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861.
蔡岩  苗志伟 《化学通报》2021,84(10):1108-1113,1119
玫瑰红景天具有上千年的药用历史,是我国传统中药中的瑰宝。大量研究表明,玫瑰红景天提取物对人体中枢神经系统、心血管系统以及内分泌系统具有保护和调节作用,尤其在抗疲劳、抗抑郁、抗肿瘤及提高人体免疫力等方面具有独特的药效。本文介绍了玫瑰红景天的药用开发历史及其特征活性成分的功能,以期提高人们对这种传统中药的认识,为进一步开发玫瑰红景天的药用功能提供借鉴和参考。  相似文献   
862.
The responsive color-changing bionic skin imitation of certain organisms such as chameleons has potential applications in the fields of chemical sensing and information transfer. Inspired by the cellular structure of the chameleon iridophores, a flexible and scalable fabrication strategy was proposed in the present study, which centers on the modular assembly of miniature color-changing pixel dots. The color-changing pixel dots were formed by self-assembling charged silica particles inside hydrogels and fabricated in bulk using microfluidic methods. The pixel dots were immobilized in hydrogels to encapsulate in a membrane structure similar to biological skin. With thermal stimulation, the bionic color-changing skin can change color from green to red and has an angle-independent color display with good environmental adaptability.  相似文献   
863.
Enzymatic catalysis with high efficiency allows them a great prospect in metabolite monitoring in living cells. However, complex tumor microenvironments, such as acidity, H2O2, and hypoxia, are bound to disturb catalytic reactions for misleading results. Here, we report a spatially compartmentalized artificial organelle to correct intratumoral glucose analysis, where the zeolitic imidazolate framework-8 immobilized glucose oxidase-horseradish peroxidase cascade core and catalase-directed shell act as signal transduction and guarding rooms respectively. The acid-digested core and stable shell provide appropriate spaces to boost biocatalytic efficiency with good tolerability. Notably, the endogenous H2O2 is in situ decomposed to O2 by catalase, which not only overcomes the interference in signal output but also alleviates the hypoxic states to maximize glucose oxidation. The marked protective effect and biocompatibility render artificial organelles to correct the signal transduction for dynamic monitoring glucose in vitro and in vivo, achieving our goal of accurate intratumoral metabolite analysis.  相似文献   
864.
Sulfur poisoning and regeneration are global challenges for metal catalysts even at the ppm level. The sulfur poisoning of single-metal-site catalysts and their regeneration is worthy of further study. Herein, sulfur poisoning and self-recovery are first presented on an industrialized single-Rh-site catalyst (Rh1/POPs). A decreased turnover frequency of Rh1/POPs from 4317 h−1 to 318 h−1 was observed in a 1000 ppm H2S co-feed for ethylene hydroformylation, but it self-recovered to 4527 h−1 after withdrawal of H2S, whereas the rhodium nanoparticles demonstrated poor activity and self-recovery ability. H2S reduced the charge density of the single Rh atom and lowered its Gibbs free energy with the formation of inactive (SH)Rh(CO)(PPh3-frame)2, which could be regenerated to active HRh(CO)(PPh3-frame)2 after withdrawing H2S. The mechanism and the sulfur-related structure–activity relationship were highlighted. This work provides an understanding of heterogeneous ethylene hydroformylation and sulfur-poisoned regeneration in the science of single-atom catalysts.  相似文献   
865.
The CRISPR/Cas system is one of the most powerful tools for gene editing. However, approaches for precise control of genome editing and regulatory events are still desirable. Here, we report the spatiotemporal and efficient control of CRISPR/Cas9- and Cas12a-mediated editing with conformationally restricted guide RNAs (gRNAs). This approach relied on only two or three pre-installed photo-labile substituents followed by an intramolecular cyclization, representing a robust synthetic method in comparison to the heavily modified linear gRNAs that often require extensive screening and time-consuming optimization. This tactic could direct the precise cleavage of the genes encoding green fluorescent protein (GFP) and the vascular endothelial growth factor A (VEGFA) protein within a predefined cutting region without notable editing leakage in live cells. We also achieved light-mediated myostatin (MSTN) gene editing in embryos, wherein a new bow-knot-type gRNA was constructed with excellent OFF/ON switch efficiency. Overall, our work provides a significant new strategy in CRISPR/Cas editing with modified circular gRNAs to precisely manipulate where and when genes are edited.  相似文献   
866.
Orsellinic acid (OA) derivatives are produced by filamentous fungi using nonreducing polyketide synthases (nrPKSs). The chain-releasing thioesterase (TE) domains of such nrPKSs were proposed to also catalyze dimerization to yield didepsides, such as lecanoric acid. Here, we use combinatorial domain exchanges, domain dissections and reconstitutions to reveal that the TE domain of the lecanoric acid synthase Preu6 of Preussia isomera must collaborate with the starter acyl transferase (SAT) domain from the same nrPKS. We show that artificial SAT-TE fusion proteins are highly effective catalysts and reprogram the ketide homologation chassis to form didepsides. We also demonstrate that dissected SAT and TE domains of Preu6 physically interact, and SAT and TE domains of OA-synthesizing nrPKSs may co-evolve. Our work highlights an unexpected domain–domain interaction in nrPKSs that must be considered for the combinatorial biosynthesis of unnatural didepsides, depsidones, and diphenyl ethers.  相似文献   
867.
Extreme fast charging (XFC) of high-energy Li-ion batteries is a key enabler of electrified transportation. While previous studies mainly focused on improving Li ion mass transport in electrodes and electrolytes, the limitations of charge transfer across electrode–electrolyte interfaces remain underexplored. Herein we unravel how charge transfer kinetics dictates the fast rechargeability of Li-ion cells. Li ion transfer across the cathode–electrolyte interface is found to be rate-limiting during XFC, but the charge transfer energy barrier at both the cathode and anode have to be reduced simultaneously to prevent Li plating, which is achieved through electrolyte engineering. By unlocking charge transfer limitations, 184 Wh kg−1 pouch cells demonstrate stable XFC (10-min charge to 80 %) which is otherwise unachievable, and the lifetime of 245 Wh kg−1 21700 cells is quintupled during fast charging (25-min charge to 80 %).  相似文献   
868.
Multi-resonance thermally activated delayed fluorescence (MR-TADF) materials are considered a class of organic materials with exceptional electronic and optical properties, which make them promising for the applications in organic light-emitting diodes (OLEDs). In this study, we improved, synthesized, and characterized a multiple-resonance type emitter based on the assembly of MR-building blocks (MR-BBs). By optimizing the geometric arrangement of MR-BBs, we were able to generate narrowband emission in the longer wavelength region and shorten the delayed excited-state lifetime, resulting in improved emission efficiency compared to the parent molecule. Our proof-of-concept molecule, m-DBCz, exhibited narrowband yellowish-green TADF emission with a full width at half-maximum of 32 nm and a small singlet-triplet energy gap of 0.04 eV. The OLED developed using m-DBCz as the emitter demonstrated electroluminescence at 548 nm and achieved a high external quantum efficiency (EQE) of 34.9 %. Further optimization of the device resulted in a high external quantum efficiency of 36.3 % and extremely low efficiency roll-off, with EQE values of 30.1 % and 27.7 % obtained even at high luminance levels of 50 000 and 100 000 cd m−2. These results demonstrate the full potential of MR-TADF materials for applications on ultrahigh-luminance OLEDs.  相似文献   
869.
Heterogeneous single-metal-site catalysts usually suffer from poor stability, thereby limiting industrial applications. Dual Pd1−Ru1 single-atom-sites supported on porous ionic polymers (Pd1−Ru1/PIPs) were constructed using a wetness impregnation method. The two isolated metal species in the form of a binuclear complex were immobilized on the cationic framework of PIPs through ionic bonds. Compared to the single Pd- or Ru-site catalyst, the dual single-atom system exhibits higher activity with 98 % acetylene conversion and near 100 % selectivity to dialkoxycarbonylation products, as well as better cycling stability for ten cycles without obvious decay. Based on DFT calculations, it was found that the single-Ru site exhibited a strong CO adsorption energy of −1.6 eV, leading to an increase in the local CO concentration of the catalyst. Notably, the Pd1−Ru1/PIPs catalyst had a much lower energy barrier of 2.49 eV compared to 3.87 eV of Pd1/PIPs for the rate-determining step. The synergetic effect between neighboring single sites Pd1 and Ru1 not only enhanced the overall activity, but also stabilized PdII active sites. The discovery of synergetic effects between single sites can deepen our understanding of single-site catalysts at the molecular level.  相似文献   
870.
Water electrolysis for H2 production is restricted by the sluggish oxygen evolution reaction (OER). Using the thermodynamically more favorable hydrazine oxidation reaction (HzOR) to replace OER has attracted ever-growing attention. Herein, we report a twisted NiCoP nanowire array immobilized with Ru single atoms (Ru1−NiCoP) as superior bifunctional electrocatalyst toward both HzOR and hydrogen evolution reaction (HER), realizing an ultralow working potential of −60 mV and overpotential of 32 mV for a current density of 10 mA cm−2, respectively. Inspiringly, two-electrode electrolyzer based on overall hydrazine splitting (OHzS) demonstrates outstanding activity with a record-high current density of 522 mA cm−2 at cell voltage of 0.3 V. DFT calculations elucidate the cooperative Ni(Co)−Ru−P sites in Ru1−NiCoP optimize H* adsorption, and enhance adsorption of *N2H2 to significantly lower the energy barrier for hydrazine dehydrogenation. Moreover, a self-powered H2 production system utilizing OHzS device driven by direct hydrazine fuel cell (DHzFC) achieve a satisfactory rate of 24.0 mol h−1 m−2.  相似文献   
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