19 research outputs found
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High molecular weight mechanochromic spiropyran main chain copolymers via reproducible microwave-assisted Suzuki polycondensation
Suzuki–Miyaura polycondensation (SPC) is widely used to prepare a variety of copolymers for a broad range of applications. Although SPC protocols are often used in many instances, the limits of this method and issues of molecular weight reproducibility are not often looked at in detail. By using a spiropyran-based (SP) mechanochromic copolymer, we present an optimized protocol for the microwave-assisted synthesis of a mechanochromic, alternating copolymer P(SP-alt-C10) via SPC that allows the reproduction of molecular weight distributions. Several parameters such as microwave power, temperature, stoichiometry, and ligand are screened, leading to molecular weights up to Mw ∼ 174 kg mol−1. The process of optimization is guided by NMR end group analysis which shows that dehalogenation, oxidative deborylation and SP cleavage are the limiting factors that impede further increase of molar mass, while other classical side reactions such as protiodeborylation are not observed. Embossing films of P(SP-alt-C10) yields the colored merocyanine (MC) copolymer P(MC-alt-C10) that undergoes a thermally facilitated back reaction to P(SP-alt-C10). DFT suggests that the barrier of the SP → MC transition has two contributions, with the first one being related to the color change and the second one to internal bond reorganizations. The barrier height is 1.5 eV, which suggests that the ease of the thermally facilitated back reaction is either due to residual energy stored in the deformed polymer matrix, or arises from an MC isomer that is not in the thermodynamically most stable state
La importancia de la personalidad del traductor en los itinerarios de especialidad y en la selección de personal
Treball Final de Grau en Traducció i Interpretació. Codi: TI0983. Curs acadèmic: 2016/2017A pesar de que a simple vista no lo pueda parecer, la personalidad de los traductores influye mucho más de lo que se cree en el proceso traductor y en la toma de decisiones, como han puesto de manifiesto estudios empÃricos. Para analizar cuáles son las diferencias individuales en la personalidad de los traductores en la elección del itinerario de especialidad, se ha llevado a cabo un estudio con los estudiantes de los cuatro itinerarios de traducción de la Universidad Jaume I, a fin de ver si podemos identificar los rasgos tÃpicos de los estudiantes de cada itinerario. Además, dada la gran importancia de la personalidad en las tareas de traducción, también se ha entrevistado a responsables de tres agencias de traducción para ver si la personalidad de los traductores es un factor relevante a la hora de reclutar personal. Se ha comprobado asà que sà hay algunos rasgos comunes en la personalidad de los estudiantes de cada itinerario y que realmente esta cuestión no es un factor relevante en las agencias de traducción, sino que se valora, sobre todo, el trabajo diario y la calidad de las pruebas de traducción
Efficient and Stable Low Iridium Loaded Anodes for PEM Water Electrolysis Made Possible by Nanofiber Interlayers
Significant reduction of the precious metal catalyst loading is one of the key challenges for the commercialization of proton-exchange membrane water electrolyzers. In this work we combine IrOx nanofibers with a conventional nanoparticle-based IrOx anode catalyst layer. With this hybrid design we can reduce the iridium loading by more than 80% while maintaining performance. In spite of an ultralow overall catalyst loading of 0.2 mg(Ir)/cm(2), a cell with a hybrid layer shows similar performance compared to a state-of-the-art cell with a catalyst loading of 1.2 mg(Ir)/cm(2) and clearly outperforms identically loaded reference cells with pure IrOx nanoparticle and pure nanofiber anodes. The improved performance is attributed to a combination of good electric contact and high porosity of the IrOx nanofibers with high surface area of the IrOx nanoparticles. Besides the improved performance, the hybrid layer also shows better stability in a potential cycling and a 150 h constant current test compared to an identically loaded nanoparticle reference.BMBF, 05KI9VFA, Ultrahochauflösende Untersuchung des Wassertransports in alkalischen Brennstoff- und Elektrolysezellen mittels Neutronenradiographie und –Tomographie (NeutroSense
Impact of Side Chains of Conjugated Polymers on Electronic Structure: A Case Study
Processing from solution is a crucial aspect of organic semiconductors, as it is at the heart of the promise of easy and inexpensive manufacturing of devices. Introducing alkyl side chains is an approach often used to increase solubility and enhance miscibility in blends. The influence of these side chains on the electronic structure, although highly important for a detailed understanding of the structure-function relationship of these materials, is still barely understood. Here, we use time-resolved electron paramagnetic resonance spectroscopy with its molecular resolution to investigate the role of alkyl side chains on the polymer PCDTBT and a series of its building blocks with increasing length. Comparing our results to the non-hexylated compounds allows us to distinguish four different factors determining exciton delocalization. Detailed quantum-chemical calculations (DFT) allows us to further interpret our spectroscopic data and to relate our findings to the molecular geometry. Alkylation generally leads to more localized excitons, most prominent only for the polymer. Furthermore, singlet excitons are more delocalized than the corresponding triplet excitons, despite the larger dihedral angles within the backbone found for the singlet-state geometries. Our results show TREPR spectroscopy of triplet excitons to be well suited for investigating crucial aspects of the structure-function relationship of conjugated polymers used as organic semiconductors on a molecular basis
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Hexylation Stabilises Twisted Backbone Configurations in the Prototypical Low-Bandgap Copolymer PCDTBT.
Publication status: PublishedConjugated donor-acceptor copolymers hold great potential as materials for high-performance organic photovoltaics, organic transistors and organic thermoelectric devices. Their low optical bandgap is achieved by alternation of donor and acceptor moieties along the polymer chain, leading to a pronounced charge-transfer character of electronic excitations. However, the influence of appended side chains and of chemical defects of the backbone on their photophysical and conformational properties remains largely unexplored on the level of individual chains. Here, we employ room temperature single-molecule photoluminescence spectroscopy on four compounds based on the prototypical copolymer PCDTBT with systematically changed chemical structure. Our results show that an increasing density of statistically added hexyl chains to the TBT comonomer distorts the molecular conformation, likely through the increase of average dihedral angles along the backbone. We find that, although the conformation becomes more twisted with high hexyl density, the side chains appear to stabilize the backbone in this twisted conformation. In addition, we demonstrate that homocoupling defects along the backbone barely influence the PL spectra of single chains, and thus intra-chain electronic properties