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  • Yongchao Chu, Tao Sun, Chen Jiang
    Chinese Chemical Letters. 2022, 33(9): 4157-4168.

    The emergence of disseminated metastasis is the leading cause of mortality in patients with malignant tumor. The pre-metastatic microenvironment, including the primary tumor-derived components, pre-metastatic niche (PMN), circulating tumor cells (CTCs), micro-metastases, and tumor immune microenvironment (TIM), are the crucial factors to initiate metastasis and form macro-metastases. It may be a more promising strategy for directly targeting pre-metastatic microenvironment-interrelated factors and cells before they have the chance to form secondary tumors to prevent metastasis. During recent years, a variety of nanosystems, with specific microstructures and functional properties, have been devised to selectively target pre-metastatic cells components and interrelated molecular, and exhibited strong potential on anti-metastatic therapy by absorbing and neutralizing primary tumor-derived components, preventing establishment of the PMN, eliminating the CTCs, eradicating the micro-metastases and modulating the TIM. In this review, we comprehensively review the emerging nanosystems based on the pre-metastatic microenvironments. Hopefully, this review can cast new lights for early preventing and attenuating metastatic progression.

  • Fan Liao, Xing Fan, Huixian Shi, Qing Li, Mengjie Ma, Wenxiang Zhu, Haiping Lin, Youyong Li, Mingwang Shao
    Chinese Chemical Letters. 2022, 33(9): 4380-4384.

    Carbon dioxide electrochemical reduction (CO2RR) has been recognized as an efficient way to mitigate CO2 emissions and alleviate the pressure on global warming and associated environmental consequences. Gold (Au) is reported as stable and active electrocatalysts to convert CO2 to CO at low overpotential due to its moderate adsorption strength of *COOH and *CO. The request for improved catalytic performance, however, is motivated by current unsatisfied catalytic selectivity because of the side hydrogen evolution reaction. In this context, the design of Au based binary catalysts that can boost CO selectivity is of great interest. In the present work, we report that Au nanoparticles can be feasibly dispersed and anchored on silicon nanowires to form Au-Si binary nanomaterials. The Au-Si may stably drive CO2RR with a CO Faraday efficiency of 95.6% at −0.6 V vs. RHE in 0.5 mol/L KHCO3 solution. Such selectivity outperforms Au particles by up to 61%. Controlled experiments illustrate that such catalytic enhancement can chiefly be ascribed to electronic effects of binary catalysts. Theoretical calculations reveal that spontaneously produced silicon oxide may not only inhibit hydrogen evolution reaction, but also stabilize the key intermediate *COOH in CO formation.

  • Yisa Xiao, Weichen Huang, Qilong Shen
    Chinese Chemical Letters. 2022, 33(9): 4277-4280.

    A method for stereoselective construction of Z-monofluoroalkenes by nickel-catalyzed defluorinative coupling of gem-difluoroalkenes in mild conditions was described. The combination of lithium organoborate and ZnBr2 generated in situ lithium aryl zincates, which facilitates the transmetalation step of the nickel-catalyzed cross coupling reaction.

  • Qingqing Xiao, Xiaotong Li, Chang Liu, Yi Yang, Yuqi Hou, Ying Wang, Mengxiang Su, Wei He
    Chinese Chemical Letters. 2022, 33(9): 4191-4196.

    Downregulated pro-apoptotic protein in cancer cells compromises the chemotherapy by a cytotoxic drug. Here, we report co-delivery of a pro-apoptotic protein, caspase 3 (Cas 3), and cytotoxic agent, oridonin (ORD), for synergistic cancer treatment, using a method of liposome-based anchoring and core encapsulation. First, ORD is modified with hyaluronic acid (HA) to improve its solubility. Then, the targeted co-delivery system is prepared by assembling the conjugate HA-ORD onto the Cas 3-loaded liposomes, which the surface HA can target the CD44 receptor on cancer cells. In vitro, the co-loaded liposomes (120 nm) are specifically taken up by 4T1 cells and endow a 1.5-fold increase of Cas 3. After intravenous injection into the tumor-bearing mice, the liposomes accumulate in the tumor with high efficacy and significantly inhibit tumor growth via promoting apoptosis and anti-proliferation of cancer cells. Mechanistically, the co-delivery works synergistically by upregulating the activated Cas form, cleaved-Cas 3.

  • Xiaojun Yu, Haitao Ma, Guiying Xu, Zhuang Liu
    Chinese Chemical Letters. 2022, 33(9): 4169-4174.

    As an extensively applied therapeutic approach to combat tumors, radiotherapy generates localized ionizing radiation to destruct tumor cells. Despite its importance in clinical oncology, radiotherapy would often cause significant organ toxicity, and its therapeutic effect is limited by tumor hypoxia. Moreover, although abscopal therapeutic effects have occasionally been observed, radiotherapy is still mostly employed as a local treatment method that could hardly control tumor metastases. In recent years, strategies involving biomaterials and nanomedicine have received increasingly high attention to enhance cancer radiotherapy. Beyond sensitizing tumors for radiotherapy via various mechanisms, many biomaterial systems with immune stimulating effects have also been introduced to boost the antitumor immunity post cancer radiotherapy. In this mini-review, we will summarize the progress of different biomaterials and nanomedicine systems in combination with radiotherapy to trigger antitumor immune responses and enhance the efficacy of immunotherapy, and discusses the perspectives and challenges of this research direction aimed at clinical translations.

  • Yan Yu, Meng Pan, Jinrong Peng, Danrong Hu, Ying Hao, Zhiyong Qian
    Chinese Chemical Letters. 2022, 33(9): 4133-4145.

    Hydrogen peroxide (H2O2) is a very simple bioactive small molecule. In living organisms, H2O2 plays an important role in intracellular signaling. It is involved in many physiological processes including cellular physiology, intracellular signaling, oxidative damage and disease progression. The tumor microenvironment enriched with H2O2. Several electrochemical sensors have been developed and some have been put on the market. Such electrochemical sensors provide efficient, cost-effective, rapid and highly selective method of H2O2 detection. So far, much progress has been made in the designing of materials and construction of H2O2 sensors. This review describes the advances in the application of H2O2 electrochemical sensors in cell detection. Enzyme-based sensors have been applied in diverse applications. In addition, recent advancements in nanotechnology have improved the development of nanozymes-based sensors. The application of noble metals, metal oxides, polymers, carbon materials and other two-dimensional materials in the design of H2O2 sensors are discussed in detail. Moreover, the bio-stimulant types of H2O2 sensor are summarized. Finally, the challenges and future perspectives in the application of H2O2 electrochemical sensors in biological detection are discussed.

  • Peng-Jun Zhou, Yi Zang, Cong Li, Lin Yuan, Huaqiang Zeng, Jia Li, Jin-Feng Hu, Juan Xiong
    Chinese Chemical Letters. 2022, 33(9): 4264-4268.

    Forrestiacids C (1) and D (2), a pair of C-25 epimeric triterpene–diterpene adducts were isolated from the needles and twigs of the vulnerable conifer Pseudotsuga forrestii. This unprecedented class of compounds might be generated via an intermolecular Michael addition reaction of a rearranged 6/6/5/5-fused spiro-lanostene with an abietene. Their structures were established by spectroscopic data and X-ray crystallography. The adducts showed inhibitory activities against the ATP-citrate lyase (ACL) and acetyl-CoA carboxylase 1 (ACC1), two rate-limiting enzymes in the de novo lipogenesis pathway.

  • Ying He, Mengjia Liu, Shun Teng, Lukasz Wojtas, Guangxin Gu, Xiaodong Shi
    Chinese Chemical Letters. 2022, 33(9): 4203-4207.

    Fluorescence (FL) active 8-aryl guanosine derivatives were prepared and applied for cation mediated self-assembly to form the H-bonded G8-quadruplexes. The p-cyano (p-CN) and 8-anthracene (8-An) substituted guanosines were identified to give the strongest fluorescence with the formation of G8-octamers (G8) both in solution (NMR) and solid state (X-ray). This well-defined G8-octamer system has provided the first direct evidence on the self-assembled G-quadruplex fluorescence emission with aggregation-induced emission (AIE), which could be applied as the foundation for FL molecular probe design toward G-quadruplex recognition.

  • Taotao Li, Yu Zheng, Chenqin Wu, Chengyu Yan, Cheng Zhang, Hong Gao, Qian Chen, Kui Zhang
    Chinese Chemical Letters. 2022, 33(9): 4238-4242.

    Room temperature phosphorescence (RTP) films have recently attracted increasing attention due to their excellent luminescent properties for information encryption, optoelectronic devices, and sensors. However, polyvinyl alcohol (PVA) films with abundant hydrogen bonds to suppress triplet energy dissipation suffered from the humidity induced phosphorescence quenching under storage in the air for a long time. In this work, poly(acrylic acid) (PAA) was selected to crosslink PVA matrix through esterification reactions for preparing water resistant RTP films. The blue, cyan, and orange emissive RTP films were successfully obtained by incorporating three different organic compounds into PVA-PAA crosslinking films. Crosslinking strategy significantly improved the phosphorescence emissions of the doped films, and effectively blocked the absorption of water molecular, leading to the excellent photostability of the developed films. As a proof of concept, the white light phosphorescence film and anti-counterfeiting applications were successfully demonstrated.

  • Longlong Xi, Liting Du, Zhuangzhi Shi
    Chinese Chemical Letters. 2022, 33(9): 4287-4292.

    A nickel-catalyzed reductive cross-coupling reactions between polyfluoroarenes and alkyl electrophiles is reported to access substituted fluoroarenes through chelation-assisted C–F activation. Diverse primary and secondary alkyl (pseudo)halides can be employed to couple with polyfluoroarenes, showing excellent regioselectivity. Furthermore, the nickel-catalyzed asymmetric cross-coupling of polyfluoroarenes with racemic alkyl halides is preliminarily explored. In addition, the practicability of the title transformation is also demonstrated by total synthesis of losmapimod and an analog as key steps. The developed method exhibits many advantages, including economic catalytic systems, commercially available alkyl electrophiles, and lack of sensitive organometallic reagents.

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