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We report a catalyst family of high-entropy alloy (HEA) atomic layers having three elements from iron-group metals (IGMs) and two elements from platinum-group metals (PGMs). Ten distinct quinary compositions of IGM-PGM-HEA with precisely controlled square atomic arrangements are used to explore their impact on hydrogen evolution reaction (HER) and hydrogen oxidation reaction (HOR). The PtRuFeCoNi atomic layers perform enhanced catalytic activity and durability toward HER and HOR when benchmarked against the other IGM-PGM-HEA and commercial Pt/C catalysts. Operando synchrotron x-ray absorption spectroscopy and density functional theory simulations confirm the cocktail effect arising from the multielement composition. This effect optimizes hydrogen-adsorption free energy and contributes to the remarkable catalytic activity observed in PtRuFeCoNi. In situ electron microscopy captures the phase transformation of metastable PtRuFeCoNi during the annealing process. They transform from random atomic mixing (25°C), to ordered L10 (300°C) and L12 (400°C) intermetallic, and finally phase-separated states (500°C).
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The current bottleneck in the development of efficient photocatalysts for hydrogen evolution is the limited availability of high-performance acceptor units. Over the past nine years, dibenzo[b,d]thiophene sulfone (DBS) has been the preferred choice for the acceptor unit. Despite extensive exploration of alternative structures as potential replacements for DBS, a superior substitute remains elusive. In this study, a symmetry-breaking strategy was employed on DBS to develop a novel acceptor unit, BBTT-1SO. The asymmetric structure of BBTT-1SO proved beneficial for increasing multiple moment and polarizability. BBTT-1SO-containing polymers showed higher efficiencies for hydrogen evolution than their DBS-containing counterparts by up to 166 %. PBBTT-1SO exhibited an excellent hydrogen evolution rate (HER) of 222.03â mmol g-1 h-1 and an apparent quantum yield of 27.5 % at 500â nm. Transient spectroscopic studies indicated that the BBTT-1SO-based polymers facilitated electron polaron formation, which explains their superior HERs. PBBTT-1SO also showed 14 % higher HER in natural seawater splitting than that in deionized water splitting. Molecular dynamics simulations highlighted the enhanced water-PBBTT-1SO polymer interactions in salt-containing solutions. This study presents a pioneering example of a substitute acceptor unit for DBS in the construction of high-performance photocatalysts for hydrogen evolution.
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The presynaptic SNARE-complex regulator complexin (Cplx) enhances the fusogenicity of primed synaptic vesicles (SVs). Consequently, Cplx deletion impairs action potential-evoked transmitter release. Conversely, though, Cplx loss enhances spontaneous and delayed asynchronous release at certain synapse types. Using electrophysiology and kinetic modeling, we show that such seemingly contradictory transmitter release phenotypes seen upon Cplx deletion can be explained by an additional of Cplx in the control of SV priming, where its ablation facilitates the generation of a "faulty" SV fusion apparatus. Supporting this notion, a sequential two-step priming scheme, featuring reduced vesicle fusogenicity and increased transition rates into the faulty primed state, reproduces all aberrations of transmitter release modes and short-term synaptic plasticity seen upon Cplx loss. Accordingly, we propose a dual presynaptic function for the SNARE-complex interactor Cplx, one as a "checkpoint" protein that guarantees the proper assembly of the fusion machinery during vesicle priming, and one in boosting vesicle fusogenicity.
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Sinapsis , Vesículas Sinápticas , Sinapsis/metabolismo , Vesículas Sinápticas/metabolismo , Potenciales de Acción , Proteínas del Tejido Nervioso/genética , Proteínas del Tejido Nervioso/metabolismo , Proteínas SNARE/genética , Proteínas SNARE/metabolismo , Transmisión Sináptica/fisiologíaRESUMEN
Activation of inert CO2 molecules for the reverse water gas shift (RWGS) reaction is tackled by incorporating magnesium oxide as a support material for copper, forming a Cu/MgO supported catalyst. The RWGS performance is greatly improved when compared with pure Cu or carbon supported Cu (Cu/C). Operating under a weight hourly space velocity (WHSV) of 300,000â mL â g-1 â h-1, the Cu/MgO catalyst demonstrates high activity, maintaining over 70 % equilibrium conversion and nearly 100 % CO selectivity in a temperature range of 300-600 °C. In contrast, both Cu/C and commercial Cu, even at ten-times lower WHSV, can only achieve up to 40 % of the equilibrium conversion and quickly deactivated due to sintering. Based on the studies of in-situ temperature resolved infrared spectroscopy and temperature programmed desorption, the improved RWGS performance is attributed to the unique adsorption behavior of CO2 on Cu/MgO. Density functional theory studies provides a plausible explanation from a surface reaction perspective and reveals the spill-over property of CO2 from MgO to Cu being critical.
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Designing an organic polymer photocatalyst for efficient hydrogen evolution with visible and near-infrared (NIR) light activity is still a major challenge. Unlike the common behavior of gradually increasing the charge recombination while shrinking the bandgap, we present here a series of polymer nanoparticles (Pdots) based on ITIC and BTIC units with different π-linkers between the acceptor-donor-acceptor (A-D-A) repeated moieties of the polymer. These polymers act as an efficient single polymer photocatalyst for H2 evolution under both visible and NIR light, without combining or hybridizing with other materials. Importantly, the difluorothiophene (ThF) π-linker facilitates the charge transfer between acceptors of different repeated moieties (A-D-A-(π-Linker)-A-D-A), leading to the enhancement of charge separation between D and A. As a result, the PITIC-ThF Pdots exhibit superior hydrogen evolution rates of 279 µmol/h and 20.5 µmol/h with visible (>420 nm) and NIR (>780 nm) light irradiation, respectively. Furthermore, PITIC-ThF Pdots exhibit a promising apparent quantum yield (AQY) at 700 nm (4.76%).
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Catalytic hydrogenolysis is a promising approach to transform waste plastic into valuable chemicals. However, the transformation of N-containing polymers, such as polyamides (i.e. nylon), remains under-investigated, particularly by heterogeneous catalysis. Here, we demonstrate the hydrogenolysis of various polyamides catalysed by platinum-group metal nanoparticles supported on CeO2. Ru/CeO2 and Pt/CeO2 are both highly active but display different selectivity; Ru/CeO2 is selective for the conversion of all polyamides into water, ammonia, and methane, whereas Pt/CeO2 yields hydrocarbons retaining the carbon backbone of the parent polyamide. Density functional theory computations illustrate that Pt nanoparticles require higher activation energy for carbon-carbon bond cleavage than Ru nanoparticles, rationalising the observed selectivity. The high activity and product selectivity of both catalysts was maintained when converting real-world polyamide products, such as fishing net. This study provides a mechanistic basis for heterogeneously catalysed polyamide hydrogenolysis, and a new approach to the valorisation of polyamide containing waste.
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By considering only one electronic state per molecule, charge transport models of molecular solids neglect intramolecular charge transfer. This approximation excludes materials with quasi-degenerate spatially separated frontier orbitals, such as non-fullerene acceptors (NFAs) and symmetric thermally activated delayed fluorescence emitters. By analyzing the electronic structure of room-temperature molecular conformers of a prototypical NFA, ITIC-4F, we conclude that the electron is localized on one of the two acceptor blocks with the mean intramolecular transfer integral of 120 meV, which is comparable with intermolecular couplings. Therefore, the minimal basis for acceptor-donor-acceptor (A-D-A) molecules consists of two molecular orbitals localized on the acceptor blocks. This basis is robust even with respect to geometry distortions in an amorphous solid, in contrast to the basis of two lowest unoccupied canonical molecular orbitals withstanding only thermal fluctuations in a crystal. The charge carrier mobility can be underestimated by a factor of two when using single site approximation for A-D-A molecules in their typical crystalline packings.
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A common obstacle of many organic semiconductors is that they show highly unipolar charge transport. This unipolarity is caused by trapping of either electrons or holes by extrinsic impurities, such as water or oxygen. For devices that benefit from balanced transport, such as organic light-emitting diodes, organic solar cells and organic ambipolar transistors, the energy levels of the organic semiconductors are ideally situated within an energetic window with a width of 2.5 eV where charge trapping is strongly suppressed. However, for semiconductors with a band gap larger than this window, as used in blue-emitting organic light-emitting diodes, the removal or disabling of charge traps poses a longstanding challenge. Here we demonstrate a molecular strategy where the highest occupied molecular orbital and lowest unoccupied molecular orbital are spatially separated on different parts of the molecules. By tuning their stacking by modification of the chemical structure, the lowest unoccupied molecular orbitals can be spatially protected from impurities that cause electron trapping, increasing the electron current by orders of magnitude. In this way, the trap-free window can be substantially broadened, opening a path towards large band gap organic semiconductors with balanced and trap-free transport.
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Conjugated polymers (CPs) have recently gained increasing attention as photocatalysts for sunlight-driven hydrogen evolution. However, they suffer from insufficient electron output sites and poor solubility in organic solvents, severely limiting their photocatalytic performance and applicability. Herein, solution-processable all-acceptor (A1 -A2 )-type CPs based on sulfide-oxidized ladder-type heteroarene are synthesized. A1 -A2 -type CPs showed upsurging efficiency improvements by two to three orders of magnitude, compared to their donor-acceptor -type CP counterparts. Furthermore, by seawater splitting, PBDTTTSOS exhibited an apparent quantum yield of 18.9% to 14.8% at 500 to 550 nm. More importantly, PBDTTTSOS achieved an excellent hydrogen evolution rate of 35.7 mmol h-1 g-1 and 150.7 mmol h-1 m-2 in the thin-film state, which is among the highest efficiencies in thin film polymer photocatalysts to date. This work provides a novel strategy for designing polymer photocatalysts with high efficiency and broad applicability.
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High-entropy alloy (HEA) nanocrystals have attracted extensive attention in catalysis. However, there are no effective strategies for synthesizing them in a controllable and predictable manner. With quinary HEA nanocrystals made of platinum-group metals as an example, we demonstrate that their structures with spatial compositions can be predicted by quantitatively knowing the reduction kinetics of metal precursors and entropy of mixing in the nanocrystals under dropwise addition of the mixing five-metal precursor solution. The time to reach a steady state for each precursor plays a pivotal role in determining the structures of HEA nanocrystals with homogeneous alloy and core-shell features. Compared to the commercial platinum/carbon and phase-separated counterparts, the dendritic HEA nanocrystals with a defect-rich surface show substantial enhancement in catalytic activity and durability toward both hydrogen evolution and oxidation. This quantitative study will lead to a paradigm shift in the design of HEA nanocrystals, pushing away from the trial-and-error approach.
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Mitochondrial dysfunction induced by acute cardiac ischemia-reperfusion (IR), may increase susceptibility to arrhythmias by perturbing energetics, oxidative stress production and calcium homeostasis. Although changes in mitochondrial morphology are known to impact on mitochondrial function, their role in cardiac arrhythmogenesis is not known. To assess action potential duration (APD) in cardiomyocytes from the Mitofusins-1/2 (Mfn1/Mfn2)-double-knockout (Mfn-DKO) compared to wild-type (WT) mice, optical-electrophysiology was conducted. To measure conduction velocity (CV) in atrial and ventricular tissue from the Mfn-DKO and WT mice, at both baseline and following simulated acute IR, multi-electrode array (MEA) was employed. Intracellular localization of connexin-43 (Cx43) at baseline was evaluated by immunohistochemistry, while Cx-43 phosphorylation was assessed by Western-blotting. Mfn-DKO cardiomyocytes demonstrated an increased APD. At baseline, CV was significantly lower in the left ventricle of the Mfn-DKO mice. CV decreased with simulated-ischemia and returned to baseline levels during simulated-reperfusion in WT but not in atria of Mfn-DKO mice. Mfn-DKO hearts displayed increased Cx43 lateralization, although phosphorylation of Cx43 at Ser-368 did not differ. In summary, Mfn-DKO mice have increased APD and reduced CV at baseline and impaired alterations in CV following cardiac IR. These findings were associated with increased Cx43 lateralization, suggesting that the mitofusins may impact on post-MI cardiac-arrhythmogenesis.
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Conservadores de la Densidad Ósea , Traumatismos Craneocerebrales , Ratones , Animales , Electrofisiología Cardíaca , IsquemiaRESUMEN
Glutamatergic synapses display variable strength and diverse short-term plasticity (STP), even for a given type of connection. Using nonnegative tensor factorization and conventional state modeling, we demonstrate that a kinetic scheme consisting of two sequential and reversible steps of release-machinery assembly and a final step of synaptic vesicle (SV) fusion reproduces STP and its diversity among synapses. Analyzing transmission at the calyx of Held synapses reveals that differences in synaptic strength and STP are not primarily caused by variable fusion probability (pfusion) but are determined by the fraction of docked synaptic vesicles equipped with a mature release machinery. Our simulations show that traditional quantal analysis methods do not necessarily report pfusion of SVs with a mature release machinery but reflect both pfusion and the distribution between mature and immature priming states at rest. Thus, the approach holds promise for a better mechanistic dissection of the roles of presynaptic proteins in the sequence of SV docking, two-step priming, and fusion. It suggests a mechanism for activity-induced redistribution of synaptic efficacy.
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Fusión de Membrana , Plasticidad Neuronal , Sinapsis , Vesículas Sinápticas , Exocitosis , Sinapsis/fisiología , Transmisión Sináptica , Vesículas Sinápticas/fisiologíaRESUMEN
The field of organic semiconductors is multifaceted and the potentially suitable molecular compounds are very diverse. Representative examples include discotic liquid crystals, dye-sensitized solar cells, conjugated polymers, and graphene-based low-dimensional materials. This huge variety not only represents enormous challenges for synthesis but also for theory, which aims at a comprehensive understanding and structuring of the plethora of possible compounds. Eventually computational methods should point to new, better materials, which have not yet been synthesized. In this perspective, it is shown that the answer to this question rests upon the delicate balance between computational efficiency and accuracy of the methods used in the virtual screening. To illustrate the fundamentals of virtual screening, chemical design of non-fullerene acceptors, thermally activated delayed fluorescence emitters, and nanographenes are discussed.
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During ongoing presynaptic action potential (AP) firing, transmitter release is limited by the availability of release-ready synaptic vesicles (SVs). The rate of SV recruitment (SVR) to release sites is strongly upregulated at high AP frequencies to balance SV consumption. We show that Munc13-1-an essential SV priming protein-regulates SVR via a Ca2+-phospholipid-dependent mechanism. Using knockin mouse lines with point mutations in the Ca2+-phospholipid-binding C2B domain of Munc13-1, we demonstrate that abolishing Ca2+-phospholipid binding increases synaptic depression, slows recovery of synaptic strength after SV pool depletion, and reduces temporal fidelity of synaptic transmission, while increased Ca2+-phospholipid binding has the opposite effects. Thus, Ca2+-phospholipid binding to the Munc13-1-C2B domain accelerates SVR, reduces short-term synaptic depression, and increases the endurance and temporal fidelity of neurotransmission, demonstrating that Munc13-1 is a core vesicle priming hub that adjusts SV re-supply to demand.
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Fosfolípidos , Transmisión Sináptica , Potenciales de Acción , Animales , Calcio/metabolismo , Ratones , Plasticidad Neuronal/fisiología , Fosfolípidos/metabolismo , Transmisión Sináptica/fisiología , Vesículas Sinápticas/metabolismoRESUMEN
Thermally-activated delayed fluorescence (TADF) is a concept which helps to harvest triplet excitations, boosting the efficiency of an organic light-emitting diode. TADF can be observed in molecules with spatially separated donor and acceptor groups with a reduced triplet-singlet energy level splitting. TADF materials with balanced electron and hole transport are attractive for realizing efficient single-layer organic light emitting diodes, greatly simplifying their manufacturing and improving their stability. Our goal here is to computationally screen such materials and provide a comprehensive database of compounds with a range of emission wavelengths, ionization energies, and electron affinities.
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The use of crystal engineering to control the supramolecular arrangement of π-conjugated molecules in the solid-state is of considerable interest for the development of novel organic electronic materials. In this study, we investigated the effect of combining of two types of supramolecular interaction with different geometric requirements, amide hydrogen bonding and π-interactions, on the π-overlap between calamitic π-conjugated cores. To this end, we prepared two series of bithiophene diesters and diamides with methylene, ethylene, or propylene spacers between the bithiophene core and the functional groups in their terminal substituents. The hydrogen-bonded bithiophene diamides showed significantly denser packing of the bithiophene cores than the diesters and other known α,ω-disubstituted bithiophenes. The bithiophene packing density reach a maximum in the bithiophene diamide with an ethylene spacer, which had the smallest longitudinal bithiophene displacement and infinite 1D arrays of electronically conjugated, parallel, and almost linear N-Hâ â â O=C hydrogen bonds. The synergistic hydrogen bonding and π-interactions were attributed to the favorable conformation mechanics of the ethylene spacer and resulted in H-type spectroscopic aggregates in solid-state absorption spectroscopy. These results demonstrate that the optoelectronic properties of π-conjugated materials in the solid-state may be tailored systematically by side-chain engineering, and hence that this approach has significant potential for the design of organic and polymer semiconductors.
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We present a fragment-based decomposition analysis tool (FB-ECDA) for the electronic coupling of charge transfer processes. This tool provides insight on the sophisticated relationship between molecular packing, electronic coupling, and the molecular transport network present in organic amorphous semiconductors. On the basis of atomic orbitals, FB-ECDA decomposes the total electronic coupling into individual electronic coupling terms arising from each molecular building blocks in a straightforward manner. The usefulness of this approach is demonstrated by revealing the structure-packing-property relationships for two series of molecules differing by the number of arm substituents and acene core length. Overall, we provide insight on the design of organic semiconductors exhibiting efficient charge transport network through achieving a subtle balance between molecular packing and electronic structure. We expect FB-ECDA to be a valuable tool for understanding sophisticated charge transfer processes in amorphous systems and guiding the rational design of organic semiconductors.
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Despite organic/inorganic lead halide perovskite solar cells becoming one of the most promising next-generation photovoltaic materials, instability under heat and light soaking remains unsolved. In this work, a highly hydrophobic cation, perfluorobenzylammonium iodide (5FBzAI), is designed and a 2D perovskite with reinforced intermolecular interactions is engineered, providing improved passivation at the interface that reduces charge recombination and enhances cell stability compared with benchmark 2D systems. Motivated by the strong halogen bond interaction, (5FBzAI)2PbI4 used as a capping layer aligns in in-plane crystal orientation, inducing a reproducible increase of ≈60 mV in the V oc, a twofold improvement compared with its analogous monofluorinated phenylethylammonium iodide (PEAI) recently reported. This endows the system with high power conversion efficiency of 21.65% and extended operational stability after 1100 h of continuous illumination, outlining directions for future work.
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We present a fragment-based decomposition analysis tool (FB-REDA) for the reorganisation energy (λ). This tool delivers insights on how to rationally design low-λ organic semiconductors. The contribution of the fragment vibrational modes to the reorganization energy is exploited to identity the individual contributions of the molecular building blocks. The usefulness of the approach is demonstrated by offering three strategies to reduce the reorganization energy of a promising dopant-free hole transport material (TPA1PM, λ = 213 meV). A reduction of nearly 50% (TPD3PM, λ = 108 meV) is achieved. The proposed design principles are likely transferable to other organic semiconductors exploiting common molecular building blocks.
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The mechanism of aggregation-induced emission, which overcomes the common aggregation-caused quenching problem in organic optoelectronics, is revealed by monitoring the real time structural evolution and dynamics of electronic excited state with frequency and polarization resolved ultrafast UV/IR spectroscopy and theoretical calculations. The formation of Woodward-Hoffmann cyclic intermediates upon ultraviolet excitation is observed in dilute solutions of tetraphenylethylene and its derivatives but not in their respective solid. The ultrafast cyclization provides an efficient nonradiative relaxation pathway through crossing a conical intersection. Without such a reaction mechanism, the electronic excitation is preserved in the molecular solids and the molecule fluoresces efficiently, aided by the very slow intermolecular charge and energy transfers due to the well separated molecular packing arrangement. The mechanisms can be general for tuning the properties of chromophores in different phases for various important applications.