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Luminescent solar concentrators (LSCs) are spectral conversion devices offering interesting opportunities for the integration of photovoltaics into the built environment and portable systems. The Förster-resonance energy transfer (FRET) process can boost the optical response of LSCs by reducing energy losses typically associated to non-radiative processes occurring within the device under operation. In this work, a new class of FRET-based thin-film LSC devices is presented, in which the synthetic versatility of linear polyurethanes (PU) is exploited to control the photophysical properties and the device performance of the resulting LSCs. A series of luminescent linear PUs are synthesized in the presence of two novel bis-hydroxyl-functionalized luminophores of suitable optical properties, used as chain extenders during the step-growth polyaddition reaction for the formation of the linear macromolecular network. By synthetically tuning their composition, the obtained luminescent PUs can achieve a high energy transfer efficiency (≈90%) between the covalently linked luminophores. The corresponding LSC devices exhibit excellent photonic response, with external and internal photon efficiencies as high as ≈4% and ≈37%, respectively. Furthermore, their optimized power conversion efficiency combined with their enhanced average visible-light transmittance highlight their suitability for potential use as transparent solar energy devices.
Assuntos
Transferência de Energia , Transferência Ressonante de Energia de Fluorescência , Poliuretanos , Energia Solar , Poliuretanos/química , Luminescência , Estrutura MolecularRESUMO
The present review summarizes the work carried out mostly in the last decade on iridium and ruthenium complexes bearing various perylene ligands, of particular interest for bioimaging, photodynamic therapy, and solar energy conversion. In these complexes, the absorption spectra and the electrochemical properties are those of the perylene subunit plus those of the metal moiety. In contrast, the emissions are completely changed with respect to perylenes considered alone. Thus, fully organic perylenes are characterized by a strong fluorescence in the visible region, lifetimes of a few nanoseconds, and luminescence quantum yields approaching 100%, whereas perylene Ir and Ru complexes usually do not emit; however, in few cases, weak phosphorescent emissions, with lifetimes in the range of microseconds and relatively low quantum yields, are reported. This is due to a strong interaction between the perylene core and the heavy metal center, taking place after the excitation. Nevertheless, an important advantage deriving from the presence of the heavy metal center is represented by the ability to generate large amounts of singlet oxygen, which plays a key role in photodynamic therapy.
Assuntos
Perileno , Rutênio , Irídio/química , Rutênio/química , Ligantes , LuminescênciaRESUMO
Three decades ago, dye-sensitized solar cells (DSSCs) emerged as a method for harnessing the energy of the sun and for converting it into electricity. Since then, a lot of work has been devoted to create better global photovoltaic efficiencies and long term stability. Among photosensitizers for DSSCs, thiocyanate-free ruthenium(II) complexes have gained increasing interest due to their better stability compared to conventional thiocyanate-based complexes, such as benchmark dyes N719 and Z907. In this mini-review, two classes of thiocyanate-free Ru(II) complexes are presented: (a) bis-bipyridyl compounds bearing an ancillary cyclometalating bidentate ligand; (b) bipyridyl compounds bearing non-cyclometalating ancillary ligands. The coverage, mainly from 2014 up to now, is not exhaustive, but illustrates the most recent design strategies and photovoltaic properties of these two families of ruthenium(II) dyes.
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Organic room temperature persistent luminescence is a fascinating but still largely unexplored phenomenon. Cyclic-triimidazole and its halogenated (Br, I) derivatives have recently revealed as intriguing phosphors characterized by multifaceted emissive behavior including room temperature ultralong phosphorescence (RTUP) associated with the presence of H-aggregates in their crystal structure. Here, we move towards a multicomponent system by incorporating a fluoropyridinic fragment on the cyclic-triimidazole scaffold. Such chromophore enhances the molecular properties resulting in a high photoluminescence quantum yield (PL QY) in solution but preserves the solid-state RTUP. By means of X-ray diffraction (XRD) analysis, theoretical calculations, steady-state and time-resolved spectroscopy on solutions, polymethylmethacrylate (PMMA) blends and crystals, the nature of the different radiative deactivation channels of the compound has been disclosed. In particular, the molecular fluorescence and phosphorescence, this latter observed in frozen solution and in PMMA blends, are associated to deactivation from S1 and T1 respectively, while the low energy RTUP, observed only for crystals, is interpreted as originated from H aggregates.
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Fluorescência , Luminescência , Temperatura , Triazinas/química , Teoria da Densidade Funcional , Análise EspectralRESUMO
We propose a new type of photonic analog-to-digital converter (ADC), designed for high-resolution (>7 bit) and high sampling rates (scalable to tens of GS/s). It is based on encoding the input analog voltage signal onto the phase of an optical pulse stream originating from a mode-locked laser, and uses spatial oversampling as a means to improve the conversion resolution. This paper describes the concept of spatial oversampling and draws its similarities to the commonly used temporal oversampling. The design and fabrication of a LiNbO(3)/silica hybrid photonic integrated circuit for implementing the spatial oversampling is shown, and its abilities are demonstrated experimentally by digitizing gigahertz signals (frequencies up to 18GHz) at an undersampled rate of 2.56GS/s with a conversion resolution of up to 7.6 effective bits. Oversampling factors of 1-4 are demonstrated.
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Windthrows seriously affect forest landscapes, causing several issues in hydrological and geomorphological terms. In this regard, Airborne Laser Scanning (ALS) topographic data recently increased the opportunity to investigate in detail physical processes at the catchment scale. Moreover, topographically based hydrological and geomorphological models allow quantifying runoff alteration due to windthrows-driven land cover changes and detect the occurrence of land degradative processes at the sub-catchment scale. In this connection, accurate investigations about windthrows role in varying local runoff regimes over time are still obscure, as well as the possibility of predicting terrain instabilities due to windstorm occurrence. This research aims to investigate the interaction between windthrows, runoff alterations and hillslope failures affecting a landslide-prone mountain catchment (northern Italy). Hydrological HEC-HMS and geomorphological RESS models were applied. Windthrows' role in altering runoff regimes and hillslope stability was investigated starting from the elaboration of ALS-derived points clouds acquired before and after the occurrence of the Vaia storm. Digital Terrain Models (DTMs) were elaborated for the two scenarios to compare daily runoff variations and predict the activation of terrain instabilities by looking at land cover changes driven by the blowdown event at the sub-catchment detail. Results attested the key role of windstorms in altering local runoff, with a maximum relative runoff increment equal to 2.56 % and a maximum runoff difference equal to 3.12 mmh-1, as well as in encouraging the activation of the observed shallow landslide. The correlation between windthrows occurrence and runoff alterations was validated by performing regression analysis (R2 = 0.76), while the accuracy of instabilities predictions was tested through the Distance to Perfect Classification (D2PC) index and True Skill Statistic (TSS) score, respectively resulted equal to 0.076 and 0.898. This research represents a valid tool for investigating similar issues at a wider scale, also providing suggestions for promoting interventions in wind-disturbed forest areas.
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A limitation of pooled CRISPR-Cas9 screens is the high false-positive rate in detecting essential genes arising from copy-number-amplified genomics regions. To solve this issue, we previously developed CRISPRcleanR: a computational method implemented as R/python package and in a dockerized version. CRISPRcleanR detects and corrects biased responses to CRISPR-Cas9 targeting in an unsupervised fashion, accurately reducing false-positive signals while maintaining sensitivity in identifying relevant genetic dependencies. Here, we present CRISPRcleanR WebApp , a web application enabling access to CRISPRcleanR through an intuitive interface. CRISPRcleanR WebApp removes the complexity of R/python language user interactions; provides user-friendly access to a complete analytical pipeline, not requiring any data pre-processing and generating gene-level summaries of essentiality with associated statistical scores; and offers a range of interactively explorable plots while supporting a more comprehensive range of CRISPR guide RNAs' libraries than the original package. CRISPRcleanR WebApp is available at https://crisprcleanr-webapp.fht.org/.