Non-fermented and fermented jabuticaba (Myrciaria cauliflora Mart.) pomaces as valuable sources of functional ingredients

abuticaba (Myrciaria cauliflora. Mart) is a highly perishable fruit native to Brazil, which is consumed both fresh and industrially processed in the form of juices, jams, wines and distilled liqueurs. This processing generates a large amount of waste by-products, which represent approximately 50% of the fruit weight. The by-products are of interest for obtaining valuable bioactive compounds that could be used as nutraceuticals or functional ingredients. In this study, fermented and non-fermented jabuticaba pomaces were studied regarding their hydrophilic and lipophilic compounds, as well as their antioxidant properties, including: soluble sugars, organic acids and tocopherols (using high performance liquid chromatography coupled to refraction index, diode array and fluorescence detector, respectively); phenolics and anthocyanins, (using liquid chromatography coupled to diode array detection, and mass spectrometry with electrospray ionization); and fatty acids (using gas-liquid chromatography with flame ionization detection). The analytical data demonstrated that jabuticaba pomaces are a rich source of bioactive compounds such as tocopherols, polyunsaturated fatty acids and phenolic compounds (namely hydrolyzable tannins and anthocyanins) with antioxidant potential. Therefore, jabuticaba pomace may have good potential as a functional ingredient in the fabrication of human foods and animal feed.

Development of the gas chromatograph – mass spectrometer to investigate volatile species in the lunar soil for the Luna-Resurs mission

Since the analysis of the lunar rocks and soil samples, brought to Earth by the Apollo missions, it is believed that the Moon has a waterless nature and also other volatile species are strongly depleted. Advancement in analysis techniques helped to identify water and other volatile species in lunar volcanic glasses. Additionally, recent lunar space missions detected water and volatile organic compounds in the region of the lunar poles where permanently shadowed craters are existing. All known lunar soil samples available on Earth come from the lunar near side, close to the equator. To verify the most recent measurement results and to enhance the knowledge of the geological history of the Moon it is of high interest to perform in situ measurements on the lunar poles. For this reason the Russian space agency, Roskosmos, developed aprogram for the scientific exploration of the lunar poles. The Gas Analysis Package (GAP) is part of the selected scientific payload aboard the Luna-Resurs Lander. This instrument uses pyrolytic cells and will apply laser spectroscopy, gas chromatography and mass spectrometry to detect and analyze volatile components trapped in the lunar soil. An existing ion optical design of a compact reflectron type time-of-flight mass spectrometer, originally built for the MEAP/P-BACE balloon mission, was chosen as a part of the GAP instrument. The scope of this thesis is the development of the interface between gas chromatography (GC) and this Neutral Gas Mass Spectrometer (NGMS) to perform coupled GC-MS measurements. In the first part of this thesis the interfacing concept was developed and verified by coupling the NGMS prototype to gas chromatography. The second part of this thesis is devoted to the development of the NGMS flight version.

Assessing the Oxidative History of Miller Range Martian Meteorites

Miller Range (MIL) Martian meteorites are oxidized nakhlites. Early studies attribute their oxidation to reduction-oxidation reactions involving assimilated sulfate. I utilize the sulfur isotope and major element composition of the MIL pairs to assess their oxidative history. MIL sulfides display an average sulfur isotope composition that is different from Nakhla sulfate and sulfide. The sulfur isotope differences produce a mixing array between juvenile sulfur and mass-independent sulfur signatures, indicating assimilation of anomalous sulfur into the melt. I estimate an fO2 of QFM (+3.5 ± 0.4) and a sulfur content of 360 ppm ± 12 – 1300 ppm ± 50. With these results, I test the hypothesis of sulfate assimilation through models of charge balance, isotope mixing, and degassing of sulfur bearing compounds. I conclude that sulfate assimilation was significant in the oxidation of the MIL pairs but, additional oxidants were assimilated.

Calcium Intake, Major Dietary Sources and Bone Health Indicators in Iranian Primary School Children

Background: Adequate calcium intake may have a crucial role with regards to prevention of many chronic diseases, including hypertension, hypercholesterolemia, different types of cancer, obesity and osteoporosis. In children, sufficient calcium intake is especially important to support the accelerated growth spurt during the preteen and teenage years and to increase bone mineral mass to lay the foundation for older age. Objectives: This study aimed to assess daily calcium intake in school-age children to ensure whether they fulfill the FGP dairy serving recommendations, the recommended levels of daily calcium intake and to assess the relationship between dietary calcium intake and major bone health indicators. Patients and Methods: A total of 501 Iranian school-age children were randomly selected. Calcium intake was assessed using a semi-quantitative food frequency questionnaire. Bone health indicators were also assessed. Results: Dairy products contributed to 69.3% of the total calcium intake of the children. Daily adequate intake of calcium was achieved by 17.8% of children. Only 29.8% met the Food guide pyramid recommendations for dairy intake. Dietary calcium intake was not significantly correlated with serum calcium and other selected biochemical indicators of bone health. Conclusions: The need for planning appropriate nutrition strategies for overcoming inadequate calcium intake in school age children in the city of Tehran is inevitable.

Elemental Analysis and Forensic Comparison of Soils by Laser-Induced Breakdown Spectroscopy (LIBS) and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS)

The elemental analysis of soil is useful in forensic and environmental sciences. Methods were developed and optimized for two laser-based multi-element analysis techniques: laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and laser-induced breakdown spectroscopy (LIBS). This work represents the first use of a 266 nm laser for forensic soil analysis by LIBS. Sample preparation methods were developed and optimized for a variety of sample types, including pellets for large bulk soil specimens (470 mg) and sediment-laden filters (47 mg), and tape-mounting for small transfer evidence specimens (10 mg). Analytical performance for sediment filter pellets and tape-mounted soils was similar to that achieved with bulk pellets. An inter-laboratory comparison exercise was designed to evaluate the performance of the LA-ICP-MS and LIBS methods, as well as for micro X-ray fluorescence (μXRF), across multiple laboratories. Limits of detection (LODs) were 0.01-23 ppm for LA-ICP-MS, 0.25-574 ppm for LIBS, 16-4400 ppm for µXRF, and well below the levels normally seen in soils. Good intra-laboratory precision (≤ 6 % relative standard deviation (RSD) for LA-ICP-MS; ≤ 8 % for µXRF; ≤ 17 % for LIBS) and inter-laboratory precision (≤ 19 % for LA-ICP-MS; ≤ 25 % for µXRF) were achieved for most elements, which is encouraging for a first inter-laboratory exercise. While LIBS generally has higher LODs and RSDs than LA-ICP-MS, both were capable of generating good quality multi-element data sufficient for discrimination purposes. Multivariate methods using principal components analysis (PCA) and linear discriminant analysis (LDA) were developed for discriminations of soils from different sources. Specimens from different sites that were indistinguishable by color alone were discriminated by elemental analysis. Correct classification rates of 94.5 % or better were achieved in a simulated forensic discrimination of three similar sites for both LIBS and LA-ICP-MS. Results for tape-mounted specimens were nearly identical to those achieved with pellets. Methods were tested on soils from USA, Canada and Tanzania. Within-site heterogeneity was site-specific. Elemental differences were greatest for specimens separated by large distances, even within the same lithology. Elemental profiles can be used to discriminate soils from different locations and narrow down locations even when mineralogy is similar.

Databases for quantitative history

This paper will propose that, rather than sitting on silos of data, historians that utilise quantitative methods should endeavour to make their data accessible through databases, and treat this as a new form of bibliographic entry. Of course in many instances historical data does not lend itself easily to the creation of such data sets. With this in mind some of the issues regarding normalising raw historical data will be looked at with reference to current work on nineteenth century Irish trade. These issues encompass (but are not limited to) measurement systems, geographic locations, and potential problems that may arise in attempting to unify disaggregated sources. It will discuss the need for a concerted effort by historians to define what is required from digital resources for them to be considered accurate, and to what extent the normalisation requirements for database systems may conflict with the desire for accuracy. Many of the issues that the historian may encounter engaging with databases will be common to all historians, and there would be merit in having defined standards for referencing items, such as people, places, locations, and measurements.

Life history of a wide-ranging deepwater lantern shark in the north-east Atlantic, Etmopterus spinax (Chondrichthyes: Etmopteridae), with implications for conservation

In this paper, the population biology of the velvet belly lanternshark Etmopterus spinax was studied and life-history coefficients determined. Age was estimated from sections of the second dorsal spine and validated by marginal increment analysis. Males attained a maximum age of 8 years while 11 year-old females were found. Several growth models were fitted and compared for both size-at-age and mass-at-age data, showing that even though this is a small-sized species, it has a relatively slow growth rate. This species matures late, specifically at 49.6 and 42.5% of the maximum observed ages for males and females, respectively. It has a low fecundity, with a mean ovarian fecundity of 9.94 oocytes and a mean uterine fecundity of 7.59 embryos per reproductive cycle. This species seems to have a long reproductive cycle, and even though no conclusive data were obtained, a 2-3 year cycle is possible. The estimated coefficients indicate that this species has a vulnerable life cycle, typical of deepwater squalid sharks. Given the high fishing pressures that it is suffering in the north-east Atlantic, this fish may already be facing severe declines or in risk of facing them in the near future. (C) 2008 The Authors Journal compilation (C) 2008 The Fisheries Society of the British Isles

Alcances y límites del principio de la responsabilidad de proteger: actuación del consejo de seguridad frente al conflicto en libia en el 2011 y Siria durante el periodo 2011-2014.

El propósito de este estudio de caso es determinar los alcances y límites de la Responsabilidad de Proteger, tomando como ejemplo la actuación del Consejo de Seguridad de Naciones Unidas ante el conflicto en Libia y Siria. Para esto es necesario analizar fuentes primarias documentos oficiales y secundarias como artículos académicos, para así comprobar que la evolución del concepto de soberanía ha permitido que se legitimen las intervenciones con fines humanitarios, ya que todos los Estados tienen la responsabilidad de garantizar la protección de los derechos humanos de sus ciudadanos, de lo contrario, la comunidad internacional debe tomar medidas para evitar o detener los crímenes masivos.

Provenance of upper Triassic sandstone, southwest Iberia (Alentejo and Algarve basins): tracing variability in the sources

Laser ablation ICP-MS U–Pb analyses have been conducted on detrital zircon of Upper Triassic sandstone from the Alentejo and Algarve basins in southwest Iberia. The predominance of Neoproterozoic, Devonian, Paleoproterozoic and Carboniferous detrital zircon ages confirms previous studies that indicate the locus of the sediment source of the late Triassic Alentejo Basin in the pre-Mesozoic basement of the South Portuguese and Ossa-Morena zones. Suitable sources for the Upper Triassic Algarve sandstone are the Upper Devonian–Lower Carboniferous of the South Portuguese Zone (Phyllite–Quartzite and Tercenas formations) and the Meguma Terrane (present-day in Nova Scotia). Spatial variations of the sediment sources of both Upper Triassic basins suggest a more complex history of drainage than previously documented involving other source rocks located outside present-day Iberia. The two Triassic basins were isolated from each other with the detrital transport being controlled by two independent drainage systems. This study is important for the reconstruction of the late Triassic paleogeography in a place where, later, the opening of the Central Atlantic Ocean took place separating Europe from North America.

Variedades e estilos na obra atribuída a Frei Carlos: novas perspetivas

Este trabalho de investigação centra-se no contributo dos exames de superfície e nas análises micro-analíticas no estudo de vinte e uma pinturas atribuídas à oficina de Frei Carlos, um dos grandes Mestres Luso-Flamengos ativos em território Nacional durante a primeira metade do século XVI. A "Pintura Luso-Flamenga" é uma expressão comummente usada na história da pintura Portuguesa do primeiro terço do século XVI e no seu sentido mais básico designa o trabalho de mestres flamengos que se instalaram em Portugal durante o reinado de D. Manuel I (1495- 1521) contribuindo decisivamente para o processo de renovação da pintura Portuguesa na época. O estudo integrado combina a pesquisa histórica em fontes documentais com exames de superfície e de caracterização material das obras de arte. O estudo material das pinturas foi realizado através de microscopia ótica, microscopia de infravermelhos com transformada de Fourier, espectroscopia de micro-Raman, microscopia eletrónica de varrimento acoplada com espectrometria de energia dispersiva de raios X, micro- difração de raios-X, cromatografia líquida de alta eficiência e pirólise acoplada à cromatografia gasosa /espectrometria de massa. Esta investigação envolveu técnicas complementares de análise de superfície e de ponto no estudo técnico e material das preparações, imprimitura, desenho subjacente, camadas pictóricas e sucessões estratigráficas, dando a conhecer os materiais utilizados na execução técnica das pinturas e evidenciando especificidades técnicas da produção artística. Este estudo pretende inclusivamente evidenciar alguns detalhes técnicos do artista que possivelmente estão relacionados com a herança das práticas Flamengas. O conhecimento de algumas particularidades da técnica deste Mestre também permitiu estabelecer comparações com duas pinturas que haviam sido atribuídas, com algumas reservas, a esta oficina de pintura Luso-Flamenga. Mais recentemente, como resultado de um estudo colaborativo, foi realizada uma ampla campanha de reflectografia infravermelhos, introduzindo novos dados acerca da execução técnica do desenho subjacente, o que contribuiu para diferenciar, nestas duas pinturas, outra "mão", atribuída então a um seguidor de Frei Carlos. Esta investigação introduz um novo e profundo conhecimento sobre a Oficina de Frei Carlos, permitindo estabelecer comparações com a obra do seu seguidor e com uma pintura também atribuída a esta oficina e que incorpora o Museu da National Gallery (NG5594), evidenciando os materiais utilizados na técnica de produção artística e especificidades técnicas aliadas aos processos criativos/ construtivos que permitem estabelecer os pontos de contacto e de diferenciação entre estas obras; Varieties and styles in the works attributed to Frei Carlos - new perspectives Abstract: This investigation is focused on the contributions of surface exams and micro-analytical research in the study of twenty one paintings attributed to Frei Carlos workshop, one of the most important Portuguese-Flemish painters active in our country during the first half of sixteen Century. "Portuguese-Flemish Painting" is a common expression used in the history of Portuguese painting of the first third of the sixteenth century and in its most basic meaning designates the work of Flemish masters who settled in Portugal during the reign of King Manuel I (1495-1521) contributing decisively to the process of renewal of Portuguese painting at the time. The integrated approach combines historical research on documental sources with surface examination and material characterization of the paintings by using state-of-art analytical techniques. Microanalysis was carried out by optical microscopy, micro-Fourier-transform infrared-spectroscopy, micro-Raman spectroscopy, scanning electron microscopy coupled with energy dispersive X-ray spectrometry, micro-X-ray diffraction analysis, high performance liquid chromatography and Pyrolysis gas chromatography mass spectrometry. This complementary surface and analytical research was involved in the technical and material characterization of grounds, underdrawings, primings, paint layers and its multi-layered build-up, providing access to the painter´s materials used in the technical execution of the paintings and details of the technique of artistic production. This study also intends to expose some usual details of the artist’s technique which are possibly related to the Master´s Flemish influence. The knowledge of some particularities of the Master´s technique also allowed a new comparison with two paintings that had been attributed with some reserves to this Portuguese-Flemish workshop. More recently, as a result of a collaborative study, an extensive infrared reflectography campaign was made, giving new data concerning underdrawings technical execution and contributing to differentiate, in these two paintings, another “hand”, attributed to a follower of Frei Carlos. Complementary analytical research also added a new and deep insight into Frei Carlos workshop, his follower and a panel that still attributed to Frei Carlos workshop that integrates the National Gallery´s Museum (NG5594), evidencing the materials used in technical production, their models and sources of artistic inspiration, techniques and pictorial construction procedures that could specifically relate or distinguish between them.

Barn owl feathers as biomonitors of mercury: sources of variation

Given their central role in mercury (Hg) excretion and suitability as reservoirs, bird feathers are useful Hg biomonitors. Nevertheless, the interpretation of Hg concentrations is still questioned as a result of a poor knowledge of feather physiology and mechanisms affecting Hg deposition. Given the constraints of feather availability to ecotoxicological studies, we tested the effect of intraindividual differences in Hg concentrations according to feather type (body vs. flight feathers), position in the wing and size (mass and length) in order to understand how these factors could affect Hg estimates. We measured Hg concentration of 154 feathers from 28 un-moulted barn owls (Tyto alba), collected dead on roadsides. Median Hg concentration was 0.45 (0.076–4.5) mg kg-1 in body feathers, 0.44 (0.040–4.9) mg kg-1 in primary and 0.60 (0.042–4.7) mg kg-1 in secondary feathers, and we found a poor effect of feather type on intra-individual Hg levels. We also found a negative effect of wing feather mass on Hg concentration but not of feather length and of its position in the wing. We hypothesize that differences in feather growth rate may be the main driver of between-feather differences in Hg concentrations, which can have implications in the interpretation of Hg concentrations in feathers. Finally, we recommend that, whenever possible, several feathers from the same individual should be analysed. The five innermost primaries have lowest mean deviations to both betweenfeather and intra-individual mean Hg concentration and thus should be selected under restrictive sampling scenarios.

Provenance of Holocene beach sand in the Western Iberian

Detrital zircons from Holocene beach sand and igneous zircons from the Cretaceous syenite forming Cape Sines (Western Iberian margin) were dated using laser ablation – inductively coupled plasma – mass spectrometry. The U–Pb ages obtained were used for comparison with previous radiometric data from Carboniferous greywacke, Pliocene–Pleistocene sand and Cretaceous syenite forming the sea cliff at Cape Sines and the contiguous coast. New U–Pb dating of igneous morphologically simple and complex zircons from the syenite of the Sines pluton suggests that the history of zircon crystallization was more extensive (ca 87 to 74 Ma), in contrast to the findings of previous geochronology studies (ca 76 to 74 Ma). The U–Pb ages obtained in Holocene sand revealed a wide interval, ranging from the Cretaceous to the Archean, with predominance of Cretaceous (37%), Palaeozoic (35%) and Neoproterozoic (19%) detrital-zircon ages. The paucity of round to subrounded grains seems to indicate a short transportation history for most of the Cretaceous zircons (ca 95 to 73 Ma) which are more abundant in the beach sand that was sampled south of Cape Sines. Comparative analysis using the Kolmogorov–Smirnov statistical method, analysing sub-populations separately, suggests that the zircon populations of the Carboniferous and Cretaceous rocks forming the sea cliff were reproduced faithfully in Quaternary sand, indicating sediment recycling. The similarity of the pre- Cretaceous ages (>ca 280 Ma) of detrital zircons found in Holocene sand, as compared with Carboniferous greywacke and Pliocene–Pleistocene sand, provides support for the hypothesis that detritus was reworked into the beach from older sedimentary rocks exposed along the sea cliff. The largest percentage of Cretaceous zircons (

Francisco Pizarro' s banner of arms: an analytical work contributing to latin America's history

The study of textiles is an open area of scientific research, which for its variety of material components and physical chemical diversity of conditions, makes a field of interest for scientific studies in the cultural heritage field. Archaeological/historical textiles offer the possibility to carry out studies on organic materials such as fibers, adhesion elements, dyes, paper, etc., as well as on inorganic compounds for instance metals, alloys, precious stones and other added ornamentation. That variety of composition, allow to use a combination of analytical techniques to solve the questions coming from the object in an archaeometric research. One kind of textile object that provides a valuable cultural information because of its linguistic representation employed by its carrier societies, are the flags/banners/emblems, objects made with a nonverbal communication purpose. As long as depending on the use and/or purpose of each object, varies both the materials/techniques used in its production and its iconography (style, color, emblem, shape), its study gives the possibility to extract information through their materials and manufacturing techniques about a temporal-spatial frame, a particular event or a specific character. The flags/banners have been used since the eleventh century as representative objects of power, hierarchy, social or military organization, or as communicative media. The use of these objects has been spread throughout the world, possibly due to its easy interpretation and/or appropriation by different societies, making it part of their own culture. The flags as symbols of territorial control, using emblems that represent a family, order or army, were introduced to the New World (America) with the arrival of the European conquerors at the end of the fifteenth century. Flags/banners representing the Royal dominion over conquered territories, the Catholic Church and conquistadors’ armies were the first to arrive. One of those flags that have endured over time, that have an invaluable cultural meaning for both American and Iberian societies, is the so-called Francisco Pizarro’s Banner of Arms. It is a textile object with metal threads decoration over a Royal emblem. According to historical sources, this object was used by Francisco Pizarro in 1532 on the conquest process of Peru, after received the permission by King Charles V to on behalf of him, to conquer the lands of the New World today known as Peru. After Pizarro’s control of the Inca territory, it is believed that Pizarro left his banner on top of the Inca’s Sun’s Temple as symbol of his rule. Centuries later, in the America libertarian campaigns, General Sucre, military at charge of the independence army in Peru, reports have found what he considered the Pizarro’s Banner, sending it to Bogotá as a symbol of victory, being kept since that time until today by the National Museum of Colombia. Due to historical discrepancies in the different movements of the so-called Pizarro’s Banner of Arms, its real meaning has been under discussion and because of the passage of time its physical condition has suffer deterioration. That is because its scientific study is now an interesting case study to respond to both historical and conservation questions of it. Through a collaboration with the National Museum of Colombia, a set of 25 samples of so-called Pizarro’s Banner of Arms were collected, covering the various components and areas from the object of study. These samples were subjected to analytical studies for physical and chemical characterization. Microscopic observation, VSEM-EDS analysis, Raman spectroscopy, chromatographic analysis (HPLC-MS, GCMS) and radiocarbon dating were done. Similarly, was sought through a direct in situ physical inspection to the object and through a research into historical sources, adequate information to solve the object’s problems. Results obtained allowed to identify as silk the textile used in the elaboration of the Banner’s fabric, as well as the use of natural dyes for dyeing the fibers used on the emblem: use of cochineal and brazil wood as a source of red, luteolin plant-based for yellow color, indigotine plant-based for blue, and a mixture of yellow and blue dyes for green were identified. Similarly, the use of animal glue in the manufacturing process and the use of rag paper was evident. The metal threads study from the Banner give a confirmation to a silver core wire gilded with a thin gold sheet, being flattened and entwined with silk threads for their use. Finally, using the radiocarbon results, it was possible to postulate with huge accuracy that the Banner date manufacture was between the XV-XVI century and subject to restoration processes with addition of textiles in modern times. Together with, was evident that the state of degradation of the fabric is due to natural degradation in the silk fibers, having that its color has faded and its mechanical properties decreased, leading to loss of rigidity and disappearance of the physical structure. Similarly, it was clear the original colors of the emblem and highlight problems of detachment of paper due to crystallization of the adhesive. In the same way, was found that the metal threads suffer corrosion by sulfur and detachment of its crystals. Finally, combining the analytical results and the historical sources data found from the so-called Francisco Pizarro’s Banner of Arms, allows to postulate that its manufacture process was done in Europe employing precious materials to obtain a long-life object with a deep message for its viewers. Also, the data obtained helps to support the possible idea that the object was employed by Francisco Pizarro in the Peru conquest process. However, by the symbols present in the object, its elaboration date and materials, this object its clearly unique in its kind, and the most important, by its linguistic message, does not represent to Francisco Pizarro or his army, meanwhile, represents the Spanish crown. Therefore, instead to be labeled as Francisco Pizarro’s Banner of Arms, it should be called the Colonial Royal Banner of Charles V in the New World; RESUMEN: El estudio de textiles es un área abierta de investigación científica, la cual por su variedad de componentes materiales y la diversidad de condiciones físico-químicas presentes en estos objetos, lo hace un campo de interés para estudios científicos en el patrimonio cultural. Los textiles arqueológicos/históricos brindan la posibilidad de realizar estudios en materiales orgánicos como fibras, elementos de adhesión, tinturas, papel, etc., e inorgánicos como metales, aleaciones, piedras preciosas y demás materiales decorativos añadidos. Por su variedad de composición, es posible emplear diversas técnicas analíticas para resolver aquellas preguntas propias del objeto en una investigación arqueométrica. Uno de los objetos textiles que brinda gran información cultural debido a su representación lingüística empleada por las sociedades portadoras, son las banderas/estandartes/emblemas. Donde varía dependiendo de su uso y/o propósito, los materiales empleados en su elaboración, al igual que su iconografía (estilo, color, emblema, forma). El estudio de estos objetos construidos con un propósito de comunicación no verbal, da la posibilidad de extraer información a través de sus materiales y técnicas de elaboración sobre un rango temporal-espacial, un evento determinado en la historia o incluso a un personaje en específico. Las banderas han sido empleadas desde el siglo XI como objetos representativos de poder, jerarquía, organización social o militar, o como medio de comunicación. El uso de estos objetos se ha extendido a lo largo del mundo posiblemente debido a su fácil interpretación y/o apropiación por distintas sociedades, haciéndolo parte de su cultura. Las banderas como símbolos de control territorial, empleando símbolos que representan a una familia, orden o armada fueron introducidas a el Nuevo Mundo (América) con la llegada de los conquistadores europeos al final del siglo XV. Las banderas/estandartes que representaban el dominio Real sobre territorios dominados, la iglesia católica y las banderas de ejércitos y/o conquistadores fueron las primeras en llegar al nuevo mundo. Una de aquellas banderas que ha soportado el paso del tiempo, teniendo un gran valor cultural tanto para las sociedades americanas como para las ibéricas, es el denominado Estandarte de armas de Francisco Pizarro. Siendo un objeto textil con decoración en hilos metálicos sobre un emblema Real. De acuerdo a fuentes históricas, este objeto fue usado por Francisco Pizarro en 1532 en el proceso de conquista del Perú, quien recibe por parte del Rey Carlos V el poder para que, en su nombre, Pizarro pueda conquistar las tierras del nuevo mundo hoy conocidas como Perú. Luego del dominio de Pizarro sobre el territorio Inca, se cree que Pizarro dejó su estandarte en la cima del templo Inca del sol como símbolo de su control. Siglos más tarde, en las campañas libertarias de América, el General Sucre, militar encargado de la armada independentista en Perú, reporta haber encontrado lo que él considera como el estandarte de Pizarro, enviándolo a Bogotá como muestra de victoria, siendo custodiada desde ese momento por el Museo Nacional de Colombia hasta la actualidad. Debido a discrepancias históricas, el verdadero significado del llamado estandarte de Pizarro ha sido objeto de discusión y debido del pasar del tiempo su estado de conservación se ha deteriorado. Dejando de este modo, un caso de estudio interesante para que por medio de estudios científicos al objeto se pueda dar respuesta a preguntas tanto históricas como de conservación del mismo. De este modo, por medio de una colaboración con el Museo Nacional de Colombia, se obtuvo un juego de 25 muestras del llamado Estandarte de armas de Francisco Pizarro, abarcando los diferentes componentes y áreas del objeto de estudio. Dichas muestras fueron sometidas a estudios analíticos para su caracterización físico-química. Análisis de observación al microscopio, análisis VSEM-EDS, espectroscopia Raman, análisis cromatográficos (HPLC-MS, GC-MS) y datación por radiocarbono catorce fueron realizados. Del mismo modo, por medio de una inspección física al objeto in situ y una profunda investigación en fuentes históricas del mismo, se buscó la información adecuada para resolver sus problemáticas. Los resultados obtenidos permitieron identificar como seda el textil empleado en la elaboración del estandarte, así como el uso de colorantes naturales para teñir las fibras en el emblema: uso de cochinilla y palo de Brasil como fuente del color rojo, plantas a base de luteolin para el color amarillo, plantas a base de indigotina para el color azul y mezcla de colorantes amarillos y azules para el color verde fueron identificadas. Del mismo modo se evidencio el uso de adhesivos animales y el uso de papel de trapos en el proceso de manufactura. El estudio de los hilos metálicos, permitió evidenciar el uso de alambres con núcleos de plata con un fino recubrimiento de oro en su exterior, siendo aplanados y entrelazados con hilos de seda para su uso. Finalmente usando la datación por radiocarbono, fue posible conocer con alta precisión que el estandarte fue elaborado entre los siglos XV-XVI y sufrió procesos de restauración con añadidura de textiles en tiempos modernos. Junto a lo anterior, es posible postular que el estado de degradación de la tela es debido a degradación natural en las fibras de seda, teniendo así que su color se ha desvanecido y sus propiedades mecánicas disminuidas, conllevando a perdida de rigidez y desaparición de la estructura. Del mismo modo se pudo conocer los colores originales del emblema y evidenciar problemas de desprendimiento del papel debido a cristalización del adhesivo. Asimismo, se comprobó que los hilos metálicos presentan corrosión por azufre y desprendimiento de sus cristales. Finalmente, combinando los resultados analíticos y la información de fuentes históricas encontradas del llamado Estandarte de armas de Francisco Pizarro, se puede postular que su elaboración fue realizada en Europa, usando materiales preciosos para obtener un objeto de larga vida con un profundo mensaje para sus observadores. También, los datos obtenidos ayudan a dar soporte la posible idea de que este objeto fue usado por Francisco Pizarro en el proceso de conquista del Perú. Sin embargo, debido a los símbolos presentes en el objeto, fecha y materiales de elaboración, este objeto es claramente único en su tipo, y lo más importante, por su mensaje lingüístico, este no representa a Francisco Pizarro o su armada, al contrario, representa a la Corona de España. Por ende, en vez de denominarse como Estandarte de armas de Francisco Pizarro, este objeto debería nombrarse como el Estandarte Real de la Colonia de Carlos V en el Nuevo Mundo.

Applied biomaterials from sustainable sources

If we look back in time at the history of humanity, we can state that our generation is living an era of outstanding efficiency and progress because of globalization and global competition, even if this is resulting in the rapid depletion of energy sources and raw materials. The environmental impact of non-biodegradable plastic wastes is of increasing global concern: nowadays, imagining a world without synthetic plastics seems impossible, though their large-scale production and their extensive use have only spread since the end of the World War II. In recent years, the demand for sustainable materials has increased significantly and, with a view to circular economy, research has also focused on the enhancement and subsequent reuse of waste materials produced by industrial processing, intensive farming and the agricultural sector. Plastic polymers have been the most practical and economical solution for decades due to their low cost, prompt availability and excellent optical, mechanical and barrier properties. Biodegradable polymers could replace them in many applications, thus reducing the problems of traditional plastics disposability and the dependence on petroleum. Natural biopolymers are in fact characterized by a high biocompatibility and biodegradability and have already prompted research in the field of regenerative medicine. During my PhD, my goal was to use natural polymers from sustainable sources as raw materials to produce biomaterials, which are materials designed to interface with biological systems to evaluate, support or replace any tissue, organ, or function of the body. I focused on the use of the most abundant biopolymers in nature to produce biomaterials in the form of films, scaffolds and cements. After a complete characterization, the materials were proposed for suitable applications in different fields, from tissue engineering to cosmetics and food packaging. Some of the obtained results were published on international scientific and peer-reviewed journals.

Monitoring of New Psychoactive Substances in the hair of patients with a history of addiction. Evaluation of the public health impact.

Introduction. The term New Psychoactive Substances (NPS) encompasses a broad category of drugs which have become available on the market in recent years and whose illicit use for recreational purposes has recently exploded. The analysis of NPS usually requires mass spectrometry based techniques. The aim of our study was to define the preva-lence of NPS consumption in patients with a history of drug addiction followed by Public Services for Pathological Addictions, with the purpose of highlighting the effective presence of NPS within the area of Bologna and evaluating their association with classical drugs of abuse (DOA). Materials and methods. Sustained by literature, a multi-analyte UHPLC-MS/MS method for the identification of 127 NPS (phenethylamines, arylcyclohexylamines, synthetic opioids, tryptamines, synthetic cannabinoids, synthetic cathinones, designer benzodiazepines) and 15 classic drugs of abuse (DOA) in hair samples was developed and validated according to International Guidelines [112]. Samples pretreatment consisted of washing steps and overnight incubation at 45°C in an acid mixture of methanol and water. After cooling, supernatant were injected into the chromatographic system coupled with a tandem mass spectrometry detector. Results. Successful validation was achieved for almost all of the compounds. The method met all the required technical parameters. LOQ was set from 4 to 80 pg/mg The developed method was applied to 107 cases (85 males and 22 females) of clinical interest. Out of 85 hair samples resulting positive to classical drugs of abuse, NPS were found in twelve (8 male and 4 female). Conclusion. The present methodology represents an easy, low cost, wide-panel method for the de-tection of 127 NPS and 15 DOA in hair samples. Such multi-analyte methods facilitates the study of the prevalence of drugs abused that will enable the competent control authorities to obtain evi-dence-based reports regarding the critical spread of the threat represented by NPS.