Evaluación mediante el Método de Espectroscopia de Impedancia Eléctrica (EIE), del proceso de geopolimerización de pastas, morteros y hormigones en conglomerantes activados alcalinamente

ABSTRACT The use of concrete as a building material is a very widespread practice throughout the world thanks to its high mechanical strength, versatility and low cost. Nevertheless, the production of one of its components, the Portland cement, involves a high environmental impact. It is not a recent or an exclusive problem of our country, but it is a global issue associated with the growth of population, among others. Through this approach and the fact that the consumption of cement will continue to increase, the scientific community is studying alternative materials, such as calcium sulfoaluminate cements, belitic cements, and alkali activated cements, also known as geopolymers. The latter acquire chemical and physical properties and many researchers consider them to be the third generation of building materials after lime and Portland cement. Materials made from Portland cement have distinctive properties such as mechanical strength and durability. These properties are related to the pore structure within the matrix. This structure depends on the pore volume, the size distribution, the connectivity and the percolation of the pores. These parameters can be determined by different methods, whose results vary depending on the technique used. There are different types of with a diameter based classification. Among them there are two main type, gel pores and capillary pores. An important aspect related to the porous microstructure that also affects the durability of the mortar or concrete matrix is the ionic transport; for this reason, there are non-destructive techniques such as electrical methods and Electrical Impedance Spectroscopy (EIS) for the characterization of this porous microstructure. In the current Doctoral Thesis, Electrical Impedance Spectroscopy (EIS) has been used in mortar and concrete of Portland cement and alkali activated mortars, to describe in detail its evolution in time by means of electrical parameters, from an Equivalent Electric Circuit (EEC) and to be able to relate the two types of porosity. In addition, the equivalent electrical circuit, which represents the electrical conductivity of mortars and concretes from more than a hundred days of curing, has been determined. The results show the variations produced in the hydration and geopolymerization process, and as well as they allow the separation of the components of electrical conductivity related to gel pores, capillary pores and the interface between them. Generally, two relaxations are obtained at medium and high frequency, in both mortars and concretes. The electrical resistivity is measured in direct current and it is related to the hydration of the cement and the process of geopolymerization of alkali activated materials. Moreover, this resistivity has been tried to correlate with the values of the mechanical resistance to compression and with its microstructural properties, obtained from tests by scanning electron microscopy (SEM), thermogravimetric analysis (TG) and Mercury Porosimetry techniques. Thus, in this Doctoral Thesis it was possible to develop a distinctive method of mortars and concretes, independently of the binder employed, either Portland cement or geopolymer matrixes, through the same type of electrical circuit.RESUMEN La utilización del hormigón como material de construcción es una práctica muy extendida a lo largo de todo el mundo gracias a su gran resistencia mecánica, versatilidad y coste relativamente bajo. No obstante, la producción de uno de sus componentes, el cemento Portland, conlleva un alto impacto ambiental. No es un problema reciente ni exclusivo de nuestro país, sino que se trata de un asunto global asociado, entre otros aspectos, al crecimiento de la población. Tras este planteamiento y el hecho de que el consumo de cemento va a continuar aumentando, la comunidad científica está estudiando materiales alternativos, como pueden ser los cementos de sulfoaluminato de calcio, cementos belíticos, y los cementos activados alcalinamente, también conocidos como geopolímeros. Estos últimos adquieren propiedades químicas y físicas tales, que se consideran por muchos investigadores, la tercera generación de materiales de construcción tras la cal y el cemento Portland. Los materiales fabricados a partir del cemento Portland tienen unas propiedades características como son la resistencia mecánica y la durabilidad. Estas dos propiedades están relacionadas con la estructura de poros que se encuentra dentro de la matriz. Esta estructura depende del volumen de poros, de la distribución de tamaños, de la conectividad y de la percolación de los mismos. Estos parámetros pueden determinarse por diferentes métodos, cuyos resultados varían dependiendo de la técnica empleada. Existen diferentes tipos de poros cuya clasificación se basa en su diámetro, entre ellos se caracterizan dos tipos, los poros tipo gel y los poros capilares. Un aspecto importante relacionado con la microestructura porosa que también afecta a la durabilidad de la matriz de mortero u hormigón es el transporte iónico; por este motivo, para la caracterización de esa microestructura porosa existen técnicas de tipo no destructivo como son los métodos eléctricos y la Espectroscopía de Impedancia Eléctrica (EIE). En esta Tesis Doctoral, se ha utilizado La Espectroscopía de Impedancia Eléctrica (EIE) en morteros y hormigones de cemento Portland y morteros activados alcalinamente, para caracterizar su evolución en el tiempo por medio de unos parámetros eléctricos, a partir de un circuito eléctrico equivalente (CEE) y poder relacionar así los dos tipos de porosidad. Además, se ha determinado el circuito eléctrico equivalente, que representa la conductividad eléctrica de los morteros y hormigones desde el día 2 hasta más de 100 días de curado, mostrando las variaciones producidas en el proceso de hidratación y geopolimerización, y permitiendo separar los componentes de la conductividad eléctrica relacionados con los poros tipo gel, los poros capilares y la interfase entre éstos. Se obtienen, en general, dos relajaciones, a media y alta frecuencia, tanto en morteros como en hormigón. Se mide la resistividad eléctrica en corriente continua y se trata de relacionar con la hidratación del cemento y el proceso de geopolimerización de los materiales activados alcalinamente. Además, dicha resistividad se ha tratado de correlacionar con los valores de la resistencia mecánica a compresión y con sus propiedades microestructurales, obtenidas a partir de ensayos con microscopía electrónica de barrido (SEM), termogravimetría (TG) y Porosimetría de mercurio. De este modo, en esta Tesis Doctoral ha sido posible desarrollar un método de caracterización, de morteros y hormigones, independientemente del conglomerante empleado, ya sea cemento Portland o matrices geopoliméricas, mediante un mismo tipo de circuito eléctrico.RESUM La utilització del formigó com a material de construcció és una pràctica molt estesa al llarg de tothom gràcies a la seua gran resistència mecànica, versatilitat I cost relativament baix. No obstant això, la producció d'un dels seus components, el ciment Portland, comporta un alt impacte ambiental. No és un problema recent ni exclusiu del nostre país, sinó que es tracta d'un assumpte global associat, entre altres aspects, al creixement de la població. Després d'aquest plantejament i el fet que el consum del ciment continuarà augmentant, la comunitat científica està estudiant materials alternatius, com poden ser els ciments de sulfoaluminat de calci, ciments belítics, I els ciments activats alcalinament, també coneguts com a geopolímers. Aquests últims adquireixen propietats químiques I físiques tals, que es consideren per molts investigadors, la tercera generació de materials de construcció després de la calç I el ciment Portland. Els materials fabricats a partir del ciment Portland tenen unes propietats característiques com són la resistència mecànica i la durabilitat. Aquestes dues propietats estan relacionades amb l'estructura de porus que es troba dins de la matriu. Aquesta estructura depén del volum de porus, de la distribució de grandàries, de la connectivitat i de la percolació d'aquests. Tals paràmetres poden determinar-se per diferents mètodes, els resultats dels quals varien depenent de la tècnica empleada. Existeixen diferents tipus de porus la classificació dels quals es basa en el seu diàmetre, entre ells es caracteritzen dos tipus, els porus de tipus gel i els porus capil·lars. Un aspecte important relacionat amb la microestructura porosa i que també afecta la durabilitat de la matriu de morter o formigó és el transport iònic; per aquest motiu, per a la caracterització d'aqueixa microestructura porosa existeixen tècniques de tipus no destructiu com són els mètodes elèctrics i l'Espectroscòpia d'Impedància Elèctrica (EIE). En aquesta Tesi Doctoral, s'ha utilitzat l'Espectroscòpia d'Impedància Elèctrica (EIE) en morters i formigons de ciment Portland i morters activats alcalinament, per a caracteritzar la seua evolució en el temps per mitjà d'uns paràmetres elèctrics, a partir d'un ircuit elèctric equivalent (CEE) i poder relacionar així els dos tipus de porositat. A més, s'ha determinat el circuit elèctric equivalent, que representa la conductivitat elèctrica dels morters i formigons des del dia 2 fins a més de 100 dies de guarit, mostrant les variacions produïdes en el procés d'hidratació i geopolimerització, i permetent separar els components de la conductivitat elèctrica relacionats amb els porus tipus gel, els porus capil·lars i la interfase entre aquests. S'obtenen, en general, dues relaxacions, a mitjana i alta freqüència, tant en morters com en formigó. Es mesura la resistivitat elèctrica en corrent continu i es tracta de relacionar amb la hidratació del ciment i el procés de geopolimerització dels materials activats alcalinament. A més, aquesta resistivitat s'ha tractat de correlacionar amb els valors de la resistència mecànica a compressió i amb les seues propietats microestructurals, obtingudes a partir d'assajos amb les tècniques de microscòpia electrònica d'escombratge (SEM), termogravimetria (TG) i Porosimetría de mercuri. D'aquesta manera, en aquesta Tesi Doctoral ha sigut possible desenvolupar un mètode de caracterització, de morters i formigons, independentment del conglomerant emprat, siga ciment Portland o matrius geopolimèriques, mitjançant un mateix tipus de circuit elèctric.Calvo Muñoz, C. (2017). Evaluación mediante el Método de Espectroscopia de Impedancia Eléctrica (EIE), del proceso de geopolimerización de pastas, morteros y hormigones en conglomerantes activados alcalinamente [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/82601TESI

Drying-rewetting cycles in ordinary Portland cement mortars investigated by electrical impedance spectroscopy

[EN] Changes caused in the porous microstructure of ordinary Portland cement (OPC) mortars were studied using electrical impedance spectroscopy (EIS) and equivalent circuit (EqC). Two successive processes, at 20 ºC and 50 °C, consisting of several drying-rewetting cycles, were applied to the mortars. After each cycle, the electrical impedance and the amount of water absorbed were measured. The EIS-EqC methodology allowed to find two distributed impedance relaxations, associated to capillary and gel-C-S-H porosities, respectively. At room temperature any microstructural change was not detected. Nevertheless, at 50 °C two microstructural changes were inferred: 1) the volume of accessible porosity increased (pore coarsening) and 2) the surface of the conductive path through C-S-H gel became more conductive (surface smoothing).The authors would like to thank the Spanish Ministry of Science and Innovation for supporting this research through the project BIA 2011-26947.Fita Fernández, IC.; Cruz González, JM.; Calvo Muñoz, C.; Soriano Martínez, L.; Paya Bernabeu, JJ.; Sánchez Martín, I. (2018). Drying-rewetting cycles in ordinary Portland cement mortars investigated by electrical impedance spectroscopy. Construction and Building Materials. 187:954-963. https://doi.org/10.1016/j.conbuildmat.2018.07.227S95496318

Lack of a synergistic effect of a non-viral ALS gene therapy based on BDNF and a TTC fusion molecule

Significant improvements in behavioral and electrophysiological results, motoneuron survival and anti-apoptotic/survival-activated pathways were observed with BDNF-TTC treatment. However, no synergistic effect was found for this fusion molecule. Although BDNF in the fusion molecule is capable of activating autocrine and neuroprotective pathways, TTC treatment alone yielded similar neuroprotection. Therefore, an accurate study of the neuroprotective effects of TTC fusion molecules should be performed to obtain a better understanding of its effect

Filaggrin and cytokines in respiratory samples of preterm infants at risk for respiratory viral infection

Respiratory viral infections (RVIs) are frequent in preterm infants possibly inducing long-term impact on respiratory morbidity. Immune response and respiratory barriers are key defense elements against viral insults in premature infants admitted to Neonatal Intensive Care Units (NICUs). Our main goals were to describe the local immune response in respiratory secretions of preterm infants with RVIs during NICU admission and to evaluate the expression and synthesis of lung barrier regulators, both in respiratory samples and in vitro models. Samples from preterm infants that went on to develop RVIs had lower filaggrin gene and protein levels at a cellular level were compared to never-infected neonates (controls). Filaggrin, MIP-1α/CCL3 and MCP-1 levels were higher in pre-infection supernatants compared to controls. Filaggrin, HIF-1α, VEGF, RANTES/CCL5, IL-17A, IL-1β, MIP-1α and MIP-1β/CCL5 levels were higher during and after infection. ROC curve and logistic regression analysis shows that these molecules could be used as infection risk biomarkers. Small airway epithelial cells stimulated by poly:IC presented reduced filaggrin gene expression and increased levels in supernatant. We conclude that filaggrin gene and protein dysregulation is a risk factor of RVI in newborns admitted at the NICU.This study has been partially supported by ISCIII – Instituto de Salud Carlos III, FIS (Fondo de Investigación Sanitaria—Spanish Health Research Fund) grants FI19/00067, PI18/00167, PI21/00896, PI18CIII/00009 and FEDER funds (Fondo Europeo de Desarrollo Regional); Sociedad Española de Alergología e Inmunología Clínica (SEAIC)Beca19A04_Valverde; Alfonso X El Sabio University Grant: VIII Convocatoria Santander-UAX; CIBER de Enfermedades Respiratorias (CIBERES), a Carlos III Institute of Health Initiative.S

Humoral and cellular immune response to mRNA SARS-CoV-2 BNT162b2 vaccine in adolescents with rheumatic diseases

Background: Data about safety and efficacy of the mRNA SARS-CoV-2 vaccine in adolescents with rheumatic diseases (RD) is scarce and whether these patients generate a sufficient immune response to the vaccine remains an outstanding question. Objective: To evaluate safety and humoral and cellular immunity of the BNT162b2 vaccine in adolescents 12 to 18 years with RD and immunosuppressive treatment compared with a healthy control group. Methods: Adolescents from 12 to 18 years with RD followed at Hospital La Paz in Madrid (n = 40) receiving the BNT162b2 mRNA vaccination were assessed 3 weeks after complete vaccination. Healthy adolescents served as controls (n = 24). Humoral response was measured by IgG antiSpike antibodies, and cellular response by the quantity of IFN-γ and IL-2 present in whole blood stimulated with SARS-CoV-2 Spike and M proteins. Results: There were no differences in spike-specific humoral or cellular response between groups (median IFN-γ response to S specific protein; 528.80 pg/ml in controls vs. 398.44 in RD patients, p 0.78, and median IL-2 response in controls: 635.68 pg/ml vs. 497.30 in RD patients, p 0.22. The most frequent diagnosis was juvenile idiopathic arthritis (26/40, 65%) followed by Lupus (6/40, 15%). 60% of cases (23/40) received TNF inhibitors and 35% (14/40) methotrexate. 40% of patients (26/64) had previous SARS-CoV-2 infection, 9 in the control group and 17 in the RD patients without differences. Of note, 70% of infections were asymptomatic. A higher IFN-γ production was found in COVID-19 recovered individuals than in naive subjects in both groups (controls: median 859 pg/ml in recovered patients vs. 450 in naïve p 0.017, and RD patients: 850 in recovered vs. 278 in naïve p 0.024). No serious adverse events or flares were reported following vaccination. Conclusions: We conclude that standard of care treatment for adolescents with RD including TNF inhibitors and methotrexate did not affect the humoral and the cellular immunity to BNT162b2 mRNA vaccination compared to a healthy control group. The previous contact with SARS-CoV-2 was the most relevant factor in the immune response.This work has been partially supported by a grant from Merck & Co (USA) MISP Call, Reference # 60465.S

Neurobrucellosis in Stranded Dolphins, Costa Rica

Ten striped dolphins, Stenella coeruleoalba, stranded along the Costa Rican Pacific coast, had meningoencephalitis and antibodies against Brucella spp. Brucella ceti was isolated from cerebrospinal fluid of 6 dolphins and 1 fetus. S. coeruleoalba constitutes a highly susceptible host and a potential reservoir for B. ceti transmission

Cranial and extracranial giant cell arteritis do not exhibit differences in the IL6 -174 G/C gene polymorphism

Since interleukin-6 (IL-6) is a pivotal proinflammatory cytokine implicated in the pathogenesis of giant cell arteritis (GCA), we aimed to determine the potential association of the functional IL6 -174 G/C polymorphism with GCA as well as if the single base change variation at the promoter region in the human IL-6 gene may account for differences in the clinical spectrum of GCA between cranial and extracranial large vessel vasculitis (LVV)-GCA

Cranial and extracranial large-vessel giant cell arteritis share a genetic pattern of interferon-gamma pathway

OBJECTIVES: Two main different clinical phenotypes of giant cell arteritis (GCA) have been described, the classic cranial pattern and the extracranial large-vessel (LV) pattern. Since interferon gamma (IFNG) has shown to be a pivotal cytokine in the pathophysiology of GCA, our aim was to evaluate for the first time the influence of IFNG and IFNG receptor 1 (IFNGR1) polymorphisms in the different clinical phenotypes of GCA. METHODS: Two IFNG polymorphisms (rs2069718 G/A and rs1861493 A/G) and one polymorphism in IFNGR1 (rs1327474 G/A) were genotyped in 191 patients with biopsy-proven cranial GCA, 109 with extracranial LV-GCA and 490 healthy controls. A comparative study was conducted between patients with cranial and extracranial LV-GCA. RESULTS: No significant differences in genotype, allele, and haplotype frequencies of IFNG polymorphisms were found between GCA patients with the classic cranial pattern and the extracranial LV-GCA pattern. Similar results were found for genotype and allele frequencies of IFNGR1 polymorphism. It was also the case when patients with extracranial LV-GCA were compared with healthy controls. CONCLUSIONS: Our results show that IFNG and IFNGR1 polymorphisms do not influence the clinical phenotype of expression of GCA. Classic cranial GCA and extracranial LV-GCA seem to share a genetic pattern of IFNG pathway

The presence of both HLA-DRB1[*]04:01 and HLA-B[*]15:01 increases the susceptibility to cranial and extracranial giant cell arteritis.

Objectives: To determine if patients with the predominant extracranial large-vessel-vasculitis (LVV) pattern of giant cell arteritis (GCA) have a distinctive HLA-B association, different from that reported in biopsy-proven cranial GCA patients. In a further step we assessed if the combination of HLA-B and HLA-DRB1 alleles confers an increased risk for GCA susceptibility, either for the cranial and extracranial LVV phenotypes. Methods: A total of 184 patients with biopsy-proven cranial GCA, 105 with LVV-GCA and 486 healthy controls were included in our study. We compared HLA-B phenotype frequencies between the three groups. Results: HLA-B*15 phenotype was significantly increased in patients with classic cranial GCA compared to controls (14.7% versus 5.8%, respectively; p<0.01; OR [95% CI] =2.81 [1.54-5.11]). It was mainly due to the HLA-B*15:01 allele (12.5% versus 4.0%, respectively; p<0.01; OR [95% CI] =3.51 [1.77-6.99]) and remained statistically significant after Bonferroni correction. Similar HLA-B*15 association was observed in patients with the LVV-GCA (11.4% versus 5.8%, p=0.04, OR [95% CI] =2.11 [1.04-4.30]). This association was also mainly due to the HLA-B*15:01 allele (10.5% versus 4.0%, respectively; p=0.0054; OR [95% CI] =2.88 [1.19-6.59]). Noteworthy, the presence of HLA-B*15:01 together with HLA-DRB1*04:01 led to an increased risk of developing both cranial and extracranial LVV-GCA. Conclusions: Susceptibility to GCA is strongly related to the HLA region, regardless of the clinical phenotype of expression of the disease.This work was partially supported by RETICS Programs, RD08/0075 (RIER), RD12/0009/0013 and RD16/0012 from ‘‘Instituto de Salud Carlos III’’ (ISCIII) (Spain). However, this research did not receive any specific grant from funding agencies in the commercial or not-for-profit sectors