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  • Jingwei Huang, Kai Li, Lei Wang, Houde She, Qizhao Wang
    Chinese Chemical Letters. 2022, 33(8): 3787-3791.

    The construction of rich phase interfaces to increase active reaction area in hybrid materials is an excellent strategy to improve electrochemical performance. Under this guideline, MIL-101@OX-metal organic framework (MOF) is constructed by the "MOF on MOF" method, then converts to MIL-101@NiFe-layered double hydroxides (LDH) by in situ transformation in alkaline solution. MIL-101@NiFe-LDH shows excellent electrochemical water oxidation performance. It needs only an overpotential of 215 mV to drive 10 mA/cm2 of oxygen evolution reaction (OER), which is less than that of NiFe-LDH, MIL-101. In addition, MIL-101@NiFe-LDH has the smallest Tafel slope (55.1 mV/dec) compared with NiFe-LDH (61.1 mV/dec), MIL-101 (150.8 mV/dec). The excellent water oxidation activity is due to the high phase interfaces derived from high specific surface area of MOF. This work offers an alternative method for making MOF/LDH heterostructures with an optimized phase interfaces and provides new insights for OER.

  • Ningkai Ding, Bin Chen, Liang Zhou, Lingzhi Wang, Yongdi Liu, Jinlong Zhang, Juying Lei
    Chinese Chemical Letters. 2022, 33(8): 3797-3801.

    In this work, Z-scheme V2O5 loaded fluorinated inverse opal carbon nitride (IO F-CN/V2O5) was synthesized as a product of ternary collaborative modification with heterostructure construction, element doping and inverse opal structure. The catalyst presented the highest photocatalytic activity and rate constant for degradation of typical organic pollutants Rhodamine B (RhB) and was also used for the efficient removal of antibiotics, represented by norfloxacin (NOR), sulfadiazine (SD) and levofloxacin (LVX). Characterizations confirmed its increased specific surface area, narrowed bandgap, and enhanced visible light utilization capacity. Further mechanism study including band structure study and electron paramagnetic resonance (EPR) proved the successful construction of Z-scheme heterojunction, which improved photo-generated charge carrier migration and provide sufficient free radicals for the degradation process. The combination of different modifications contributed to the synergetic improvement of removal efficiency towards different organic pollutants.

  • Meng-Yuan Chen, Chu-Bo Qi, Xiao-Meng Tang, Jiang-Hui Ding, Bi-Feng Yuan, Yu-Qi Feng
    Chinese Chemical Letters. 2022, 33(8): 3772-3776.

    RNA molecules contain diverse modifications that display important functions in a variety of physiological and pathological processes. So far over 150 chemical modifications have been characterized to be present in various RNA species, such as in messenger RNA (mRNA), ribosomal RNA (rRNA), and transfer RNA (tRNA). Previous studies revealed that certain RNA modifications were correlated to specific human diseases, indicating RNA modifications could serve as the potential indicator of human diseases. However, systemic investigation of the alteration of RNA modifications in different RNA species of carcinoma tissues are still lacked. Herein, we carried out the comprehensive profiling and evaluation of the alteration of RNA modifications in thyroid carcinoma by liquid chromatography-tandem mass spectrometry (LC-ESI-MS/MS) analysis. The developed method allowed us to simultaneously detect 48 different types of RNA modifications. Using this method, we detected 10, 15, 14, and 25 modifications in mRNA, 18S rRNA, 28S rRNA and small RNA (< 200 nt), respectively. Compared to the normal tissues, we revealed a total of 14 RNA modification exhibited significant increase and 2 RNA modifications showed significant decrease in thyroid carcinoma tissues. Our study provided the first comprehensive profile as well as the alteration of modifications in different RNA species in thyroid carcinoma and matched tumor-adjacent normal tissues. The altered pattern RNA modifications may serve as the indicator of thyroid carcinoma. Moreover, this study may promote the in-depth understanding of the regulatory roles of RNA modifications in thyroid carcinoma.

  • Yunda Li, Yanfei Zhang, Zhenning Yu, Yuzhi Xu, Si-Yang Liu, Zong Dai, Xiaoyong Zou
    Chinese Chemical Letters. 2022, 33(8): 3777-3781.

    5-Hydroxymethylcytosine (5hmC), an intermediate product of DNA demethylation, is important for the regulation of gene expression during development and even tumorigenesis. The challenges associated with determination of 5hmC level include its extremely low abundance and high structural similarity with other cytosine derivatives, which resulted in sophisticated treatment with large amount of sample input. Herein, we developed a primer-initiated strand displacement amplification (PISDA) strategy to quantify the global 5hmC in genomic DNA from mammalian tissues with high sensitivity/selectivity, low input and simple operation. This sensitive fluorescence method is based on 5hmC-specific glucosylation, primer ligation and DNA amplification. After the primer was labeled on 5hmC site, DNA polymerase and nicking enzyme will repeatedly act on each primer, causing a significant increase of fluorescence signal to magnify the minor difference of 5hmC content from other cytosine derivatives. This method enables highly sensitive analysis of 5hmC with a detection limit of 0.003% in DNA (13.6 fmol, S/N = 3) from sample input of only 150 ng, which takes less than 15 min for determination. Further determination of 5hmC in different tissues not only confirms the widespread presence of 5hmC but also indicates its significant variation in different tissues and ages. Importantly, this PISDA strategy exhibits distinct advantages of bisulfite-free treatment, mild conditions and simple operation without the involvement of either expensive equipment or large amount of DNA sample. This method can be easily performed in almost all research and medical laboratories, and would provide a promising prospect to detect global 5hmC in mammalian tissues.

  • Jing-Jing Zhang, Si-Ying Wang, Pan Zhang, Shu-Chen Fan, Hai-Tao Dai, Yin Xiao, Yong Wang
    Chinese Chemical Letters. 2022, 33(8): 3873-3878.

    Chiral recognition of essential amino acids (EAAs) is a huge challenge that keeps plaguing analytical scientists due to their cryptochirality and limited steric interaction sites. Inspired by the superior enantioselectivity of functional supramolecular cyclodextrins (CDs) and strong signal amplification ability of field effect transistors (FETs), this work firstly reports a cationic supramolecular charge switch for facile enantiodiscrimination of EAAs based on extended-gate organic FET (EG-OFET). The cationic phenylcarbamoylated-CD single isomer acts as a charge switch via interacting with different enantiomers and the weak stereo-differentiation intermolecular interaction signals between the cationic perphenylcarbamoylated CDs and EAAs on the EG can be strongly and rapidly amplified through an OFET. Efficient chiral differentiation of six EAAs, including phenylalanine, tryptophan, leucine, isoleucine, lysine and valine, are successfully achieved without any derivation process and the detection limit for D-phenylalanine is down to 10−13 mol/L. We believe that this study provides a new and facile sensing perspective for natural amino acids and may afford deeper understanding of molecular chirality.

  • Tiantian Si, Xiaofeng Lu, Haixia Zhang, Shuai Wang, Xiaojing Liang, Yong Guo
    Chinese Chemical Letters. 2022, 33(8): 3869-3872.

    Here, silica microspheres were decorated with two-dimensional metal–organic frameworks (2D MOFs) nanosheets and ionic liquids, and evaluated as the mixed-mode stationary phase for chromatographic separation. The ionic liquids were used to assist the synthesis of 2D MOFs nanosheets, and also acted as adhesives among the nanosheets and silica. In contrast with the 2D MOFs-based column without ionic liquids and commercial columns, the prepared column exhibited enhanced chromatographic separation performance for partially hydrophilic compounds such as alkaloids, sulfonamides and antibiotics, etc. In addition to excellent chromatographic repeatability and stability, it has also been verified that the composites could be easily and repeatedly prepared. The relative standard deviation of the retention time of the same type of analyte between the three batches of materials was ranging from 0.21% to 1.7%. In short, these results indicated that the synthesized composites were promising separation material for liquid chromatography, which made it possible to broaden the application of 2D MOFs in the field of chromatography.

  • Mengyuan Cheng, Yufeng Liu, Weixin Du, Jingwen Shi, Junhua Li, Haiying Wang, Ke Li, Guoping Yang, Dongdi Zhang
    Chinese Chemical Letters. 2022, 33(8): 3899-3902.

    Two novel uranium-containing selenotungstates Na3[H19(UO2)2(μ2-O)(Se2W14O52)2]·41H2O (U2) and (NH4)10[H4(SeO)2(UO2)2(H2O)2(H2Se2W14O52)(Se2W14O52)]·66H2O (Se2U2) based on the {Se2W14O52} unit were successfully prepared and fully characterized. To our knowledge, the uranium is firstly introduced into the selenotungstates. Moreover, it is notable that U2 exhibits excellent Lewis acid-base catalytic activities in the condensation cyclization of sulfonyl hydrazides with diketones to synthesize polysubstituted pyrazoles. All the desired products were obtained in moderate to good yields (up to 99%).

  • Xiao Wang, Kaixiang Zou, Weijing Wu, Yuanfu Deng, Guohua Chen
    Chinese Chemical Letters. 2022, 33(8): 3883-3888.

    Designing a carbon material with a unique composition and surface functional groups for offering high specific capacity in a wide voltage window is of great significance to improve the energy density for the supercapacitor in a cheap and eco-friendly aqueous electrolyte. Herein, we develop an efficient strategy to synthesize a N, O co-doped hierarchically porous carbon (NODPC-1.0) with moderate specific surface area and pore volume as well as rich heteroatoms using a deep eutectic solvent (DES) as an activator. It is found that NODPC-1.0 with a large proportion of pseudocapacitive functional groups (pyrrole-N, pyridine-N and carbonyl-quinone) can work stable in an acidic 2 mol/L Li2SO4 (pH 2.5) electrolyte, exhibiting specific capacities of 375 and 186 F/g at the current densities of 1.0 and 100 A/g, respectively. Also, the assembled symmetric capacitor using the NODPC-1.0 as the active material and 2 mol/L acidic Li2SO4 (pH 2.5) as the electrolyte shows an outstanding energy density of 74.4 Wh/kg at a high power density of 1.44 kW/kg under a broad voltage window (2.4 V). Relevant comparative experiments indicate that H+ of the acidic aqueous electrolyte plays a crucial part in enhancement the specific capacity, and the abundant pseudocapacitive functional groups on the surface of the NODPC-1.0 sample play the key role in the improvement of electrochemical cycle stability under a broad voltage window.

  • Jiamu Cao, Jing Zhou, Mingxue Li, Junyu Chen, Yufeng Zhang, Xiaowei Liu
    Chinese Chemical Letters. 2022, 33(8): 3745-3751.

    Hydrogen evolution reaction (HER) catalytic electrodes under actual working conditions show interesting mass transfer behaviors at solid (electrode)/liquid (electrolyte)/gas (hydrogen) three-phase interfaces. These behaviors are essential for forming a continuous and effective physical contact region between the electrolyte and the electrode and require further detailed understanding. Here, a case study on 1T-2H phase molybdenum disulfide (MoS2)/carbon fiber paper (CFP) catalytic electrodes is performed. Rapid gas-liquid mass transfer at the interface for enhancing the working area stability and capillarity for increasing the electrode working area is found. The real scenario, wherein the energy utilization efficiency of the as-prepared non-noble metal catalytic electrode exceeds that of the noble metal catalytic electrode, is disclosed. Specifically, a fluid dynamics model is developed to investigate the behavior mechanism of hydrogen bubbles from generation to desorption on the catalytic electrode surface with different hydrophilic and hydrophobic properties. These new insights and theoretical evidence on the non-negligible three-phase interface behaviors will identify opportunities and motivate future research in high-efficiency, stability, and low-cost HER catalytic electrode development.

  • Hao Zhang, Caihong He, Sumei Han, Zeyang Du, Ling Wang, Qinbai Yun, Wenbin Cao, Bowei Zhang, Ya-Hui Tian, Qipeng Lu
    Chinese Chemical Letters. 2022, 33(8): 3641-3649.

    Developing high-performance electrocatalysts for CO2 reduction reaction (CO2RR) is crucial since it is beneficial for environmental protection and the resulting value-add chemical products can act as an alternative to fossil feedstocks. Nonetheless, the direct reduction of CO2 into long-chain hydrocarbons and oxygenated hydrocarbons with high selectivity remains challenging. Copper (Cu) shows a distinctive advantage that it is the only pure metal catalyst for reducing CO2 into multi-carbon (C2+) products and the certain facets (e.g., (100), (111), (111)) of Cu nanocrystals exhibit relatively low energy barriers for the formation of specific products (e.g., CO, HCOOH, CH4, C2H4, C2H5OH, and other C2+ products). Therefore, extensive studies have been carried out to explore the relationship between the facets of Cu nanocrystals and corresponding catalytic products. In this review, we will discuss the crystal facet-dependent electrocatalytic CO2RR performance in metallic Cu catalysts, meanwhile, the detailed reaction mechanisms will be systematically summarized. In addition, we will provide a personal perspective for the future research directions in this emerging field. We believe this review is helpful to guide the design of high-selectivity Cu-based electrocatalysts for CO2RR.

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