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  • Tianlong Ni, Jiuyang Lin, Lingxue Kong, Shuaifei Zhao
    Chinese Chemical Letters. 2021, 32(11): 3298-3306.

    As an emerging thermal-driven membrane technology, membrane distillation (MD) has attracted immense attention for desalination and water purification. The membranes for MD generally have hydrophobic or superhydrophobic properties to enable vapor permeation without liquid passage (e.g., wetting). However, conventional MD membranes cannot undergo long term stable operations due to gradual wetting in practical applications where the feed solution often contains multiple low-surface tension contaminants (e.g., oil). Recently, omniphobic membranes repelling all sorts of liquids and typically having ultralow surface energy and re-entrant structures have been developed for robust MD to mitigate wetting and fouling. In this paper, we aim to provide a comprehensive review of recent progress on omniphobic membranes. Fundamentals, desirable properties, advantages and applications of omniphobic membranes are discussed. We also summarize the research efforts and methods to engineer omniphobic membranes. Finally, the challenges and future research directions on omniphobic membranes are discussed.

  • Chengqian Cui, Guodong Li, Zhiyong Tang
    Chinese Chemical Letters. 2021, 32(11): 3307-3321.

    Metal-organic framework nanosheets (MONs) as the emerging materials have been attracting great interest because the nanosheets possess a range of fascinating attributes including high surface areas and sufficient accessible active sites, and their nanoscale thicknesses are favorable for mass diffusion and transfer of substrates and products with respect to bulk metal-organic frameworks (MOFs). This review first summarizes the synthetic methods of various MONs from top-down and bottom-up methods as well as their diverse composites with different components. Then, the catalytic applications of MON based nanocatalysts are discussed and the relationships among the composition, structure and catalytic performances are revealed. Finally, the challenges and future outlook about the synthesis of diverse MONs and their composites for heterogeneous catalysis are prospected.

  • Lintao Wu, Chun Han, Xiaobi Jing, Yong Yao
    Chinese Chemical Letters. 2021, 32(11): 3322-3330.

    Pillar[5]arenes, designed and prepared by Ogoshi et al. in 2008 initially, refer to fifth classical macrocyclics. Among a wide range of pillar[5]arenes, rim-differentiated pillar[5]arenes containing five identical substituents on one rim and five different identical groups on the other rims are considered the most noteworthy type of pillar[5]arenes. As compared with the perfunctionalized pillar[5]arene, the self-assembly properties of rim-differentiated pillar[5]arenes have more varieties. On the other hand, in comparison with other types of pillar[5]arenes, the rim-differentiated pillar[5]arenes exhibit a more rigid symmetrical structure. In the present review, the synthetic methods, host-guest interactions, self-assembly properties and applications of rim-differentiated pillar[5]arenes are summarized. Hopefully, this review will be conducive to researchers in macrocyclic supramolecular chemistry.

  • Lijun Mao, Manfei Zhou, Xueliang Shi, Hai-Bo Yang
    Chinese Chemical Letters. 2021, 32(11): 3331-3341.

    Triphenylamine (TPA) derivatives and their radical cation counterparts have successfully demonstrated a great potential for applications in a wide range of fields including organic redox catalysis, organic semiconductors, magnetic materials, etc., mainly because of their excellent redox activity. The stability of TPA radical cation has significant effect on the properties of the TPA-based functional materials, especially in relation to their electronic properties. Considering the instability of parent TPA radical cation, many efforts have been devoted to the development of stable TPA radical cations and related materials. Among them, TPA radical cation-based macrocycles have attracted particular attention because their large delocalized structures can stabilize the TPA radicals, thus endow them with outstanding redox behaviors, multiple resonance structures, and wide application in various optoelectronic devices. In this review, we give a brief introduction of organic radicals and the documented stable TPA radicals. Subsequently, a number of TPA radical cation-based macrocycles are comprehensively surveyed. It is expected that this minireview will not only summarize the recent development of TPA radical cations and their macrocycles, but also shed new light on the prospect of the design of more sophisticated radical cation-based architectures and related materials.

  • Yingjie Yu, Aiyao Liu, Gagan Dhawan, Haibo Mei, Wei Zhang, Kunisuke Izawa, Vadim A. Soloshonok, Jianlin Han
    Chinese Chemical Letters. 2021, 32(11): 3342-3354.

    Thirteen new fluorine-containing drugs, which have been granted approval by the US Food and Drug Administration (FDA) in 2020, are profiled in this review. Therapeutic areas of these new fluorinated pharmaceuticals include medicines and diagnostic agents for Cushing's disease, neurofibromatosis, migraine, Alzheimer's disease, myelodysplastic syndromes, hereditary angioedema attacks, and various cancers. Molecules of these approved drugs feature aromatic fluorine (Ar-F) (11 compounds), aromatic Ar-CF3 (1), aliphatic CHF (1) and CF2 (1) groups. For each compound, we provide a spectrum of biological activity, medicinal chemistry discovery, and synthetic approaches.

  • Qian Li, Yuchao Wang, Jian Zeng, Qiumei Wu, Qichen Wang, Lian Sun, Liang Xu, Tong Ye, Xin Zhao, Lei Chen, Zhiyan Chen, Limiao Chen, Yongpeng Lei
    Chinese Chemical Letters. 2021, 32(11): 3355-3358.

    Designing non-noble metal electrocatalysts toward alkaline hydrogen evolution reaction (HER) with high performance at a large current density is urgent. Herein, a CoO/CoP heterostructure catalyst (termed POZ) was designed by a phosphating strategy. The strong electron transfer on the interface of CoO/CoP was experimentally and theoretically proven. POZ showed a low overpotential of 236 mV at 400 mA/cm2, which was 249 mV lower than non-phosphated sample. It also exhibited a remarkable solar-to-hydrogen conversion efficiency of 10.5%. In this work, the construction of CoO/CoP interface realized by a simple phosphating strategy could provide an important reference to boost the HER performance on those materials not merely metal oxides.

  • Zhuofeng Hu, Weiqing Guo
    Chinese Chemical Letters. 2021, 32(11): 3359-3363.

    The electrode/electrlyte interface is of great signifance to photoelectrochemical (PEC) water oxidation as the reaction mainly occur here. Herein, we focus on the effect of supercapactance of the electrode/electrlyte interface on the performance of PEC. It is discovered that the supercapacitor on the interface is crucial because it links the charge transport and solution ion adsorption on its two sides. In this study, we demonstrate an approach to promote the performance of TiO2 nanowire array (TiO2 NWs) photoanode in photoelectrochemical cells (PECs) by increasing its supercapacitance. A 2−5 nm carbon layer was coated and the interface supercapacitance increases by about 150 times. This enhances the separation rate of electron-hole pairs by collecting more holes. Meanwhile, it also promotes the water oxidation rate by adsorbing more OH− on its surface. As a result, the photocurrent density of C-TiO2 NWs was about 8 times higher than that of its carbon-free counterpart. This approach of increasing the supercapacitance of photoanodes would be attractive for enhancement of the efficiency of PECs and this work demonstrate the importance of supercapacitance of the interface for PECs.

  • Xiaoqian Jiang, Chenfang Sun, Congcong Zhang, Shanshan Cheng
    Chinese Chemical Letters. 2021, 32(11): 3364-3367.

    High responsivity and sensitivity play essential roles in the development of organic field-effect transistors (OFETs)-based biosensors with regard to biological detections, particularly for disease diagnosis. Nonetheless, how to design a biosensor which improves these two outstanding properties while achieving low cost, easy processing, and time saving is a daunting challenge. Herein, a novel biosensor based on OFET with copolymer thin film, whose surface is illuminated with a suitable light beam is reported. This film can be used as both an organic semiconductor material and as a photoelectric active material. Due to amplification of signals as a result of the film's strong response to light, the biosensor possesses higher responsivity and sensitivity compared to dark condition and even realizes a maximum responsivity of up to 103 for alpha-fetoprotein (AFP) detection. The simple combination of light and transistor builds a bridge between photoelectric effect and biological system. In addition, the emergence of more excellent photoelectric active materials is expected to pave a way for ultrasensitive bio-chemical diagnostic tools.

  • Fei Qu, Ziwei Guo, Dafeng Jiang, Xian-En Zhao
    Chinese Chemical Letters. 2021, 32(11): 3368-3371.

    Dopamine (DA) is easy to be oxidized and polymerizes to form polydopamine (pDA) in alkaline conditions, while the synthesis is usually time-consuming (48 h). Herein, the polymerization of DA is completed with 4 h under the catalysis of acid phosphatase (ACP). The high efficiency makes the detection of DA feasibility based on the self-polymerization of DA. In this assay, pDA is grown in situ on the surface of covalent organic frameworks (COFs), and then the fluorescence of COFs is quenched significantly. The linear range of DA is achieved from 0.5–50 μmol/L with a detection limit of 0.16 μmol/L. The detection of DA is not interfered with uric acid, ascorbic acid, and some phenolic compounds, because these substances cannot polymerize in the presence of ACP. Moreover, benefiting from the good sensitivity and selectivity, DA has been successfully determined by this strategy in human urine samples with satisfactory recoveries.

  • Yongrui He, Tiantian Shi, Meiling Qi
    Chinese Chemical Letters. 2021, 32(11): 3372-3376.

    This work presents a novel strategy for engineering a GC stationary phase with high selectivity, inertness and thermal stability by introducing the 3D π-rich TP moieties to the terminals of a polar chain polymer. Herein, we provide the first example, i.e., a new TP-terminated polycaprolactone polymer (TPP) as the stationary phase for GC analyses. As demonstrated, the TPP column achieved distinctly improved inertness to fatty acids and aldehydes, and dramatically enhanced thermal stability (about 100 ℃ higher) over the PCL column. Also, the TPP column exhibited high resolving capability towards the positional isomers of phenols, anilines and alkylated/halobenzenes and showed good potential in detecting minor impurities in chemical products. Importantly, the proposed strategy is facile, feasible and generally applicable to analogous polymers.

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