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  • Jing Li, Zhuanjun Zhao, Yiran Song, Yang You, Jie Li, Xiuwen Cheng
    Chinese Chemical Letters. 2021, 32(10): 3231-3236.

    A magnesium doped ferrihydrite-humic acid coprecipitation (Mg-doped Fh-HA) was synthesized by coprecipitation method. The removal of heavy metals such as Pb(Ⅱ) and Cd(Ⅱ) was assessed. The isotherms and kinetic studies indicated that the Mg-doped Fh-HA exhibited a remarkable Pb(Ⅱ) and Cd(Ⅱ) sorption capacity (maximum 120.43 mg/g and 27.7 mg/g, respectively.) in aqueous solution. The sorption of Pb(Ⅱ) and Cd(Ⅱ) onto best fitted pseudo-second-order kinetic equation and Langmuir model. The adsorption mechanism of Mg-doped Fh-HA on Pb(Ⅱ) and Cd(Ⅱ) involves surface adsorption, surface complexation and surface functional groups (such as carboxyl group, hydroxyl group). In addition, ion-exchange and precipitation cannot be ignored. The Mg-doped Fh-HA is a low-cost and high-performance adsorption material and has a wide range of application prospects.

  • Ruifeng Bai, Dong Sun, Yuqin Shan, Zhiqiong Guo, Dafeng Chu, John Paul Fawcett, Jingkai Gu
    Chinese Chemical Letters. 2021, 32(10): 3237-3240.

    Polyoxyethylene glycerol ricinoleate (PGR) serves as a solubilizer/emulsifier that is commonly used in pharmaceutical formulations despite being associated with severe anaphylactoid hypersensitivity reactions. Cremophor EL® (CrEL) is the most representative PGR produced from reacting ethylene oxide with castor oil. To help clarify the cause of side effects and potentially improve the safety of PGR-based drug delivery vehicle, we have developed separate but related analytical methods for the quantitation of CrEL and its main metabolites, glycerol ethoxylate (GE) and ricinoleic acid (RA). Since CrEL and GE are highly disperse mixtures of polymers that are not amenable to analysis by conventional liquid chromatography-tandem mass spectrometry (LC-MS/MS), we used liquid chromatography-triple-quadrupole-time-of-flight mass spectrometry (LC-Q-TOF MS) combined with product ion data acquisition by MSALL and sequential window acquisition of all theoretical fragments mass spectrometry (SWATH MS), respectively to perform the analysis. In contrast, RA is a single molecular entity that could be readily analyzed using conventional LC-HR MS/MS. Selection of specific fragment ions for CrEL, GE, RA and their internal standards enabled a precise quantitation of such a complex analytes system in rat plasma after a single and simple sample preparation method. Assay validation indicated linearity for CrEL, GE and RA over the concentration ranges 0.2~20.0 μg/mL, 0.1~10.0 μg/mL and 0.1~20.0 μg/mL, respectively with satisfactory results for other validation parameters. A subsequent pharmacokinetic study involving single intravenous 200 mg/kg injections of CrEL to rats showed the methods enable comprehensive and high throughput quantitation of CrEL and its metabolites in a biological matrix. Our combination of assays provides effective application in investigating the cause of the hypersensitivity reaction of PGR and potentially to improve its safety for using as a vehicle in drug formulations.

  • Jing Xu, Juan Chen, Yanhui Ao, Peifang Wang
    Chinese Chemical Letters. 2021, 32(10): 3226-3230.

    Low dimension nano photocatalysts show great potential in the field of treating contaminated water for their large surface area and size effect. In this study, a 0D/1D AgI/MoO3 Z-scheme photocatalyst with striking photocatalytic performance was constructed successfully. The one-dimensional MoO3 nanobelts were prepared by a simple hydrothermal method, and then it was modified by AgI nanoparticles in a handy deposition approach. When choosing sulfamethoxazole (SMZ) as the target contaminant, the rate constant value of the optimal 0D/1D AgI/MoO3 composite could hit up to 0.13 min-1, which is nearly 22.4 times and 32.5 times as that of pure MoO3 (0.0058 min-1) and AgI (0.0040 min-1), respectively. A series of detailed characterizations give evidences that the charge transfer in the composite followed Z scheme mechanism. Therefore, efficient separation/transfer and the remained high redox activity of photogenerated carriers played a vital role in the sharply enhanced photocatalytic properties. The possible degradation pathways of SMZ were proposed based on the intermediates detected by high-performance liquid chromatography-mass spectrometry (HPLC-MS). Meanwhile, the magnificent cyclic stability makes the material a promising material in the practical application.

  • Xinyang Li, Yannan Li, Hao Zhang, Zhen Shen, Shuang Cheng, Guicheng Liu, Hong Yao
    Chinese Chemical Letters. 2021, 32(10): 3221-3225.

    Electrochemical heterogeneous catalytic ozonation (E-catazone) is a promising and advanced oxidation technology that uses a titanium dioxide nanoflower (TiO2-NF)-coated porous Ti gas diffuser as an anode material. Our previous study has highlighted that the importance of the TiO2-NF coating layer in enhancing OH production and rapidly degrading O3-resistant drugs. It is well known that the properties of TiO2-NF are closely related to its sintering temperature. However, to date, related research has not been conducted in E-catazone systems. Thus, this study evaluated the effect of the sintering temperature on the degradation of the O3-resistant drug para-chlorobenzoic acid (p-CBA) using both experimental and kinetic modeling and revealed its influence mechanism. The results indicated that the TiO2-NF sintering temperature could influence p-CBA degradation and OH production. TiO2-NF prepared at 450 ℃ showcased the highest p-CBA removal efficiency (98.5% in 5 min) at a rate of 0.82 min-1, and an OH exposure of 8.41 × 10-10molL-1s. Kinetic modeling results and interface characterization data revealed that the sintering temperature could alter the TiO2 crystallized phase and the content of surface-adsorbed oxygen, thus affecting the two key limiting reactions in the E-catazone process. That is, ≡TiO2 surface reacted with H2O to form TiO2-(OH)2, which then heterogeneously catalyzed O3 to form OH. Consequently, E-catazone with a TiO2-NF anode prepared at 450 ℃ generated the highest surface reaction rate (5.00 × 10-1 s-1 and 4.00 × 10-3 L mol-1 s-1, respectively), owing to its higher anatase content and adsorbed oxygen. Thus, a rapid O3-TiO2 reaction was achieved, resulting in an enhanced OH formation and a highly effective p-CBA degradation. Overall, this study provides novel baseline data to improve the application of E-catazone technology.

  • Youzhe Chen, Chengbo Xu, Weiping Wang, Xiaoliang Wang, Qinglan Guo, Jiangong Shi
    Chinese Chemical Letters. 2021, 32(10): 3257-3260.

    Three phthalide-derived analogues, oxaspiroangelioic acids A–C (13), were isolated as minor components of an aqueous extract of the Angelica sinensis root heads (guitou). Oxaspiroangelioic acids A and B were racemates separated into enantiomers by chiral HPLC. Their structures including absolute configurations were determined by spectroscopic data analysis, single crystal X-ray diffraction, exciton chirality method and electronic circular dichroism (ECD) calculation. These compounds share an undescribed carbon skeleton, for which biosynthetic pathways are proposed. Compound 1 and its enantiomers showed almost identical activity inhibiting Tandem of P domains in a weak inwardly rectifying K+ channel 1 (TREK-1).

  • Xiaofan Xiang, Laiyan Wu, Junjiang Zhu, Jiazhou Li, Xi Liao, Hongcheng Huang, Jiajie Fan, Kangle Lv
    Chinese Chemical Letters. 2021, 32(10): 3215-3220.

    Antibiotics such as sulfonamides are widely used in agriculture as growth promoters and medicine in treatment of infectious diseases. However, the release of these antibiotics has caused serious environmental problems. In this paper, photocatalytic oxidation technology was used to degrade sulfadiazine (SDZ), one of the typical sulfonamides antibiotics, in UV illuminated TiO2 suspensions. It was found that TiO2 nanosheets (TiO2-NSs) with exposed (001) facets exhibit much higher photoreactivity towards SDZ degradation compared to TiO2 nanoparticles (TiO2-NPs) with a rate constant increases from 0.017 min-1 to 0.035 min-1, improving by a factor of 2.1. Under the attacking of reactive oxygen species (ROSs) such as superoxide radicals (O2) and hydroxyl radicals (OH), SDZ was steady degraded on the surface of TiO2-NSs. Based on the identification of the produced intermediates by LC–MS/MS, possible degradation pathways of SDZ, which include desulfonation, oxidation and cleavage, were put forwards. After UV irradiation for 4 h, nearly 90% of the total organic carbon (TOC) can be removed in suspensions of TiO2-NSs, indicating the mineralization of SDZ. TiO2-NSs also exhibits excellent stability in photocatalytic degradation of SDZ in wide range of pH. Even after recycling used for 7 times, more than 91.3% of the SDZ can be efficiently removed, indicating that they are promising to be practically used in treatment of wastewater containing antibiotics.

  • Feiqiang He, Xinyu Zhu, Lirong Zhong, Zhuyao Li, Yong Qian
    Chinese Chemical Letters. 2021, 32(10): 3175-3179.

    In this work, nitric oxide absorption process by using ferrate(Ⅵ)/urea was proposed. The respective influences of the four factors including pH value, ferrate(Ⅵ) concentration, urea concentration, and the temperature and the interactive function of them on nitric oxide absorption were investigated with the response surface methodology (RSM) by central composite design (CCD). The proposed model system showed good consistency with the experiment results, by a correlated coefficient ( R2) of 0.9875. In addition, the interactive influences between any two variables were elaborated through analysis of response surface. The optimal parameters were found at pH of 7.1, reaction temperature of 43.8 ℃, urea concentration of 6.3 wt%, ferrate(Ⅵ) concentration of 4.4 mmol/L for 85.2% NO absorption. Finally, N-containing product analysis shows that nitric oxide was primarily transformed to N2 and NO3.

  • Xu Zhou, Chunyan Wang, Fulin Liu, Chengyu He, Shiming Zhang
    Chinese Chemical Letters. 2021, 32(10): 3261-3263.

    The composite photoanodes composed by cobalt phosphate catalyst (Co−Pi) modified semiconductor have been widely used for solar water splitting, but the improvement mechanism has not been experimentally confirmed. Here we use transient photoelectrochemical measurements and impedance spectroscopy to investigate the effect of Co−Pi catalyst on hematite nanowire photoanode. It is found that under illumination the Co−Pi catalyst can efficiently promote the transfer of photo-generated holes to the Co−Pi layer by increasing the electrical conductivity of the composite structure under a low potential. The Co−Pi catalyst can recombine with photo-generated electrons to reduce the surface recombination efficiency of photo-generated holes and electrons under a high potential. These results provide important new understanding of the performance improvement mechanism for the Co−Pi-modified semiconductor nanowire composite photoanodes.

  • Yi Li, Chao Teng, Helena S. Azevedo, Lifang Yin, Wei He
    Chinese Chemical Letters. 2021, 32(10): 3071-3075.

    Codelivery of drugs by drug carriers is a promising strategy against several diseases such as infections and cancer. However, traditional drug carriers are typically characterized by low drug payload, limiting their treatment efficacy. Using nanocrystals of insoluble drug as carriers, a carrier free platform was developed previously to deliver a second insoluble drug for codelivery. To extend the concept, we hypothesized, herein, that the platform allows for codelivery of hydrophobic and hydrophilic drugs using a cocrystalization-like strategy. To obtain proof-of-concept, paclitaxel (PTX), an insoluble chemotherapeutic agent, and dichloroacetic acid (DCA), a water-soluble inhibitor of pyruvate dehydrogenase kinase, were utilized as model drugs. PTX-DCA hybrid nanocrystals (PTX-DCA NCs) were prepared by anti-solvent precipitation and characterized. Their in vitro antitumor activity against cancer cells was evaluated. PTX-DCA NCs prepared from the optimized formulation had a diameter of 160 nm and a rod-shape morphology and possessed encapsulated efficacy of approximately 30% for DCA. The use of the hybrid crystals enabled synergy to kill cancer cells, in particular in PTX-resistant cells in a dose-dependent pattern. In conclusion, by using a cocrystalization-like strategy, a hydrophilic drug can be formulated into a drug's nanocrystal for codelivery.

  • Shuai Chen, Xuewei Zhang, Yongliang Yu, Jianhua Wang
    Chinese Chemical Letters. 2021, 32(10): 3043-3047.

    Discrimination of glycoproteins and cell types is a significant but difficult issue. Herein, we presented a novel fluorescence sensor array for the detection and identification of glycoproteins and cancer cells based on the specific affinity between boronic acid-containing carbon dots (BA-CDs) and cis-diol residues of polysaccharides. The differential binding affinity of three BA-CDs to various glycoproteins resulted in a different fluorescence turn-on signal pattern caused by aggregation-enhanced emission (AEE), along with negligible response from other proteins. Therefore, BA-CDs encompassing sensing elements and signal indicator into one can enable a fast and accurate discrimination of glycoproteins with simple and easy operation. Seven glycoproteins could be well discriminated at a very low concentration of 10 nmol/L. The discriminating capability of glycoproteins is not sacrificed in both human urine and serum. Notably, different glycoprotein compositions of cancer cells provide more recognizable features for identification of cancer cells, comparing to the total protein. Five cell types could be identified in 15 min at a low concentration of 1000 cells/mL. This method is fast, accurate, and easy operation, and has a potential application in cancer diagnosis.

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