Carbazole-based Diradicals for Dynamic Covalent Chemistry

Dynamic covalent chemistry (DCC) is focused on the creation of structural scaffolds based on chemical components that interact through strong but reversible bonds. In fact, dynamic covalent bonds receive lot of attention because of their unique feature to become reversible under mild conditions.1 conjugated diradical compounds has emerged as essential building blocks in DCC.2 In this work, we will review our most recent works on the formation of stimuli-responsive cyclophanes by self-assembly of carbazole-based diradicals. To this end, we use a combined experimental and theoretical approach that links vibrational spectroscopy with DFT calculations. In this sense, it is interesting to note that we have recently demonstrated the potential of a para-substituted carbazole with terminal dicyanomethylene (DCM) groups to act as building blocks in DCC.3 This quinoid carbazole monomer transforms to a macrocycle cyclophane upon soft external stimuli (temperature, pressure, light), showing strong chromic features. In addition, we have also recently explored how the different DCM substitution position affects the interesting chromoactive properties of carbazole compounds.4 Finally, we are currently exploring the effect of the elongation of the carbazole backbone on the formation of stimuli-responsive cyclophanes.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Multiresponsive chromic soft materials: formation of strongly coupled σ-dimers from IndoloCarbazole-based biradicaloids

Dynamic covalent chemistry is focused on the creation of structural scaffolds based on chemical components that interact through strong but reversible bonds. In fact, dynamic covalent bonds receive lot of attention because of their unique feature to become reversible under mild conditions.1 π-conjugated biradical compounds has emerged as essential building blocks in DCC (dynamic covalent chemistry).2 We have recently demonstrated the potential of a para-substituted carbazole with terminal dicyanomethylene groups to act as building blocks in DCC.3 In fact, this quinoid carbazole monomer transform to a macrocycle cyclophane upon soft external stimuli (temperature, pressure, light), showing strong chromic features. Here, we explore the effect of the elongation of the carbazole backbone on the formation of stimuli-responsive cyclophanes by self-assembly. To this end, we use a join experimental and theoretical approach that links vibrational spectroscopy (Raman and IR) with DFT calculationsUniversidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Formation of stimuli-responsive cyclophanes by self-assembly: the case of carbazole-based biradicals

Dynamic covalent bonds has recently received lot of attention because of their unique feature to become reversible under mild conditions.[1] In this context, π-conjugated biradical compounds has emerged as essential building blocks.[2] For instance, we have demonstrated that 2,7-dicyanomethylene-9-(2-ethylhexyl)carbazole biradical reversibly converts to a macrocycle cyclophane upon soft stimuli (temperature, pressure, light), showing strong chromic effects.[3] We now extent this study towards longer conjugated carbazole backbone (i.e., indolocarbazole shown in Figure 1), aiming at investigating how the elongation of the conjugated backbone impacts on the formation of stimuli-responsive cyclophanes. The self-assembly process is investigated both in solution and solid state by linking theory and experiments.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Terutroban, A TP-receptor antagonist, reduces portal pressure in cirrhotic rats

Increased production of vasoconstrictive prostanoids, such as thromboxane A2 (TXA2 ), contributes to endothelial dysfunction and increased hepatic vascular tone in cirrhosis. TXA2 induces vasoconstriction by way of activation of the thromboxane-A2 /prostaglandin-endoperoxide (TP) receptor. This study investigated whether terutroban, a specific TP receptor blocker, decreases hepatic vascular tone and portal pressure in rats with cirrhosis due to carbon tetrachloride (CCl4 ) or bile duct ligation (BDL). Hepatic and systemic hemodynamics, endothelial dysfunction, liver fibrosis, hepatic Rho-kinase activity (a marker of hepatic stellate cell contraction), and the endothelial nitric oxide synthase (eNOS) signaling pathway were measured in CCl4 and BDL cirrhotic rats treated with terutroban (30 mg/kg/day) or its vehicle for 2 weeks. Terutroban reduced portal pressure in both models without producing significant changes in portal blood flow, suggesting a reduction in hepatic vascular resistance. Terutroban did not significantly change arterial pressure in CCl4 -cirrhotic rats but decreased it significantly in BDL-cirrhotic rats. In livers from CCl4 and BDL-cirrhotic terutroban-treated rats, endothelial dysfunction was improved and Rho-kinase activity was significantly reduced. In CCl4 -cirrhotic rats, terutroban reduced liver fibrosis and decreased alpha smooth muscle actin (α-SMA), collagen-I, and transforming growth factor beta messenger RNA (mRNA) expression without significant changes in the eNOS pathway. In contrast, no change in liver fibrosis was observed in BDL-cirrhotic rats but an increase in the eNOS pathway. CONCLUSION: Our data indicate that TP-receptor blockade with terutroban decreases portal pressure in cirrhosis. This effect is due to decreased hepatic resistance, which in CCl4 -cirrhotic rats was linked to decreased hepatic fibrosis, but not in BDL rats, in which the main mediator appeared to be an enhanced eNOS-dependent vasodilatation, which was not liver-selective, as it was associated with decreased arterial pressure. The potential use of terutroban for portal hypertension requires further investigation

Merging Theoretical Spectroscopy & Computational Chemistry: Thermally Activated Delayed Fluorescence (TADF) as a new light-emitting mechanism for OLEDs

We present recent advances and investigations related with a new mechanism for lightemission in conjugated molecules, Thermally Activated Delayed Fluorescence (TADF), seeking to harvest both the singlet and triplet excitons generated under electrical excitation ideally achieveing a 100% of efficiency. The new strategy may fuel the use and manufacturing of 3rd generation OLEDs, although a complete understanding of the molecular mechanism is not fully uncovered yet. Therefore, we will review our recent efforts to address some challenging issues using quantum and atomistic models [1-6]. Among them, we will remark how the mixed nature of the excited-states involved (chargetransfer or locally-excited) ultimately control the singlet-triplet energy difference, and how this is a dynamic process mediated by conformational fluctuations and spin-orbit couplingCampus de Excelencia Internacional Andalucía TEC

Red de Seguimiento e indicadores en el Máster Universitario en Ingeniería de Telecomunicación

El profesorado de la red docente, que forma parte de la comisión académica del Máster, realizó durante el curso 2011/12 un proyecto para el estudio de los indicadores de calidad del Máster, en función de los indicadores de calidad de las Agencias acreditadoras y dependiendo de las tasas de éxito y eficacias durante el primer curso de implantación del Máster

Seguimiento de calidad de las asignaturas de tercer curso del Grado en Ingeniería Informática

En esta memoria se describe el proyecto llevado a cabo para mejorar el seguimiento y la calidad de la docencia de las asignaturas del tercer curso del Grado en Ingeniería Informática. En concreto, en este proyecto, nos centramos en los mecanismos de evaluación y en su distribución a lo largo del curso, así como en los conceptos fundamentales que se asocian a las diferentes asignaturas que se imparten en tercer curso del Grado en Ingeniería Informática. Se realizaron diversas reuniones entre los coordinadores de las distintas asignaturas para poner en común problemas relacionados con la planificación de las asignaturas así como dudas sobre las actividades de evaluación. Las reuniones permitieron intercambiar diferentes planteamientos con los que se habían abordado la evaluación de las asignaturas participantes en la red y que posibilitaron resolver problemas comunes. De igual forma se plantearon cuestiones abiertas sobre la planificación y la evaluación de las asignaturas que se dirigieron desde la red a la coordinación de la titulación en la Escuela Politécnica Superior. Finalmente, también se discutieron diferentes propuestas junto con las redes de otros cursos de la titulación para abordarlas en futuras redes

Structure des grands bassins glaciaires dans le nord de la péninsule ibérique: comparaison entre les vallées d'Andorre (Pyrénées orientales), du Gállego (Pyrénées centrales) et du Trueba (Chaîne Cantabrique).

Les grandes vallées glaciaires de la Péninsule Ibérique sont situées dans la chaîne pyrénéo-cantabrique, principalement dans le bassin de l'Èbre. Ainsi, les vallées d'Andorre, de la Noguera Pallaresa et de la haute vallée du Gállego, dans les Pyrénées, ont eu des appareils glaciaires longs de 42, 50 et 40 km respectivement. Dans les vallées du Sil (bassin du Miño) et du Trueba, dans la Chaîne Cantabrique, ils atteignaient 42 et 16,5 km (Serrano-Cañadas, 1996 ; Gómez-Ortiz et al., 2001 ; Turu & Peña, 2006a et b ; Redondo-Vega et al., 2006). L'une des caractéristiques géomorphologiques de la plupart de ces vallées est l'existence d'une dépression morphologique du substratum dans les parties moyennes et terminales, interprétée comme la conséquence de l'érosion glaciaire. Dans tous les cas, on observe une architecture litho-stratigraphique commune (Vilaplana & Casas, 1983 ; Bordonau et al., 1989 ; Bordonau, 1992 ; Turu et al., 2002) représentée par trois unités géoélectriques : une unité inférieure très épaisse, avec des résistivités électriques basses (70 - 200 Ohms par mètre), qui traduit la présence de matériaux fins considérés comme d'origine lacustre ; une unité intermédiaire, moins épaisse, avec des valeurs de résistivité plus élevées (400 - 800 Ohms par mètre), pouvant être interprétée comme un système fluvio-deltaïque pro-glaciaire et une unité géoélectrique supérieure, avec des valeurs de résistivité très variables (100 - 1500 Ohms par mètre), constituée de sédiments alluviaux subactuels. La comparaison des données de type géophysique et géomécanique (sismique à réfraction et essais pressiométriques) montre que l'unité intermédiaire, considérée comme d'origine fluvio-deltaïque, présente des valeurs de vitesse sismique anormalement élevées, ainsi que de hautes valeurs de consolidation. Cette observation effectuée pour la première fois dans la vallée d'Andorre (Turu, 2000) montre des remarquables corrélations entre les hautes vitesses sismiques et les valeurs élevées de consolidation, ainsi que la très nette corrélation entre les hautes valeurs de consolidation et les tills sous-glaciaires. Elle permet d'interpréter l'unité intermédiaire comme essentiellement glaciaire et de remettre en question le modèle simple d'une séquence de comblement lacustre et deltaïque proposé jusqu´à maintenant

Adiciones y correcciones a la orquidoflora valenciana, VII

Se aportan datos sobre algunos táxones de Orchidaceae que resultan escasos en la Comunidad Valenciana o en determinadas de sus comarcas; a destacar la presencia de Ophrys santonica y O. × pseudospeculum en Alicante.It is shown some data about rare taxa of Orchidaceae at the Valencian Community (E Spain) or expansions of area to new shires; to emphasize the presence of Ophrys santonica and O. × pseudospeculum in Alicante