敏化型电致发光器件原理与技术

近年来,高性能荧光有机电致发光器件(FOLEDs)的开发受到了广泛关注。由于荧光材料仅能利用25%的单重态激子辐射发光,FOLEDs的外量子效率(EQE)理论极限为5%。通过能量转移,充分利用主体分子的单重态与三重态激子敏化荧光客体发光,可以提高激子利用率。目前敏化型FOLEDs(SFOLEDs)的最高EQE已达26.1%。本文详细介绍了SFOLEDs的敏化原理和机制,并根据敏化机制的不同,系统地总结了热活化延迟荧光敏化、激基复合物敏化、三重态湮灭敏化和局域电荷转移杂化激发态(HLCT)敏化等各类SFOLEDs的材料与器件结构特点及其研究进展。最后本综述对该类器件的研究前景进行了展望,期待吸引更多专业的研究人员的研究兴趣,进而推动该领域的发展。     

催化还原降解Cr(Ⅵ)

工业化的快速发展导致含有六价铬(Cr(Ⅵ))的废水排放量日益增加,Cr(Ⅵ)的毒性和高流动性造成极大的环境污染问题。将Cr(Ⅵ)还原成低毒性和低流动性三价铬(Cr(Ⅲ))是当前的有效处理方式之一。与传统方法相比,利用太阳光、电和微波等驱动氧化还原反应进行Cr(Ⅵ)降解,无催化剂消耗,还原剂用量少,且不会造成二次污染和有限资源损耗,成为处理Cr(Ⅵ)污染的有效解决方案。基于此,本文综述了光催化剂、电催化剂及微波催化剂等在还原Cr(Ⅵ)领域的应用现状,在总结分析前人研究成果的基础上,对今后Cr(Ⅵ) 催化还原技术的研究方向和重点进行了展望。     

Computational Insights into Allosteric Conformational Modulation of P-Glycoprotein by Substrate and Inhibitor Binding

The ATP-binding cassette (ABC) transporter P-glycoprotein (P-gp) is a physiologically essential membrane protein that protects many tissues against xenobiotic molecules, but limits the access of chemotherapeutics into tumor cells, thus contributing to multidrug resistance. The atomic-level mechanism of how substrates and inhibitors differentially affect the ATP hydrolysis by P-gp remains to be elucidated. In this work, atomistic molecular dynamics simulations in an explicit membrane/water environment were performed to explore the effects of substrate and inhibitor binding on the conformational dynamics of P-gp. Distinct differences in conformational changes that mainly occurred in the nucleotide-binding domains (NBDs) were observed from the substrate- and inhibitor-bound simulations. The binding of rhodamine-123 can increase the probability of the formation of an intermediate conformation, in which the NBDs were closer and better aligned, suggesting that substrate binding may prime the transporter for ATP hydrolysis. By contrast, the inhibitor QZ-Leu stabilized NBDs in a much more separated and misaligned conformation, which may result in the deficiency of ATP hydrolysis. The significant differences in conformational modulation of P-gp by substrate and inhibitor binding provided a molecular explanation of how these small molecules exert opposite effects on the ATPase activity. A further structural analysis suggested that the allosteric communication between transmembrane domains (TMDs) and NBDs was primarily mediated by two intracellular coupling helices. Our computational simulations provide not only valuable insights into the transport mechanism of P-gp substrates, but also for the molecular design of P-gp inhibitors.     

Accelerated Nuclear Magnetic Resonance Spectroscopy with Deep Learning

Nuclear magnetic resonance (NMR) spectroscopy serves as an indispensable tool in chemistry and biology but often suffers from long experimental times. We present a proof‐of‐concept of the application of deep learning and neural networks for high‐quality, reliable, and very fast NMR spectra reconstruction from limited experimental data. We show that the neural network training can be achieved using solely synthetic NMR signals, which lifts the prohibiting demand for a large volume of realistic training data usually required for a deep learning approach.     

Highly Selective Production of Ethylene by the Electroreduction of Carbon Monoxide

Conversion of carbon monoxide to high value‐added ethylene with high selectivity by traditional syngas conversion process is challenging because of the limitation of Anderson‐Schulz–Flory distribution. Herein we report a direct electrocatalytic process for highly selective ethylene production from CO reduction with water over Cu catalysts at room temperature and ambient pressure. An unprecedented 52.7 % Faradaic efficiency of ethylene formation is achieved through optimization of cathode structure to facilitate CO diffusion at the surface of the electrode and Cu catalysts to enhance the C?C bond coupling. The highly selective ethylene production is almost without other carbon‐based byproducts (e.g. C₁–C₄ hydrocarbons and CO₂) and avoids the drawbacks of the traditional Fischer–Tropsch process that always delivers undesired products. This study provides a new and promising strategy for highly selective production of ethylene from the abundant industrial CO.     

Responsive Exosome Nano‐bioconjugates for Synergistic Cancer Therapy

Exosomes hold great potential in therapeutic development. However, native exosomes usually induce insufficient effects in vivo and simply act as drug delivery vehicles. Herein, we synthesize responsive exosome nano‐bioconjugates for cancer therapy. Azide‐modified exosomes derived from M1 macrophages are conjugated with dibenzocyclooctyne‐modified antibodies of CD47 and SIRPα (aCD47 and aSIRPα) through pH‐sensitive linkers. After systemic administration, the nano‐bioconjugates can actively target tumors through the specific recognition between aCD47 and CD47 on the tumor cell surface. In the acidic tumor microenvironment, the benzoic‐imine bonds of the nano‐bioconjugates are cleaved to release aSIRPα and aCD47 that can, respectively, block SIRPα on macrophages and CD47, leading to abolished “don't eat me” signaling and improved phagocytosis of macrophages. Meanwhile, the native M1 exosomes effectively reprogram the macrophages from pro‐tumoral M2 to anti‐tumoral M1.     

Unraveling the Impact of Gold(I)–Thiolate Motifs on the Aggregation‐Induced Emission of Gold Nanoclusters

Aggregation‐induced emission (AIE) provides an efficient strategy to synthesize highly luminescent metal nanoclusters (NCs), however, rational control of emission energy and intensity of metal NCs is still challenging. This communication reveals the impact of surface Au^I‐thiolate motifs on the AIE properties of Au NCs, by employing a series of water‐soluble glutathione (GSH)‐coordinated Au complexes and NCs as a model ([Au₁₀SR₁₀], [Au₁₅SR₁₃], [Au₁₈SR₁₄], and [Au₂₅SR₁₈]^?, SR=thiolate ligand). Spectroscopic investigations show that the emission wavelength of Au NCs is adjustable from visible to the near‐infrared II (NIR‐II) region by controlling the length of the Au^I‐SR motifs on the NC surface. Decreasing the length of Au^I‐SR motifs also changes the origin of cluster luminescence from AIE‐type phosphorescence to Au⁰‐core‐dictated fluorescence. This effect becomes more prominent when the degree of aggregation of Au NCs increases in solution.     

Modular Synthesis of Nona‐Decasaccharide Motif from Psidium guajava Polysaccharides: Orthogonal One‐Pot Glycosylation Strategy

The synthesis of long, branched, and complex carbohydrate sequences remains a challenging task in chemical synthesis. Reported here is an efficient and modular one‐pot synthesis of a nona‐decasaccharide and shorter sequences from Psidium guajava polysaccharides, which have the potent α‐glucosidase inhibitory activity. The synthetic strategy features: 1) several one‐pot glycosylation reactions on the basis of N‐phenyltrifluoroacetimidate (PTFAI) and Yu glycosylation to streamline the chemical synthesis of oligosaccharides, 2) the successful and efficient assembly sequences (first O3′, second O5′, final O2′) toward the challenging 2,3,5‐branched Araf motif, 3) the stereoselective 1,2‐cis‐glucosylation by reagent control, and 4) the convergent [6+6+7] one‐pot coupling reaction for the final assembly of the target nona‐decasaccharide. This orthogonal one‐pot glycosylation strategy can streamline the chemical synthesis of long, branched, and complicated carbohydrate chains.     

Photoredox‐Catalyzed Isomerization of Highly Substituted Allylic Alcohols by C−H Bond Activation

Photoredox‐catalyzed isomerization of γ‐carbonyl‐substituted allylic alcohols to their corresponding carbonyl compounds was achieved for the first time by C?H bond activation. This catalytic redox‐neutral process resulted in the synthesis of 1,4‐dicarbonyl compounds. Notably, allylic alcohols bearing tetrasubstituted olefins can also be transformed into their corresponding carbonyl compounds. Density functional theory calculations show that the carbonyl group at the γ‐position of allylic alcohols are beneficial to the formation of their corresponding allylic alcohol radicals with high vertical electron affinity, which contributes to the completion of the photoredox catalytic cycle.     

Quantitative evaluation on oil diffusion mechanisms in nano‐organic‐montmorillonite modified caster oil‐based polyurethane foam for oil/water separation

To improve the oil absorbency of caster oil‐based polyurethane foam, nano‐organic‐montmorillonite (OMMT) was used for the additives. The aim of this study is to evaluate the oil diffusion mechanism and dispersion uniformity of OMMT modified caster oil‐based polyurethane (MPU) using experiments and molecular dynamic simulation. Molecule movement and molecule trajectory of oil was investigated by molecular dynamic simulation and numerical simulation. According to the quantitative analyzing results, the diffusion model was put forward. The average diffusion coefficient of crude oil in 0, 1, 2 wt%, 4, and 6 wt% MPU is 2.4 × 10^?4 cm²/s, 2.6 × 10^?4 cm²/s, 3.0 × 10^?4 cm²/s, 3.2 × 10^?4 cm²/s, and 3.3 × 10^?4 cm²/s, respectively. It indicated that crude oil appeared gradient in the MPU. The optimal diffusion direction of crude oil is (0, 0, 1) crystal face, and the small particles of crude oil are easy to be adsorbed. The two‐dimensional diffusion trajectory of crude oil is nonlinear. The diffusion model includes the diffusion of crude oil at the interface of oil and polyurethane, surface diffusion and pore diffusion, and pore adsorption. Furthermore, the diffusion model showed that the van der Waals force was the main reason for crude oil diffusion or adsorption. OMMT could improve the ability of oil/water separation of polyurethane.