Bio-ethylene production: alternatives for green chemicals and polymers

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Bimodal polarons as a function of morphology in high efficiency polymer/acceptor blends for organic photovoltaics

The polymer PffBT4T-C9C13 (poly[(5,6-difluoro-2,1,3-benzothiadiazole-4,7-diyl)[3,3′′′-bis (2-decyltetradecyl)[2,2′:5′,2′′:5′′,2′′ -quaterthiophene]-5,5′′′-diyl]]) produces organic solar cells of >11% efficiency with both fullerenes and non-fullerenes. We present a comprehensive morphology and spectroscopy study of this polymer and its blends, focusing on atomic force microscopy, x-ray diffraction, and transient absorption spectroscopy on microsecond timescales. Unusually, fullerene-induced ordering is observed, with the polymer/fullerene blend displaying a greater crystallinity compared to the pristine polymer. This was correlated with the appearance of bimodal polarons: fast-decaying polarons in the pristine amorphous polymer domains and trapped polarons localised in the fullerene-induced ordering (crystallline) domains. The lifetime of the trapped polaron was significantly enhanced upon thermal annealing, and the complex relationship observed between lifetime and film crystallinity suggest a contribution from trap states at the interfaces between ordered and disordered domains that lead to inhibited recombination. In contrast, blends incorporating the well-known analogue PffBT4T-2OD (with a shorter alkyl chain length) exhibit neither fullerene-induced ordering nor bimodal polarons. However, both PffBT4T-C9C13 and PffBT4T-2OD polymer blends show clear evidence of polymer triplet formation, which is the first time triplets have been identified in PffBT4T-based blends. In this study, we remark upon the complex relationship between morphology and the photophysics. This relationship will open the door to the synthesis of new molecules to control the blend morphology and thus optimise organic photovoltaic performance

Improved Charge Separation and Photovoltaic Performance of BiI3 Absorber Layers by Use of an In Situ Formed BiSI Interlayer

Stable and nontoxic bismuth iodide (BiI3) is emerging as a promising absorber material for solar cell applications as it possesses favorable optical properties such as a narrow bandgap (1.7 eV) and a high absorption coefficient (105 cm–1) in the visible region. Despite these promising features, solar cells employing this material have only achieved power conversion efficiencies in the region of 1% as of yet, which is distant from the theoretical efficiency limit of 28%. It is reasonable to suppose that the relatively low performance of BiI3-based solar cells may originate from very short carrier lifetimes (180–240 ps) in BiI3, which makes efficient separation of mobile charges a crucial factor for the improvement of the photovoltaic performance of this material. Herein, transient optical spectroscopy is employed to show that the use of a bismuth sulfide iodide interlayer between the electron transport layer (ETL) and the bismuth iodide absorber promotes efficient charge separation. On the basis of this knowledge, we report BiI3 solar cells with a power conversion efficiency of 1.21% using a solar cell architecture comprised of ITO/SnO2/BiSI/BiI3/organic HTM/Au

Discerning Bulk and Interfacial Polarons in a Dual Electron Donor/Acceptor Polymer

The active layer of organic solar cells typically possesses a complex morphology, with amorphous donor/acceptor mixed domains present in addition to purer, more crystalline domains. These crystalline domains may represent an energy sink for free charges that aids charge separation and suppresses bimolecular recombination. The first step in exploiting this behavior is the identification and characterization of charges located in these different domains. Herein, the generation and recombination of both bulk and interfacial polarons are demonstrated in the dual electron donor/acceptor polymer XIND using transient absorption spectroscopy. The absorption spectra of XIND bulk polarons, present in pristine polymer domains, are clearly distinguishable from those of polarons present at the donor/acceptor interface. Furthermore, it is shown that photogenerated polarons are transferred from the interface to the bulk. These findings support the energy sink hypothesis and offer a way to maximize morphology relationships to enhance charge generation and suppress recombination

Dual Pharmacological Targeting of HDACs and PDE5 Inhibits Liver Disease Progression in a Mouse Model of Biliary Inflammation and Fibrosis

Liver fibrosis, a common hallmark of chronic liver disease (CLD), is characterized by the accumulation of extracellular matrix secreted by activated hepatic fibroblasts and stellate cells (HSC). Fibrogenesis involves multiple cellular and molecular processes and is intimately linked to chronic hepatic inflammation. Importantly, it has been shown to promote the loss of liver function and liver carcinogenesis. No effective therapies for liver fibrosis are currently available. We examined the anti-fibrogenic potential of a new drug (CM414) that simultaneously inhibits histone deacetylases (HDACs), more precisely HDAC1, 2, and 3 (Class I) and HDAC6 (Class II) and stimulates the cyclic guanosine monophosphate (cGMP)-protein kinase G (PKG) pathway activity through phosphodiesterase 5 (PDE5) inhibition, two mechanisms independently involved in liver fibrosis. To this end, we treated Mdr2-KO mice, a clinically relevant model of liver inflammation and fibrosis, with our dual HDAC/PDE5 inhibitor CM414. We observed a decrease in the expression of fibrogenic markers and collagen deposition, together with a marked reduction in inflammation. No signs of hepatic or systemic toxicity were recorded. Mechanistic studies in cultured human HSC and cholangiocytes (LX2 and H69 cell lines, respectively) demonstrated that CM414 inhibited pro-fibrogenic and inflammatory responses, including those triggered by transforming growth factor β (TGFβ). Our study supports the notion that simultaneous targeting of pro-inflammatory and fibrogenic mechanisms controlled by HDACs and PDE5 with a single molecule, such as CM414, can be a new disease-modifying strateg

The submarine volcano eruption at the island of El Hierro: physical-chemical perturbation and biological response

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Effect of Interfacial Energetics on Charge Transfer from Lead Halide Perovskite to Organic Hole Conductors

The control and optimization of interfacial charge transfer processes is crucial to the design of efficient perovskite solar cells. Herein, we measure the yield and kinetics of hole transfer across the methylammonium lead triiodide perovskite|polymeric hole transport material heterojunction, as a function of the interfacial energy offset, ΔE, between the highest occupied molecular orbital of the hole transport material and the valence band edge of the perovskite. A combination of steady-state and time-resolved photoluminescence, along with transient absorption spectroscopy, revealed that only a small driving energy (ΔE ∼ 0.07 eV) is required to induce highly efficient hole transfer. The findings of this paper suggest that further improvements in the open-circuit voltage, and so the power conversion efficiency, of perovskite solar cells could be achieved by incorporating hole transport materials that provide an interfacial energy offset in the range 0 < ΔE < 0.18 eV