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  • Hao Xu, Yujun Liu, Xu-Ming Xie
    Chinese Chemical Letters. 2023, 34(4): 107470-.

    Hydrogel-based quasi-solid-state electrolytes (Q-SSEs) swollen with electrolyte solutions are important components in stretchable supercapacitors and other wearable devices. This work fabricates a super-tough, fatigue-resistant, and alkali-resistant multi-bond network (MBN) hydrogel aiming to be an alkaline Q-SSE. To synthesize the hydrogel, a 2-ureido-4[1H]-pyrimidone (UPy) motif is introduced into a poly(acrylic acid) polymer chain. The obtained MBN hydrogels with 75 wt% water content exhibit tensile strength as high as 2.47 MPa, which is enabled by the large energy dissipation ability originated from the dissociation of UPy dimers due to their high bond association energy. Owing to the high dimerization constant of UPy motifs, the dissociated UPy motifs are able to partially re-associate soon after being released from external forces, resulting in excellent fatigue-resistance. More importantly, the MBN hydrogels exhibit excellent alkali-resistance ability. The UPyGel-10 swollen with 1 mol/L KOH display a tensile strength as high as ~1.0 MPa with elongation at break of ~550%. At the same time, they show ionic conductivity of ~17 mS/cm, which do not decline even when the hydrogels are stretched to 500% strain. The excellent mechanical property and ionic conductivity of the present hydrogels demonstrate potential application as a stretchable alkaline Q-SSE.

  • Pingli Feng, Wenshuo Hou, Zhe Bai, Yu Bai, Kening Sun, Zhenhua Wang
    Chinese Chemical Letters. 2023, 34(4): 107427-.

    Lithium-sulfur batteries as one of the most promising next-generation high-energy storage system, the shuttle effect, the expansion of cathode and the slow electrode redox kinetics limit its further development. Herein, we report a two-dimensional, ultrathin and ultra-light bimetal-NiCo-organic framework as the interlayer for Li-S batteries. This kind of interlayer can effectively block polysulfides and accelerate the conversion with a thickness of only 1 µm and a load of 0.1 mg/cm2. Because the MOF nanosheets with a thickness of a few nanometers have a large specific surface and a large number of exposed accessible active sites. At the same time, the intrinsic activity of each site is enhanced and the catalytic performance is improved due to the synergistic effect of mixed metals and the unique coordination environment around the active sites. So, 2D NiCo MOF/CNT totally meets the requirements for the lightweight and effective interlayer. The initial discharge capacity of cell with 2D NiCo MOF/CNT interlayer can reach 1132.7 mAh/g at 0.5 C. It remained 709.1 mAh/g after 300 cycles, showing good cycling stability and rate performance.

  • Xin Lu, Yue Wang, Zhixuan Feng, Liang Fu, Dandan Zhou
    Chinese Chemical Letters. 2023, 34(4): 107617-.

    The coevolution and coexistence of bacterial–fungal consortium have been widely reported in various natural ecosystems. The transboundary communication mediated by bacterial acyl–homoserine lactone signals probably is the driving force of fungal spore germination. This study aimed to report a functional bacterial signal molecule, C10-acyl homoserine lactone, which could be sensed by Galactomyces geotrichum. The spore germination rates of G. geotrichum increased by 22%. Meanwhile, carbohydrate production improved by 1.0- to 2.5-fold. G. geotrichum signaled to C10-HSL through receptor gene Rho1 and made a response in cell wall assembly and carbohydrate biosynthesis by the upregulated expression (above 1-fold) of functional genes, such as Smi1, Utr2, and Chs2. It contributed to spore germination and morphology transformation together. This study provides a novel perspective for understating the transboundary cooperation between fungi and bacteria by cell-to-cell communication.

  • Zongyuan You, Wei Hua, Na Li, Huanyan Liu, Jian-Gan Wang
    Chinese Chemical Letters. 2023, 34(4): 107525-.

    Rechargeable aqueous Zn/MnO2 batteries raise massive research activities in recent years. However, both the working principle and the degradation mechanism of this battery chemistry are still under debate. Herein, we provide an in-depth electrochemical and structural investigation on this controversial issue based on α-MnO2 crystalline nanowires. Mechanistic analysis substantiates a two-electron reaction pathway of Mn2+/Mn4+ redox couple from part of MnO2 accompanying with a reversible precipitation/dissolution of flaky zinc sulfate hydroxide (ZSH) during the discharge/charge processes. The formation of the ZSH layer is double-edged, which passivates the deep dissolution of MnO2 upon discharging, but promotes the electrochemical deposition kinetics of active MnO2 upon charging. The cell degradation originates primarily from the corrosion failure of metallic zinc anode and the accumulation of irreversible ZnMn2O4 phases on the cathode. The addition of MnSO4 to the electrolyte could afford supplementary capacity contribution via electro-oxidation of Mn2+. However, a high MnSO4 concentration will expedite the cell failure by corroding the metallic zinc anodes. The present study will shed a fundamental insight on developing new strategies toward practically viable Zn/MnO2 batteries.

  • Chuanxiang Zhang, Jie Zhou, Tingting Ma, Wenfei Guo, Dan Wei, Yimin Tan, Yan Deng
    Chinese Chemical Letters. 2023, 34(4): 107670-.

    Phthalates esters (PAEs) are extensively used as additives for polymers in plastic, particularly in polyvinyl chloride (PVC) and polyethylene terephthalate (PET). These compounds are not part of the polymer chains and can be released easily from products and migrate into beverages and foods that come into direct contact, causing environmental and human health impacts. Simple and rapid detection of such substances is of great significance for ensuring environmental food safety and consumer health. At present, optical sensor and electrochemical sensor detection technologies have been applied to PAEs detection due to their advantages, such as simple, rapid, low cost, high sensitivity, simple operation, portability and high specificity. They can make up for the shortcomings of chromatographic detection technology, such as expensive equipment, cumbersome operation, the need for professional and technical personnel, and difficulty in achieving a large number of sample screening objectives. In this paper, research progress on optical sensors and electrochemical sensors for the detection of phthalates in recent ten years is reviewed and discussed. This is helpful to better understand preparation methods for sensors and their detection mechanisms for phthalates. The review will also be used in developing a more effective trace detection sensor for phthalates.

  • Shuangling Luo, Chao Liang, Qianling Zhang, Pingyu Zhang
    Chinese Chemical Letters. 2023, 34(4): 107666-.

    Hypoxic tumor microenvironment is a major challenge for photodynamic therapy (PDT). To overcome this problem, PDT combined hypoxia-activated chemotherapy is a promising strategy for hypoxic cancer therapy. Herein, a multifunctional liposome (AQ4N-Ir1-sorafenib-liposome) is prepared by encapsulating a hypoxia-activated prodrug AQ4N, a photosensitizer iridium(Ⅲ) complex and hepatocellular carcinoma (HCC) targeting drug sorafenib, for synergistic therapy of HCC. Ir1-mediated PDT upon irradiation induces ROS generation and hypoxic environment, which leads to the disassembly of the liposome and activates the antitumor activity of AQ4N. Meantime, the co-delivered sorafenib could effectively target therapy of HCC. It is noted that ferroptosis mechanism is proved during the treatment. This work contributes to the design of hypoxia-responsive multifunctional liposome for combination of chemotherapy, targeting therapy and PDT. It is a promising strategy for hypoxic HCC therapy.

  • Yujie Sun, Lei Wen, Huili Ma, Wenlin Ma, Zhenqian Fu, Yinhui Li, Chengwu Zhang, Lin Li, Jinhua Liu
    Chinese Chemical Letters. 2023, 34(4): 107654-.

    Mulit-enzyme cascades are a major type of chemical transformations and play a crucial role in biological signal transduction and metabolism. Herein, a trienzyme cascade-triggered fluorescent immunosensor platform was constructed by sequentially integrating alkaline phosphatase (ALP), tyrosinase (TYR) and horseradish peroxidase (HRP). The proposed platform was based on HRP-induced a rapid in situ fluorogenic reaction between dopamine (DA) and 1,5-dihydroxynaphthalene (DHA) to produce a strong yellow azamonardine fluorescent compound (AFC). The obtained AFC was clearly characterized by high-resolution mass spectrum, 1H NMR, 13C NMR and theoretical calculations. The integration of the two-enzyme system (TYR and HRP) or three-enzyme system (ALP, TYR and HRP) led to a maximum of 400.0-fold and 250.0-fold fluorescence enhancements, respectively. Using cardiac troponin Ⅰ (cTnI) as the model antigen, a trienzyme cascade-triggered fluorescent immunosensor platform was developed for quantitative detecting cTnI in a wide linear range from 2 ng/mL to 150 ng/mL with a detection limit of 0.67 ng/mL. In addition, the proposed platform was successfully applied in detection of cTnI in serum of clinical patients. Overall, the developed fluorescent immunosensor performs powerful implications for researching enzyme cascade systems in the field of biomedicine.

  • Jianguang Xu, Hongyan Hang, Chen Chen, Boman Li, Jiale Zhu, Wei Yao
    Chinese Chemical Letters. 2023, 34(4): 107500-.

    Recently, MAX phases show great potential in lithium-ion uptake due to their excellent electrical conductivity and unique lamellar-structure accommodating lithium ions. However, the reports about MAX electrodes for lithium-ion battery up to now are relatively low. Herein we report the preparation of surface oxygen-deficient Ti2SC with abundant oxygen vacancies by a facile surface engineering method. When using as a lithium storage anode, this oxygen-deficient Ti2SC delivers a high capacity of 350 mAh/g at a current density of 400 mA/g as well as excellent rate performance, doubling the capacity compared to that of Ti2SC without oxygen vacancies. Confirmed by electrochemical impedance spectroscopy (EIS) and kinetic mechanism analyses, after reducing surface oxides and generation of oxygen vacancies, the as-received Ti2SC exhibits higher electrical conductivity and faster lithium ion diffusion. Thus this work offers a facial and effective strategy of optimizing the surface structure of MAX phases, further to achieve an enhanced lithium-ion uptake for lithium-ion batteries or capacitors.

  • Shunlong Pan, Xi Nie, Xinrui Guo, Hao Hu, Biming Liu, Yongjun Zhang
    Chinese Chemical Letters. 2023, 34(4): 107620-.

    Traditional treatment processes cannot completely remove phosphonates in circulating cooling water by one-step method. Herein, we designed peroxymonosulfate/UV irradiation/hydrated zirconium oxide (PMS/UV/HZO) coupling process to enhance the phosphonates removal. In particular, nitrilotris-methylenephosphonic acid (NTMP) removal efficiency by PMS/UV/HZO process was much higher than that of PMS/UV process, UV/HZO process and other processes in comparison experiments. Specifically, almost 97.2% NTMP in water was degraded, and the total phosphorous (TP) reduced from 9.3 mg/L to 0.26 mg/L at pH 7 within 180 min. TP removal efficiency still reached above 90% after 5 cycles adsorption-desorption of HZO. Moreover, Cl¯, NO3¯ and SO42¯ ions all had negligible effect on NTMP removal. During the process, NTMP was first destroyed to form phosphates and other intermediates by the reactive oxygen species (ROS), then phosphates were in situ immobilized via HZO adsorption. Sulfate radical (SO4•−) has been confirmed to be the major ROS in the reaction system by quenching experiment and electron paramagnetic resonance (EPR) characterization. And the excellent selective adsorption capacity of HZO for phosphate produced was attributed to the strong inner-sphere coordination between H2PO4¯/HPO42¯ and Zr-OH on the surface of HZO. These results suggest that PMS/UV/HZO process is a promising technique for enhanced phosphonates decontamination.

  • Hanqing Jin, Siyi Zou, Qinglin Wen, Yali Li, Fandi Ning, Pengpeng Xu, Saifei Pan, Xiaochun Zhou
    Chinese Chemical Letters. 2023, 34(4): 107441-.

    Air-breathing proton exchange membrane fuel cells (PEMFCs) are very promising portable energy with many advantages. However, its power density is low and many additional supporting parts affect its specific power. In this paper, we aim to improve the air diffusion and fuel cell performance by employing a novel condensing-tower-like curved flow field rather than an additional fan, making the fuel cell more compact and has less internal power consumption. Polarization curve test and galvanostatic discharge test are carried out and proved that curved flow field can strengthen the air diffusion into the PEMFC and improve its performance. With appropriate curved flow field, the fuel cell peak power can be 55.2% higher than that of planar flow field in our study. A four-layer stack with curved cathode flow field is fabricated and has a peak power of 2.35 W (120 W/kg).

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