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  • Fan Yang, Jie Zhang, Jiacheng Li, Wenbo Ye, Ang Li, Weiwei He
    Chinese Chemical Letters. 2023, 34(1): 107438-.

    Taking advantage of the Warburg effect in cancer cells, glucose conjugation has emerged as a useful strategy for targeted delivery of anticancer agents. Pristimerin is a naturally occurring triterpenoid that displays potent but non-selective cytotoxicity. We developed a convergent and modular approach to construction of glucose−payload conjugates featuring copper-mediated azide−alkyne cycloaddition and prepared a glucose conjugate of pristimerin through this approach. The anticancer activity of this conjugate was evaluated in cancer cells and normal cells; however, the selectivity toward cancer cells was not significantly improved. We then examined the extracellular stability of the conjugate and found that its ester linkage was cleaved rapidly in Dulbecco's Modified Eagle's Medium at 37 ℃, which resulted in the release of pristimerin. In fact, the inorganic components in this medium were sufficient to induce the cleavage. Given that the subtle difference between intrinsic stability and extracellular stability of the conjugate linker is often underappreciated, this work highlights the importance of the latter in the development of target-selective conjugates.

  • Xulin Hu, Weiming Zhao, Zhen Zhang, Jianping Xie, Jian He, Jianfei Cao, Qing Li, Yajing Yan, Chengdong Xiong, Kainan Li
    Chinese Chemical Letters. 2023, 34(1): 107451-.

    The biodegradable substitution materials for bone tissue engineering have been a research hotspot. As is known to all, the biodegradability, biocompatibility, mechanical properties and plasticity of the substitution materials are the important indicators for the application of implantation materials. In this article, we reported a novel binary substitution material by blending the poly(lactic-acid)-co-(trimethylene-carbonate) and poly(glycolic-acid)-co-(trimethylene-carbonate), which are both biodegradable polymers with the same segment of flexible trimethylene-carbonate in order to accelerate the degradation rate of poly(lactic-acid)-co-(trimethylene carbonate) substrate and improve its mechanical properties. Besides, we further fabricate the porous poly(lactic-acid)-co-(trimethylene-carbonate)/poly(glycolic-acid)-co-(trimethylene-carbonate) scaffolds with uniform microstructure by the 3D extrusion printing technology in a mild printing condition. The physicochemical properties of the poly(lactic-acid)-co-(trimethylene-carbonate)/poly(glycolic-acid)-co-(trimethylene-carbonate) and the 3D printing scaffolds were investigated by universal tensile dynamometer, fourier transform infrared reflection (FTIR), scanning electron microscope (SEM) and differential scanning calorimeter (DSC). Meanwhile, the degradability of the PLLA-TMC/GA-TMC was performed in vitro degradation assays. Compared with PLLA-TMC group, PLLA-TMC/GA-TMC groups maintained the decreasing Tg, higher degradation rate and initial mechanical performance. Furthermore, the PLLA-TMC/GA-TMC 3D printing scaffolds provided shape-memory ability at 37 ℃. In summary, the PLLA-TMC/GA-TMC can be regarded as an alternative substitution material for bone tissue engineering.

  • Zhouhao Zhu, Hengcong Tao, Jingbin Fu, Yingtang Zhou, Jian Guo, Chunyang Zhai
    Chinese Chemical Letters. 2023, 34(1): 107476-.

    Developing convenient, fast-response and high-performance formaldehyde detection sensor is significant but challenging. Herein, two CeO2 phases (Fm3m and P42/mnm), three facets (CeO2(100), CeO2(110) and CeO2(111)) and three adsorption sites (top, bridge and hollow) are selected as substrate to interact with formaldehyde. Twenty-eight candidated transition metals (TM) are doped on CeO2 surfaces to investigate the performance of detecting formaldehyde by density functional theory. It shows that (ⅰ) CeO2 in a cubic fluorite structure with the space group Fm3m is suitable for formaldehyde adsorption compared with P42/mnm; (ⅱ) TM-CeO2(100) (TM = Au, Hf, Nb, Ta, Zr) are considered as candidated materials to absorb formaldehyde ascribed to lower adsorption energies. The d-band center, partial density of states, charge density difference and electron localization function are employed to clarify the mechanism of TM-doped CeO2 improving the performance of formaldehyde adsorption. It obviously displays that TM doped CeO2(100) changes the d orbit and rearranges electrons resulting in the superior ability to the adsorbed formaldehyde. This work provides theoretical guidance and experimental motivation for the development of novel formaldehyde sensor based on metal oxide semiconductor materials.

  • Desen Li, Minjie Yang, Rongfang Mu, Shihong Luo, Yuegui Chen, Wenyuan Li, An Wang, Kai Guo, Yan Liu, Shenghong Li
    Chinese Chemical Letters. 2023, 34(1): 107469-.

    Two chimeric sesterterpene synthases (AaTPS1 and AaTPS2) were functionally characterized from Alternaria alternata MB-30 isolated from the leaves of a sesterterpenoid-producing Lamiaceae plant Leucosceptrum canum. AaTPS1 generated a 5/8/6/5 tetracyclic sesteraltererol (1) and its absolute stereochemistry was determined by X-ray crystallographic analysis of its derivative 10, 11-epoxysesteraltererol (2), which enabled revision of the absolute configuration of C7 of sesterfisherol produced by NfSS and PTTS014 characterized previously and its derivative 10, 11-epoxysesterfisherol. AaTPS2 produced a 5/15 bicyclic preterpestacin I (3). Site-directed mutagenesis suggested that F192 in AaTPS1 was likely involved in controlling of the hydroxylation of C12, and eight amino acids were important for the enzyme activity of AaTPS1 and AaTPS2. The engineered Escherichia coli and Saccharomyces cerevisiae strains were constructed for the productions of compounds 1 and 3, and the highest titer of compound 1 reached 62.3 mg/L in shake-flask culture. Both compounds 1 and 2 showed anti-adipogenic activity.

  • Chinese Chemical Letters. 2023, 34(1): 107937-.
  • Wenwen Cui, Yu Li, Xufeng Li, Junxin Li, Xiuyan Song, Jian Lv, Yuan-Ye Jiang, Daoshan Yang
    Chinese Chemical Letters. 2023, 34(1): 107477-.

    Transition-metal-catalyzed decarboxylative and CH functionalization strategy for the construction of Csp2-Csp2, Csp2-Csp, and Csp2-Csp3 bonds has been extensively studied. However, research surveys of this synthetic strategy for the Csp3-Csp3 bond forming reactions are surprisingly scarce. Herein, we present an efficient approach for the rapid formation of Csp3–Csp3 bond through copper-catalyzed decarboxylative Csp3–H functionalization. The present method should provide a useful access to C3-substituted indole scaffolds with possible biological activities. Mechanistic experiments and DFT calculations supported a dual-Cu(Ⅱ)-catalytic cycle involving rate-determining decarboxylation in an outer-sphere radical pathway and spin-crossover-promoted CC bond formation. This strategy offers a promising synthesis method for the construction of Csp3–Csp3 bond in the field of synthetic and pharmaceutical chemistry and extends the number of still limited copper-catalyzed decarboxylative Csp3–Csp3 bond forming reaction.

  • Ke Zhang, Hongyang Cao, Afzal Dar, Danqing Li, Lina Zhou, Chuanyi Wang
    Chinese Chemical Letters. 2023, 34(1): 107308-.

    Oxygen vacancy induced photothermal effect is of great significant but lack of adequate attentions for environmental remediation. In this paper, green recyclable ZnO/ZnFe2O4 with oxygen vacancy was prepared by a solvothermal-calcination method. The UV-vis light capture ability of ZnO/ZnFe2O4 microspheres is improved with the multiple light reflections due to the yolk-shell structure, and the oxygen vacancy expands the absorption range of photocatalyst and enhances photothermal conversion. The optimized photocatalyst can heat the solution from room temperature to 70 ℃ within 60 min of visible light illumination, and the light to heat conversion efficiency is achieved by 61.3%. Compared with the degradation efficiency at 20 ℃, photothermal catalysis achieves a stable degradation in 80 min, and the degradation efficiency is increased by 41.5%. This can be attributed to the fact that light induced thermal energy accelerates the migration of electrons and holes, and promotes the diffusion of free radicals by heating active centers in situ. The active species contributing to the degradation, in order of importance, are the superoxide radical, hydroxyl radical, hole and electron. The light-to-thermal assisted photocatalysis with ZnO/ZnFe2O4 provides a new sight for the pollution control in the future practical applications.

  • Xiaohua Deng, Zhu Jiang, Yingying Chen, Dai Dang, Quanbing Liu, Xiaoyang Wang, Xu Yang
    Chinese Chemical Letters. 2023, 34(1): 107389-.

    Heteroatom doped porous carbon materials have emerged as essential cathode material for metal-air battery systems in the context of soaring demands for clean energy conversion and storage. Herein, a three-dimensional nitrogen-doped carbon self-supported electrode (TNCSE) is fabricated through thermal treatment and acid activation of raw wood. The resulting TNCSE retains the hierarchical porous architecture of parent raw lumber and holds substantial defect sites and doped N sites in the carbon skeleton. Assembled as a cathode in the rechargeable zinc-air battery, the TNCSE exhibits a superior peak power density of 134.02 mW/cm2 and an energy density of 835.92 mAh/g, significantly exceeding the ones reference commercial 20% Pt/C does. More strikingly, a limited performance decay of 1.47% after an ultra long-period (500 h) cycle is also achieved on the TNCSE. This work could offer a green and cost-save approach for rationally converting biomass into a robust self-supporting cathode material for a rechargeable zinc-air battery.

  • Mingjun Zhong, Qimeng Wu, Liang Ma, Jie Li, Yifan Wang, Yansong Wang, Xin Li, Yajie Zhang, Jingtao Lü, Yongfeng Wang
    Chinese Chemical Letters. 2023, 34(1): 107813-.

    Spin properties of organic molecules have attracted great interest for their potential applications in spintronic devices and quantum computing. Fe-tetraphenyl porphyrin (FeTPP) is of particular interest for its robust magnetic properties on metallic substrates. FeTPP is prepared in vacuum via on-surface synthesis. Molecular structure and spin-related transport properties are characterized by low-temperature scanning tunneling microscope and spectroscopy at 0.5 K. Density functional theory calculations are performed to understand molecular adsorption and spin distribution on Au(111). The molecular structure of FeTPP is distorted upon adsorption on the substrate. Spin excitations of FeTPP are observed on the Fe atom and high pyrrole groups in differential conductance spectra. The calculated spin density distribution indicates that the electron spin of FeTPP is mainly distributed on the Fe atom. The atomic transmission calculation indicates that electrons transport to substrate is mediated through Fe atom, when the tip is above the high pyrrole group.

  • Yanling Wu, Deyu Liu, Huanglong Zhuang, Jiabo Le, Yongbo Kuang
    Chinese Chemical Letters. 2023, 34(1): 107480-.

    Organic semiconductors are promising candidates as photoactive layers for photoelectrodes used in photoelectrochemical (PEC) cells due to their excellent light absorption and efficient charge transport properties with the help of interfacial materials. However, the use of multilayers will make the charge transfer mechanism more complicated and decrease the PEC performance of the photoelectrode caused by the increased contact resistance. In this work, a PM6:Y6 bulk heterojunction (BHJ)-based photocathode is fabricated for efficient PEC hydrogen evolution reaction (HER) in an acidic aqueous solution. With RuO2 as an interfacial modification layer, the photocathode with a simple structure (fluorine-doped tin oxide (FTO)/PM6:Y6/RuO2) generates a maximum photocurrent density up to −15 mA/cm2 at 0 V vs. reference hydrogen electrode (RHE), outperforming all previously reported BHJ-based photocathodes in terms of PEC performance. The highest ratiometric power-saved efficiency of 3.7% is achieved at 0.4 V vs. RHE.

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