Iodoethynyl derivatives scaffolds in supramolecular chemistry: the interplay of design and synthesis

El manuscrito de tesis se enmarca dentro del ámbito de la Química Supramolecular, la cual fue definida por Jean Marie Lehn como “la química más allá de la molécula”.1 Es un campo altamente interdisciplinario que cubre tanto aspectos químicos, como físicos y biológicos, de las especies químicas de complejidad más grande que las moléculas mismas que se mantienen unidas y organizadas por medio de interacciones no covalentes. Uno de los aspectos más importantes y rápidamente desarrollados de la química supramolecular es la síntesis de cristales moleculares, la cual es también un objetivo mayor de otra área relativamente nueva, la ingeniería cristalina. La ingeniería cristalina se define como el estudio de las interacciones intermoleculares en el contexto del empaquetamiento cristalino, por un lado, y como la utilización del dicho entendimiento en el diseño de los sólidos nuevos con las propiedades físicas y químicas deseadas, por el otro. Los cristales moleculares, que consisten de las moléculas orgánicas, organometálicas o de los complejos de coordinación, cuales están ensamblados en el estado sólido como la consecuencia de las interacciones no-covalentes, son los objetos de investigaciones numerosas durante las últimas décadas. El interés hacia tales materiales es el resultado de la posibilidad de manipular con las propiedades de los cristales singulares en el estado sólido a través de la variación sistemática de sus estructuras moleculares y de las propiedades de sus componentes moleculares. Dentro de la química supramolecular también se encuentran los cristales líquidos. El estado cristal líquido2 se define como un estado de agregación de la materia intermedio entre el estado cristalino y el líquido, y surge como consecuencia de fuerzas intermoleculares en un proceso de auto-organización supramolecular. La inusual combinación en estos sistemas de propiedades, como fluidez y anisotropía, han permitido que estos materiales tengan, desde hace 50 años, una gran cantidad de aplicaciones en la vida cotidiana (relojes, calculadoras, televisores, cosméticos, etc.). No obstante, lo aprendido a lo largo de estos años ha permitido así mismo constatar lo que probablemente en la actualidad suponga el mayor atractivo, interés e innovación de los cristales líquidos: que este estado de agregación de la materia sea considerada como una herramienta de trabajo en la consecución de nuevos sistemas y aplicaciones.En la última década una de las líneas de investigación del Grupo de Cristales Líquidos y Polímeros se ha centrado en la preparación y caracterización de nuevas materiales basados en enlaces de halógeno. Las propiedades de un material no dependen únicamente de las moléculas que lo componen sino también de su organización en estado sólido. Además, de las interacciones clásicas (enlace de hidrógeno, dipolo-dipolo, enlace de coordinación) están cobrando una gran importancia los enlaces de halógeno. Este tipo de interacciones se ha empleado en la preparación de conductores orgánicos y cristales líquidos ya que presentan una fuerza y direccionalidad similar a los enlaces de hidrógeno.OBJETIVOS Y METODOLOGÍAObjetivos:El trabajo que se va a desarrollar en esta Tesis Doctoral tiene como objetivo principal estudiar y aportar nuevas posibilidades de las estructuras basadas en enlace de halógeno en Química Supramolecular, centrando nuestra atención en la fuerza y direccionalidad que posee el enlace de halógeno basado en moléculas con yodo unidas a un carbono con hibridación sp. Ilustración 1 Molécula con dos grupos yodoetinil.El estudio de estos compuesto no solo nos permitirá la obtención de nuevos materiales, como los cristales líquidos tipo bent-core (no descritos hasta la fecha vía enlace de halógeno)2, calamíticos y discóticos. Además de materiales porosos.Así mismo nos permitirá una comparación directa con el enlace de hidrogeno, tanto como la competitividad o/y la cooperatividad entre ambos. Metodología:Para la consecución de estos objetivos se han seleccionado y sintetizado moléculas halogenadas con diferentes geometrías. Además de los dadores de enlace de halógeno, se seleccionaron diferentes aceptores de enlace de halógeno: halogenuros y derivados nitrogenados principalmente.De esta manera, los objetivos particulares y metodología de trabajo de esta tesis doctoral pueden dividirse en los siguientes apartados:1. Síntesis y caracterización:- Síntesis y caracterización de derivados de yodoetinil ditopicos y tritopicos con diferentes geometrías. Capítulo 1.- Síntesis y caracterización de bases de Tröger halogenadas para formación de redes supramoleculares porosas. Capítulo 3.La síntesis de estos compuestos combina diferentes reacciones de esterificación, halogenación, etc.Todos los compuestos preparados, tanto intermedios como finales, se caracterizarán según las técnicas habituales para determinar su estructura química: espectroscopia de resonancia magnética nuclear de protón y de carbono (1H-RMN y 13C-RMN), espectroscopia infrarroja (IR) y espectrometría de masas (MS). Además se estudiarán sus propiedades en el monocristal.2. Estudio y caracterización de las propiedades:- En el capítulo 4 se estudiará la formación de cocristales mediante enlaces de halógeno como interacción principal, y los enlaces de hidrógeno como herramientas para aumentar la dimensionalidad estructural.- En el capítulo 5 se estudiarán las propiedades térmicas y mesomorfas de los materiales mediante microscopía óptica con luz polarizada, calorimetría diferencial de barrido (DSC), termogravimetría (TGA) y difracción de rayos X.- En el capítulo 6 se sintetiza, caracteriza y estudia las propiedades de una molécula con 4 posibilidades diferentes de interacción, además del enlace de halógeno, hilo conductor de esta tesis, la posibilidad de coordinación metálica, enlaces de hidrógeno o interacciones π-π.Asimismo en el capítulo 5 y en el capítulo 4 se hará uso de otras técnicas como espectroscopia Raman, espectroscopia fotoelectrónica de rayos X (XPS), calorimetría isoterma de titulación (ITC), difracción de rayos X de monocristal y de polvo para completar los estudios de cristales líquidos del capítulo 5 y en el capítulo 4 también se pretende comparar las propiedades en disolución con las del estado sólido, por ello el uso del ITC. [1] J.-M. Lehn, Angewandte Chemie International Edition in English 1990, 29, 1304-1319.[2] L. Gonzalez, N. Gimeno, R. Maria Tejedor, V. Polo, M. Blanca Ros, S. Uriel and J. Luis Serrano, Chem. Mat. 2013, 25, 4503-4510.<br /

Determinación de un plan operativo semanal para la Red Andaluza de Laboratorios Clínicos

Presentamos un modelo para coordinar el funcionamiento en una Red Regional de Laboratorios Clínicos, cuya resolución permite la reasignación de recursos, la redistribución de cargas y la reorganización de los flujos de muestras clínicas en dicha. Para ello, se determina un plan de producción y transporte: primero en un nivel táctico (anual) y luego a un nivel operativo (semanal). Se plantea como un problema de flujo multicommodity que conduce a una formulación entera mixta. Se presenta experimentación aplicada a la reordenación de las derivaciones de muestras entre los 32 nodos principales de la Red Andaluza de Laboratorios Clínicos.Andalucía. Junt

Testing for alpha-1 antitrypsin in COPD in outpatient respiratory clinics in Spain: A multilevel, cross-sectional analysis of the EPOCONSUL study

Background Alpha-1 antitrypsin deficiency (AATD) is the most common hereditary disorder in adults, but is under-recognized. In Spain, the number of patients diagnosed with AATD is much lower than expected according to epidemiologic studies. The objectives of this study were to assess the frequency and determinants of testing serum α1-antitrypsin (AAT) levels in COPD patients, and to describe factors associated with testing. Methods EPOCONSUL is a cross-sectional clinical audit, recruiting consecutive COPD cases over one year. The study evaluated serum AAT level determination in COPD patients and associations between individual, disease-related, and hospital characteristics. Results A total of 4,405 clinical records for COPD patients from 57 Spanish hospitals were evaluated. Only 995 (22.5%) patients had serum AAT tested on some occasion. A number of patient characteristics (being male [OR 0.5, p < 0.001], ≤55 years old [OR 2.38, p<0.001], BMI≤21 kg/m2 [OR 1.71, p<0.001], FEV1(%)<50% [OR 1.35, p<0.001], chronic bronchitis [OR 0.79, p < 0.001], Charlson index ≥ 3 [OR 0.66, p < 0.001], or history or symptoms of asthma [OR 1.32, p<0.001]), and management at a specialized COPD outpatient clinic [OR 2.73,p<0.001] were identified as factors independently associated with ever testing COPD patients for AATD. Overall, 114 COPD patients (11.5% of those tested) had AATD. Of them, 26 (22.8%) patients had severe deficiency. Patients with AATD were younger, with a low pack-year index, and were more likely to have emphysema (p<0.05). Conclusion Testing of AAT blood levels in COPD patients treated at outpatient respiratory clinics in Spain is infrequent. However, when tested, AATD (based on the serum AAT levels ≤100 mg/dL) is detected in one in five COPD patients. Efforts to optimize AATD case detection in COPD are needed.SEPA

Meta-analytic study on the frequency and treatment of oral antral communications

Objective: To determine the optimum surgical treatment for oral antral communications (OAC) and to understand the main post-operative complications.Study Design: Meta-analytical, observational and retrospective study of 1,072 cases of OAC obtained from a literature review of 15 articles. Results: OAC occur slightly more often in men and during the fourth decade of life. Its primary etiological factor is dental extraction, most often affecting the third molar. The most common treatment has been the use of Bichat's fat pad grafts, whereas the technique with the highest percentage of complications has been the use of the palatal rotation flap. The most frequent complication has been the fistulization of the OAC. Conclusions: Early diagnosis of OAC and its treatment within 48 hours of evolution are fundamental in order to properly resolve this pathology. The use of Bichat's fat pad grafts is a simple technique that offers excellent vascularization and results. © Medicina Oral

Incidencia de los ingresos corrientes y de capital del Distrito Turístico y Cultural Cartagena de Indias en las variables fundamentales de su desarrollo social 2000-2008

This document shows some methods of measuring relationship, using the tools of statistics to try and reconcile the incidence that the structure of the public finances of the District Cartagena de Indias exerts on the main variables of its social development. The analysis presented here is mainly focused to describe how the district income has had an impact on the improvement of the social variables, that is to say, we propose describing the incidence of public finances from the perspective of the current income and capital budget of the public on certain social variables of the district. It is pertinent to clarify, however, that the results shown here do not intend to become a technical exercise, but rather in an argumentative and interpretive analysis that seeks glimpse important aspects on how these revenues fail or not, generate impact on some issues related to the welfare of the population. The method of relationality used is based on the implementation of the R2, and also takes into account the approximation graph that results in the plane with the related variables a in each axis. Taking into account the above, some of the results obtained show that the income of capital contributed mostly on the variable unemployment in contrast with the impact on the same variable was affected by the current income during the period of study. However, the latter had a greater impact on the education variable with respect to that took on this income from capital. In the end, it presents a thoughtful analysis by way of general conclusions, which offers some strategies that could serve as a basis for the formulation of public policies, aimed at improving the function and the exercise of the local public finance.El presente documento muestra algunos métodos de medición de relación, utilizando las herramientas de la estadística, para tratar de aproximar la incidencia que la estructura de las finanzas públicas del Distrito Cartagena de Indias ejerce sobre las principales variables de su desarrollo social. El análisis aquí presentado está enfocado principalmente a describir la forma como los ingresos distritales han repercutido sobre el mejoramiento de las variables sociales, es decir, se propone describir la incidencia de las finanzas públicas desde la perspectiva de los ingresos corrientes y de capital del presupuesto público sobre determinadas variables sociales del distrito. Es pertinente aclarar sin embargo, que los resultados aquí mostrados no pretenden convertirse en un ejercicio técnico, sino más bien en un análisis argumentativo e interpretativo que busca entrever aspectos importantes sobre la forma cómo estos ingresos logran o no, generar impacto sobre algunos asuntos relacionados con el bienestar de la población. El método de relacionalidad utilizado se basa en la aplicación del R2, y tiene además en cuenta la aproximación gráfica que se obtiene en el plano con las variables relacionadas una en cada eje. Teniendo en cuenta lo anterior, algunos de los resultados obtenidos muestran que los ingresos de capital incidieron mayormente sobre la variable desempleo en contraste con la incidencia que sobre esta misma variable fue afectada por los ingresos corrientes durante el periodo de estudio. Sin embargo, éstos últimos tuvieron una mayor incidencia sobre la variable educación respecto de la que tuvieron sobre ésta los ingresos de capital. Al final se presenta un análisis reflexivo a manera de conclusiones generales, que propone algunas estrategias que podrían servir de base para la formulación de políticas públicas, encaminadas a mejorar la función y el ejercicio de la hacienda pública local.

Use of direct radiation forecasts to improve the reliability of solar thermal energy

Presentación realizada en: Using ECMWF's Forecasts (UEF2018), celebrada del 5 al 8 de junio de 2018 en Reading (Inglaterra).Concentrated Solar Power (CSP) is one of the two main techniques employed to harness the energy from the Sun. It has the distinctive advantage of being able to store energy, using it subsequently when needed (for example, at night). PreFlexMS project (www.preflexms.eu) aims to extend the flexibility of CSP to daytime, storing energy when it is sunny and dispatching it when it is cloudy. Forecasts from two meteorological models, the global IFS and the local area model Arome-Harmonie, have been used as inputs to help the CSP plant to decide the optimal schedule to follow. Both models have been verified against observations from AEMET Radiation Network to estimate their reliability, within the framework of PreFlexMS project. In this talk results will be shown (see attached figures) for the period studied, from March 2015 to February 2018. Another related project, done jointly with Red Electrica, the Spanish Transmission System Operator (TSO) will be also explained in this presentation. A combination of ECMWF radiation forecasts and Copernicus Atmosphere Monitoring Service (CAMS) aerosol forecasts has been used to improve solar power predictions for days with high aerosol content. Although aerosols don't affect scores significantly when averaged for a long period, it will be shown their huge impact in some events, and how our method can reduce the forecasting error

Aggregation of under canopy and bare soils in a Mediterranean environment affected by different fire intensities

7 páginas, 4 figuras, 3 tablas.Soil macroaggregation in relation to soil organic matter (SOM) and calcium carbonate(CaCO3) content was studied, before and after experimental fires of different intensities, in two environments (under canopy and on bare soil). In 1995, two experimental fire treatments, based on the addition of different biomass amounts, were applied on a set of nine plots at the Permanent Field Station of La Concordia (Valencia, Spain). Three plots were burned with high intensity fire (T1), three with moderate intensity (T2) and three plots were left unburned to be used as control treatment (T3). Soils under canopy were characterized by higher macroaggregate stability (SMS), SOM content and mean weight diameter of aggregates (MWD) than bare soils, which presented higher CaCO3 contents. After the fires, tendencies to increase were observed in the SOM and SMS of all burned soils, probably because of the incorporation of partially burned plant material. The trends of SMS and SOM in T1 burned soils were towards to decrease with the occurrence of the first erosive rainfalls. These trends continued until the end of the study. MWD of under canopy soils on T1 and of soils on T2 showed a decreasing trend immediately after fire treatments. Not significant differences between sampling periods were found for CaCO3 content, with the exception of under canopy soils on T1 which tended to increase, and showed higher values at the end of the studied period. The differences observed initially between under canopy and bare soil disappeared after one year of fire in T1, which suggests a major degradation of soils affected by this treatment. Significant changes of the studied properties were not observed in unburned soils during one year of research. In these soils, organic matter showed significant correlations with macroaggregate stability and mean weight diameter. However, significant statistical relationships were not observed between the Studied properties in burned soils, showing that fire impact probably affected other soil characteristics related to soil aggregation.We thank the financial support from the Agreement Generalitat Valenciana — CSIC (2005020112) “Impacto de los incendios forestalesrepetidos sobre los procesos de erosión hídrica del suelo y la recuperación de la cubierta vegetal. Seguimiento y evaluación en una estación permanente de campo”, and the Ministerio de Educación y Ciencia of the Spanish Government project “Procesos y balances hidrológicos y de sedimentos a diferentes escalas espaciales en ambientes mediterráneos: Efectos de la variabilidad climática y los cambios de uso del suelo” (PROBASE CGL2006-11619).Peer reviewe

Hydrological properties of a Mediterranean soil burned with different fire intensities

8 páginas, 5 figuras, 3 tablas.The influence of vegetation cover on soil hydrological properties and its response to the impact of different fire intensities, in a Mediterranean forest environment, has been evaluated. The study was carried out in the Permanent Experimental Field Station of La Concordia (Lliria-Valencia, Spain), on a set of nine erosion plots (4 x 20 m(2)). The Station is located on a calcareous hillside S-SE oriented, with soils of Rendzic Leptosol type and supporting Mediterranean shrubland vegetation. All runoff generated and sediment produced in every rain event was collected from each plot. The set up includes a system of sensors for the continuous monitoring of climatic parameters (air temperature and humidity, rain volume, intensity, etc.). In June 1995, a set of experimental fires was carried out to the Station. Three of the plots were burned with high intensity fire, three with moderate intensity and the remaining were left unaltered. Soil water content and water retention capacity (WRC) were measured in the different plots and in two different vegetation covers: under canopy (UC) and in bare soil (BS). The pF curves were also obtained for each fire treatment. A year after the fires (June 1995-June 1996), great differences, reaching 77.15%, in runoff generation between fire treatments and the control plots were observed. No significant differences were detected on water retention capacity between soils UC and BS in the burned plots. However, these differences appeared in the control plots, giving UC and BS values of 13% and 18%, respectively. Plots corresponding to the high intensity fire treatment showed values of WRC significantly higher than those of the moderate intensity and of the control treatments. The pF curves show that the values of water volume, at the different pressure points studied, were slightly greater on UC soil. Values obtained for BS samples are higher in the fire treatments, showing significant differences in respect to the control plots at pF 1 and 2. These differences were also observed for UC soil, but in this case at pF 2, 2.5 and 4.2.This work has been supported by the European Union (QLRT-2000-00289), the Spanish Ministry of Science and Technology (CICYT) REN2001-1716 and Convenio (Agreement) Generalitat Valenciana – CSIC (02020024).Peer reviewe

Characterization of the substrate noise spectrum for mixed-signal ICs

© 2005 IEEE. Personal use of this material is permitted. Permission from IEEE must be obtained for all other uses, in any current or future media, including reprinting/republishing this material for advertising or promotional purposes,creating new collective works, for resale or redistribution to servers or lists, or reuse of any copyrighted component of this work in other works.This paper presents a simplified analytical model of the substrate noise generated by digital circuitry that captures the most relevant frequency domain characteristics and relates them with parameters of the digital circuit and the package. Simulations and experimental results are used to validate the analytical model.Peer ReviewedPostprint (published version

Changes in biomarkers of redox status in serum and saliva of dogs with hypothyroidism

Hypothyroidism is the most common endocrine disorder diagnosed in dogs, leading to deleterious effects on a dog's life quality. This study aims to evaluate changes in the redox status in canine hypothyroidism. For this purpose, a comprehensive panel of antioxidants and oxidants biomarkers were measured in serum and saliva of 23 dogs with hypothyroidism, 21 dogs with non-thyroidal illness, and 16 healthy dogs. Among the antioxidants, cupric reducing antioxidant capacity (CUPRAC), ferric reducing ability of plasma (FRAP), Trolox equivalent antioxidant capacity (TEAC), thiol, paraoxonase type 1 (PON-1) and glutathione peroxidase (GPx) were determined in serum and CUPRAC, ferric reducing ability of saliva (FRAS) and TEAC in saliva. The oxidant biomarkers included were total oxidant status (TOS), peroxide-activity (POX-Act), reactive oxygen-derived compounds (d-ROMs), advanced oxidation protein products (AOPP), and thiobarbituric acid reactive substances (TBARS) in serum and AOPP and TBARS in saliva. Results showed a significantly higher TEAC, PON-1, GPx, TOS, POX-Act, and d-ROMs, and a significantly lower AOPP in serum of dogs with hypothyroidism. Meanwhile, significantly lower FRAS and AOPP were observed in saliva of dogs with hypothyroidism. Once salivary concentrations were corrected based on their total protein concentrations, the only analyte showing significant changes was TBARS which was significantly higher in dogs with hypothyroidism. Our results show that dogs with hypothyroidism present alterations in the redox status in both serum and saliva. This study should be considered a preliminary study and further research addressing these changes should be made using larger populations. The online version contains supplementary material available at 10.1186/s12917-023-03586-4