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  • Yi Wei, Wenhui Hou, Peng Zhang, Razium A. Soomro, Bin Xu
    Chinese Chemical Letters. 2022, 33(6): 3212-3216.

    Bismuth sulfide (Bi2S3) is a promising anode material for high-performance potassium ion batteries due to its high theoretical capacity. However, the poor conductivity and substantial volume expansion hinder its practical application. We proposed an iodine-doped graphene encapsulated Bi2S3 nanorods composite (Bi2S3/IG) as an efficient anode for PIBs. The uniform-sized Bi2S3 nanorods evenly in-situ encapsulated in iodine-doped graphene framework, facilitating the electron transportation and structural stability. The potassium storage performance was evaluated in three electrolytes, with the best option of 5 mol/L KFSI in DME. The reversible capacity of representative Bi2S3/IG reached 453.5 mAh/g at 50 mA/g. Meanwhile, it could deliver an initial reversible capacity of 413.6 mAh/g at 100 mA/g, which maintained 256.9 mAh/g after 200 cycles. The proposed strategy contributes to improving potassium storage performance of metal sulfide anodes.

  • Yefan Duan, Qi Li, Panpan He, Yan Li, Jingrun Song, Jing Wang, Junjie Liu, Jiang Zhou, Fei Chen, Zhusheng Huang, Jianfei Sun, Ying Zhang, Zhimin Luo
    Chinese Chemical Letters. 2022, 33(6): 3217-3220.

    Iron chalcogenides have attracted great interest as potential substitutes of nature enzymes in the colorimetric biological sensing due to their unique chemodynamic characteristics. Herein, we report the preparation of ultrathin FeS nanosheets (NSs) by a simple one-pot hydrothermal method and the prepared FeS NSs exhibit strong Fenton-reaction activity to catalyze hydrogen peroxide (H2O2) for generation of hydroxyl radical (OH). Based on the chromogenic reaction of resultant OH with 3, 3′, 5, 5′-tetramethylbenzidine (TMB), we develop colorimetric biosensors for highly sensitive detection of H2O2 and glutathione (GSH). The fabricated biosensors show wide linear ranges for the detection of H2O2 (5–150 µmol/L) and GSH (5–50 µmol/L). Their detection limits for H2O2 and GSH reach as low as 0.19 µmol/L and 0.14 µmol/L, respectively. The experimental results of sensing intracellular H2O2 and GSH demonstrate that this colorimetric method can realize the accurate detection of H2O2 and GSH in normal cells (L02 and 3T3) and cancer cells (MCF-7 and HeLa). Our results have demonstrated that the synthesized FeS NSs is a promising material to construct colorimetric biosensors for the sensitive detection of H2O2 and GSH, holding great promising for medical diagnosis in cancer therapy.

  • Yunxing Lu, Zhaoduo Tong, Zhenhua Wu, Xiaoyu Jian, Lin Zhou, Shihui Qiu, Chuanjie Shen, Hao Yin, Hongju Mao
    Chinese Chemical Letters. 2022, 33(6): 3188-3192.

    Exosomes are now raising focus as a prospective biomarker for cancer diagnostics and prognosis owing to its unique bio-origin and composition. Exosomes take part in cellular communication and receptor mediation and transfer their cargos (e.g., proteins, mRNA and DNA). Quantitative analysis of tumor-related nucleic acid mutations can be a potential method to cancer diagnosis and prognosis in early stages. Here we present an integrated microfluidic system for exosome on-chip isolation and lung cancer RNA analysis through droplet digital PCR (ddPCR). Gradient dilution experiments show great linearity over a large concentration range with R2 = 0.9998. Utilizing the system, four cell lines and two mutation targets were parallelly detected for mutation analysis. The experiments demonstrated mutation heterogeneity and the results were agree with cell researches. These results proved our integrated microfluidic system as a promising means for early cancer diagnosis and prognosis in the era of liquid biopsy.

  • Qi Li, Wuji Wei, Zhenzhen Xue, Ying Mu, Jie Pan, Jixiang Hu, Guoming Wang
    Chinese Chemical Letters. 2022, 33(6): 3203-3206.

    Tuning white-light emission via free radicals is still a challenge in molecular-based functional materials. Herein, a new photoactive Zn2+ oxalate-based chain containing a polypyridine ligand was designed and synthesized with remarkably bifunctional photochromism and photo-actuated greenish white-light emission after UV, sunlight or Xe lamp light irradiation at room temperature. The photo-actuated coloration process was induced by the photogeneration of stable radicals originated from intermolecular electron transfers from oxalate components to the protonated polypyridine units, as demonstrated by UV–vis, IR, electron spin resonance and X-ray photoelectron spectra and magnetic measurements. Importantly, the on/off greenish white light emission (WLE) could be reversibly switched by generation and elimination of radicals via light irradiation and heat treatment, providing a feasible strategy for designing photoswitchable light emission diodes materials.

  • Dezhi Yang, Hongjuan Wang, Qiwen Liu, Penghui Yuan, Ting Chen, Li Zhang, Shiying Yang, Zhengzheng Zhou, Yang Lu, Guanhua Du
    Chinese Chemical Letters. 2022, 33(6): 3207-3211.

    The specific crystalline form of a compound remarkably affects its physicochemical properties. Therefore, a detailed analysis of the structural features and intermolecular interactions of a multi-component crystal is feasible to understand the relationships among the structure, physicochemical properties and the formation mechanism. In the present study, three novel cocrystal salt solvates of rhein and berberine were reported for the first time. Various solid characterizations and theoretical computations based on density functional theory (DFT) were carried out to demonstrate the intermolecular interactions. The theoretical computation shows that the strongest interaction existed between berberine cation and rhein anion, and the electrostatic interaction play a dominant role. However, no salt bond was observed between them. Further intrinsic dissolution rate analysis in water shows that the monohydrate exhibits 17 times enhancement in comparison with rhein. The rhein and berberine combined in ionic state in cocrystal salt is the main reason for the solubility improvement. This paper suggests that the interactions between the different components can be visualized and qualitatively and quantitatively analyzed by theoretical computation, which is helpful to understand the relationship between stereochemical structure and physicochemical properties of multi-component complex.

  • Min Hou, Dinggeng He, Huizhen Wang, Jin Huang, Hong Cheng, Kejin Wan, Hung-Wing Li, Zifeng Tang, Xiaoxiao He, Kemin Wang
    Chinese Chemical Letters. 2022, 33(6): 3183-3187.

    Simultaneous and quantitative detection of multiple exosomal microRNAs (miRNAs) was successfully performed by a surface-enhanced Raman scattering (SERS) assay consisting of Raman probes and capture probes. In this design, the asymmetric core-shell structured Au@Au@Ag nanoparticles were first synthesized by layer-by-layer self-assembly method and modified with different Raman molecules and recognition sequences (polyA-DNA) to prepare the surface-enhanced Raman probes. Then, the streptavidin-modified magnetic beads were used to immobilize the biotinylated DNA capture sequences (biotin-DNA) to obtain capture probes. In the presence of target exosomal miRNAs, the Raman probes and capture probes could bind to the target exosomal miRNAs in the partial hybridization manner. Thus, the developed SERS sensor could indicate the target miRNAs levels in the buffer solution. Using breast cancer-related miRNAs as model targets, the limits of detection of this sensor were determined to be 1.076 fmol/L for synthetic miR-21, 0.068 fmol/L for synthetic miR-126, and 4.57 fmol/L for synthetic miR-1246, respectively. Such SERS sensors were further employed to detect the miR-21 in 20% human serum and the extraction solution of exosomes, respectively. Therefore, simultaneous and multiplex detection of cancer-related exosomal miRNAs by this assay could provide new opportunities for further biomedical applications.

  • Juan Qiao, Xiangfei Li, Li Qi
    Chinese Chemical Letters. 2022, 33(6): 3193-3196.

    The temperature monitoring of treated cancer cells is critical in photothermal therapy. Current methods of detecting intracellular temperatures have low accuracy and poor spatial resolution, which limits their application to photothermal therapy. Herein, a strategy for targeted recognition and selective capture of MCF-7 breast cancer cells based on fluorescent polymer poly(N-isopropylacrylamide-benzoxadiazole-2-vinyl-4,4-dimethyl azlactone, PNMV) and modified gold nanobipyramids (AuNBPs-PNMV) was developed for temperature sensing during photothermal therapy. A mucin-1 protein aptamer (Apt) was applied to selectively target mucin-1 protein overexpressed on the surfaces of the MCF-7 cells, which can reduce interference by affinity interaction between the Apt and proteins. During photothermal therapy, the significant AuNBPs photothermal effect increases the fluorescence intensity of PNMV with temperature. Irradiation of MCF-7 cells cultured with AuNBPs-PNMV@Apt by an 808 nm laser increases the temperature of the system, while the cells can be inactivated because of the remarkable AuNBPs-PNMV@Apt photothermal effect. The results indicate that variation in the fluorescence of AuNBPs-PNMV@Apt can be applied as thermometers to monitor the intracellular effect of photothermal therapy.

  • Jiayuan Yu, Wanqiang Yu, Bin Chang, Xiao Li, Jin Jia, Dufu Wang, Zhinian Xu, Xiaoli Zhang, Hong Liu, Weijia Zhou
    Chinese Chemical Letters. 2022, 33(6): 3231-3235.

    Tailor-made advanced electrocatalysts with high active and stable for hydrogen evolution reaction (HER) play a key role in the development of hydrogen economy. Herein, a N, P-co-doped molybdenum carbide confined in porous carbon matrix (N, P-Mo2C/NPC) with a hierarchical structure is prepared by a resources recovery process. The N, P-Mo2C/NPC compound exhibits outstanding HER activity with a low overpotential of 84 mV to achieve 10 mA/cm2, and excellent stability in alkaline media. The electrochemical measurements confirm that the enhanced HER activity of N, P-Mo2C/NPC is ascribe to the synergy of N, P-codoped and porous carbon matrix. Density functional theory calculations further reveal that the electron density of active sites on Mo2C can be regulated by the N/P doping, leading to optimal H adsorption strength. In this work, the proof-of-concept resource utilization, a microorganism derived molybdenum carbide electrocatalyst for HER is fabricated, which may inaugurate a new way for designing electrocatalysts by the utilization of solid waste.

  • Tian Tian, Yuhan Ho, Chen Chen, Hebin Sun, Janan Hui, Panhui Yang, Yuqing Ge, Ting Liu, Jian Yang, Hongju Mao
    Chinese Chemical Letters. 2022, 33(6): 3167-3171.

    Liver is the foremost organ of human being for drug metabolism, and it played a significant role in toxicity evaluation of drugs. Establishing a liver model in vitro can accelerate the process of the drug screening and new drug research and development. We provide a 3D printing based hepatic sinusoid-on-a-chip microdevice that reconstitutes organ-level liver functions to create a drug screening model of toxicity evaluation on chip. The microfluidic device, which recapitulates the hepatic sinusoid microenvironment, consists of PET polyporous membranes which mimic the perisinusoidal space, and experience fluid flow to mimic the hepatic arterial capillaries. The PET membrane was used to separate the hepatocyte and endotheliocyte. The endotheliocyte was cultured on the downside of the membrane and the hepatocyte were 3D seeded on the membrane via the 3D printer. This device was used to reproduce the in vitro liver model for drug toxicity assays. The expression of several biomarkers of liver was compared with the monoculture and 2D cultured conditions, and the results reveal that this organ-on-a-chip microdevice mimics the drug hepatoxicity that has not been possible by 2D cell-based and animal models, providing a useful platform for screening the drugs and developing an effective therapy in hepatopathy.

  • Jun Duan, Long Chen, Haodong Ji, Peishen Li, Fan Li, Wen Liu
    Chinese Chemical Letters. 2022, 33(6): 3172-3176.

    Peracetic acid (PAA)-based system is becoming an emerging advanced oxidation process (AOP) for effective removal of organic contaminants from water. Various approaches have been tested to activate PAA, while no previous researches reported the application of metal-organic frameworks (MOFs) materials for PAA activation. In this study, zeolitic imidazole framework (ZIF)-67, a representative MOFs, was facile synthesized via direct-mixing method at room temperature, and tested for PAA activation and sulfachloropyridazine (SCP) degradation. The as-synthesized ZIF-67 exhibited excellent performance for PAA activation and SCP degradation with 100% of SCP degraded within 3 min, owing to the specific MOFs structure and abundant Co2+ sites. The pseudo-first-order kinetic model was applied to fit the kinetic data, with rate constant k1 of ZIF-67 activated PAA system 34.2 and 156.5 times higher than those of conventional Co3O4 activated PAA and direct oxidation by PAA. Radical quenching experiments and electron paramagnetic resonance (EPR) analysis indicated that CH3C(O)OO· played a major role in this PAA activation system. Then, the Fukui index based on density functional theory (DFT) calculation was used to predict the possible reaction sites of SCP for electrophilic attack by CH3C(O)OO·. In addition, the degradation pathway of SCP was proposed based on Fukui index values and intermediates detection, which mainly included the S-N bond cleavage and SO2 extrusion and followed by further oxidation, dechlorination, and hydroxylation. Therefore, ZIF-67 activated PAA is a novel strategy and holds strong potential for the removal of emerging organic contaminants (EOCs) from water.

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