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  • Jinli Qiu, Cailiang Yue, Wenting Zheng, Fuqiang Liu, Junjie Zhu
    Chinese Chemical Letters. 2021, 32(11): 3431-3434.

    A facile approach was successfully employed to prepare Fe2O3/Co3O4 nanosheet arrays on nickel foams (Fe2O3/Co3O4@NF), which owned such advantages as narrow band gap energies and high separation rate of photoexcited electron-hole pairs. The combination of Fe2O3 and Co3O4 dramatically enhanced the photocatalytic activity towards sulfamethoxazole (SMZ) degradation, with the highest catalytic efficiency of k = 0.0538 min−1, which was much higher than that of Fe2O3@NF (0.0098 min−1) and Co3O4@NF (0.0094 min−1). The introduction of Ni foam could not only act as the support to anchor photocatalyst, but also work as the electron mediator to promote the transition of electron-hole pairs. Reactive species trapping experiments combined with electron paramagnetic resonance analysis confirmed ·O2− was primarily responsible for SMZ degradation. Furthermore, Fe2O3/Co3O4@NF was effective and almost unaffected by inorganic cations and anions in aqueous solution. This study could provide a facile and promising path for the construction of self-supported metal oxide-based heterojunction with high efficiency and strong stability.

  • Jiahui Lu, Jinping Zhong, Quanming Ren, Jiaqi Li, Linghe Song, Shengpeng Mo, Mingyuan Zhang, Peirong Chen, Mingli Fu, Daiqi Ye
    Chinese Chemical Letters. 2021, 32(11): 3435-3439.

    A facile hydrothermal method was applied to gain stably and highly efficient CuO-CeO2 (denoted as Cu1Ce2) catalyst for toluene oxidation. The changes of surface and inter properties on Cu1Ce2 were investigated comparing with pure CeO2 and pure CuO. The formation of Cu-Ce interface promotes the electron transfer between Cu and Ce through Cu2+ + Ce3+ ↔ Cu+ + Ce4+ and leads to high redox properties and mobility of oxygen species. Thus, the Cu1Ce2 catalyst makes up the shortcoming of CeO2 and CuO and achieved high catalytic performance with T50 = 234 ℃ and T99 = 250 ℃ (the temperature at which 50% and 90% C7H8 conversion is obtained, respectively) for toluene oxidation. Different reaction steps and intermediates for toluene oxidation over Cu1Ce2, CeO2 and CuO were detected by in situ DRIFTS, the fast benzyl species conversion and preferential transformation of benzoates into carbonates through C=C breaking over Cu1Ce2 should accelerate the reaction.

  • Yi Pan, Fan-Feng Deng, Zheng Fang, Han-Jiao Chen, Zhou Long, Xian-Deng Hou
    Chinese Chemical Letters. 2021, 32(11): 3440-3445.

    Hydrogen fuel cells are among the promising energy sources worldwide, which could accomplish cyclic production of energy and avoid the emission of green-house or contaminative byproducts. However, sulfur compounds (SCs) even at trace level (nmol/mol) are usually involved in cell construction and further H2 production, which would cause degradation of the catalysts and shorten the lifetime of the fuel cells. Moreover, the highly reactive SCs could cause varied species and concentrations of them in complex matrices, so online rather than offline analysis of SCs in H2 would be preferred. In this context, we developed a new system combining online cryogenic preconcentration of nine SCs and subsequent determination by GC-SCD (sulfur chemiluminescent detector), with the correlation coefficients of the calibration curves higher than 0.999, calculated limits of detection no higher than 0.050 nmol/mol, analytical time around 30 min per sample, and satisfactory precision and accuracy (RSD < 5% and SD < 15%). The analytical performance was much better than or at least comparable to the previously reported and the developed system was successfully applied for real sample analysis.

  • Yuanyuan Wu, Lei Zhao, Yaran Chang, Liang Zhao, Guangsheng Guo, Xiayan Wang
    Chinese Chemical Letters. 2021, 32(11): 3446-3449.

    Single-cell imaging, a powerful analytical method to study single-cell behavior, such as gene expression and protein profiling, provides an essential basis for modern medical diagnosis. The coding and localization function of microfluidic chips has been developed and applied in living single-cell imaging in recent years. Simultaneously, chip-based living single-cell imaging is also limited by complicated trapping steps, low cell utilization, and difficult high-resolution imaging. To solve these problems, an ultra-thin temperature-controllable microwell array chip (UTCMA chip) was designed to develop a living single-cell workstation in this study for continuous on-chip culture and real-time high-resolution imaging of living single cells. The chip-based on ultra-thin ITO glass is highly matched with an inverted microscope (or confocal microscope) with a high magnification objective (100 × oil lens), and the temperature of the chip can be controlled by combining it with a home-made temperature control device. High-throughput single-cell patterning is realized in one step when the microwell array on the chip uses hydrophilic glass as the substrate and hydrophobic SU-8 photoresist as the wall. The cell utilization rate, single-cell capture rate, and microwell occupancy rate are all close to 100% in the microwell array. This method will be useful in rare single-cell research, extending its application in the biological and medical-related fields, such as early diagnosis of disease, personalized therapy, and research-based on single-cell analysis.

  • Yangzi Shangguan, Yuanhao Zhou, Renji Zheng, Xuezhen Feng, Qiuyue Ge, Ranhao Wang, Dazhong Yang, Wenfei Wei, Xiaoyong Wu, Jia Lin, Hong Chen
    Chinese Chemical Letters. 2021, 32(11): 3450-3456.

    Bandgap engineering through single-atom site binding on semiconducting photocatalyst can boost the intrinsic activity, selectivity, carrier separation, and electron transport. Here, we report a mixed-valence Ag(0) and Ag(Ⅰ) single atoms co-decorated semiconducting chalcopyrite quantum dots (Ag/CuFeS2 QDs) photocatalyst. It demonstrates efficient photocatalytic performances for specific organic dye (rhodamine B, denoted as RhB) as well as inorganic dye (Cr(Ⅵ)) removal in water under natural sunlight irradiation. The RhB degradation and Cr(Ⅵ) removal efficiencies by Ag/CuFeS2 QDs were 3.55 and 6.75 times higher than those of the naked CuFeS2 QDs at their optimal pH conditions, respectively. Besides, in a mixture of RhB and Cr(Ⅵ) solution under neutral condition, the removal ratio has been elevated from 30.2% to 79.4% for Cr(Ⅵ), and from 95.2% to 97.3% for RhB degradation by using Ag/CuFeS2 QDs after 2 h sunlight illumination. The intrinsic mechanism for the photocatalytic performance improvement is attributed to the narrow bandgap of the single-atomic Ag(Ⅰ) anchored CuFeS2 QDs, which engineers the electronic structure as well as expands the optical light response range. Significantly, the highly active Ag(0)/CuFeS2 and Ag(Ⅰ)/CuFeS2 effectively improve the separation efficiency of the carriers, thus enhancing the photocatalytic performances. This work presents a highly efficient single atom/QDs photocatalyst, constructed through bandgap engineering via mixed-valence single noble metal atoms binding on semiconducting QDs. It paves the way for developing high-efficiency single-atom photocatalysts for complex pollutions removal in dyeing wastewater environment.

  • Hua Lu, Yiyan Yin, Jianghui Sun, Weixiang Li, Xiaotong Shen, Xiujuan Feng, Jin Ouyang, Na Na
    Chinese Chemical Letters. 2021, 32(11): 3457-3462.

    The rapid degradation of organic pollutants, process monitoring and online controlling to obtain advanced products and decreased by-products are great and challenging tasks in environmental treatments. Herein, an accelerated plasma degradation in milliseconds was achieved by combining electrospray-based acceleration and plasma-based degradation. Taking the degradation of chloroaniline as an example, 97% of the degradation can be achieved in milliseconds. The velocity distribution of droplets was determined to be 40–50 m/s after being degraded for 0.30 ms, which exhibited different degradation behaviors in different milliseconds. Simultaneously, by virtue of the real-time and on-line detection ability of ambient mass spectrometry, intermediates, by-products and advanced products were monitored. Therefore, degradation mechanisms for different degradation times were proposed, which would provide theoretical guidance on obtaining efficient and green degradation. The fabrication, examining and understanding of accelerated plasma degradation not only enlarged application of accelerated reactions, but also promoted green and efficient degradation for environmental treatments.

  • Qingfeng Li, Can Ren, Chuntian Qiu, Tingchao He, Qitao Zhang, Xiang Ling, Yangsen Xu, Chenliang Su
    Chinese Chemical Letters. 2021, 32(11): 3463-3468.

    Ultrabroad spectral absorption is required for semiconductor photocatalysts utilized for solar-to-chemical energy conversion. The light response range can be extended by element doping, but the photocatalytic performance is generally not enhanced correspondingly. Here we present a solid alkali activation strategy to synthesize near-infrared (NIR) light-activated carbon-doped polymeric carbon nitride (A-cPCN) by combining the copolymerization of melamine and 1, 3, 5-trimesic acid. The prepared A-cPCN is highly crystalline with a narrowed bandgap and enhanced efficiency in the separation of photogenerated electrons and holes. Under irradiation with NIR light (780 nm ≥ λ ≥ 700 nm), A-cPCN shows an excellent photocatalytic activity for H2 generation from water with rate of 165 µmol g−1 h−1, and the photo-redox activity for H2O2 production (109 µmol g−1 h−1) from H2O and O2, whereas no observed photocatalytic activity over pure PCN. The NIR photocatalytic activity is due to carbon doping, which leads to the formation of an interband level, and the alkali activation that achieved shrinking the transfer distance of photocarriers. The current synergistic strategy may open insights to fabricate other carbon-nitrogen-based photocatalysts for enhanced solar energy capture and conversion.

  • Ping Wang, Bin Guo, Zhi Zhang, Weinan Gao, Wei Zhou, Huaxin Ma, Wenyu Wu, Junfeng Han, Ruijun Zhang
    Chinese Chemical Letters. 2021, 32(11): 3469-3473.

    The development of the preparation strategy for high-quality and large-size graphene via eco-friendly routes is still a challenging issue. Herein, we have successfully developed a novel route to chemically exfoliate natural graphite into high-quality and large-size graphene in a binary-peroxidant system. This system is composed of urea peroxide (CO(NH2)2·H2O2) and hydrogen peroxide (H2O2), where CO(NH2)2·H2O2 is used in preparing graphene for the first time. Benefiting from the complete decomposition of CO(NH2)2·H2O2 and H2O2 into gaseous species under microwave (MW) irradiation, no water-washing and effluent-treatment are needed in this chemical exfoliation procedure, thus the preparation of graphene in an eco-friendly way is realized. The resultant graphene behaves a large-size, high-quality and few-layer feature with a yield of ~100%. Then 4 µm-thick ultrathin graphene paper fabricated from the as-exfoliated graphene is used as an electromagnetic interference (EMI) shielding material. And its absolute effectiveness of EMI shielding (SSE/t) is up to 34, 176.9 dB cm2/g, which is, to the best of our knowledge, among the highest values so far reported for typical EMI shielding materials. The EMI shielding performance demonstrates a great application potential of graphene paper in meeting the ever-increasingly EMI shielding demands in miniaturized electronic devices.

  • Jing Zhang, Meifeng Hou, Guanyu Chen, Huifang Mao, Wenqian Chen, Wenshen Wang, Jinghua Chen
    Chinese Chemical Letters. 2021, 32(11): 3474-3478.

    Exosomal miRNAs, as potential biomarkers in liquid biopsy for cancer early diagnosis, have aroused widespread concern. Herein, an electrochemical biosensor based on DNA "nano-bridge" was designed and applied to detect exosomal microRNA-21 (miR-21) derived from breast cancer cells. In brief, the target miR-21 can specifically open the hairpin probe 1(HP1) labeled on the gold electrode (GE) surface through strand displacement reaction. Thus the exposed loop region of HP1 can act as an initiator sequence to activate the hybridization chain reaction (HCR) between two kinetically trapped hairpin probes: HP2 immobilized on the GE surface and biotin labeled HP3 in solution. Cascade HCR leads to the formation of DNA "nano-bridge" tethered to the GE surface with a great deal of "piers". Upon addition of avidin-modified horseradish peroxidase (HRP), numerous HRP were bound to the formed "nano-bridge" through biotin-avidin interaction to arouse tremendous current signal. In theory, only a single miR-21 is able to trigger the continuous HCR between HP2 and HP3 until all of the HP2 are exhausted. Therefore the proposed biosensor achieved ultrahigh sensitivity toward miR-21 with the detection limit down to 168 amol/L, as well as little cross-hybridization even at the single-base-mismatched level. Successful attempts were also made in the detection of exosomal miR-21 obtained from the MCF-7 of breast cancer cell line. To our knowledge, this is the first attempt to built horizontal DNA nano-structure on the electrode surface for exosomal miRNAs detection. In a word, the high sensitivity, selectivity, low cost make the proposed method hold great potential application for early point-of-care (POC) diagnostics of cancer.

  • Mengting Pan, Yunming Liu, Xiaofang Zheng, Meijuan Zhou, Changjun You, Xiaoxia Dai
    Chinese Chemical Letters. 2021, 32(11): 3479-3482.

    Recent studies have shown that CTP may act as a ligand to regulate the activity of its target proteins in many biological processes. However, proteome-wide identification of CTP-binding proteins remains challenging. Here, we employed a biotinylated CTP affinity probe coupled with stable isotope labeling by amino acids in cell culture (SILAC)-based quantitative proteomics approach to capture, identify and quantify CTP-binding proteins in human cells. By performing two types of competitive SILAC experiments with high vs. low concentrations of CTP probe (100 vs. 10 µmol/L) or with CTP probe in the presence of free CTP, we identified 90 potential CTP-binding proteins which are involved in a variety of biological processes, including protein folding, nucleotide binding and cell-cell adhesion. Together, we developed a chemical proteomic method for uncovering the CTP-binding proteins in human cells, which could be widely applicable for profiling CTP-binding proteins in other biological samples.

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