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  • Feng Wu, Xuemin Kong, Yixuan Liu, Shuli Wang, Zhong Chen, Xu Hou
    Chinese Chemical Letters. 2024, 35(8): 109754-.

    The isolation of circulating tumor cells (CTCs) from complex biological samples is of paramount significance for advancing cancer diagnosis, prognosis, and treatment. However, the low concentration of CTCs and nonspecific adhesion of white blood cells (WBCs) present challenges that hinder the efficiency and purity of captured CTCs. Microfluidic-based strategies utilize precise fluid control at the micron level to incorporate specific micro/nanostructures or recognition molecules, enabling effective CTCs separation. Moreover, by employing surface modification designs that exhibit exceptional anti-adhesion properties against WBCs, the purity of isolated CTCs can be further enhanced. This review offers an in-depth exploration of recent advancements, challenges, and opportunities associated with microfluidic-based CTCs isolation from biological samples. Firstly, we will comprehensively introduce the microfluidic-based strategies for achieving high-efficiency CTCs isolation, which includes the morphological design of microchannels for physical force-based CTCs isolation and the specific modification of microchannel surfaces for affinity-based CTCs isolation. Subsequently, a review of recent research advances in microfluidic-based high-purity CTCs isolation is presented, focusing on strategies that decrease the nonspecific adhesion of WBCs through surface micro-/nanostructure construction or chemical and biological modification. Finally, we will summarize the article by providing the prospective opportunities and challenges for the future development of microfluidic-based CTCs isolation.

  • Yue Zhang, Xiaoya Fan, Xun He, Tingyu Yan, Yongchao Yao, Dongdong Zheng, Jingxiang Zhao, Qinghai Cai, Qian Liu, Luming Li, Wei Chu, Shengjun Sun, Xuping Sun
    Chinese Chemical Letters. 2024, 35(8): 109806-.

    Electrocatalytic synthesis of urea through CN bond formation, converting carbon dioxide (CO2) and nitrate (NO3–), presents a promising, less energy-intensive alternative to industrial urea production process. In this communication, we report the application of Mo2C nanosheets-decorated carbon sheets (Mo2C/C) as a highly efficient electrocatalyst for facilitating CN coupling in ambient urea electrosynthesis. In CO2-saturated 0.2 mol/L Na2SO4 solution containing 0.05 mol/L NO3–, the Mo2C/C catalyst achieves an impressive urea yield of 579.13 µg h–1 mg–1 with high Faradaic efficiency of 44.80% at –0.5 V versus the reversible hydrogen electrode. Further theoretical calculations reveal that the multiple Mo active sites enhance the formation of *CO and *NH2 intermediates and facilitate their CN coupling. This research propels the use of Mo2C-based electrodes in electrocatalysis and accentuates the capabilities of binary metal-based catalysts in CN coupling reactions.

  • Fabrice Nelly Habarugira, Ducheng Yao, Wei Miao, Chengcheng Chu, Zhong Chen, Shun Mao
    Chinese Chemical Letters. 2024, 35(8): 109886-.

    Photocatalytic synthesis of hydrogen peroxide has gradually become a promising method for in-situ production of hydrogen peroxide, which relies on sustainable solar energy. However, the commonly used photocatalyst, i.e., carbon nitride (CN), still suffers from the drawbacks of narrow light absorption range and fast charge recombination. Here, we report a facile method to introduce nitrogen defects into carbon nitride together with sodium ion. By adjusting the ratio of sodium dicyandiamide, the band gap of carbon nitride can be controlled, while the carrier separation and transfer ability of carbon nitride is improved. The modified CN with sodium doping and nitrogen defect (SD-CN) demonstrates outstanding H2O2 production performance (H2O2 yield rate of 297.2 µmol L−1 h−1) under visible light irradiation, which is approximately 9.8 times higher than that of pristine CN. This work deepens the understanding of the coordinated effect of structural defect and element doping of carbon nitride on the photocatalytic H2O2 production performance, and provides new insight into the design of photocatalytic system for efficient production of H2O2.

  • Yu-Hang Li, Shuai Gao, Lu Zhang, Hanchun Chen, Chong-Chen Wang, Haodong Ji
    Chinese Chemical Letters. 2024, 35(8): 109894-.

    Herein, we constructed defective UiO-66 with rich Zr vacancy structure model, in which the defective structure was verified by various characterizations. Also, the Pb adsorption experiments affirmed that defective UiO-66 could display better adsorption and selective adsorption ability than that of perfect UiO-66. The results of partial density of states (PDOS) and Mulliken charge population indicated that the blue shift of O 2p and Zr 4d orbit induced the electron rearrangement of atoms closed to the bonding sites, while the positive charge number of Zr atoms decreased than before. Combining with the expansion of pore size, Pb atom was more inclined to transfer and bond with unsaturated coordination oxygens. More significantly, quantitative structure-activity relationships (QSARs) demonstrated that selective capture of Pb instead of Zn, Cu, Cd and Hg displayed by defective UiO-66 was determined jointly by bond strength, adsorption energy and electron transfer. This work provided some theoretical direction for the purpose of the fabrication of adsorbent and the investigation of mechanism.

  • Mei Peng, Wei-Min He
    Chinese Chemical Letters. 2024, 35(8): 109899-.
  • Jieqiong Qin, Zhi Yang, Jiaxin Ma, Liangzhu Zhang, Feifei Xing, Hongtao Zhang, Shuxia Tian, Shuanghao Zheng, Zhong-Shuai Wu
    Chinese Chemical Letters. 2024, 35(7): 108845-.

    Two-dimensional (2D) mesoporous pseudocapacitive polymer/graphene heterostructures combine the advanced merits of 2D materials and mesoporous materials, possessing unique nanosheet structure, large specific surface area (SSA), abundant oxygen/nitrogen-containing groups, desirable electrical conductivity and admirable electrochemical redox activity, and hold great potential for constructing high-performance planar micro-supercapacitors (MSCs). Herein, we demonstrate the interfacial assembly of 2D mesoporous polydopamine/graphene (mPDG) heterostructures with well-defined mesopore structure (12 nm) and adjustable thickness (7.5–14.1 nm) for planar high-energy pseudocapacitive MSCs. Attributed to medium thickness, exposed mesopore of 12 nm and large SSA of 108 m2/g, the mPDG with 10.8 nm thickness reveals prominent mass capacitance of 419 F/g and impressive cycling stability with ~96% capacitance retention after 5000 cycles. Furthermore, the symmetric mPDG-based MSCs with "water-in-salt" gel electrolyte present wide voltage window of 1.6 V, superior volumetric energy density of 11.5 mWh/cm3, outstanding flexibility and self-integration ability. Therefore, this work offers a new platform of controllably synthesizing 2D mesoporous heterostructures for high-performance MSCs.

  • Yunyu Zhao, Chuntao Yang, Yingjian Yu
    Chinese Chemical Letters. 2024, 35(7): 108865-.

    In recent years, rechargeable zinc-ion batteries (ZIBs) are considered to be a promising alternative to lithium-ion batteries owing to their high safety and theoretical capacity with low cost. Nevertheless, the in-depth development of rechargeable zinc-ion batteries is restricted by a sequence of issues, such as the dissolution and structure collapse of cathode materials, the formation of by-products, severe anode corrosion, passivation, and the growth of zinc dendrites. The covalent organic frameworks (COFs) can solve the above problems to a certain extent owing to their ideal characteristics, such as rigid structure, insolubility, high porosity, and abundant active sites. COFs, as advanced materials for ZIBs, have attracted researchers' attention. In this review, we systematically summarized the synthesis methods of COFs and discussed the application of several advanced characterization technologies in COFs, which would provide a reference for the in-depth research of COFs. In addition, we elucidated the use of COFs as cathode materials and anode protective layers in rechargeable ZIBs. Finally, we discussed the challenges and solutions in the development of COF materials, which would provide constructive insights into the future direction of COFs.

  • Shuangliang Xie, Yuyue Chen, Qing He, Liang Chen, Jikun Yang, Shiqing Deng, Yimei Zhu, He Qi
    Chinese Chemical Letters. 2024, 35(7): 108871-.

    Relaxor ferroic dielectrics have garnered increasing attention in the past decade as promising materials for energy storage. Among them, relaxor antiferroelectrics (AFEs) and relaxor ferroelectrics (FEs) have shown great promise in term of high energy storage density and efficiency, respectively. In this study, a unique phase transition from relaxor AFE to relaxor FE was achieved for the first time by introducing strong-ferroelectricity BaTiO3 into NaNbO3-BiFeO3 system, leading to an evolution from AFE R hierarchical nanodomains to FE polar nanoregions. A novel medium state, consisting of relaxor AFE and relaxor FE, was identified in the crossover of 0.88NaNbO3–0.07BiFeO3–0.05BaTiO3 ceramic, exhibiting a distinctive core-shell grain structure due to the composition segregation. By harnessing the advantages of high energy storage density from relaxor AFE and large efficiency from relaxor FE, the ceramic showcased excellent overall energy storage properties. It achieved a substantial recoverable energy storage density Wrec ~ 13.1 J/cm3 and an ultrahigh efficiency η ~ 88.9%. These remarkable values shattered the trade-off relationship typically observed in most dielectric capacitors between Wrec and η. The findings of this study provide valuable insights for the design of ceramic capacitors with enhanced performance, specifically targeting the development of next generation pulse power devices.

  • Qian Wang, Ting Gao, Xiwen Lu, Hangchao Wang, Minggui Xu, Longtao Ren, Zheng Chang, Wen Liu
    Chinese Chemical Letters. 2024, 35(7): 108887-.

    All solid-state lithium metal batteries (ASSLMBs) based on polymer solid electrolyte and lithium metal anode have attracted much attention due to their high energy density and intrinsic safety. However, the low ionic conductivity at room temperature and poor mechanical properties of the solid polymer electrolyte result in increased polarization and poor cycling stability of the Li metal batteries. In order to improve the ionic conductivity at room temperature while maintaining mechanical strength, we combine the conductivity of short chain polyethylene oxide (PEO) and strength of styrene-maleic anhydride copolymer (SMA) to obtain a grafted block copolymer with nanophase separation structure, which has room temperature ionic conductivity up to 1.14 × 10−4 S/cm and tensile strength up to 1.4 MPa. Li||Li symmetric cell can work stably for more than 1500 h under the condition of 0.1 mA/cm2. Li||LiFePO4 full cells can deliver a high capacity of 151.4 mAh/g at 25 ℃ and 0.2 C/0.2 C charge/discharge conditions, showing 85.6% capacity retention after 400 cycles. Importantly, the all solid state Li||LiFePO4 pouch cell shows excellent safety performance under different abuse conditions. These results demonstrate that the nanophase separated, grafted alternate copolymer electrolyte has huge potential for application in Li metal batteries.

  • Yu Deng, Yan Liu, Yonghui Deng, Jinsheng Cheng, Yidong Zou, Wei Luo
    Chinese Chemical Letters. 2024, 35(7): 108898-.

    Benzene series as highly toxic gases have inevitably entered human life and produce great threat to human health and ecological environment, and thus it is distinctly meaningful to monitor benzene series with quickly, real-time and efficient technique. Herein, novel sulfur-doped mesoporous WO3 materials were synthesized via classical in-situ solvent evaporation induced co-assembly strategy combined with doping engineering, which possessed highly crystallized frameworks, high specific surface area (40.9–63.8 m2/g) and uniform pore size (~18 nm). Benefitting from abundant oxygen vacancy and defects via S-doping, the tailored mesoporous S/mWO3 exhibited excellent benzene sensing performance, including high sensitivity (50 ppm vs. 48), low detection limit (ca. 500 ppb), outstanding selectivity and favorable stability. In addition, the reduction of band gap resulted from S-doping promotes the carrier migration in the sensing materials and the reaction at the gas–solid sensing interfaces. It provides brand-new approach to design sensitive materials with multiple reaction sites.

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