https://hdl.handle.net/2072/478933 2026-04-08T20:40:50Z https://hdl.handle.net/2445/223631 Confronting positions: para- vs. meta-functionalization in triindole for p-type air-stable OTFTs Cuadrado Santolaria, Alba; Bujaldón Carbó, Roger; Fabregat, Clara; Puigdollers i González, Joaquim; Velasco Castrillo, Dolores The 5,10,15-trihexyl-10,15-dihydro-5H-diindolo[3,2-a:3′,2′-c]carbazole core, namely triindole, is well-known for its prominent hole-transporting properties and air stability. The functionalization of this core is also rather versatile, which allows the modulation of its properties by anchoring targeted scaffolds to different positions, e.g. 3,8,13 (para with respect to the nitrogens), 2,7,12 (analogously meta) or the nitrogen heteroatoms. Therefore, triindole excels as a pivotal semiconductor to be exploited in long-lasting organic thin-film transistors (OTFTs). This report aims to shed light on the effect of functionalizing whether para or meta positions with sulfurated moieties, in the pursuit of an enhanced performance in OTFTs. Remarkably, meta-substituted derivatives outshone their para- counterparts in terms of thermal, optical, intermolecular arrangement and semiconductor properties, claiming mobility values up to 2 × 10−3 cm2 V−1 s−1 and a shelf lifetime beyond the analyzed period of 5 months. Analysis of the thin films by grazing incidence X-ray diffraction (GIRXD) and atomic force microscopy (AFM) revealed that the meta-substitution also induces a higher degree of order and better morphology, further corroborating the potential of this structural approach. 2025-10-13T17:21:12Z https://hdl.handle.net/2445/223965 Crystallographic and Computational Analysis of Oxyma B Cocrystals with Nitrogen-Containing Coformers: The Relevant Role of <em>n</em> → π* Interactions in Their Diverse Supramolecular Architectures Jemai, Mahdi; Barbas Cañero, Rafael; Barceló-Oliver, Miquel; Marouani, Houda; Albericio Palomera, Fernando; Frontera, Antonio; Prohens López, Rafael Three new cocrystals of Oxyma-B, an important racemization suppressor for peptide synthesis, with 6-methylquinoline (I), 2,3,5,6-tetramethylpyrazine (II), and 1,10-phenanthroline (III) were synthesized and their single crystal structures analyzed. They show a rich network of noncovalent interactions, including classical and nonclassical hydrogen bonds (CH···O, OH···N, CH···N), CH···π, π-stacking, and, notably, lone pair···π (</span><em style="color:rgb( 21 , 21 , 21 )">n</em><span style="color:rgb( 21 , 21 , 21 )"> → π*) interactions. Distinctive supramolecular synthons were identified, including the R22(7) motif found in both 6-methylquinoline/Oxyma-B and 2,3,5,6-tetramethylpyrazine/Oxyma-B cocrystals. In 1,10-phenanthroline/Oxyma-B, larger ring motifs such as R44(20) and R55(24) were observed, further supported by additional synthons of types </span><em style="color:rgb( 21 , 21 , 21 )">R</em><span style="color:rgb( 21 , 21 , 21 )">12(5) and </span><em style="color:rgb( 21 , 21 , 21 )">R</em><span style="color:rgb( 21 , 21 , 21 )">12(6). Hirshfeld surface analysis and density functional theory (DFT) calculations, including MEP surface, QTAIM, and NCIplot analyses, were carried out to quantify the intermolecular contributions and rationalize the experimental findings with a focus on the cooperative role of hydrogen bonding, π-stacking, and lone pair···π (</span><em style="color:rgb( 21 , 21 , 21 )">n</em><span style="color:rgb( 21 , 21 , 21 )"> → π*) interactions in stabilizing and shaping the architectures of these new multicomponent crystalline materials. 2025-10-30T09:42:49Z https://hdl.handle.net/2445/224132 Computational Study of a Copper-Catalyzed Synthesis of Fluoroalcohols from Alkylboranes and Ketones Gómez-Mudarra, Francisco A.; Aullón López, Gabriel; Jover Modrego, Jesús Fluoroalcohols are a class of organic compounds containing one or more fluorine atoms together with an alcohol group in their molecular structure. These fluorinated species have a wide range of applications due to their unique properties and are used in medicine and electronics. Herein, we propose a new synthetic procedure, promoted by a copper(I) catalyst, for preparing fluoroalcohols from alkylboranes and symmetric ketones. The reaction has been computationally explored to propose a plausible mechanism, which allows identifying the rate-limiting step and quantitatively evaluating the electronic effects of each substrate on the overall reactivity. These DFT calculations suggest that the combination of electron-poor ketones with electron-rich alkylboranes produce the most efficient catalytic systems for preparing fluoroalcohols. Microkinetic modeling of the studied systems allow the prediction of the activation barrier limit to achieve fully functional reactions and multilinear regression techniques provide a methodology to estimate the overall reaction barriers in a simple manner, opening the way for proposing new catalytic systems. 2025-11-05T19:35:08Z https://hdl.handle.net/2445/219115 MAF amplification licenses ERα through epigenetic remodelling to drive breast cancer metastasis.  Llorente Lope, Alicia; Blasco, M. T.; Espuny, Irene; Guiu, Marc; Ballaré, C.; Blanco, E.; Caballé, A.; Bellmunt, Anna; Salvador, F.; Morales, A.; Nuñez, M.; Loren, Guillem; Imbastari, Francesca; Fidalgo, Marta; Figueras-Puig, Cristina; Gibler, Patrizia; Graupera, M.; Monteiro, F.; Riera i Escalé, Antoni; Holen, I.; Avgustinova, A.; Di Croce, L.; Gomis, R. R. MAF amplification increases the risk of breast cancer (BCa) metastasis through mechanisms that are still poorly understood yet have important clinical implications. Oestrogen-receptor-positive (ER+) BCa requires oestrogen for both growth and metastasis, albeit by ill-known mechanisms. Here we integrate proteomics, transcriptomics, epigenomics, chromatin accessibility and functional assays from human and syngeneic mouse BCa models to show that MAF directly interacts with oestrogen receptor alpha (ERα), thereby promoting a unique chromatin landscape that favours metastatic spread. We identify metastasis-promoting genes that are de novo licensed following oestrogen exposure in a MAF-dependent manner. The histone demethylase KDM1A is key to the epigenomic remodelling that facilitates the expression of the pro-metastatic MAF/oestrogen-driven gene expression program, and loss of KDM1A activity prevents this metastasis. We have thus determined that the molecular basis underlying MAF/oestrogen-mediated metastasis requires genetic, epigenetic and hormone signals from the systemic environment, which influence the ability of BCa cells to metastasize. 2025-02-21T17:56:21Z