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  • Wen-Hui Mi, Teng-Yu Huang, Yu-Fei Ao, Xu-Dong Wang, Qi-Qiang Wang, De-Xian Wang
    Chinese Chemical Letters. 2024, 35(5): 109077-.

    Presented here is a one-pot strategy starting from rationally designed macrocyclic precursors for the diverse construction of sophisticated ultracycles. The type and amount of the base were found to significantly influence the macrocyclization outcome. The use of 4.0 equiv. CsF resulted in ultracycles of both types A and B while the presence of CsF larger than 6.0 equiv. produced only type B ultracycles. Existence of anion template increased the total yields and affected the distribution of the ultracycles. The ultracycles can accommodate large organic dicarboxylates anions via multiple anion–π and hydrogen bonds, and show selectivity to the size-matched heptanedioate (C72−). Based on all possible species and relevant equilibrium constants as well as material and charge balances, a numerical iterative algorithm was developed and applied to fit the association constants of B2H with dicarboxylates from glutarate (C52−) to octanedioate (C82−), which gave association constants up to 103 L/mol.

  • Yuqing Wang, Zhemin Li, Qingjun Lu, Qizhao Li, Jiaxin Luo, Chengjie Li, Yongshu Xie
    Chinese Chemical Letters. 2024, 35(5): 109093-.

    To develop efficient sensitizers for dye-sensitized solar cells (DSSCs), we recently reported doubly concerted companion (DCC) dye XW83 with a wrapped porphyrin sub-dye unit linked to an organic sub-dye unit through a flexible chain, which exhibits panchromatic absorption and excellent anti-aggregation ability. To further improve the absorption, we herein report XW87 and XW88 by inserting an ethynyl group into the organic sub-dye unit of XW83 near the donor and acceptor, respectively. For the corresponding organic dyes Z3 and Z4, the introduced ethynyl group improves their absorption, but induces aggravated charge recombination, leading to lowered power conversion efficiencies (PCEs). Similar to the organic dyes, the introduced ethynyl group improves the absorption of DCC dyes XW87 and XW88 as well. In addition, the ethynyl group near the acceptor of the organic sub-dye unit can be well protected by the long wrapping chains from the porphyrin unit. As a result, XW88 affords the highest JSC (21.84 mA/cm2), VOC (782 mV) and PCE (12.2%) among the DCC dyes. These results provide an effective method for developing efficient DSSC dyes by inserting an ethynyl group at a suitable position of a DCC dye.

  • Weiwei He, Hongbo Zhang, Xudong Lin, Lili Zhu, Tingting Zheng, Hao Pei, Yang Tian, Min Zhang, Guoyue Shi, Lei Wu, Jianlong Zhao, Gulinuer Wumaier, Shengqing Li, Yufang Xu, Honglin Li, Xuhong Qian
    Chinese Chemical Letters. 2024, 35(5): 109091-.

    This review explores the concept of life-on-a-chip, which involves the creation of miniaturized biological systems, such as organs, tissues, and model organisms, on microscale platforms called microfluidic chips. These chips consist of intricately etched channels, wells, and chambers that enable precise control and observation of fluids, cells, and biochemical reactions, facilitating the simulation of various aspects of human or animal physiology and the study of responses to different stimuli, drugs, or disease conditions. The review highlights the application of a novel technology, "Beyond Limit Manufacturing" (BLM), in the development of sophisticated three-dimensional cell models and model organism microchips. Model-organism-on-a-chip and organ-on-a-chip (OoC) are among the thriving developments in the field of microfluidics, allowing for the reconstruction of living microenvironments and implementation of multiple stimuli. The review discusses the latest advancements in life-on-a-chip technology using BLM and outlines potential future research directions, emphasizing the significant role of these chips in studying complex biological processes in a controlled and scalable manner.

  • Jun Zhang, Zhiyao Zheng, Can Zhu
    Chinese Chemical Letters. 2024, 35(5): 109160-.

    Chiral alcohols and amines are important structural units widely existing in pharmaceuticals, agrochemicals, and food additives. Dynamic kinetic resolution (DKR) is an efficient strategy to deliver optically active alcohols and amines from their racemates. For the development of DKR method, racemization catalyst plays as a crucial element with the requirement of compatibility with the kinetic resolution (KR) system. In this paper, recent advance in the catalytic racemization of secondary alcohols and amines is summarized based on different types of racemizing intermediates, which are redox racemization via ketone/imine intermediates, racemization via radical intermediates, and racemization via carbocation intermediates. Enzymatic racemization of secondary alcohols and amines is also enclosed.

  • Yan Cheng, Hua-Peng Ruan, Yan Peng, Longhe Li, Zhenqiang Xie, Lang Liu, Shiyong Zhang, Hengyun Ye, Zhao-Bo Hu
    Chinese Chemical Letters. 2024, 35(4): 108554-.

    The application of multifunctional materials in various fields such as electronics and signal processors has attracted massive attention. Herein, a new organic-inorganic hybrid material [Et3NCH2Cl]2[MnBr4] (1) is reported, which contains two organic amines cations and one [MnBr4] tetrahedral ion. Compound 1 has a dielectric anomaly signal at 338 K, which proves its thermodynamic phase transition. The single crystal measurements at 200 K and 380 K show that the phase transition of compound 1 is caused by the thermal vibration of organic amine cations in the lattice. Moreover, compound 1 shows yellow-green luminescence under UV light irradiation. The magnetism measurements indicate that compound 1 shows switchable magnetic properties. This organic–inorganic material is a multifunctional material with dielectric, optical, and magnetic synergetic switchable effects, which expands a new direction for designing multifunctional materials.

  • Tao Ban, Xi-Yang Yu, Hai-Kuo Tian, Zheng-Qing Huang, Chun-Ran Chang
    Chinese Chemical Letters. 2024, 35(4): 108549-.

    One-step conversion of methane and formaldehyde into ethanol is a 100% atom-efficient process for carbon resources utilization and environment protection but still faces eminent challenges due to the lacking of efficient catalysts. Therefore, developing active and stable catalysts is crucial for the co-conversion of methane and formaldehyde. Herein, twelve kinds of "Single-Atom" - "Frustrated Lewis Pair" (SA-FLP) dual-active-site catalysts are designed for the direct conversion of methane and formaldehyde to ethanol based on density functional theory (DFT) calculations and microkinetic simulations. The results show that the SA-FLP dual active sites can simultaneously activate methane at the SA site and activate formaldehyde at the FLP site. Among the twelve designed SA-FLP catalysts, Fe1-FLP shows the best performance in the co-conversion of methane and formaldehyde to ethanol with the rate-determining barrier of 1.15 eV. Ethanol is proved as the main product with the turnover frequency of 1.32 × 10−4 s−1 at 573 K and 3 bar. This work provides a universal strategy to design dual active sites on metal oxide materials and offers new insights into the effective conversion of methane and formaldehyde to desired C2 chemicals.

  • Qiangwei Wang, Huijiao Liu, Mengjie Wang, Haojie Zhang, Jianda Xie, Xuanwei Hu, Shiming Zhou, Weitai Wu
    Chinese Chemical Letters. 2024, 35(4): 108743-.

    Here, we report an observation that illustrate the potential of polyelectrolyte microgels in salt-free solutions to display a high ionic conductivity. Laser light scattering and ionic conductivity tests on very dilute aqueous dispersions of the microgels indicate that both small size and swollen state of gel particles play vital roles, which should favor the counterions to freely penetrate and leave gel particles, and thus can contribute to the ion-conducting property. Upon discovering this on microgels that are composed of imidazolium-based poly(ionic liquid), we also illustrate the generality of the finding to single lithium-ion polyelectrolyte microgels that are of more technically relevant features for applications, for instance, as injectable liquid "microgel-in-solution" electrolytes of high conductivity (ca. 8.2 × 10−2 S/m at 25.0 ℃ for 1.0 × 10−2 g/mL of microgels in a LiNO3-free 1:1 v/v mixture of 1,2-dioxolane and dimethoxymethane) and high lithium-ion transference number (0.87) for use in the rechargeable lithium-sulfur battery.

  • Junhan Luo, Qi Qing, Liqin Huang, Zhe Wang, Shuang Liu, Jing Chen, Yuexiang Lu
    Chinese Chemical Letters. 2024, 35(4): 108483-.

    Microplasma based on glow discharge could act as a non-contact gaseous electrode and has attracted much attention in both fundamental research and application. Herein, with microplasma as the anode, the electrodeposition process of a series of metal and metal alloys in molten salt has been systemically studied. Four metal cations with different valence states, silver (Ag+), nickel (Ni2+), copper (Cu2+), and iron (Fe3+), could all be reduced on the solid cathode with high current efficiency and the corresponding metal products were of high purity. The electrodeposition of aluminum-lanthanum (Al-Ln) alloy on the aluminum cathode was also successfully carried out with microplasma as the anode, and the same alloy was obtained by using the conventional anode electrode. These results indicated that microplasma anode based on non-contact direct-current (DC) glow discharge is a promising electrode to be applied in molten salt electrolysis.

  • Lang Gao, Cen Zhou, Rui Wang, Feng Lan, Bohang An, Xiaozhou Huang, Xiao Zhang
    Chinese Chemical Letters. 2024, 35(4): 108832-.

    Inverse vulcanized polymers (IVPs) that generated from elemental sulfur and smaller amounts of alkenes have found broad promising applications such as cathode materials for Li-S batteries, dynamic and repairable materials, optics applications, and metal sorption. However, their exploration in organic synthesis is still unprecedented. Here we first report the application of inverse vulcanized polymers in catalysis for organic transformations. A biomass-derived inverse vulcanized polymer (IVP-EAE) is found to be capable of catalyzing cross-coupling reactions in a transition-metal-free fashion under visible light. This method allows the direct CH functionalization of pyrroles and N-arylacrylamides with (hetero)aryl halides, respectively, leading to the formation of two sets of structurally important scaffolds including pyrrole-containing biaryls and 3,3′-disubstituted oxindoles with high selectivity. We anticipate this study will not only unveil the new potential of IVPs, but also offer a distinct type of catalysts for organic transformations.

  • Shuaiwen Li, Zihui Chen, Feng Yang, Wanqing Yue
    Chinese Chemical Letters. 2024, 35(4): 108793-.

    Nanomaterials with enzyme-mimic (nanozyme) activity have garnered considerable attention as a potential alternative to natural enzymes, thanks to their low preparation cost, high activity, ease of preservation, and unique physicochemical properties. Vanadium (V) is a transition metal that integrates the benefits of valence-richness, low cost, and non-toxicity, making it a desirable candidate for developing a range of emerging nanozymes. In this review, we provide the first systematic summary of recent research progress on V-based nanozymes. First, we summarize the preparation of V-based nanozymes using both top-down and bottom-up synthesis methods. Next, we review the mechanism of V-based nanozymes that mimic the activity of various enzymes. We then discuss methods for regulating V-based nanozyme activity, including morphology, size, valence engineering, defect engineering, external triggering, and surface engineering. Afterward, we outline various biomedical applications, including therapeutic, anti-inflammatory, antibacterial, and biosensing. Finally, we prospect the challenges and countermeasures for V-based nanozymes based on their development. By summarizing recent research progress on V-based nanozymes, we hope to provide useful insights for researchers to further explore their potential applications and overcome their existing challenges.

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