Aplicación de la técnica de microscopia electrónica de barrido de emisión de campo con haz de iones focalizado-microanálisis de rayos x a colecciones numismáticas

Los objetos metálicos, y en particular, las colecciones numismáticas, han sido el objeto de estudio de numerosas investigaciones arqueométricas centradas en el conocimiento de las sociedades del pasado, ya que de éstos es posible obtener una gran cantidad de información relativa a los usos y desarrollo tecnológico de esas civilizaciones a través de su procedencia, el proceso de manufactura o las materias primas empleadas. Las técnicas de análisis aplicadas para este fin han ido evolucionando con el tiempo, de forma que, actualmente, además del estudio metalográfico, se dispone de un amplio abanico de técnicas instrumentales que proporcionan información acerca de la composición, estructura y morfología del objeto metálico. En este trabajo se ha explorado las posibilidades de un nuevo método de análisis de colecciones numismáticas basado en el uso del Microscopio Electrónico de Barrido de Emisión de Campo con Haz de Iones Focalizado y Microanálisis de Rayos X (FESEM-FIB-EDX). Entre las ventajas que ofrece esta técnica, aplicada por primera vez en el estudio de objetos de metal arqueológico, está su carácter mínimamente invasivo para las piezas ya que no requiere toma de muestra y la alteración producida en el objeto se sitúa en la escala nanoscópica.La presente investigación está financiada con el proyecto I+D: “Aplicación de las técnicas nanoelectroquimicas y biotecnologías en el estudio y conservación del patrimonio en metal” Referencia: CTQ2014-53736-C3 cofinanciado con fondos FEDER adscrito al Programa estatal de fomento de la investigación científica y técnica de excelencia, subprograma estatal de generación del conocimiento, MINECO. (2015-2017). Los autores agradecen la colaboración de Dr. José Luis Moya y Manuel Planes, técnicos responsables del Servicio de Microscopía Electrónica de la Universitat Politècnica de València.Álvarez Romero, C.; Domenech Carbo, MT. (2017). Aplicación de la técnica de microscopia electrónica de barrido de emisión de campo con haz de iones focalizado-microanálisis de rayos x a colecciones numismáticas. Arché. (11 - 12):65-70. http://hdl.handle.net/10251/101195657011 - 1

Microchemical surface analysis of historic copper-based coins by the combined use of FIB-FESEM-EDX, OM, FTIR spectroscopy and solid-state electrochemical techniques

[EN] A multi-technique strategy, including microscopy, spectroscopic and electrochemical techniques, is proposed to study thin corrosion layers that form on the surface of historic copper-based coins. An accurate characterisation of this external corrosion layer is important for selecting a suitable conservation and/or restoration treatment. For this purpose, a series of copper-based coins from different historical periods and provenances, which mainly exhibited atmospheric corrosion, was analysed. The morphology of the corrosion layer and the upper core of coins was studied in trenches done on coin surfaces with a focused ion beam gun, coupled to a field emission scanning electron microscope-X-ray microanalysis (FIB-FESEM-EDX). The X-ray microanalysis performed with FESEM-EDX on trenches allowed elemental composition profiles on the corrosion layer to be obtained. These results were complemented with the compositional data of the corrosion products provided by the voltammetry of immobilised microparticles (VIMP) and Fourier transform infrared spectroscopy (FTIR), and by studying visual appearance by optical microscopy and colorimetry. Cuprite and tenorite (the latter increased with coin age) were the main identified corrosion products, which were accompanied, to a lesser extent, by copper trihydroxychloride polymorphs. Interestingly, metal oxalates and metal-carboxylate complexes were identified on the corrosion layer of most coins. These unusual alteration products of copper-based coins were formed from the organic matter deposited on coin surfaces given their use when placed in circulation or by further manipulations of collectors.Financial support is gratefully acknowledged from the Spanish "R + D + I" project CTQ2017-85317-C2-1-P, CTQ2014-53736-C3-1-P and CTQ2014-53736-C3-2-P, which are supported by the Ministerio de Ciencia, Innovation y Universidades, Fondo Europeo de Desarrollo Regional (ERDF) funds and Agencia Estatal de Investigation (AEI). The authors wish to thank Mr. Manuel Planes, Dr. Jose Luis Moya and Mrs. Alicia Nuez Inbernon, technical supervisors of the Electron Microscopy Service of the Universitat Politecnica de Valencia.Domenech Carbo, MT.; Álvarez-Romero, C.; Doménech Carbó, A.; Osete Cortina, L.; Martínez Bazán, ML. (2019). Microchemical surface analysis of historic copper-based coins by the combined use of FIB-FESEM-EDX, OM, FTIR spectroscopy and solid-state electrochemical techniques. Microchemical Journal. 148:573-581. https://doi.org/10.1016/j.microc.2019.05.039S57358114

Estudio arqueométrico de maravedís de Felipe IV (1660-1664)

"La presente investigación está fnanciada con el proyecto I+D: “Aplicación de las técnicas nanoelectroquímicas y biotecnologías en el estudio y conservación del CTQ2014-53736-C3 cofnanciado con fondos FEDER adscrito al Programa estatal de fomento de la investigación científca y técnica de excelencia, subprograma estatal de generación del conocimiento, MINECO (2015-2017). Los autores agradecen la colaboración de Dr. José Luis Moya y Manuel Planes, técnicos responsables del Servicio de Microscopía Electrónica de la Universitat Politècnica de València y a Manuel Gozalbes, conservador del Museu de Prehistòria de Valènciapatrimonio en metal” Referencia:"Álvarez-Romero, C.; Domenech Carbo, A.; Domenech Carbo, MT.; Pasies-Oviedo, T.; Buendía Ortuño, MDM. (2017). Estudio Arqueométrico de Maravedís de Felipe IV (1660-1664). SAGVNTVM (Online). 49:235-239. https://doi.org/10.7203/SAGVNTVM.49.109122352394

Hematite as an Electrocatalytic Marker for the Study of Archaeological Ceramic Clay bodies: A VIMP and SECM Study**

[EN] The electrocatalytic effect exerted by hematite, a ubiquitous component of clay bodies, on the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) can be used to acquire information on archaeological ceramics. The solid-state voltammetric response of different hematite and ochre specimens, accompanied by SECM analysis in contact with 0.10 M HCl aqueous solution, is described. In air-saturated solutions, catalytic effects on the ORR and OER are accompanied by Fe(III)/Fe(II) and Fe(IV)/Fe(III) redox reactions. Such processes are conditioned by a variety of factors, the hydroxylation degree of the mineral surfaces being particularly influential, and exhibit significant variations upon heating the specimens between 300 and 900 degrees C. Voltammetric measurements carried out on a set of archaeological samples of Apulian red-figured pottery dated back within 5(th) and 4(th) centuries BCE permit to obtain site-characteristic voltammetric profiles.The work was carried out within the framework of project PID2020-113022GB-I00 which was financially support by Ministerio de Ciencia e Innovacion and Agencia Estatal de Investigacion (AEI) of the Spanish government.Doménech-Carbó, A.; Giannuzzi, M.; Mangone, A.; Giannossa, LC.; Di Turo, F.; Cofini, E.; Domenech Carbo, MT. (2022). Hematite as an Electrocatalytic Marker for the Study of Archaeological Ceramic Clay bodies: A VIMP and SECM Study**. ChemElectroChem. 9(2):59-68. https://doi.org/10.1002/celc.20210119759689

The Release of Soluble Factors Contributing to Endothelial Activation and Damage after Hematopoietic Stem Cell Transplantation Is Not Limited to the Allogeneic Setting and Involves Several Pathogenic Mechanisms

AbstractThis study evaluated the relative impact of the intensity of the conditioning regimen and the alloreactivity in the endothelial dysfunction occurring after allogeneic hematopoietic stem cell transplantation (allo-HSCT). It involved a comparative analysis of the effect of incubating human umbilical vein endothelial cells (ECs) with serum samples from patients receiving autologous HSCT (auto-HSCT) or unrelated donor allo-HSCT. In both groups, blood samples were collected through a central line before conditioning (Pre), before transplantation (day 0), and at days 7, 14, and 21 after transplantation. Changes in the expression of EC receptors and adhesion proteins, adhesion of leukocytes and platelets under flow, and signaling pathways were analyzed. Endothelial activation and damage were observed in both groups, but with differing patterns. All markers of endothelial dysfunction demonstrated a progressive increase from day Pre to day 14 in the auto-HSCT group and exhibited 2 peaks of maximal expression (at days 0 and 21) in the allo-HSCT group. Both treatments induced a proinflammatory state (ie, expression of adhesion receptors, leukocyte adhesion, and p38 MAPK activation) and cell proliferation (ie, morphology and activation of ErK42/44). Prothrombotic changes (ie, von Willebrand factor expression and platelet adhesion) predominated after allo-HSCT, and a proapoptotic tendency (ie, activation of SAPK/JNK) was seen only in this group. These findings indicate that endothelial activation and damage after HSCT also occur in the autologous setting and affect macrovascular ECs. After the initial damage induced by the conditioning regimen, other factors, such as granulocyte colony-stimulating factor (G-CSF) toxicity, engraftment, and alloreactivity, may contribute to the endothelial damage seen during HSCT. Further studies are needed to explore the association between this endothelial damage and the vascular complications associated with HSCT

Novel compound mutations in the mitochondrial translation elongation factor (TSFM) gene cause severe cardiomyopathy with myocardial fibro-adipose replacement

Primary mitochondrial dysfunction is an under-appreciated cause of cardiomyopathy, especially when cardiac symptoms are the unique or prevalent manifestation of disease. Here, we report an unusual presentation of mitochondrial cardiomyopathy, with dilated phenotype and pathologic evidence of biventricular fibro-adipose replacement, in a 33-year old woman who underwent cardiac transplant. Whole exome sequencing revealed two novel compound heterozygous variants in the TSFM gene, coding for the mitochondrial translation elongation factor EF-Ts. This protein participates in the elongation step of mitochondrial translation by binding and stabilizing the translation elongation factor Tu (EF-Tu). Bioinformatics analysis predicted a destabilization of the EF-Ts variants complex with EF-Tu, in agreement with the dramatic steady-state level reduction of both proteins in the clinically affected myocardium, which demonstrated a combined respiratory chain enzyme deficiency. In patient fibroblasts, the decrease of EF-Ts was paralleled by up-regulation of EF-Tu and induction of genes involved in mitochondrial biogenesis, along with increased expression of respiratory chain subunits and normal oxygen consumption rate. Our report extends the current picture of morphologic phenotypes associated with mitochondrial cardiomyopathies and confirms the heart as a main target of TSFM dysfunction. The compensatory response detected in patient fibroblasts might explain the tissue-specific expression of TSFM-associated disease

About the skull of `Cova del Parpalló¿ (Gandia): news on its diagnostic study and restoration

[ES] Uno de los retos que aborda el Laboratorio de Restauración del Museu de Prehistòria de València es el tratamiento de piezas que ya han sufrido en el pasado algún proceso de intervención. Por lo general se trata de materiales sobre los que se han empleado protecciones poco estables, refuerzos inadecuados o ¿rellenos¿ de faltantes aplicados de forma indiscriminada. En el presente artículo se presenta el estudio diagnóstico e intervención del cráneo y la mandíbula de un individuo femenino de Homo sapiens de la Cova del Parpalló (Gandia), correspondiente al Paleolítico superior. Esta pieza, tras su descubrimiento en 1930, fue llevada en 1935 al Laboratori d¿Arqueologia de la Universitat de Barcelona, donde fue reconstruida y restaurada no sin dificultad, añadiéndole refuerzos metálicos, adhesivos y reconstrucciones de ceras que claramente se presentaban ya envejecidas. Ha sido necesario, por tanto, llevar a cabo una nueva intervención y replantearse los criterios de actuación, avalados por los estudios analíticos pertinentes que han aportado información sobre la composición de los materiales empleados en la restauración anterior.[EN] One of the challenges of the Restoration Laboratory of the Museu de Prehistòria de València is the treatment of pieces that have suffered previous interventions in the past. This are generally materials that were restored with instable protections, inadequate reinforcements or missing fillers that were applied indiscriminately. This article shows the diagnostic study and intervention of the skull and mandible of a female Homo sapiens from `Cova del Parpalló¿ (Gandia), dated in the Upper Paleolithic. This piece, after its discovery in 1930, was taken in 1935 to the Laboratori d¿Arqueologia of the Universitat de Barcelona, where it was rebuilt and restored not without difficulty, adding metallic reinforcements, adhesives, and wax reconstructions which were clearly already aged. Therefore, it has been necessary to carry out a new intervention rethinking the performance criteria, backed by the relevant analytical studies that have provided information about the composition of the applied materials on the previous restoration.Pasíes Oviedo, T.; Renovell Anglés, C.; Domenech Carbo, MT.; Madrid García, JA.; Carrascosa Moliner, MB. (2020). Sobre el cráneo de la Cova del Parpalló (Gandia): novedades en su estudio diagnóstico y restauración. Archivo de Prehistoria Levantina. 33:255-282. http://hdl.handle.net/10251/167208S2552823

Multiple-scan voltammetry of immobilized particles of ancient copper/bronze coins

[EN] The application of a multiple-scan strategy to study the structure of the corrosion patina of copper/bronze ancient objects using the voltammetry of immobilized microparticles (VIMP) is described. Upon nanosample attachment to graphite electrodes in contact with aqueous acetate buffer, voltammetric signatures characterizing cuprite with variable degree of crystallinity are recorded by means of successive cathodic scans reflecting the composition of the corrosion patina. The reported methodology, complemented with ion beam-field emission scanning electron microscopy (FIB-FESEM) and high-resolution field emission scanning electron microscopy (HRFESM-EDX), is applied to a set of coins fabricated between 1709 and 1962 revealing different corrosion patterns.Project CTQ2017-85317-C2-1-P, supported with Ministerio de Economia, Industria y Competitividad (MINECO), Fondo Europeo de Desarrollo Regional (ERDF) and Agencia Estatal de Investigacion (AEI), is gratefully acknowledged. The authors wish to thank Mr. Manuel Planes, Dr. Jose Luis Moya and Alicia Nuez Imbernon technical supervisors of the Electron Microscopy Service of the Polytechnical University of Valencia.Domenech Carbo, A.; Donnici, M.; Álvarez-Romero, C.; Daniele, S.; Domenech Carbo, MT. (2021). Multiple-scan voltammetry of immobilized particles of ancient copper/bronze coins. Journal of Solid State Electrochemistry. 25(1):195-206. https://doi.org/10.1007/s10008-020-04770-4S19520625

Servicio de información turística

El negocio que propone la empresa Ecutrips S.A. consiste en el desarrollo de una aplicación para smartphones, especialmente diseñada para usuarios que buscan información turística de la ciudad. Esta iniciativa pretende contribuir con el desarrollo turístico del Ecuador, reforzar el civismo y mejorar la experiencia del usuario en la ciudad; a la vez que permitirá acercar los establecimientos turísticos a sus clientes potenciales de forma más eficiente. El principal valor agregado de esta aplicación lo brindarán audioguías, que además serán su característica diferenciadora y además conformarán la ventaja competitiva de la compañía. Las audioguías proporcionan información en audio de los puntos de interés de la ciudad de una forma interpretativa y relatada con efectos especiales que ambientan la escena y trasladan al usuario hacia el momento narrado. De esta forma, las audioguías, a más de proporcionar información, mejoran la experiencia del usuario, ya que le permite apreciar la ciudad y conocer de forma didáctica y puntual su cultura e historia. Con esta propuesta de valor, Ecutrips S.A. busca motivar al usuario a descargar la aplicación y generar una masa crítica que le permita posicionarse como la aplicación turística del Ecuador

Integrin-independent role of CalDAG-GEFI in neutrophil chemotaxis

Chemotaxis and integrin activation are essential processes for neutrophil transmigration in response to injury. CalDAG-GEFI plays a key role in the activation of β1, β2, and β3 integrins in platelets and neutrophils by exchanging a GDP for a GTP on Rap1. Here, we explored the role of CalDAG-GEFI and Rap1b in integrin-independent neutrophil chemotaxis. In a transwell assay, CalDAG-GEFI−/− neutrophils had a 46% reduction in transmigration compared with WT in response to a low concentration of LTB4. Visualization of migrating neutrophils in the presence of 10 mM EDTA revealed that CalDAG-GEFI−/− neutrophils had abnormal chemotactic behavior compared with WT neutrophils, including reduced speed and directionality. Interestingly, Rap1b−/− neutrophils had a similar phenotype in this assay, suggesting that CalDAG-GEFI may be acting through Rap1b. We investigated whether the deficit in integrin-independent chemotaxis in CalDAG-GEFI−/− neutrophils could be explained by defective cytoskeleton rearrangement. Indeed, we found that CalDAG-GEFI−/− neutrophils had reduced formation of F-actin pseudopodia after LTB4 stimulation, suggesting that they have a defect in polarization. Overall, our studies show that CalDAG-GEFI helps regulate neutrophil chemotaxis, independent of its established role in integrin activation, through a mechanism that involves actin cytoskeleton and cellular polarization