Preparation of LiNi0.5Mn1.5O4 cathode materials by using different-sized Mn3O4 nanocrystals as precursors

Journal of Solid State Electrochemistry - High-voltage LiNi0.5Mn1.5O4 with a spinel structure is considered as important cathode materials for high-energy density Li-ion batteries (LIBs). In this...     

捕捉环加成反应中的有机亚铜中间体构筑氮杂环化合物研究进展

铜(I)盐催化的环加成反应,如叠氮-炔[3+2]环加成(Cu AAC)、不饱和化合物与异氰基化合物的[3+2]环加成、硝酮-炔的环加成(Kinugasa反应)是构建多类氮杂环的高效合成方法,被广泛应用于有机合成的各个领域.近年来,针对几类环加成反应中产生的有机亚铜中间体的多样性转化吸引了国内外很多课题组的注意,基于对这些环加成反应中有机亚铜中间体的捕捉,多类串联及多组分反应得以发展,从而成功实现了一系列多取代杂环或稠环结构的高效构建.本综述总结了这一领域的研究进展,按照所经历的有机亚铜中间体的类型进行分类,包括:(1)Cu AAC反应中产生的三氮唑亚铜中间体;(2)炔烃与异氰化合物[3+2]环加成反应中产生的2H-吡咯基亚铜中间体;(3) Kinugasa反应中产生的烯醇亚铜中间体.期望此综述能够有助于研究者了解有机亚铜中间体捕捉策略的发展、应用现状及不足之处,进一步推动铜催化转化的发展.     

碱性电解液中K3[Fe(CN)6]在锌阳极上的自发还原和吸附延长锌镍电池的循环寿命

In view of the continuously worsening environmental problems, fossil fuels will not be able to support the development of human life in the future. Hence, it is of great importance to work on the efficient utilization of cleaner energy resources. In this case, cheap, reliable, and eco-friendly grid-scale energy storage systems can play a key role in optimizing our energy usage. When compared with lithium-ion and lead-acid batteries, the excellent safety, environmental benignity, and low toxicity of aqueous Zn-based batteries make them competitive in the context of large-scale energy storage. Among the various Zn-based batteries, due to a high open-circuit voltage and excellent rate performance, Zn-Ni batteries have great potential in practical applications. Nevertheless, the intrinsic obstacles associated with the use of Zn anodes in alkaline electrolytes, such as dendrite, shape change, passivation, and corrosion, limit their commercial application. Hence, we have focused our current efforts on inhibiting the corrosion and dissolution of Zn species. Based on a previous study from our research group, the failure of the Zn-Ni battery was caused by the shape change of the Zn anode, which stemmed from the dissolution of Zn and uneven current distribution on the anode. Therefore, for the current study, we selected K₃[Fe(CN)₆] as an electrolyte additive that would help minimize the corrosion and dissolution of the Zn anode. In the alkaline electrolyte, [Fe(CN)₆]^3– was reduced to [Fe(CN)₆]^4– by the metallic Zn present in the Zn-Ni battery. Owing to its low solubility in the electrolyte, K₄[Fe(CN)₆] adhered to the active Zn anode, thereby inhibiting the aggregation and corrosion of Zn. Ultimately, the shape change of the anode was effectively eliminated, which improved the cycling life of the Zn-Ni battery by more than three times (i.e., from 124 cycles to more than 423 cycles). As for capacity retention, the Zn-Ni battery with the pristine electrolyte only exhibited 40% capacity retention after 85 cycles, while the Zn-Ni battery with the modified electrolyte (i.e., containing K₃[Fe(CN)₆]) showed 72% capacity retention. Moreover, unlike conventional organic additives that increase electrode polarization, the addition of K₃[Fe(CN)₆] not only significantly reduced the charge-transfer resistance in a simplified three-electrode system, but also improved the discharge capacity and rate performance of the Zn-Ni battery. Importantly, considering that this strategy was easy to achieve and minimized additional costs, K₃[Fe(CN)₆], as an electrolyte additive with almost no negative effect, has tremendous potential in commercial Zn-Ni batteries.     

化工原理课程思政教学改革与实践

介绍了化工原理课程思政的育人目标,据此构建课程内容与育人元素的支撑矩阵;融入绿色工程理念,确定课程对绿色工程十二项原则指标点的支撑;深度融合信息技术,基于原有慕课建设专门的课程思政慕课;以精馏章节为例,分享化工原理课程思政教学案例设计思路和方案。同时,对学生测评和学习成果、育人点、重要性及切入自然性进行调研评价,说明通过课程思政教学实践,在潜移默化中培养学生树立正确的世界观、人生观和价值观。为化工类专业课程思政教学提供参考和借鉴。     

Turn-on Circularly Polarized Luminescence in Chiral Indium Chlorides by 5s2 Metal Centers

Introducing chirality into the metal-halide hybrids has enabled many emerging properties including chiroptical activity, spin-dependent transport, and ferroelectricity. However, most of the chiral metal-halide hybrids to date are non-emissive, and the underlying mechanism remains elusive. Here, we show a new strategy to turn on the circularly polarized luminescence (CPL) in chiral metal-halide hybrids. We demonstrate that alloying Sb³⁺ into chiral indium-chloride hybrids dramatically increases the photoluminescence quantum yield in two new series of chiral indium-antimony chlorides. These materials exhibit strong CPL signals with tunable energy and a high dissymmetry factor up to 1.5×10⁻². Mechanistic studies reveal that the emission originates from the self-trapped excitons centered in 5s² Sb³⁺. Moreover, near-ultraviolet pumped white light is demonstrated with a polarization up to 6.0 %. Our work demonstrates new strategies towards highly luminescent chiral metal-halide hybrids.     

Selective In Situ Analysis of Mature microRNAs in Extracellular Vesicles Using a DNA Cage-Based Thermophoretic Assay

Mature microRNAs (miRNAs) in extracellular vesicles (EVs) are involved in different stages of cancer progression, yet it remains challenging to precisely detect mature miRNAs in EVs due to the presence of interfering RNAs (such as longer precursor miRNAs, pre-miRNAs) and the low abundance of tumor-associated miRNAs. By leveraging the size-selective ability of DNA cages and polyethylene glycol (PEG)-enhanced thermophoretic accumulation of EVs, we devised a DNA cage-based thermophoretic assay for highly sensitive, selective, and in situ detection of mature miRNAs in EVs with a low limit of detection (LoD) of 2.05 fM. Our assay can profile EV mature miRNAs directly in serum samples without the interference of pre-miRNAs and the need for ultracentrifugation. A clinical study showed that EV miR-21 or miR-155 had an overall accuracy of 90 % for discrimination between breast cancer patients and healthy donors, which outperformed conventional molecular probes detecting both mature miRNAs and pre-miRNAs. We envision that our assay can advance EV miRNA-based diagnosis of cancer.     

Elaborating E/Z-Geometry of Alkenes via Cage-Confined Arylation Catalysis of Terminal Olefins

A visible light photosensitizing metal-organic cage is applied as an artificial supramolecular reactor to control the reaction of aryl radicals with terminal olefins under green light/solvent conditions, which facilitates selective transformation in the confined enzyme-mimicking environment to give a series of geometrically defined E/Z-alkenes. The hydrophobic cage displays good host–guest inclusion with aromatic substrates, promoting Meerwein arylation and protecting E-isomeric products during reaction; while a small amount of benzonitrile can turn on efficient E→Z isomerization. Besides π–π stacking, the hydrogen bonding and halogen bonding interactions also act as control forces for the arylation of aliphatic terminal olefins known as poor acceptors in classic Meerwein arylation. The application of this switchable cage-confined arylation catalysis has been demonstrated by the syntheses of Tapinarof and a marine natural product from the same substrate via controllable E/Z selectivity.     

Ru(bpy)32+-Enabled Cell-Surface Photocatalytic Proximity Labeling toward More Efficient Capture of Physically Interacting Cells

Intercellular proximity labeling has emerged as a promising approach to enable the study of cell-cell interactions (CCIs), but the efficiency of current platforms is limited. Here, we use Ru(bpy)₃²⁺ to construct an efficient photocatalytic proximity labeling (PPL) system on the cell surface that allows the highly discriminative CCI detection with spatiotemporal resolution. Through the mechanism study and quantitative characterization on living cells, we demonstrate that the singlet-oxygen (¹O₂) mechanism is more efficient and specific than the single electron transfer (SET) mechanism in Ru-mediated PPL. Ru(bpy)₃²⁺ catalysts with different cell-anchoring moieties are prepared to facilitate the catalyst loading on primary cells. Finally, based on this system, we develop a “live” T cell receptor (TCR) multimer with TCR-T cells that could sensitively identify and discriminate cells presenting antigens of different affinity, providing a powerful tool to better understand the heterogeneity of antigen presenting cells.     

Solvent-Free Heterogeneous Catalytic Hydrogenation of Polyesters to Diols

The utilization of carbon resources stored in plastic polymers through chemical recycling and upcycling is a promising approach for mitigating plastic waste. However, most current methods for upcycling suffer from limited selectivity towards a specific valuable product, particularly when attempting full conversion of the plastic. We present a highly selective reaction route for transforming polylactic acid (PLA) into 1,2-propanediol utilizing a Zn-modified Cu catalyst. This reaction exhibits excellent reactivity (0.65 g g_cat⁻¹ h⁻¹) and selectivity (99.5 %) towards 1,2-propanediol, and most importantly, can be performed in a solvent-free mode. Significantly, the overall solvent-free reaction is an atom-economical reaction with all the atoms in reactants (PLA and H₂) fixed into the final product (1,2-propanediol), eliminating the need for a separation process. This method provides an innovative and economically viable solution for upgrading polyesters to produce high-purity products under mild conditions with optimal atom utilization.     

Sulfur-Containing Foldamer-Based Artificial Lithium Channels

Unlike many other biologically relevant ions (Na⁺, K⁺, Ca²⁺, Cl⁻, etc) and protons, whose cellular concentrations are closely regulated by highly selective channel proteins, Li⁺ ion is unusual in that its concentration is well tolerated over many orders of magnitude and that no lithium-specific channel proteins have so far been identified. While one naturally evolved primary pathway for Li⁺ ions to traverse across the cell membrane is through sodium channels by competing with Na⁺ ions, highly sought-after artificial lithium-transporting channels remain a major challenge to develop. Here we show that sulfur-containing organic nanotubes derived from intramolecularly H-bonded helically folded aromatic foldamers of 3.6 Å in hollow cavity diameter could facilitate highly selective and efficient transmembrane transport of Li⁺ ions, with high transport selectivity factors of 15.3 and 19.9 over Na⁺ and K⁺ ions, respectively.