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  • Yang Li, Ying Ma, Jingjing Zhan, Yaobin Zhang, Zisheng Zhao, Zhiqiang Zhao
    Chinese Chemical Letters. 2022, 33(6): 3106-3112.

    Considering that cathode of microbial electrochemical system (MES) is a good electrons source for methane production via direct/indirect electron transfer to electroactive microorganisms, and that Fe(0) is also a confirmed electron donor for some electroactive microorganisms through metal-microbe direct electron transfer (DET), Fe(0)-cathode was equipped into an MES digester to enhance cathodic methane production. The results of this study indicated that the potential DET participator, Clostridium possibly obtained electrons directly from Fe(0)-cathode via metal-microbe electrons transfer, then transferred electrons directly to the definite DET participators, Methanosarcina/Methanothrix via microbe-microbe electrons transfer for CH4 production. In addition, Methanobacterium is another specially enriched methanogen on Fe(0)-cathode, which might obtain electrons directly from Fe(0)-cathode to produce CH4 via metal/electrode-microbe DET. The increment of conductivity of cathodic sludge in Fe(0)-cathode MES digester (R1) further confirmed the enrichment of electroactive microorganisms participating in DET process. As a consequence, a higher CH4 production (1205–1508 mL/d) and chemical oxygen demand (COD) removal (79.0%-93.8%) were achieved in R1 compared with graphite-cathode MES digester (R2, 720–1090 mL/d and 63.6%-85.6%) and the conventional anaerobic digester (R3, 384–428 mL/d and 35.2%-41.0%). In addition, energy efficiency calculated indicated that the output energy of CH4 production was 8.16 folds of electricity input in Fe(0)-cathode MES digester.

  • Zhiyu Chen, Lei Fu, Xin-An Liu, Zhiyi Yang, Wenbo Li, Fang Li, Qian Luo
    Chinese Chemical Letters. 2022, 33(6): 3101-3105.

    Nicotine ingested from smoking exerts neuroprotection and developmental neurotoxicity in central nervous system. It can produce several changes of cognitive behaviors through regulating the release of different neurotransmitters in the brain. However, the effects of nicotine exposure or withdrawal on neurotransmitter metabolism of hippocampus are still unclear. In this study, we real-time evaluated the dynamic alterations in neurotransmitter metabolism of hippocampal neuronal (HT22) cells induced by nicotine exposure and withdrawal at relevant exposure levels of smoking and secondhand smoke by using a microfluidic chip-coupled with liquid chromatography-mass spectrometry (MC-LC-MS) system. We found HT22 cells mainly released related neurotransmitters of tryptophan and choline metabolism, both nicotine exposure and withdraw altered its neurotransmitters and their metabolites release. Exposure to nicotine mainly altered the secretion of serotonin, kynurenic acid, choline and acetylcholine of HT22 cells to improve hippocampal dependent cognition, and the change are closely related to the dose and duration of exposure. Moreover, the altered metabolites could rapidly recover after nicotine withdrawal, but picolinic acid was elevated. MC-LC-MS system used in present study showed a greater advantage to detect unstable metabolites than conventional method by using in vitro model, and the results of dynamic alterations of neurotransmitter metabolism induced by nicotine might provide a potential targets for drug development of neuroprotection or cognitive improvement.

  • Jihong Xu, Jianxin Song, Yulin Min, Qunjie Xu, Penghui Shi
    Chinese Chemical Letters. 2022, 33(6): 3113-3118.

    The nitrogen-doped carbon derived from graphitic carbon nitride (g-C3N4) has been widely deployed in activating peroxymonosulfate (PMS) to remove organic pollutants. However, the instability of g-C3N4 at high temperature brings challenges to the preparation of materials. The nitrogen-doped graphitic carbon nanosheets (N-GC750) were synthesized by magnesium thermal denitrification. Magnesium undergoes the displacement reaction with small molecules produced by the pyrolysis of g-C3N4, thereby effectively fixing carbon on the in-situ template of Mg3N2 and avoiding direct product volatilization. N-GC750 exhibited excellent performance during the PMS activation process and bisphenol A (BPA, 0.2 g/L) could be thoroughly removed in 30 min. A wide range of pH (3–11), temperature (10–40 ℃) and common anions were employed in studying the impact on system. Additionally, N-GC750 showed satisfactory reusability in cycle tests and promising applicability in real water samples. Quenching experiments and electron paramagnetic resonance (EPR) measurements indicated that singlet oxygen was the main active species coupled with partial electron transfer in N-GC750/PMS system. Furtherly, the oxidation products were identified, and their ecotoxicity was evaluated. This work is expected to provide a reference for the feasibility of preparing g-C3N4 derived carbon materials and meaningful for PMS activation.

  • Mengying Liang, Delu Liu, Yangyang Nie, Yanli Liu, Xiaoqiang Qiao
    Chinese Chemical Letters. 2022, 33(6): 3123-3126.

    High performance liquid chromatography-mass spectrometry is one of the most commonly used strategies for lipid analysis. The development of versatile chromatographic stationary phases to meet the increasing demands for separation of complex lipids is very important. Styrene-maleic acid (SMA) copolymer is an amphiphilic polymer, which has been proven to have the ability to solubilize lipid molecules of various structures. In this study, styrene-maleic anhydride copolymer coated silica was first prepared by the thiol-ene click reaction. With l-cysteine hydrochloride or dodecanol as the post-modification reagents, Sil-SMA-amino acid and Sil-SMA-dodecanol stationary phase materials were further successfully fabricated via nucleophilic ring-opening reaction. The Fourier-transform infrared, thermogravimetric analysis, and elemental analysis results confirmed the two stationary phase materials were successfully prepared. Furthermore, both the Sil-SMA-dodecanol column and the Sil-SMA-amino acid column possessed reversed-phase/hydrophilic interaction/ion exchange mixed-mode retention mechanisms. The column efficiency of the Sil-SMA-derivatives columns reached 77,300 N/m. Based on the mixed-mode retention characteristics, the Sil-SMA-derivatives columns achieved both the lipid classes and species separation via a single column. The Sil-SMA-amino acid column was further successfully used to separate lipid extract from gastric cancer cell membrane. All these results demonstrated that the SMA-based stationary phase materials have a good potential for use in lipid separation.

  • Xuexia Lin, Jianlong Su, Shufeng Zhou
    Chinese Chemical Letters. 2022, 33(6): 3133-3138.

    Concentration gradient and fluid shear stress (FSS) for cell microenvironment were investigated through microfluidic technology. The Darcy–Weisbach equation combined with computational fluid dynamics modeling was exploited to design the microfluidic chip, and the FSS distribution on the cell model with varying micro-channels (triangular, conical, and elliptical). The diffusion with the incompressible laminar flow model by solving the time-dependent diffusion–convection equation was applied to simulate the gradient profiles of concentration in the micro-channels. For the study of single cell in-depth, the FSS was investigated by the usage of polystyrene particles and the concentration diffusion distribution was studied by the usage of different colors of dyes. A successful agreement between model simulations and experimental data was obtained. Finally, based on the established method, the communication between individual cells was envisaged and modeled. The developed method provides valuable insights and allows to continuously improve the design of microfluidic devices for the study of single cell, the occurrence and development of tumors, and therapeutic applications.

  • Xinyue Xiong, Zhanglin Liu, Li Zhao, Mei Huang, Lichun Dai, Dong Tian, Jianmei Zou, Yongmei Zeng, Jinguang Hu, Fei Shen
    Chinese Chemical Letters. 2022, 33(6): 3097-3100.

    In this work, a modification method of H3PO4 plus H2O2 (PHP) was introduced to targetedly form abundant oxygenated functional groups (OFGs) on biochar, and methylene blue (MB) was employed as a model pollutant for adsorption to reflect the modification performance. Results indicated that parent biochars, especially derived from lower temperatures, substantially underwent oxidative modification by PHP, and OFGs were targetedly produced. Correspondingly, approximately 21.5-fold MB adsorption capacity was achieved by PHP-modified biochar comparing with its parent biochar. To evaluate the compatibility of PHP-modification, coefficient of variation (CV) based on MB adsorption capacity by the biochar from various precursors was calculated, in which the CV of PHP-modified biochars was 0.0038 comparing to 0.64 of the corresponding parent biochars. These results suggested that the PHP method displayed the excellent feedstock compatibility on biochar modification. The maximum MB adsorption capacity was 454.1 mg/g when the H3PO4 and H2O2 fraction in PHP were 65.2% and 7.0%; the modification was further intensified by promoting temperature and duration. Besides, average 94.5% H3PO4 was recovered after 10-batch modification, implying 1.0 kg H3PO4 (85%) in PHP can maximally modify 2.37 kg biochar. Overall, this work offered a novel method to tailor biochar towards OFGs-rich surface for efficient adsorption.

  • Yiran Guo, Peng Chen, Zhaolong Gao, Yiwei Li, Shunji Li, Xiaojun Feng, Bi-Feng Liu
    Chinese Chemical Letters. 2022, 33(6): 3091-3096.

    The cellular response to the complex extracellular microenvironment is highly dynamic in time and type of extracellular matrix. Accurately reconstructing this process and analyzing the changes in receptor conformation on the cell membrane surface and intracellular or intercellular signaling has been a major challenge in analytical chemistry and biophysical methodology. In this paper, a time-coded multi-concentration microfluidic chemical waveform generator was developed for the dynamic signaling probing with single-cell array of high temporal resolution, high throughput, and multi-concentration combination stimulation. Based on innovative microchannel structure, sophisticated external control methods and multiplexing technology, the system not only allowed for temporally sequential permutations of the four concentrations of stimuli (time code), but also generated pulsed and continuous waveforms at different frequencies in a highly controllable manner. Furthermore, the single-cell trap array was set up to efficiently capture cells in suspension, dramatically increasing throughput and reducing experiment preparation time. The maximum frequency of the platform was 1 Hz, and one cell could be stimulated at multiple frequencies. To show the ability of the system to investigate rapid biochemical events in high throughput, pulse stimulation and continuous stimulation of different frequencies and different time codes, combined with four concentrations of histamine (HA), were generated for probing G protein-coupled receptor (GPCR) signaling in HeLa cells. Then, statistical analysis was performed for the mean peak height and mean peak area of the cellular response. We believe that the time-coded multi-concentration microfluidic chemical waveform generator will provide a novel strategy for analytical chemistry, biophysics, cell signaling, and individualized medicine applications.

  • Xiang Yuan, Jianshuang Jiang, Yanan Yang, Xu Zhang, Ziming Feng, Peicheng Zhang
    Chinese Chemical Letters. 2022, 33(6): 2923-2927.

    Sophoralines A-C, three novel [2 + 2] cycloaddition dimers of matrine-based alkaloids with an unprecedented 6/6/6/6/4/6/6/6/6 nonacyclic skeleton containing 11 stereogenic centers, were isolated from Sophora alopecuroides. Their structures were determined by spectroscopic methods, and the absolute configurations were further determined by single-crystal X-ray diffraction analysis for 1 and quantum chemical calculations of electronic circular dichroism (ECD) spectra for 2 and 3. Moreover, 1 exhibited excellent hepatoprotective activities in acetaminophen-induced liver injury in vitro and in vivo.

  • Junliang Du, Rong Zhang, Feifei Wang, Hua Zhou, Xuemei Wang, Xinzhen Du
    Chinese Chemical Letters. 2022, 33(6): 3119-3122.

    Fabrication of selective adsorption coatings plays a crucial role in solid-phase microextraction (SPME). Herein, new strategies were developed for the in-situ fabrication of novel cobalt-based carbonaceous coatings on the nickel-titanium alloy (NiTi) fiber substrate using ZIF-67 as a precursor and template through the chemical reaction of ZIF-67 with glucose, dopamine (DA) and melamine, respectively. The adsorption performance of the resulting coatings was evaluated using representative aromatic compounds coupled to high-performance liquid chromatography (HPLC) with ultraviolet detection (HPLC-UV). The results clearly demonstrated that the adsorption selectivity was subject to the surface elemental composition of the fiber coatings. The cobalt and nitrogen co-doped carbonaceous coating showed better adsorption selectivity for ultraviolet filters. In contrast, the cobalt-doped carbonaceous coating exhibited higher adsorption selectivity for polycyclic aromatic hydrocarbons. The fabricated fibers present higher mechanical stability and higher adsorption capability for model analytes than the commercial polydimethylsiloxane and polyacrylate fibers. These new strategies will continue to expand the NiTi fibers as versatile fiber substrates for metal-organic frameworks (MOFs)-derived coating materials with controllable nanostructures and tunable properties.

  • Litao Ma, Jiamin Xie, Xiaoshan Yan, Zhiwei Fan, Heguo Li, Lin Lu, Likun Chen, Yi Xin, Panchao Yin
    Chinese Chemical Letters. 2022, 33(6): 3241-3244.

    The urgent need for immediate personal protection against chemical warfare agents (CWAs) spurs the requirement on robust and highly efficient catalytic systems that can be conveniently integrated to wearable devices. Herein, as a new concept for CWA decontamination catalyst design, sub-nanoscale, catalytically active zirconium-oxo molecular clusters are covalently integrated in flexible polymer network as crosslinkers for the full exposure of catalytic sites as well as robust framework structures. The obtained membrane catalysts exhibit high swelling ratio with aqueous content as 84 wt% and therefore, demonstrate quasi-homogeneous catalytic activity toward the rapid hydrolysis of both CWA, soman (GD) (t1/2 = 5.0 min) and CWA simulant, methyl paraoxon (DMNP) (t1/2 = 8.9 min). Meanwhile, due to the covalent nature of cross-linkages and the high flexibility of polymer strands, the membranes possess promising mechanical strength and toughness that can stand the impact of high gas pressures and show high permeation for both CO2 and O2, enabling their extended applications in the field of collective/personal protective materials with body comfort.

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