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  • Xiang Li, Xingyue Shu, Yixin Shi, Haolin Li, Xibo Pei
    Chinese Chemical Letters. 2023, 34(7): 107986-.

    Metal-organic frameworks (MOFs), a class of hybrid materials, consist of organic linkers and bridging metal ions or clusters. Their tunable pore sizes, large surface area, good biocompatibility, structural variability in combination with materials and chemicals, and osteogenic effects provide potential approaches for bone tissue engineering and bone diseases. And there are more and more research on MOFs in the field of osteogenesis in recent years. This review presents an overall summary of the application in the bone tissue engineering and bone diseases of MOFs and their composites, starting with the synthesis of MOFs, which discusses the advantages and disadvantages of different syntheses. Then, the biological functions of MOFs are discussed, which are the basics of MOFs applied in the organism. Importantly, mechanisms and abundant applications of MOFs are detailed in the bone tissue engineering and bone diseases. Finally, some prospects of MOFs are discussed, for instance, exploring whether MOFs can be used to treat other bone diseases.

  • Yuhao Liu, Songhang Li, Shiyu Lin, Sirong Shi, Taoran Tian, Bowen Zhang, Tao Zhang, Yunfeng Lin
    Chinese Chemical Letters. 2023, 34(7): 107987-.

    Synthetic antigen-encoding mRNA plays an increasingly significant role in tumor vaccine technology owing to its antigen-specific immune-activation. However, its immune efficacy is challenged by inferior delivery efficiency and demand for suitable adjuvants. Here, we develop a novel mRNA nanovaccine based on a multifunctional nanocapsule, which is a dual-adjuvant formulation composed of cytosine-phosphate-guanine motifs loaded tetrahedral framework nucleic acid (CpG-tFNA) and an immunopeptide murine β-defensin 2 (mDF2β). This mRNA nanovaccine successfully achieves intracellular delivery, antigen expression and presentation of dendritic cells, and proliferation of antigen-specific T cells. In a tumor prophylactic vaccination model, it exerts an excellent inhibitory effect on lymphoma occurrence through cellular immunity. This mRNA nanovaccine has promising prophylactic applications in tumors and many other diseases.

  • Jianfeng Ma, Lingbo Gong, Yingying Cen, Lin Feng, Yan Su, Xingfen Liu, Jie Chao, Ying Wan, Shao Su, Lianhui Wang
    Chinese Chemical Letters. 2023, 34(7): 108012-.

    Selective and sensitive detection of trace microRNA is important for early diagnosis of diseases due to its expression level related to diseases. Herein, a triple signal amplification strategy is developed for trace microRNA-21 (miRNA-21) detection by combining with target-triggered cyclic strand displacement reaction (TCSDR), hybridization chain reaction (HCR) and enzyme catalytic amplification. Four DNA hairpins (H1, H2, H3, H4) are employed to form an ultralong double-strand DNA (dsDNA) structure, which is initiated by target miRNA-21. As H3 and H4 are labeled with horseradish peroxidase (HRP), numerous HRPs are loaded on the long dsDNA, producing significantly enhanced electrocatalytic signals in the hydrogen peroxide (H2O2) and 3,3′,5,5′-tetramethylbenzidine (TMB) reaction strategy. Compared with single signal amplification, the triple signal amplification strategy shows higher electrochemical response, wider dynamic range and lower detection limit for miRNA-21 detection with excellent selectivity, reproducibility and stability. Taking advantage of the triple signal amplification strategy, the proposed electrochemical biosensor can detect miRNA-21 in 10 HeLa cell lysates, suggesting that it is a promising method for fruitful assay in clinical diagnosis.

  • Siyu Kuang, Minglu Li, Xiaoyi Chen, Haoyuan Chi, Jianlong Lin, Zheng Hu, Shi Hu, Sheng Zhang, Xinbin Ma
    Chinese Chemical Letters. 2023, 34(7): 108013-.

    Copper is one of the most efficient catalysts widely investigated in electrochemical CO2 reduction, however, the further development of copper-based catalysts is constrained by severe stability problems. In this work, we developed a method for the synthesis of highly ordered CuAu intermetallic nanoalloys (o-CuAu) under mild conditions (< 250 ℃), which can convert carbon dioxide to carbon monoxide with high selectivity and can operate stably for 160 h without current decay. The improved stability is believed to be due to the increased mixing enthalpy and stronger atomic interactions between Cu and Au atoms in the intermetallic nanoalloy. In addition, XPS results, Tafel slope and in situ IR spectroscopy demonstrate that high valence gold atoms on o-CuAu surface promote the reduction of CO2. In contrast, the disordered CuAu nanoalloy (d-CuAu) underwent atomic rearrangement to form a Cu-rich structure on the surface, leading to reduced stability. These findings may provide insight into the rational design of stable CO2RR electrocatalysts through proper structural engineering.

  • Xiaoli Wu, Sheng Zhao, Lijie Yin, Luqi Wang, Linlin Li, Feng Hu, Shengjie Peng
    Chinese Chemical Letters. 2023, 34(7): 108016-.

    The rational construction of electrocatalysts with desired features is significant but challenging for superior water splitting at high current density. Herein, amorphous CoNiS nanosheets are synthesized on nickel foam (NF) through a facile structure evolution strategy and present advanced performance at high current densities in water splitting. The high catalytic activity can be attributed to the sufficient active sites exposed by the flexible amorphous configuration. Moreover, the hydrophilicity and aerophobicity of a-CoNiS/NF promote surface wettability of the self-supporting electrode and avoid the aggregation of bubbles, which expedites the diffusion of electrolyte and facilitates the mass transfer. As a result, the optimized electrode demonstrates low overpotentials of 289 and 434 mV at 500 mA/cm2 under alkaline conditions for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively. Impressively, an electrolytic water splitting cell assembled by bifunctional a-CoNiS/NF operates with a low cell voltage of 1.46 V@10 mA/cm2 and reaches 1.79 V at 500 mA/cm2. The strategy sheds light on a competitive platform for the reasonable design of non-precious-metal electrocatalysts under high current density.

  • Weitao Yan, Mingwen Zheng, Peihsuan Chuang, Hao Sun, Shiping Wang, Chunfa Xu, Fen-Er Chen
    Chinese Chemical Letters. 2023, 34(7): 108021-.

    A highly efficient coupling of glycosyl stannanes and sulfonium salts enabled by synergistic Pd/Cu catalysis is disclosed, facilitating the construction of C-aryl/alkenyl glycals under mild conditions in high yields. The protocol tolerates a wide scope of functional groups including ketone, cyano, ester, amide, nitro, halide. The one-pot formal CH glycosylation starting from arene is demonstrated with a reaction sequence of dibenzothiophenylation/Stille coupling. Besides, a gram-scale reaction is performed successfully, showing the high applicability of this protocol.

  • Ming-Hui Sun, Ming-Yu Qi, Chang-Long Tan, Zi-Rong Tang, Yi-Jun Xu
    Chinese Chemical Letters. 2023, 34(7): 108022-.

    Ternary composites of reduced graphene oxide (GR)-CdS-Pd have been successfully synthesized via solvothermal and photodeposition methods for photocatalytic selective conversion of benzyl alcohol (BA) coupled with hydrogen (H2) production, which exhibit significantly improved photoactivity and selectivity than bare CdS. Mechanistic studies unveil that the cooperative effect of the close interface contact and matched energy level alignment between electrical conducting GR nanosheets (NSs) and CdS nanoparticles (NPs) in GR-CdS-Pd composite not only benefits the separation and transfer of photogenerated carriers but also improves the photocorrosion resistance of CdS. The photodeposited Pd NPs further promote the photogenerated charge separation and accelerate the formation of intermediate products (α-hydroxybenzyl radicals), thereby contributing to enhanced conversion of BA. This work would facilitate the rational design of GR as cocatalyst to construct an efficient and stable CdS-based composite photocatalyst for cooperative coupling of fine chemical synthesis and H2 evolution.

  • Yiqiu Hu, Xiujuan Hong, Zhijun Yuan, Jiayi Mu, Xiaoxiao Zhang, Zhihao Fang, Ying Yuan, Shu Zheng, Cheng Guo
    Chinese Chemical Letters. 2023, 34(7): 108023-.

    Accumulating evidence in recent years indicates that DNA methylation (5-methyl-2′-deoxycytidine, 5-mdC) and hydroxymethylation (5-hydroxymethyl-2′-deoxycytidine, 5-hmdC) have been implicated in various biological processes, and the aberrations of these DNA cytosine modifications is tightly associated with cancer. N6-methyl-2′-deoxyadenosine (m6dA), as a newly discovered epigenetic modification in genome of mammals, has been demonstrated to play vital regulatory roles in tumorigenesis. However, the content information of m6dA in human tumor tissues is still limited and pan-cancer analysis of these DNA epigenetic modifications is lacked. Herein, we developed a sensitive and robust stable isotope-diluted hydrophilic interaction liquid chromatography-tandem mass spectrometry (HILIC-MS/MS) method for accurate quantification of m6dA, 5-mdC and 5-hmdC in genomic DNA from 82 pairs of human tumor tissues and matched tumor-adjacent normal tissues. The types of tumors included esophagus cancer, lung cancer, breast cancer, liver cancer, pancreatic cancer, gastric cancer, stromal tumor and colorectal cancer. Compared to the normal tissues, we revealed the level of m6dA was increased in tumor tissues of esophagus cancer, lung cancer and liver cancer, whereas the level of m6dA was diminished in tumor tissues of pancreatic cancer and gastric cancer; while the contents of 5-mdC and 5-hmdC exhibited significant decrease in tumor tissues of most types of cancer. It is worth noting that we revealed, for the first time, the content of genomic m6dA in pancreatic cancer, stromal tumor and colorectal cancer. The significant changes of these DNA epigenetic modifications indicate they may serve as indicators of cancers. In addition, this study will benefit for better understanding of the regulatory roles of these DNA epigenetic modifications in cancers.

  • Sen Xu, Zhihua Zhong, Yu Wang, Lingyi Zhang, Weibing Zhang
    Chinese Chemical Letters. 2023, 34(7): 108024-.

    A novel chromatography stationary phase with a quasi-graphitized carbon modified shell has been developed. Coal pitch was directly carbonized on the surface of porous silica with in-situ carbonization. The carbonized coal pitch coating exhibits some degree of graphitization with a 78 nm-thick layer on the surface of silica and a 0.5 nm-thick layer on the inner surface of the mesopores. Based on the special structure of the graphitized carbon coating, the novel stationary phase can provide multiple interactions such as hydrophobic interaction, π-π interaction and dipole-dipole interaction. The novel composite material exhibited unique separation selectivity and excellent separation efficiency for polar compounds, including imidazoles, nucleosides and pesticides. Besides, the packed column also exhibited great repeatability with the RSDs of the retention time of nucleosides between 0.07%-0.50% (n = 5). Finally, satisfied result was achieved in the separation of fullerenes on the new column, suggesting the great potential in the industrial-scale purification of fullerenes.

  • Bo Li, Shihao Liu, Wu Fan, Xiaotong Shen, Jing Xu, Suhua Li
    Chinese Chemical Letters. 2023, 34(7): 108027-.

    Decarbonylation of aldehydes is a basic organic transformation, which has been developed for more than six-decade. However, as comparing to well-studied aromatic aldehydes, fewer examples for catalytic decarbonylation of aliphatic aldehydes were reported, mainly on simple or special substrates. For α-bulky or highly functionalized ones, stoichiometric Rh(Ⅰ) were usually required for decent yields. Herein, we present a rare example of Ir(Ⅰ)-catalyzed direct decarbonylation of α-quaternary aldehydes with broad substrate scope and good functional group compatibility via judicious selection of ligand. The α-chirality is memorized in this decarbonylation process. In addition, we report a broad-spectrum decarbonylation of α-secondary and α-tertiary aldehydes containing multifunctional groups with an improved Rh(Ⅰ)/DPPP recipe. Finally, we realized selective decarbonylation of α-tertiary aldehydes in the presence of α-quaternary one via the reactivity differences.

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