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  • Qiang Fu, Shouhong Sun, Kangzhi Lu, Ning Li, Zhanhua Dong
    Chinese Chemical Letters. 2024, 35(7): 109136-.

    Due to their superior fluorescence, phosphorescence, and catalytic capabilities, carbon dots (CDs), an emerging class of fluorescent carbon nanomaterials, have a wide range of potential applications. The properties of CDs have recently been controlled extensively by heteroatom doping. Boron atoms have been effectively doped into the structure of CDs due to their similar size to carbon atoms and excellent electron-absorbing ability to further improve the performance of CDs. In this review, we summarize the research progress of boron-doped CDs in recent years from the aspects of doping strategies, effects of boron doping on different performances of CDs and applications. Starting from the two aspects of single boron doping and boron and other atom co-doping, from different precursor materials to different synthesis methods, the doping strategies of boron-doped CDs are reviewed in detail. Then, the effects of boron doping on the fluorescence, phosphorescence and catalytic performance of CDs and applications of boron-doped CDs in optical sensors, information encryption and anti-counterfeiting are discussed. Finally, we further provide a prospect towards the future development of boron-doped CDs.

  • Xueyang Zhao, Bangwei Deng, Hongtao Xie, Yizhao Li, Qingqing Ye, Fan Dong
    Chinese Chemical Letters. 2024, 35(7): 109139-.

    Diatomic-site catalysts (DASCs) have emerged as a kind of promising heterogeneous candidate catalysts for electrochemical CO2 reduction (ECR), which is considered to retain the advantage of single-atom catalysts (SACs) but also introduce opportunities to exceed the limit of single-atom catalysts. In the past few years, tremendous progress has been achieved in this field. Herein, the recent progress in ECR on DASCs has been summarized. It will start with the classification of DASCs. Then the challenges in the precise fabrication and characterization of DASCs have been emphasized. By introducing the advanced ECR performance on DASCs, superior to that on SACs, the synergistic effects of the dual metal atoms are highlighted, as this origin of the advanced ECR performance on DASCs is comprehensively summarized. Finally, the major challenges and perspectives of DASCs have been proposed to shed light on the development of DASCs for ECR application.

  • Zhi Li, Wenpei Li, Shaoping Jiang, Chuan Hu, Yuanyu Huang, Maxim Shevtsov, Huile Gao, Shaobo Ruan
    Chinese Chemical Letters. 2024, 35(7): 109150-.

    Insufficient intratumoral retention of nanomedicines remains the major challenge for broad implementation in clinical sets. Herein, we proposed a legumain-triggered aggregable gold nanoparticle (GNP) delivery platform (GNPs-A&C). GNPs-A&C could form intratumoral or intracellular aggregates in response to the overexpressed legumain. The aggregates with size increase not only could reduce back-flow from interstitial space to peripheral bloodstream but also could restrict the cellular exocytosis, leading to enhanced intratumoral retention. In vitro studies demonstrated that GNPs-A&C possessed an excellent legumain responsiveness and the increased size was closely relevant with legumain expression. In vivo studies demonstrated GNPs-A&C possessed slower clearance rate and much higher intratumoral retention within legumain-overexpressed tumor compared to non-aggregable NPs, regardless of intravenous or intratumoral injection. More importantly, this delivery platform significantly improved the chemotherapeutic effect of doxorubicin (DOX) towards subcutaneous xenograft C6 tumor. The effectiveness of this stimulus-responsive aggregable delivery system provides a thinking for designing more intelligent size-tunable nanomedicine that can substantially improve intratumoral retention.

  • Xin Li, Xuan Ding, Junkun Zhou, Hui Shi, Zhenxi Dai, Jiayi Liu, Yongcun Ma, Penghui Shao, Liming Yang, Xubiao Luo
    Chinese Chemical Letters. 2024, 35(7): 109158-.

    The preparation of hydrogel adsorbents with admirable performance for efficient selective remove Pb(Ⅱ) in complex wastewater still remains a great challenge. Herein, a novel bifunctional modified polymer hydrogel PAM-PAMPS was prepared by crosslinking acrylamide (AM) and 2-acrylamido-2-methylpropanesulfonic acid (AMPS). Compared with PEG, PAA and PAMPS, PAM-PAMPS exhibited both the maximum adsorption capacity of Pb(Ⅱ) (541.90 mg/g) and satisfactory selectivity for Pb(Ⅱ) in multiple heavy metal ions coexistence solutions. Various characterizations indicated that SO3H and NH2 as active sites on PAM-PAMPS occur the synergistic effects of ion-exchange and coordination with Pb(Ⅱ) during the adsorption process, respectively. The adsorption energy Ead(PAM-PAMPS) obtained from density functional theory (DFT) calculations was lower than the other three hydrogels, manifesting that PAM-PAMPS formed the most stable complex with Pb(Ⅱ), which further demonstrated that Pb(Ⅱ) preferred to combine with PAM-PAMPS to selective capture of Pb(Ⅱ). The practice utilization of PAM-PAMPS was assessed by wastewater of electroplate containing Pb(Ⅱ). Meanwhile, the removal ratio of PAM-PAMPS was maintained at about 89% after 4 adsorption-desorption cycles. This study establishes a new and effective idea for the design and fabrication of bifunctionalized modified polymer hydrogels.

  • Jingqi Xin, Shupeng Han, Meichen Zheng, Chenfeng Xu, Zhongxi Huang, Bin Wang, Changmin Yu, Feifei An, Yu Ren
    Chinese Chemical Letters. 2024, 35(7): 109165-.

    Tumor microenvironment (TME)-activatable probes have been proven to effectively increase signal-to-background ratios (SBRs) and improve the success rate of complete tumor resection. However, many fluorescence probes have to be loaded into a nanocarrier for tumor targeted delivery, which consequently encounters poor drug loading, heterogeneous composition and non-encapsulated drug aggregates occurred during nanoformulation fabrications. Herein, a nitroreductase (NTR)-activated "OFF-ON" near-infrared fluorescence nanoprobe, named NanoBodipy, was synthesized by the spontaneous self-assembling of NTR-responsive dye-polyethylene glycol (PEG) amphiphilic polymer in water. The NTR-responsive dye acted as the hydrophobic segment in the amphiphilic polymer, yielding a homogeneous composition and a high loading of 12.2 wt% (according to calculation) in the synthesized NanoBodipy. The synthesized NanoBodipy can efficiently accumulate in tumors via the enhanced permeability and retention (EPR) effect, enabling non-invasive tumor-targeted fluorescence imaging and guiding complete tumor resection. Once the synthesized NanoBodipy entered the tumor cells, they dissociated and were activated by overexpressed NTR. With the real-time fluorescence guide of NanoBodipy, complete tumor resection surgery was performed successfully.

  • Xueling Yu, Lixing Fu, Tong Wang, Zhixin Liu, Na Niu, Ligang Chen
    Chinese Chemical Letters. 2024, 35(7): 109167-.

    Chemical sensor arrays can obtain more comprehensive analyte information through high-dimensional data. It is of great significance in the analysis of multi-component complex samples. This review summarizes the development and status of chemical sensor arrays. We focused on the design of chemical sensor arrays based on various sensing materials. In addition, several pattern recognition methods in chemometrics are introduced. And applications of chemical sensor arrays in food monitoring, medical diagnosis, and environmental monitoring are illustrated. Based on the analysis of the limitations of current sensor array technology, the direction of the array is also predicted. This review aims to help the broad readership understand the research state of chemical sensor arrays and their development prospects.

  • Yating Zheng, Yulan Huang, Jing Luo, Xuqi Peng, Xiran Gui, Gang Liu, Yang Zhang
    Chinese Chemical Letters. 2024, 35(7): 109169-.

    Biomacromolecules are attractive in biomedical applications as therapeutic agents and potential drug carriers due to their natural active components, good biocompatibility, and high targeting. However, their large relative molecular weight, complex structure, susceptibility to degradation, and poor stability limit their usefulness. Nanotechnology can address these issues by improving the therapeutic value, bioavailability, permeability, and absorption of biomacromolecules while regulating their retention time in the body. Especially, compelling evidence has been reported that supercritical fluid (SCF) technology has emerged as an alternative that maintains the integrity of biomacromolecules and reduces environmental contamination. In this review, we highlight a set of unique nanosizing strategies based on SCF technology for biomacromolecular nanomedicine, and extensively discuss their characteristics and mechanisms. In particular, the protein-based, nucleic acid-based, and polysaccharide-based nanomedicine preparations via SCF technology and their biomedical applications are summarized, and the potential for industrial production of biomacromolecular drugs is also considered. We further provide perspectives on the opportunities and challenges in this excellent field of biomacromolecular drugs nanotechnology.

  • Yu Qin, Mingyang Huang, Chenlu Huang, Hannah L. Perry, Linhua Zhang, Dunwan Zhu
    Chinese Chemical Letters. 2024, 35(7): 109171-.

    Photothermal therapy (PTT) and photodynamic therapy (PDT) have received tremendous attention owing to their great potential for tumor treatment. However, two main issues hamper the antitumor performance of PDT: overexpression of glutathione (GSH) in tumors, which consumes PDT-induced reactive oxygen species (ROS), and hypoxia within the tumor microenvironment. The drawbacks of PTT include uneven temperature distribution and the upregulation of the heat-shock proteins in tumors, both of which result in ineffective treatment. To address these issues, a MnO2 doped nano-delivery system (HTIM-PMs) was synthesized by one-step self-assembly of disulfide bond bridged copolymers for indocyanine green (ICG) and MnO2 loading. The surface of polymeric micelles was layered with hyaluronan (HA) and transactivator (TAT) peptides to improve active targeting and increase cell penetration. After internalization, HTIM-PMs showed responsiveness to the tumor microenvironment (acid pH, high glutathione, high H2O2). Breaking the disulfide bond reduced the intratumoral GSH level and simultaneously released the MnO2 and ICG. The released MnO2 further reduced the GSH level and promoted O2 generation, thus enhancing the PDT effect. The PTT-mediated hyperthermia accelerated blood flow, which is beneficial for O2 distribution, and promotes ROS diffusion. These PTT-mediated adjuvant effects further overcame the limitations of PDT and the robust PDT effect in turn compensated for the deficiency of PTT. This promising platform exhibited a significant improvement in the PTT-PDT cancer treatment strategy compared to previously reported nanostructures.

  • Yun Wei, Lei Zhou, Wenbin Hu, Liming Yang, Guang Yang, Chaoqiang Wang, Hui Shi, Fei Han, Yufa Feng, Xuan Ding, Penghui Shao, Xubiao Luo
    Chinese Chemical Letters. 2024, 35(7): 109172-.

    The efficient and environmentally friendly recycling technology of waste residue that including abundant heavy metal produced during the recovery of lithium batteries has become a research hotspot. Herein, a novelty process of acid leaching-selective electrodeposition-deep impurity removal-regeneration was proposed to recovery of the CuS slag, which has been efficient transferred to high purity cathode copper and commercially available ternary precursors. Copper cathode with a purity of 99.67% was prepared under electrochemical reaction conditions at −0.55 V for 2 h. A novel impurity remover-Mn powder, which was used to remove the residual impurities and as a feedstock for the ternary precursor. Finally, NCM523 was regenerated by co-precipitation. The process is superior to the traditional process in economy, energy consumption, CO2 emissions, product purity and process duration. This study provides a new approach for solid waste recovery and precious metal enrichment.

  • Shiyu Pan, Bo Cao, Deling Yuan, Tifeng Jiao, Qingrui Zhang, Shoufeng Tang
    Chinese Chemical Letters. 2024, 35(7): 109185-.

    To surmount the obstacles of traditional Fenton method and synchronously utilize Cu2+ and polyphenol in water, an improved Fenton-like reaction applying calcium peroxide (CaO2) as H2O2 source and regulating by the complex of Cu2+-tartaric acid (TA, a representative of polyphenol) was constructed. A typical antibiotic, metronidazole (MTZ) could be effectively eliminated by the Cu2+/TA/CaO2 system, and the optimized parameters were as follows: 0.1 mmol/L Cu2+, 2 mmol/L TA, 2 mmol/L CaO2, and initial pH 5. UV spectrum confirmed the formation of Cu2+-TA complex, which promoted the Cu2+/Cu+ circulation through decreasing the Cu2+/Cu+ couple redox potential, which further enhanced the H2O2 decomposition and the formation of reactive species. Hydroxyl radical was dominant for MTZ degradation, followed by oxygen and superoxide radical. The degradation intermediates of MTZ were detected and their evolution way was speculated. Furthermore, the ternary process showed a wide pH tolerance (3–8) for removing MTZ and broad applicability for eliminating other dyes and antibiotics. This work provided a reference for Cu-based Fenton-like strategy for organic wastewater settlement.

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