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  • Xiaxi Yao, Xiuli Hu, Yingying Cui, Jialei Huang, Wenjun Zhang, Xuhong Wang, Dawei Wang
    Chinese Chemical Letters. 2021, 32(2): 750-754.

    Light utilization is one of the key factors for the improvement of photocatalytic performance. Herein, we design C-TiO2 hollow nanoshells with strong Mie resonance for enhanced photocatalytic hydrogen evolution in a dye-sensitized system under visible light irradiation (λ≥420 nm). By tuning the inner diameters of hollow nanoshells, the Mie resonance in hollow nanoshells is adjusted for better excitation of dye molecules, which thus greatly enhances the light utilization in visible light region. This work shows the potential of Mie resonance in nanoshells can be an alternative strategy to increase the light utilization for photocatalysis.

  • Yurong Li, Qifei Guo, Yimin Jiang, Wei Shen, Ming Li, Rongxing He
    Chinese Chemical Letters. 2021, 32(2): 755-760.

    Transition-metal chalcogenides with hollow nanostructure, especially cobalt sulfides, are considered as the most promising non-precious metal catalysts for oxygen evolution reaction. However, it is difficult to synthesize oxygen-containing cobalt sulphides with hollow structure due to the different physical/chemical properties between metal sulfides and metal cobalts. Herein, we report a novel oxygen-containing amorphous cobalt sulfide ball-in-ball hollow spheres (Co-S-O BBHS) synthesized by an anion exchange method. Taking advantage of the ball-in-ball hollow structure, the amorphous Co-S-O BBHS shows superior oxygen evolution reaction (OER) electrocatalytic performance with a low overpotential of 285 mV at 10 mA/cm2, small Tafel slope of 49.67 mV/dec, high Faraday efficiency of 96%, and satisfied durability. Experiments and DFT calculations demonstrate that the introduction of oxygen and sulfur modulates the electronic structure of Co-S-O BBHS, thus enhancing the adsorption of *O (adsorbed O species on catalyst surface) intermediate, which greatly boosts the catalytic activity towards OER. This work provides a new strategy for controllable synthesis of complex hollow structures of transition-metal chalcogenides for OER.

  • Xueke Zhou, Haitao Zhao, Shaojun Liu, Yang Yang, Ruiyang Qu, Chenghang Zhen, Xiang Gao
    Chinese Chemical Letters. 2021, 32(2): 761-764.

    CeO2 morphology was proposed to be a crucial factor for reducing nitrobenzene to azoxybenzene under the base-free condition. Herein, the structure-activity relationship of CeO2 catalysts was explored to improve the azoxybenzene yield. A series of CeO2 catalysts were synthesized with seven morphologies to obtain different Ce3+ proportion and various surface areas. Notably, the catalytic performance of these samples for reducing nitrobenzene to azoxybenzene enhanced with the increasing Ce3+ proportion. With the highest surface Ce3+ proportion, the Rod-CeO2 catalyst exhibited 100% conversion of nitrobenzene and 89.8% azoxybenzene selectivity in 7 h at 150 ℃ under 1 MPa CO. Moreover, the preliminary mechanistic analysis indicated that the inhabitation of azoxybenzene to by-product azobenzene resulted in the high selectivity of azoxybenzene.

  • Ke Chen, Shaofeng Deng, Yun Lu, Mingxing Gong, Yezhou Hu, Tonghui Zhao, Tao Shen, Deli Wang
    Chinese Chemical Letters. 2021, 32(2): 765-769.

    The Platinum (Pt)-based catalysts exhibit excellent catalytic performance for the hydrogen evolution reaction (HER) while suffering from poor stability due to the weak interaction between the carbon support and Pt. Herein, a molybdenum-doped titanium dioxide (Ti0.9Mo0.1O2) supported low-Pt electrocatalyst with stronger interaction between catalyst and support is applied to tune the electrocatalytic performance of Pt. The Ti0.9Mo0.1O2 support can not only tolerate the corrosion environment in the catalytic system, but also generate strong metal-support interaction (SMSI) between the oxide and catalyst. A facile solvothermal method is used to prepare Ti0.9Mo0.1O2 as support to anchor Pt nanoparticles. The 5% Pt supported on Ti0.9Mo0.1O2 catalyst exhibits 4.4-fold mass activity (MA) at an overpotential of 50 mV and higher stability than 20% Pt/C with only 1/4 Pt loading. The SMSI between the Ti0.9Mo0.1O2 and Pt prevents the Pt aggregation to achieve excellent stability, and hydrogen spillover effect in the interface between Pt and support benefits the hydrogen production process. This work presents a novel sight for the fabrication and design of oxide supported catalysts in various catalytic system by reasonably employing support effect.

  • Yanwei Cao, Huan Zheng, Gangli Zhu, Haihong Wu, Lin He
    Chinese Chemical Letters. 2021, 32(2): 770-774.

    Selective hydrogenation of aromatic amines, especially chemicals such as aniline and bis(4-aminocyclohexyl)methane for non-yellowing polyurethane, is of particular interests due to the extensive applications. To conquer the existing difficulties in selective hydrogenation, the Ru0-Ruδ+/CeO2 catalyst with solid frustrated Lewis pairs was developed for aromatic amines hydrogenation with excellent activity and selectivity under relative milder conditions. The morphology, electronic and chemical properties, especially the Ru0-Ruδ+ clusters and reducible ceria were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electronic microscopy (SEM), X-ray photoelectron spectroscopy (XPS), CO2 temperature programmed desorption (CO2-TPD), H2 temperature programmed reduction (H2-TPR), H2 diffuse reflectance Fourier transform infrared spectroscopy (H2-DRIFT), Raman, etc. The 2% Ru/CeO2 catalyst exhibited good conversion of 95% and selectivity greater than 99% toward cyclohexylamine. The volcano curve describing the activity and Ru state was found. Owning to the "acidic site isolation" by surrounding alkaline sites, condensation between the neighboring amine molecules could be effectively suppressed. The catalyst also showed good stability and applicability for other aromatic amines and heteroarenes containing different functional groups.

  • Jiafu Chang, Wenxin Lv, Jiahui Wu, Haiyin Li, Feng Li
    Chinese Chemical Letters. 2021, 32(2): 775-778.

    Herein, we propose a novel photoelectrochemical (PEC) biosensor for dual microRNAs (miRNAs) highly sensitive and simultaneous biosensing based on strand displaced amplification (SDA) reaction. The recognition of HmiR-21 and Hlet-7a by microRNA-21 and let-7a leads to their change in hairpin structures, subsequently initiating the immobilization of abundant CdS quantum dots (CdS QDs) and methylene blue (MB) based on SDA reaction. The immobilized CdS QDs and MB produce both high PEC currents under 430 nm light and 627 nm light illumination, respectively, and the generated PEC currents are closely relied on target miRNAs amounts. Thus, highly sensitive and simultaneous detection of microRNA-21 Herein, we propose a novel photoelectrochemical (PEC) biosensor for dual microRNAs (miRNAs) highly sensitive and simultaneous biosensing based on strand displaced amplification (SDA) reaction. The recognition of HmiR-21 and Hlet-7a by microRNA-21 and let-7a leads to their change in hairpin structures, subsequently initiating the immobilization of abundant CdS quantum dots (CdS QDs) and methylene blue (MB) based on SDA reaction. The immobilized CdS QDs and MB produce both high PEC currents under 430 nm light and 627 nm light illumination, respectively, and the generated PEC currents are closely relied on target miRNAs amounts. Thus, highly sensitive and simultaneous detection of microRNA-21 and let-7a was readily achieved with detection limit at 6.6 fmol/L and 15.4 fmol/L based on 3σ, respectively. Further, this PEC biosensor was applied in simultaneous analysis of miRNA-21 and let-7a in breast cancer patient's serum with acceptable results. We expect this biosensor will find more useful application in diagnosis of miRNA-related diseases.

  • Zishan Feng, Wei Zhang, Longjie Li, Bocheng Tu, Weicong Ye, Xiaofeng Tang, Hongbo Wang, Xianjin Xiao, Tongbo Wu
    Chinese Chemical Letters. 2021, 32(2): 779-782.

    We presented a low-abundance mutation detection method with lambda exonuclease and DNA three-way junction structure. The assistant strand in the DNA three-way junction structure could regulate the reaction system from the kinetics and thermodynamics aspects. The optimization of the assistant strand helps to improve the selectivity of the mutant-type DNA to the wild-type DNA about 35 times. Moreover, the cost of the optimization process could be saved by about 90%. The method was applied to the detection of a human ovarian cancer-related gene mutation BRCA1 (rs1799949, c.2082C>T). The limit of detection to the mutation abundance in the DNA three-way junction structure system (0.2%) was one order lower compared with that in the double-stranded DNA structure system (2%). The mutation abundance in different standard samples was quantitively measured, and the results were consistent with the initial abundance in the standard samples.

  • Hua Chai, Peng Miao
    Chinese Chemical Letters. 2021, 32(2): 783-786.

    Circulating tumor DNA (ctDNA) refers to a class of acellular nucleic acids carrying genetic features of primary tumor, which can be regarded as a promising noninvasive biomarker for cancer diagnosis. The development of ctDNA assay is an important component of liquid biopsy. In this study, we have fabricated a novel electrochemical strategy for ultrasensitive detection of ctDNA combining the merits of strand displacement amplification and DNA nanostructures. Stable DNA triangular prism is firstly self-assembled and modified on the electrode surface. After target initiated strand displacement polymerization reaction, the generated DNA product helps the formation of three-way junction nanostructure on triangular prism, which localizes electrochemical species. By carefully investigating the electrochemical responses, the limit of detection (LOD) for ctDNA assay as low as 48 amol/L is achieved. This proposed electrochemical biosensor shows great potential for clinical applications.

  • Yu Liang, Chenhui Li, Lanjun Chen, Jia Huo, Mohammed Loubidi, Yangyang Zhou, Yanbo Liu
    Chinese Chemical Letters. 2021, 32(2): 787-790.

    Herein, we report a microwave-assisted acid-induced post-treatment method for the formation of linker vacancies within Zr-based metal organic frameworks (Zr-MOFs). The number of linker vacancies can be easily regulated with this method by changing the concentration of the HCl solution and the duration of microwave irradiation. The optimized defective UiO-66 showed higher linker defects with a higher specific surface area and thermal stability. The results of the catalytic cyclization of citronella showed that the Zr-MOFs with more defects exhibited enhanced catalytic performance. This work may provide a new method for the creation of defective MOFs with high activity and stability.

  • Xiaoqi Tao, Ziyi Liao, Yaqing Zhang, Fei Fu, Mengqi Hao, Yang Song, Erqun Song
    Chinese Chemical Letters. 2021, 32(2): 791-795.

    The detection of bacterial pathogen such as Staphylococcus aureus (S. aureus) is essential for the regulation of food hygiene and disease diagnosis. Herein, we developed a simple one-step fluorescence resonance energy transfer (FRET)-based sensor for specific and sensitive detection of S. aureus in food and serum samples, in which aptamer-modified quantum dots (aptamer-QDs) was employed as the energy donor and antibiotic of teicoplanin functionalized-gold nanoparticles (Teico-AuNPs) was chosen as the energy acceptor. Within 1 h, the FRET-based sensor showed a linear range of from 10 cfu/mL to 5×108 cfu/mL, with the low limit of detection (LOD, 2 cfu/mL) for S. aureus in buffer. When further applied to assay S. aureus in real samples, the FRET-based sensor showed good recoveries ranging from 84.5% to 110.0%, with relative standard derivations (RSDs) of 0.01%–0.44% and a LOD of 100 cfu/mL in milk, orange juice and human serum.

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