Untangling the eclectronic propierties of triindole-based semiconductors

Organic semiconductors have emerged as an important class of materials that offer interesting prospects for high throughput, low-cost and flexible electronic circuits. In this sense, triindole-based systems have demonstrated great potential as p-type semiconductors in organic field-effect transistors (OFETs).[1] Recently, we have performed a combined experimental and theoretical study of three new crystalline N-trimethyltriindoles endowed with different functionalities at 3, 8 and 13 positions, either unsubstituted or with three methoxy or acetyl groups (Figure 1a), with the main goal of exploring the correlation between the electronic nature of the substituents and their solid-state organization, electronic properties and semiconductor behavior.[2] On the other hand, the design and synthesis of covalent organic framework materials (constructed from the union of different covalently linked conjugated platforms) are being deeply investigated in organic electronics.[3] In line with this , we have also investigated how the structural and the electronic properties of 2D triindole-based polymers (Figure 1b) can be modulated by the (i) modification of the linkage position from para (T2) to meta (T3), (ii) by the insertion of different π-bridges between the cores and (iii) by the increment of the number of π-bridges from 3 to 6 units (T2,3).[4] Overall, the results of this work open the door to the control of the degree of the π-conjugation for their subsequent synthesis and real application in organic electronic devices.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Biodiversity and distribution of macroinfauna assemblages on sandy beaches along the Gulf of Cadiz (SW Spain)

In the current study, the macroinfauna communities inhabiting 12 sandy beaches along the Spanish coast of the Gulf of Cadiz were describe in order to characterize their unexplored biodiversity, their zonation patterns and their environmental features. A total of 66 macroinfauna taxa were recorded on 12 sandy beaches, ranging from 4 to 33 species. Density reached 848 individual per m2. The individual zonation pattern ranged from two to three zones, regardless of the morphodynamic state. A common zonation pattern of the whole set of beaches was established, comprising three across-shore biological zones. Generally, the supralittoral zone was typified by the air-breathing amphipod Talitrus saltator and coleopterans; the middle zone was dominated by true intertidal species, such as Haustoriidae amphipods (Haustorius arenarius), Cirolanidae isopods (Eurydice affinis), Spionidae polychaetes (Scolelepis spp.) and nemerteans; and the lower or sublittoral zone was typified by Pontoporeiidae amphipods, mysids and spionid polychaetes. Sediment moisture, average grain size, organic matter content and elevation were the main predictor variables of zonation patterns. We used the conservation and recreation potential indices to show how this information can be useful for coastal management. Most beaches studied show a score above 5 on the conservation index, so the beaches have a reasonable potential for conservation management.En el presente estudio, se describen las comunidades de macroinfauna de doce playas arenosas de la costa española del Golfo de Cádiz con el objetivo de caracterizar su biodiversidad, sus patrones de zonación, y sus características ambientales. Un total de 66 taxones de macroinfauna fueron registrados en las playas de estudio, oscilando entre 4 y 33 especies, mientras que la densidad total fue de 848 individuos por m2. El patrón de zonación individual varió de dos a tres zonas, independientemente del estado morfodinámico de la playa. Se estableció un patrón de zonación común de todo el conjunto de playas, formado por tres zonas biológicas. En general, la zona supralitoral fue tipificada por el anfípodo Talitrus saltator y diversas familias de coleópteros. La zona media fue dominada por verdaderas especies intermareales, como anfípodos de la famila Haustoriidae (Haustorius arenarius), isópodos cirolánidos (Eurydice affinis), poliquetos (Scolelepis spp.) y nemertinos. La zona sublitoral se caracterizó por anfípodos de la familia Pontoporeiidae, misidáceos y poliquetos espiónidos. La humedad del sedimento, el tamaño medio de grano, el contenido en materia orgánica y la elevación fueron las principales variables influyentes en los patrones de zonación. Por último, toda esta información fue integrada para la aplicación de los índices de Conservación y Recreación, para mostrar cómo esta información puede ser útil para la gestión costera. La mayoría de las playas mostraron una puntuación superior a 5 en el Índice de Conservación, indicando un razonable potencial para la conservación.Gobierno de Andalucía P09- HUM-4717Ministerio de Educación AP-2009-390

Theoretical understanding of the increment of upon protonation of pyridine peripheral octupolar molecules: Toward nonlinear optical sensors

6 pages, 6 tables, 4 figures.In this article, we present a computational study of the nonlinear optical properties of pyridine-based octupolar molecules in their neutral and fully triprotonated states. The effect of the core substitution and the degree of conjugation with the periphery has been also established and confirms the possibility of fine-tuning the nonlinear optical response. Computations involving the time-dependent density-functional theory approach serve to further explore the existence of excited states with nonzero dipole moment. From these results, the origin of the high second-order nonlinear optical activity upon protonation is addressed.The present work was supported in part by the Dirección General de Enseñanza Superior DGES, MEC, Spain through research Project Nos. CTQ2006-14987-C02-01 and CTQ2005-01368. The authors are also indebted to Junta de Andalucía and Gobierno de Aragón Spain for funding their research groups FQM-0159 and E39. M.C.R.D. is grateful to the MEC/Fulbright for her Postdoctoral Fellowship at the Georgia Institute of Techology. J.C. is grateful to the MEC of Spain for an I3 professorship position of Chemistry at the University of Málaga and M.M.O. acknowledges the MEC for a personal grant.Peer reviewe

Tuning the Diradical Character of Indolocarbazoles: Impact of Structural Isomerism and Substitution Position

In this study, a set of 10 positional indolocarbazole (ICz) isomers substituted with dicyanomethylene groups connected via para or meta positions are computationally investigated with the aim of exploring the efficiency of structural isomerism and substitution position in controlling their optical and electronic properties. Unrestricted density functional theory (DFT), a spin-flip time-dependent DFT approach, and the multireference CASSCF/NEVPT2 method have been applied to correlate the diradical character with the energetic trends (i.e., singlet–triplet energy gaps). In addition, the nucleus-independent chemical shift together with ACID plots and Raman intensity calculations were used to strengthen the relationship between the diradical character and (anti)aromaticity. Our study reveals that the substitution pattern and structural isomerism represent a very effective way to tune the diradical properties in ICz-based systems with meta-substituted systems with a V-shaped structure displaying the largest diradical character. Thus, this work contributes to the elucidation of the challenging chemical reactivity and physical properties of diradicaloid systems, guiding experimental chemists to produce new molecules with desirable properties.Funding for open access charge: Univesidad de Málaga/CBUA. The work at the University of Málaga was funded by the MICINN (PID2019-110305GB-I00) and Junta de Andalucía (UMA18-FEDERJA-080, P09FQM-4708, and P18-FR-4559) projects. The authors thankfully acknowledge the computer resources, technical expertise, and assistance provided by the SCBI (Supercomputing and Bioinformatics) centre of the University of Málaga. The work at the University of Alicante was supported by the MICINN (PID2019-106114GB-I00). The work at the University of Bologna was supported by University of Bologna (RFO) funds

Quantum chemical DFT and spectroscopic UV-Vis-NIR analysis of a series of push-pull oligothiophenes end capped by amino-cyanovinyl groups

A series of push-pull chromophores built around thiophene-based -conjugating spacers and bearing various types of amino-donors and cyanovinyl-acceptors have been analyzed by means of UV-Vis- NIR spectroscopic measurements. Density functional theory (DFT) calculations have also been performed to help the assignment of the most relevant electronic features and to derive useful information about the molecular structure of these NLO-phores. The effects of the donor/acceptor substitution in the electronic and molecular properties of the -conjugated spacer have been addressed. The effectiveness of the intramolecular charge transfer (ICT) has also been tested as a function of the nature of the end groups (i.e., electron-donating or electron-withdrawing capabilities).Research at the University of Málaga was supported by the Ministerio de Educación y Ciencia (MEC) of Spain through project CTQ2006-14987-C02-01, and by the Junta de Andalucía for funding our FQM- 0159 scientific group. J.C. is grateful to the Ministerio de Ciencia y Tecnología of Spain for a Ramón y Cajal position of Chemistry at the University of Málaga. M.C.R.D. is also grateful to the Ministerio de Educación y Ciencia of Spain for a personal grant. The group at the University of Minho acknowledges the Foundation for Science and Technology (Portugal) for financial support through Centro de Química (UM) and through POCTI, FEDER (ref. POCTI/QUI/37816/2001). M. Manuela M. Raposo and A. Maurício C. Fonseca are also grateful to Professor G. Kirsch from University of Metz (France) for his collaboration

Ladder-type bithiophene imide-based organic semiconductors: understanding charge transport mechanisms in organic field effect transistors

Different charge transport mechanisms at the device interface are found for a series of ladder-type semiconductors with increasing chain length

Studying the electronic and charge transport properties of two cyclocarbazole derivates

Molecular systems have proven to be efficient active materials in electronics, being possible alternatives to the inorganic semiconductors used nowadays in electronic devices. For this reason, organic electronics has emerged as a research field with great potential and interest. In this project, an experimental and theoretical study of two carbazole-based macrocycles is presented (Figure 1). Specifically, we investigated the impact of the inclusion of acetylene groups on the electronic and molecular structures of these macrocycles, as well as their potential as charge transporting materials. The first studied compound (Cz) is composed by four carbazole groups linked at their para position with respect to the nitrogen atom[1]. In the second compound (ACz), the carbazole units are connected through ethynylene groups[2]. For this study, Raman and UV-Vis absorption spectroscopies have been used in combination with theoretical calculations based on the density functional theory (DFT). In addition, the two studied compounds have been implemented in organic field-effect transistors (OFETs), to assess their potential as active materials in organic electronics. Overall, the inclusion of ethynylene groups as π-conjugated spacers is found to be a good strategy to improve the electronic delocalization in macrocycles.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Biochemical biomarkers for multiple sclerosis

Introduction: Multiple sclerosis (MS) is the most frequent demyelinating disease of the central nervous system. Although there is currently no definite cure for MS, new therapies have recently been developed based on a continuous search for new biomarkers. Development: MS diagnosis relies on the integration of clinical, imaging and laboratory findings as there is still no single pathognomonic clinical feature or diagnostic laboratory biomarker. The most commonly laboratory test used is the presence of immunoglobulin G oligoclonal bands (OCB) in cerebrospinal fluid of MS patients. This test is now included in the 2017 McDonald criteria as a biomarker of dissemination in time. Nevertheless, there are other biomarkers currently in use such as kappa free light chain, which has shown higher sensitivity and specificity for MS diagnosis than OCB. In addition, other potential laboratory tests involved in neuronal damage, demyelination and/or inflammation could be used for detecting MS. Conclusions: CSF and serum biomarkers have been reviewed for their use in MS diagnosis and prognosis to stablish an accurate and prompt MS diagnosis, crucial to implement an adequate treatment and to optimize clinical outcomes over time