa Sabrina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Parque Centenario. Museo Argentino de Ciencias Naturales “Bernardino Rivadavia”; Argentina Fil: Muniain, Claudia Cristina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Parque Centenario. Museo Argentino de Ciencias Naturales “Bernardino Rivadavia”; Argentina Fil: Haddad, Renato. Universidade Estadual de Campinas; Brasil Fil: Eberlin, N.. Universidade Estadual de Campinas; Brasil

In addition to the known furanones 1 and 2, the aerial parts of the shrub Mutisia friesiana afforded a new prenylated furanone, Mutisifuranone A (3), together with the known triterpenoids oleanic (4) and ursolic (5) acids and some sesquiterpenoids and n-alkanes. Their structures were elucidated by spectroscopic methods.

Carminic acid, isolated from cochineal, was analyzed by matrix-assisted laser desorption/ionization (MALDI) and electrospray mass spectrometry (ESI-MS). Application of both techniques to the analysis of carminic acid suspended in linseed oil and applied to a piece of canvas, demonstrated the ability of MALDI and ESI-MS to identify this organic dye in a mixture as those used in easel painting.

Four macrocyclic trichothecenes, roridin A, roridin E, verrucarin A and verrucarin J, produced by the hypocrealean epibiont of Baccharis coridifolia, were evaluated for their inhibitory activity against the arenavirus Junin (JUNV), the etiological agent of Argentine hemorrhagic fever. The trichothecenes achieved a dose-dependent inhibition of JUNV multiplication at concentrations not affecting cell viability. The 50% inhibitory concentration (IC50) values determined by a virus yield inhibition assay were in the range 1.2-4.9 ng/ml. The most active compound was verrucarin J which reduced JUNV yield more than 2 log units and had a similar effect against the arenavirus Tacaribe. The trichothecenes lacked virucidal effects on JUNV virions. From time of addition and removal experiments, it can be concluded that verrucarin J inhibited a late stage in the replicative cycle of JUNV, after 5 h of adsorption. Fil: Garcia, Cybele. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Biológica. Laboratorio de Virología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química Biológica de la Facultad de Ciencias Exactas y Naturales. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química Biológica de la Facultad de Ciencias Exactas y Naturales; Argentina Fil: Rosso, M. L.. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina Fil: Bertoni, María D.. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina Fil: Maier, Marta Silvia. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina Fil: Damonte, Elsa Beatriz. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Biológica. Laboratorio de Virología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química Biológica de la Facultad de Ciencias Exactas y Naturales. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química Biológica de la Facultad de Ciencias Exactas y Naturales; Argentina

Two new sulfated steroidal hexaglycosides, anasterosides A (2) and B (3), along with the known versicoside A (1) have been isolated from the Patagonian starfish Anasterias minuta. Their structures have been elucidated by spectroscopic analysis (NMR and FABMS) and chemical transformations. Compounds 1 and 2 and the synthetic pentaglycoside 1b derived from versicoside A showed antifungal activity against the plant pathogenic fungus Cladosporium cucumerinum. Desulfation of hexaglycoside 1 rendered a totally inactive saponin.