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  • Chen Ma, Yida Zhang, Zhijuan Jiao, Chunmeng Ma, Xiaoyan Liu, Haixia Zhang
    Chinese Chemical Letters. 2020, 31(6): 1635-1639.

    Transmembrane anion transporters have attracted significant attention as therapeutic agents because of their potential to disrupt cellular ion homeostasis, in which, most of the synthetic anionic transporters are organic small molecules whose synthesis routes are usually complex and tedious, and the related biological research is also only in infancy. Hence, we synthesized a kind of chloride anion (Cl-) and sodium cation (Na+) nanocarrier based on poly(D, L-lactic-co-glycolic acid) (PLGA) which was coated with polydopamine (PDA) to provide target release factor. When the nanocarrier arrives in acidic environment such as lysosomes through endocytosis, Cl- and Na+ will be released fast from the nanocarrier resulting in imbalance of cell homeostasis for inducing apoptosis. Cell experiments show that the nanocarrier promotes apoptosis and leads to an increased concentration of reactive oxygen species. By exploring the concentration of cytochrome c in mitochondria and cytoplasm and the activities of key enzymes caspase-9 and caspase-3 in apoptosis process, it is proved that the apoptotic pathway is caspase-dependent. This novel strategy allows the research of anion transporter no longer limited to artificial synthesis of small molecular and provides a novel and effective direction to investigate ion homeostasis, ion transport and cancer treatment.

  • Hou Yaqi, Ye Yi, Du Zhongjie, Zhang Chen, Mi Jianguo, Hou Xu
    Chinese Chemical Letters. 2020, 31(6): 1640-1643.

    The physicochemical properties of surfaces have a great effect on the micro-morphologies of the crystal structures which are in contact with them. Understanding the interaction mechanism between the internal driving forces of the crystal and external inducing forces of the surfaces is the prerequisite of controlling and obtaining the desirable morphologies. In this work, the dynamic density functional theory was applied to construct the free energy functional expression of polyethylene (PE) lattice, and the micro-dynamic evolution processes of PE lattice morphology near the surfaces with different properties were observed to reveal the interaction mechanism at atomic scale. The results showed that the physical and chemical properties of the external surfaces synergistically affect the morphologies in both the defect shapes and the distribution of the defect regions. In the absence of the contact surfaces, driven by the oriented interactions among different CH2 groups, PE lattices gradually grow and form a defect-free structure. Conversely, the presence of contact surfaces leads to lattice defects in the interfacial regions, and PE lattice shows different self-healing abilities around different surfaces.

  • Yiming Liu, Zhongxun An, Mingxia Wu, Anbao Yuan, Hongbin Zhao, Jiujun Zhang, Jiaqiang Xu
    Chinese Chemical Letters. 2020, 31(6): 1644-1647.

    Peony pollen is a cheap and readily available biomass material with a relatively high protein content. In this work, it was employed as an N-rich precursor to prepare the nitrogen-doped porous carbon for supercapacitor application. The porous carbon microspheres were prepared through a hydrothermal method and subsequent carbonization process. Notably, ammonium borofruoride and potassium hydroxide were employed respectively as an etchant and an activator to modify the porosity of the materials. The as prepared ANPPCs-700 has a super high BET specific surface area of 824.69 m2/g. The microstructure, chemical state and electrochemical properties of the product were investigated in detail. The prepared nitrogen-doped carbon microspheres exhibits excellent specific capacity of 209 F/g at a current density of 1 A/g and remained 92.5% of the initial capacitance after 5000 deep cycles at 5 A/g.

  • Fan Yu, Laichun Wang, Qiuju Xing, Dengke Wang, Xunheng Jiang, Guangchao Li, Anmin Zheng, Fanrong Ai, Jian-Ping Zou
    Chinese Chemical Letters. 2020, 31(6): 1648-1653.

    Rational modification by functional groups was regarded as one of efficient methods to improve the photocatalytic performance of graphitic carbon nitride (g-C3N4). Herein, g-C3N4 with yellow (Y-GCN) and brown (C-GCN) were prepared by using the fresh urea and the urea kept for five years, respectively, for the first time. Experimental results show that the H2 production rate of the C-GCN is 39.06 μmol/h, which is about 5 times of the Y-GCN. Meantime, in terms of apparent quantum efficiency (AQE) at 420 nm, C-GCN has a value of 6.3% and nearly 7.3 times higher than that of Y-GCN (0.86%). The results of XRD, IR, DRS, and NMR show, different from Y-GCN, a new kind of functional group of —N=CH— was firstly in-situ introduced into the C-GCN, resulting in good visible light absorption, and then markedly improving the photocatalytic performance. DFT calculation also confirms the effect of the —N=CH— group band structure of g-C3N4. Furthermore, XPS results demonstrate that the existence of —N=CH— groups in C-GCN results in tight interaction between C-GCN and Pt nanoparticles, and then improves the charge separation and photocatalytic performance. The present work demonstrates a good example of "defect engineering" to modify the intrinsic molecular structure of g-C3N4 and provides a new avenue to enhance the photocatalytic activity of g-C3N4 via facile and environmental-friendly method.

  • Shu Zhang, Xibo Pei, Yiyuan Xue, Jingyuan Xiong, Jian Wang
    Chinese Chemical Letters. 2020, 31(6): 1654-1659.

    The carbon quantum dots (CQDs) and their functionalized materials are promising in biomedical field because of their unique properties; meanwhile, a growing concern has been raised about the potential toxicity of these modified materials in biosystem. In this study, we synthesized original CQDs and two common functionalized CQDs including N-doped CQDs (NCQDs) and folic acid-modified CQDs (FA-CQDs), and compared the toxicity and biocompatibility with each other in vitro and in vivo. L929, C6 and normal cell MDCK were selected to detect the adverse reaction of these materials in vitro. No acute toxicity or obvious changes were noted from in vitro cytotoxicity studies with the dose of these CQD materials increasing to a high concentration at 1 mg/mL. Among these materials, the FA-CQDs show a much lower toxicity. Moreover, in vivo toxicity studies were performed on the nude mice for 15 days. The experimental animals in 10 or 15 mg/kg groups were similar with animals treated by phosphate buffer solution (PBS) after 15 days. The results of the multifarious biochemical parameters also suggest that the functionalized products of CQDs do not influence the biological indicators at feasible concentration. Our findings in vitro and in vivo through toxicity tests demonstrate that CQDs and their modified materials are safe for future biological applications.

  • Cao Cao, Yan Shi, Xiaohui Wu, Liqun Zhang
    Chinese Chemical Letters. 2020, 31(6): 1660-1664.

    Poly(N, N-dimethyl acrylamide)-block-poly(styrene)-block-poly(N, N-dimethyl acrylamide) (PDMAc-b-PSt-b-PDMAc) amphiphilic triblock copolymer micro/nano-objects were synthesized through reversible addition-fragmentation chain transfer (RAFT) dispersion polymerization of St mediated with poly(N, N-dimethyl acrylamide) trithiocarbonate (PDMAc-TTC-PDMAc) bi-functional macromolecular RAFT agent. It is found that the morphology of the PDMAc-b-PSt-b-PDMAc copolymer micro/nano-objects like spheres, vesicles and vesicle with hexagonally packed hollow hoops (HHHs) wall can be tuned by changing the solvent composition. In addition, vesicles with two sizes (600 nm, 264 nm) and vesicles with HHHs features were also synthesized in high solid content systems (30 wt% and 40 wt%, respectively). Besides, as compared with typical AB diblock copolymers (A is the solvophilic, stabilizer block, and B is the solvophobic block), ABA triblock copolymers tend to form higher order morphologies, such as vesicles, under similar conditions. The finding of this study provides a new and robust approach to prepare block copolymer vesicles and other higher order micelles with special structure via PISA.

  • Hang Zhou, Yuwei Wang, Fuqiang Wang, Hao Deng, Yongchen Song, Changping Li, Zheng Ling
    Chinese Chemical Letters. 2020, 31(6): 1665-1669.

    Recent studies have shown impressive transport behaviors of water and ions within lamellar MXene membranes, which endows great promise in developing advanced separation application based high performance MXene membranes. However, most of the researches focused on modification of MXene nanoflakes and optimizing interlayer distance, leaving the impact of membrane fabrication process marginal. In this work, we studied the water flux of membranes made by vacuum filtration using delaminated MXene nanoflakes as the building-blocks. Our results show that the water permeability is extremely sensitive to the process, especially at the drying process, loading and deposit rate of nanoflakes (the feeding concentration). We find that the voids from less ordered stack rather than in-plane defects and interlayer galleries contribute to the large water permeability. The voids can be effectively avoided via deposition of MXene nanoflakes at a slow rate. Manipulating the stack of MXene nanoflakes during vacuum filtration and drying are critical for development of MXene membranes with desired performance for water permeation.

  • Jinfeng Sun, Lingzhi Guo, Miaomiao Gao, Xuan Sun, Jinyang Zhang, Longwei Liang, Yang Liu, Linrui Hou, Changzhou Yuan
    Chinese Chemical Letters. 2020, 31(6): 1670-1673.

    Herein, we first report one-step synthesis of uniform Mo2C microflowers (MCMFs) from low-cost precursors via industrialized solid-state strategy. With fine optimization in precursor ratio and pyrolysis temperatures, the as-fabricated MCMFs are assembled well with interconnected single-crystalline nanosheet subunits. More encouragingly, the resultant MCMFs are further highlighted as a competitive anode with robust and long-duration lithium-storage behaviors towards high-performance Li-ion batteries

  • Zibin Ni, Shenyuan Bao, Xue-Qing Gong
    Chinese Chemical Letters. 2020, 31(6): 1674-1679.

    Recently, ZnO-based gas sensors have been successfully fabricated and widely studied for their excellent sensitivity and selectivity, especially in CO detection. However, detailed explorations of their mechanisms are rather limited. Herein, aiming at clarifying the sensing mechanism, we carried out density functional theory (DFT) calculations to track down the CO adsorption and oxidation on the ZnO (1010) and (1120) surfaces. The calculated results show that the lattice O of ZnO(1010) is more reactive than that of ZnO(1120) for CO oxidation. From the calculated energetics and structures, the main reaction product on both surfaces can be determined to be CO2 rather than carbonate. Moreover, the surface conductivity changes during the adsorption and reaction processes of CO were also studied. For both ZnO (1010) and (1120), the conductivity would increase upon CO adsorption and decrease following CO oxidation, in consistence with the reported experimental results. This work can help understand the origins of ZnO-based sensors' performances and the development of novel gas sensors with higher sensitivity and selectivity.

  • Jiawei Ni, Tao Zhao, Lei Tang, Pengpeng Qiu, Wan Jiang, Lianjun Wang, Pengcheng Xu, Wei Luo
    Chinese Chemical Letters. 2020, 31(6): 1680-1685.

    H2S can cause multiple diseases and poses a great threat to human health. However, the precise detection of extremely toxic H2S at room temperature is still a great challenge. Here, a facile solvent evaporation induced aggregating assembly (EIAA) method has been applied for the production of ordered mesoporous carbon (OMCs) in an acidic THF/H2O solution with high-molecular-weight poly(ethylene oxide)-b-polystyrene (PEO-b-PS) copolymers as the structure-directing agent, formaldehyde and resorcinol as carbon precursors. Along with the continuous evaporation of THF from the mixed solution, cylindrical micelles are formed in the solution and further assemble into highly ordered mesostructure. The obtained OMCs possesses a two-dimensional (2D) hexagonal mesostructure with uniform and large pore diameter (~19.2 nm), high surface area (599 m2/g), and large pore volume (0.92 cm3/g). When being used as the resonant cantilever gas sensor for room-temperature H2S detection, the OMCs has delivered not only a superior gas sensing performance with ultrafast response (14 s) and recovery (21 s) even at low concentration (2 ppm) but also an excellent selectivity toward H2S among various common interfering gases. Moreover, the limit of detection is better than 0.2 ppm, indicating its potential application in environmental monitoring and health protection.

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