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991.
Here, a near-infrared (NIR)-absorbing small-molecule acceptor (SMA) Y-SeNF with strong intermolecular interaction and crystallinity is developed by combining selenophene-fused core with naphthalene-containing end-group, and then as a custom-tailor guest acceptor is incorporated into the binary PM6:L8-BO host system. Y-SeNF shows a 65 nm red-shifted absorption compared to L8-BO. Thanks to the strong crystallinity and intermolecular interaction of Y-SeNF, the morphology of PM6:L8-BO:Y-SeNF can be precisely regulated by introducing Y-SeNF, achieving improved charge-transporting and suppressed non-radiative energy loss. Consequently, ternary polymer solar cells (PSCs) offer an impressive device efficiency of 19.28% with both high photovoltage (0.873 V) and photocurrent (27.88 mA cm−2), which is one of the highest efficiencies in reported single-junction PSCs. Notably, ternary PSC has excellent stability under maximum-power-point tracking for even over 200 h, which is better than its parental binary devices. The study provides a novel strategy to construct NIR-absorbing SMA for efficient and stable PSCs toward practical applications.  相似文献   
992.
Intelligent micromachines that respond to external light stimuli have a broad range of potential applications, such as microbots, biomedicine, and adaptive optics. However, artificial light-driven intelligent micromachines with a low actuation threshold, rapid responsiveness, and designable and precise 3D transformation capability remain unachievable to date. Here, a single-material and one-step 4D printing strategy are proposed to enable the nanomanufacturing of agile and low-threshold light-driven 3D micromachines with programmable shape-morphing characteristics. The as-developed carbon nanotube-doped composite hydrogel simultaneously enhanced the light absorption, thermal conductivity, and mechanical modulus of the crosslinked network, thus significantly increasing the light sensitivity and response speed of micromachines. Moreover, the structural design and assembly of asymmetric microscale mechanical metamaterial unit cells enable the highly efficient additive nanomanufacturing of 3D shape-morphable micromachines with large dynamic modulation and spatiotemporal controllability. Using this strategy, the world's smallest artificial beating heart with programmable light-stimulus responsiveness for the cardiac cycle is successfully printed. This 4D printing method paves the way for the construction of multifunctional intelligent micromachines for bionics, drug delivery, integrated microsystems, and other fields.  相似文献   
993.
Liquid crystalline polymers (LCPs), especially liquid crystalline elastomers (LCEs) can generate ultrahigh shape change amplitude but has lower mechanical strength. Although some attempts have been tried to improve the mechanical performance of LCE, there are still limitations including complicated fabrication and high actuation temperature. Here, a versatile method is reported to fabricate light-driven actuator by covalently cross-linking polyurethane (PU) into LCP networks (PULCN). This new scheme is distinct from the previous interpenetrating network strategy, the hydrogen bonds and covalent bonds are used in this study to improve the miscibility of non-liquid-crystalline PU and LCP materials and enhance the stability of the composite system. This material not only possesses the shape memory properties of PU but shows shape-changing behavior of LCPs. With a shrinkage ratio of 20% at the phase transition temperature, the prepared materials reached a maximum mechanical strength of 20 MPa, higher than conventional LCP. Meanwhile, the resulting film shows diverse and programmable initial shapes by constructing crosslinking density gradient across the thickness of the film. By integration of PULCN with near-infrared light-responsive polydopamine, local and sequential light control is achieved. This study may provide a new route for the fabrication of programmable and mechanically robust light-driven soft actuator.  相似文献   
994.
Reverse water-gas shift (RWGS) reaction is the initial and necessary step of CO2 hydrogenation to high value-added products, and regulating the selectivity of CO is still a fundamental challenge. In the present study, an efficient catalyst (CuZnNx@C-N) composed by Zn single atoms and Cu clusters stabilized by nitrogen sites is reported. It contains saturated four-coordinate Zn-N4 sites and low valence CuNx clusters. Monodisperse Zn induces the aggregation of pyridinic N to form Zn-N4 and N4 structures, which show strong Lewis basicity and has strong adsorption for *CO2 and *COOH intermediates, but weak adsorption for *CO, thus greatly improves the CO2 conversion and CO selectivity. The catalyst calcined at 700 °C exhibits the highest CO2 conversion of 43.6% under atmospheric pressure, which is 18.33 times of Cu-ZnO and close to the thermodynamic equilibrium conversion rate (49.9%) of CO2. In the catalytic process, CuNx not only adsorbs and activates H2, but also cooperates with the adjacent Zn-N4 and N4 structures to jointly activate CO2 molecules and further promotes the hydrogenation of CO2. This synergistic mechanism will provide new insights for developing efficient hydrogenation catalysts.  相似文献   
995.
Underwater optical communication (UOC) has attracted considerable interest in the continuous expansion of human activities in marine/ocean environments. The water-durable and self-powered photoelectrodes that act as a battery-free light receiver in UOC are particularly crucial, as they may directly face complex underwater conditions. Emerging photoelectrochemical (PEC)-type photodetectors are appealing owing to their intrinsic aqueous operation characteristics with versatile tunability of photoresponses. Herein, a self-powered PEC photodetector employing n-type gallium nitride (GaN) nanowires as a photoelectrode, which is decorated with an iridium oxide (IrOx) layer to optimize charge transfer dynamics at the GaN/electrolyte interface, is reported. Strikingly, the constructed n-GaN/IrOx photoelectrode breaks the responsivity-bandwidth trade-off limit by simultaneously improving the response speed and responsivity, delivering an ultrafast response speed with response/recovery times of only 2 µs/4 µs while achieving a high responsivity of 110.1 mA W−1. Importantly, the device exhibits a large bandwidth with 3 dB cutoff frequency exceeding 100 kHz in UOC tests, which is one of the highest values among self-powered photodetectors employed in optical communication system.  相似文献   
996.
Cobalt phthalocyanine (CoPc) anchored on heterogeneous scaffold has drawn great attention as promising electrocatalyst for carbon dioxide reduction reaction (CO2RR), but the molecule/substrate interaction is still pending for clarification and optimization to maximize the reaction kinetics. Herein, a CO2RR catalyst is fabricated by affixing CoPc onto the Mg(OH)2 substrate primed with conductive carbon, demonstrating an ultra-low overpotential of 0.31 ± 0.03 V at 100 mA cm−2 and high faradaic efficiency of >95% at a wide current density range for CO production, as well as a heavy-duty operation at 100 mA cm−2 for more than 50 h in a membrane electrode assembly. Mechanistic investigations employing in situ Raman and attenuated total reflection surface-enhanced infrared absorption spectroscopy unravel that Mg(OH)2 plays a pivotal role to enhance the CO2RR kinetics by facilitating the first-step electron transfer to form anionic *CO2 intermediates. DFT calculations further elucidate that introducing Lewis acid sites help to polarize CO2 molecules absorbed at the metal centers of CoPc and consequently lower the activation barrier. This work signifies the tailoring of catalyst-support interface at molecular level for enhancing the turnover rate of CO2RR.  相似文献   
997.
Despite the rapid developments are achieved for perovskite solar cells (PSCs), the existence of various defects in the devices still limits the further enhancement of the power conversion efficiency (PCE) and the long-term stability of devices. Herein, the efficient organic potassium salt (OPS) of para-halogenated phenyl trifluoroborates is presented as the precursor additives to improve the performance of PSCs. Studies have shown that the 4-chlorophenyltrifluoroborate potassium salt (4-ClPTFBK) exhibits the most effective interaction with the perovskite lattice. Strong coordination between  BF3/halogen in anion and uncoordinated Pb2+/halide vacancies, along with the hydrogen bond between F in  BF3 and H in FA+ are observed. Thus, due to the synergistic contribution of the potassium and anionic groups, the high-quality perovskite film with large grain size and low defect density is achieved. As a result, the optimal devices show an enhanced efficiency of 24.50%, much higher than that of the control device (22.63%). Furthermore, the unencapsulated devices present remarkable thermal and long-term stability, maintaining 86% of the initial PCE after thermal test at 80 °C for 1000 h and 95% after storage in the air for 2460 h.  相似文献   
998.
Radiotherapy is identified as a crucial treatment for patients with glioblastoma, but recurrence is inevitable. The efficacy of radiotherapy is severely hampered partially due to the tumor evolution. Growing evidence suggests that proneural glioma stem cells can acquire mesenchymal features coupled with increased radioresistance. Thus, a better understanding of mechanisms underlying tumor subclonal evolution may develop new strategies. Herein, data highlighting a positive correlation between the accumulation of macrophage in the glioblastoma microenvironment after irradiation and mesenchymal transdifferentiation in glioblastoma are presented. Mechanistically, elevated production of inflammatory cytokines released by macrophages promotes mesenchymal transition in an NF-κB-dependent manner. Hence, rationally designed macrophage membrane-coated porous mesoporous silica nanoparticles (MMNs) in which therapeutic anti-NF-κB peptides are loaded for enhancing radiotherapy of glioblastoma are constructed. The combination of MMNs and fractionated irradiation results in the blockage of tumor evolution and therapy resistance in glioblastoma-bearing mice. Intriguingly, the macrophage invasion across the blood-brain barrier is inhibited competitively by MMNs, suggesting that these nanoparticles can fundamentally halt the evolution of radioresistant clones. Taken together, the biomimetic MMNs represent a promising strategy that prevents mesenchymal transition and improves therapeutic response to irradiation as well as overall survival in patients with glioblastoma.  相似文献   
999.
Catalysis always proceeds in a chaotic fashion. Therefore, identifying the working principles of heterogeneous catalysts is a challenging task. Creating atomic order in heterogeneous catalysts simplifies this task and also offers new opportunities for rationally designing active sites to manipulate catalytic performance. The recent rapid advances in heterogeneous electrocatalysis have led to exciting progress in the construction of atomically ordered materials. Here, the latest progress in electrocatalysts with the periodic atomic arrangement, including intermetallic compounds with long-range order and metal atom-array catalysts with short-range order is summarized. The synthesis principles and the intriguing physical and chemical properties of these electrocatalysts are discussed. Furthermore, the compelling prospects of atomically ordered catalysts in the frontier of catalyst research are outlined.  相似文献   
1000.
The accumulation of reactive oxygen species (ROS) and minimal osteogenic raw material in the osteoporotic bone microenvironment greatly inhibits the activity of osteoblasts. Herein, it is originally proposed to construct a biomatrix multifaceted bone microenvironment amendment -Mineralized zippered G4-Hemin DNAzyme hydrogel (MDH)-to improve osteoporotic osteogenic capacity and promote high-quality bone defect repair. The programmed design of the rolling circle amplified DNA hydrogel synthesis system allows the introduction of massive amounts of zippered G4-Hemin DNAzyme in MDH. The zippered G4-Hemin DNAzyme highly mimics the tight catalytic configuration of horseradish peroxidase and exerts excellent enzyme-like activity with considerable ROS molecule scavenging ability. In addition, the DNA amplification by-product pyrophosphate is ingeniously employed as a sufficient phosphorus source, thus constituting an autonomous mineralization system for waste reuse through the introduction of pyrophosphate hydrolase and calcium ions, which deposits in MDH as an osteogenic raw material and addresses the challenge of DNA hydrogel bio-application stability. The remarkable in vitro and in vivo outcomes demonstrate that MDH can effectively improve the oxidative stress status of osteoblasts, restore the balance of mitochondrial membrane potential, and reduce apoptosis, ultimately demonstrating superior osteogenic capacity.  相似文献   
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