【特约专题】
响应面法优化N-乙酰氨基葡萄糖发酵液精制纯化工艺
刘硕a, b，刘鲁杰a, b，王永红a，赵黎明*a, b
(华东理工大学 a. 生物工程学院，b. 发酵工业分离提取技术研发中心，上海 200237)
摘要：为从发酵液中精制N-乙酰氨基葡萄糖（NAG），以预处理的NAG发酵液为研究对象，开发NAG发酵液精制纯化工艺，筛选适用于NAG发酵液精制纯化的树脂，考察树脂用量、上样浓度、温度、料液流速对发酵液脱盐率、脱色率与NAG回收率的影响，在单因素实验的基础上，采用响应面分析法对NAG发酵液的精制纯化工艺进行优化。从6种树脂中，筛选出DS-1树脂对发酵液脱盐效果最优、HS-3树脂对发酵液脱色效果最优，优化后的最佳条件为阴阳离子交换树脂体积比0.35:1、上样浓度65 mg/mL、温度41 ℃，此时发酵液脱盐率为96.9%，脱色率为79.5%，NAG回收率为84.5%，NAG结晶纯度可达99.8%。该精制纯化工艺可以有效地去除降低NAG品质的无机盐和色素，提高NAG纯度与结晶率并减少母液量。
关键词：响应面分析法；发酵液；NAG；离子交换树脂；纯化
中图分类号：TQ028 文献标识码：A 文章编号：0258-3283（2023）
DOI:10.13822/j.cnki.hxsj.2023.0176
Optimization of Impurity Removal Process of N-acetylglucosamine Fermentation Broth by Response Surface Method LIU Shuoa, b, LIU Lu-jiea, b, WANG Yong-honga, ZHAO Li-ming*a, b (a. School of Bioengineering, b. Fermentation Industry Separation and Extraction Technology Research and Development Center, East China University of Science and Technology, Shanghai 200237, China)
Abstract：In order to refine N-acetylglucosamine (NAG) from fermentation broth, the pretreated NAG fermentation broth was utilized to develop the purification process of NAG fermentation broth. The suitable resins for purification of NAG fermentation liquor were screened, and the effects of resin dosage, sample concentration, temperature and solid-liquid flow rate on the desalting rate, decolorization rate and NAG recovery rate of the fermentation liquor were investigated. On the basis of single factor experiments, response surface analysis was used to optimize the purification process of NAG fermentation liquid. Among the six resins, DS-1 resin was selected to have the best desalting effect on the fermentation solution, and HS-3 resin had the best decolorizing effect on the fermentation solution. The best conditions were the volume ratio of anion/cation exchange resin 0.35:1, sample concentration 65 mg/mL, temperature 41 ℃. Thus, the desalting rate and decolorization rate of fermentation broth were 96.9% and 79.5%, respectively, the recovery rate of NAG was 84.5%, and the crystal purity of NAG could reach 99.8%. The purification process can effectively remove the inorganic salts and pigments which reduce the quality of NAG, improve the purity and crystallization rate of NAG and reduce the amount of mother liquor.
Key words：response surface analysis; fermentation broth; NAG; ion exchange resin; purification
引用本文：刘硕，刘鲁杰，王永红，等. 响应面法优化N-乙酰氨基葡萄糖发酵液精制纯化工艺[J]. 化学试剂，2023，45（7）：1-9.
新型分离纯化技术在药用蔗糖制备工艺中的应用
王刚1,2，刘鲁杰1，秦建国2，赵黎明*1
(1. 华东理工大学 生物工程学院，生物反应器工程国家重点实验室，上海 200237；2. 国药集团化学试剂有限公司，上海 200002)
摘要：药用蔗糖是一种重要的药用辅料，是关系到国计民生的重要物资。目前国内药用蔗糖的制备工艺发展相对滞后，品种单一，高端品种严重不足。药用蔗糖制备的关键在于分离纯化工艺，随着我国对药用蔗糖的需求逐步提高，开发新型的分离纯化技术并应用到药用蔗糖制备中已迫在眉睫。综述了目前国内外药用蔗糖的分离纯化工艺及相关分离纯化技术，阐述了新型分离纯化技术在药用蔗糖制备过程中的研究进展，并对未来药用蔗糖纯化工艺的开发提出建议。
关键词：药用蔗糖；药用辅料；高纯；分离纯化技术；生产工艺
中图分类号：TQ028 文献标识码：A 文章编号：0258-3283（2023）
DOI:10.13822/j.cnki.hxsj.2023.0160
Application of Novel Separation and Purification Technology for the Preparation of Medicinal Sucrose WANG Gang1,2, LIU Lu-jie1, QIN Jian-guo2, ZHAO Li-ming*1 (1. State Key Laboratory of Bioreactor Engineering, School of Biotechnology, East China University of Science and Technology, Shanghai 200237, China; 2. Sinopharm Chemical Reagent CO., Ltd, Shanghai 200002, China)
Abstract：Medicinal sucrose is one of the important pharmaceutical excipients in pharmaceutical industry of our country. It is an important material related to national economy and people's livelihood. The key step in the preparation of medicinal sucrose lies in the separation and purification process. With the increasing demand of medicinal sucrose in our country, the preparation of domestic medicinal sucrose faces some challenges, such as the slow development of preparation technology, single variety, and the insufficient output of high-quality products. It is urgent to develop novel separation and purification techniques and to apply them to the preparation of medicinal sucrose. Herein, the preparation process, separation and purification methods of medicinal sucrose domestic and abroad are reviewed, and the future development of medicinal sucrose purification technology is also discussed.
Key words：medicinal sucrose; pharmaceutical excipients; high purity; separation and purification techniques; production process
引用本文：王刚，刘鲁杰，秦建国，赵黎明. 新型分离纯化技术在药用蔗糖制备工艺中的应用[J]. 化学试剂，2023，45（7）： 10-16.
有机溶剂纳滤膜在化学品纯化方面的应用进展
罗立汉b，童奕皓b，贾蕊b，韩蕊b，许振良b，杨虎b，徐孙杰* a,b
(华东理工大学 a. 材料科学与工程学院，b. 化工学院，上海 200237)
摘要：有机溶剂纳滤(OSN)过程具有能耗低、无相变、高分离效率、可控性强等优势，广泛应用于化工、医药、食品等行业中。将OSN膜应用于各类化学试剂的物质分离、纯化和回收是当前的研究热点。以有机材料膜为主，从整体非对称膜和薄层复合膜两个方向展开，基于传质模型和工程应用对近期研究进展进行了讨论。未来的研究应注重膜材料与结构的耐溶胀和其在不同溶剂中的分离性能不一致性等关键问题，为OSN膜的发展与工业应用提供新的思路。
关键词：有机溶剂纳滤；分离；纯化；回收；分离性能不一致性
DOI:10.13822/j.cnki.hxsj.2023.0121
Application Progress of Organic Solvent Nanofiltration Membranes in the Purification of Chemicals LUO Li-hanb, TONG Yi-haob, JIA Ruib, HAN Ruib, XU Zhen-liangb, YANG Hub, XU Sun-jie*a,b (a. School of Materials Science and Engineering, b. School of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China)
Abstract： Organic solvent nanofiltration (OSN) has advantages such as low energy consumption, no phase change, high separation efficiency, and strong controllability, and is widely used in industries such as chemical, pharmaceutical, and food. The introduction of membrane separation into processes such as separation, purification, and recycling are currently a research hotspot. This article discusses recent research progress in the two directions of overall asymmetric membranes and thin-layer composite membranes based on organic material membranes, combined with mass transfer models and engineering applications. Future research should focus on key issues such as the resistance to swelling of membrane material and structures and the separation performance inconformity of membrane, providing new ideas for the development and industrial application of OSN membranes.
Key words：organic solvent nanofiltration; separation; purification; recycling; separation performance inconformity
引用本文：罗立汉，童奕皓，贾蕊，等. 有机溶剂纳滤膜在化学品纯化方面的应用进展[J]. 化学试剂，2023，45(7)：17-24.
【综述与专论】
靶向细胞器的次氯酸/次氯酸盐的小分子荧光探针研究进展
李林柯1，徐俊红2，麻秋娟*1，朱楠楠1，刘淑珍1
（1. 河南中医药大学 药学院，河南 郑州 450046；2. 华北水利水电大学 电气工程学院，河南 郑州 450011）
摘要：次氯酸（HClO）/次氯酸盐（ClO-）是生物体内重要的活性氧（ROS）之一，其浓度水平与生物体生理和病理进程密切相关。荧光成像分析法由于具有灵敏度高、时空分辨率高和原位实时等优点，已被广泛用于细胞内HClO/ClO-的检测。为了在亚细胞水平探究HClO/ClO-在相关生理病理过程中的作用机制，科研工作者开发了许多细胞器靶向HClO/ClO-的荧光探针。对近五年细胞器靶向HClO/ClO-的用于生物成像的小分子荧光探针进行综述，阐述这些荧光探针的设计原理、检测机制和生物学应用，为细胞器靶向HClO/ClO-荧光探针的开发和应用提供一些参考。
关键词：次氯酸/次氯酸盐；细胞器；荧光探针；研究进展；生物成像
中图分类号：O657.3 文献标识码：A 文章编号：0258-3283（2023）
DOI:10.13822/j.cnki.hxsj.2023.0045
Recent Advances of Organelle-Targeted Fluorescent Probes for Hypochlorous Acid/ Hypochlorite LI Lin-ke1, XU Jun-hong2, MA Qiu-juan1*, ZHU Nan-nan1, LIU Shu-zhen1 (1. School of Pharmacy, Henan University of Chinese Medicine, Zhengzhou 450046, China; 2. Department of Electrical Engineering, North China University of Water Resources and Electric Power, Zhengzhou 450011, China)
Abstract: Hypochloric acid (HClO)/hypochlorite (ClO-) is one of the important reactive oxygen species (ROS) in organisms, and its concentration level is closely related to the physiological and pathological processes of organisms. Fluorescence imaging analysis has been widely used for the detection of intracellular HClO/ClO- due to its advantages of high sensitivity, high spatiotemporal resolution, and real-time in situ. In order to explore the mechanism of HClO/ClO- in related physiological and pathological processes at the subcellular level, researchers have developed many organelle-targeted HClO/ClO- fluorescent probes. This article mainly reviews the latest progress of organelle-targeted fluorescent probes for HClO/ClO- in the past five years. The design principle, detection mechanism, and biological applications of these fluorescent probes are described in detail, providing some help for the development and application of organelle-targeted fluorescent probes for the detection of HClO/ClO-.
Key words: hypochlorous acid/hypochlorite; organelles; fluorescent probe; recent advances; bioimaging
引用本文：李林柯, 徐俊红, 麻秋娟, 等. 靶向细胞器的次氯酸/次氯酸盐的小分子荧光探针研究进展[J]. 化学试剂, 2023, 45(7)：25-33。
四氧化三铁纳米粒子在酶催化领域的应用研究进展
石婧怡，李兆周∗ ，王耀∗ ，陈秀金，牛华伟，李芳，高红丽
（河南科技大学 食品与生物工程学院，河南省食品绿色加工与质量安全控制国际联合实验室，河南 洛阳 471000）
摘要：Fe3O4纳米粒子（Fe3O4 nanoparticles，Fe3O4 NPs）具有高比表面积、超顺磁性、易改性和低毒等优点，在固定化酶和仿生催化等领域日益受到重视。综述了Fe3O4 NPs在固定化酶和模拟酶领域的应用，论述了Fe3O4纳米酶、Fe3O4固定化酶以及Fe3O4印迹模拟酶的制备方法和优缺点，探讨了Fe3O4印迹模拟酶在农用化学品和抗菌药物催化降解、光诱导有机物催化降解、电化学传感信号放大及肿瘤治疗等方面的研究进展，总结了Fe3O4 NPs在酶催化领域所面临的挑战和未来的发展方向。Fe3O4 NPs的应用越来越广泛，相关的影响因素和作用机理日趋复杂，所涉及的基础理论和技术措施仍需进一步深入研究。
关键词：Fe3O4；纳米酶；固定化酶；模拟酶；催化
中图分类号：O631 文献标识码：A 文章编号：0258-3283（2023）--
DOI: 10.13822/j.cnki.hxsj.2023.0197
Research Progress on the Application of Fe3O4 Nanoparticles in the Field of Enzyme Catalysis SHI Jing-yia, b, LI Zhao-zhou*a, b, WANG Yao*a, b, CHEN Xiu-jina, b, NIU Hua-weia, b, LI Fanga, b, GAO Hong-lia, b (a. College of Food and Bioengineering, b. Henan International Joint Laboratory of Food Green Processing and Quality Safety Control, Henan University of Science and Technology, Luoyang 471000, China)
Abstract：With the advantages of high specific surface area, superparamagnetism, easy modification and low toxicity, Fe3O4 nanoparticles (Fe3O4 NPs) are paying increasing attention in the fields of enzyme immobilization and biomimetic catalysis. The applications of Fe3O4 NPs in the fields of enzyme immobilization and mimic enzymes were reviewed. The preparation methods of Fe3O4 nanozyme, Fe3O4 immobilized enzyme and Fe3O4 imprinted mimic enzyme were elucidated. Their advantages and disadvantages were compared and analyzed. Furthermore, the research progress of Fe3O4 imprinted mimic enzyme was discussed in the fields of catalytic degradations of agricultural chemicals and antibacterial drugs, photoinduced catalytic degradation of organic substances, electrochemical sensing signal amplification and tumor treatment, etc. Additionally, the facing challenges and future directions were summarized. The application of Fe3O4 NPs is becoming more and more widespread and the related influencing factors and mechanisms of action are becoming increasingly complicated. Therefore, the basic theories and technical measures involved in the research still need to be further investigated.
Key words：Fe3O4; nanozyme; enzyme immobilization; mimic enzyme; catalysis
引用本文：石婧怡，李兆周，王耀，等. 四氧化三铁纳米粒子在酶催化领域的应用研究进展[J]. 化学试剂, 2023, 45(7)：34-42.
【生化与药用试剂】
噻洛芬酸衍生物的合成、分子对接及其抗菌活性研究
卫鑫宝a，李玉芳a，陆思颖b，王立升*b
（广西大学 a.化学化工学院； b.医学院，广西 南宁 530004）
摘要：优化了噻洛芬酸的合成路线并对其进行结构修饰，通过1HNMR、13CNMR、HR-MS确定了所得物质的结构，并采用二倍稀释法测试了其对大肠杆菌、铜绿假单胞菌、金黄色葡萄球菌、痤疮丙酸杆菌和白色念珠菌的抗菌活性。结果表明，大部分化合物均具有一定的抗菌活性，其中化合物A16对白色念珠菌具有良好的抗菌活性，其最低抑菌浓度（MIC）为3.14 mg/mL，强于阳性对照药氟康唑。最后，对化合物A1、A11、A16、A17与白色念珠菌相关蛋白4WMZ进行分子对接，从计算的角度进一步解释了化合物A16活性较好的原因推测是该化合物羰基、羧基与蛋白之间有较强的氢键作用。
关键词：噻洛芬酸；衍生物；合成；抗菌；分子对接
中图分类号：O626.4 文献标识码：A 文章编号：0258-3283（2023）--
DOI:10.13822/j.cnki.hxsj.2023.0092
Synthesis, Docking, and Antibacterial Activity of Tiaprofenic Acid Derivatives WEI Xin-baoa, LI Yu-fanga, LU Si-yingb, WANG Li-sheng*b (a. School of Chemistry and Chemical Engineering, b. School of Medicine, Guangxi University, Nanning 530004, China)
Abstract: The synthetic route of tiaprofenic acid was optimized and its structure was modified. The structures of its derivatives were confirmed by 1H NMR, 13C NMR, and HRMS analyses. Their antibacterial activity against several pathogenic bacteria such as Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, Propionibacterium acnes, and Candida albicans was tested via the double-dilution method. The results showed that most of the compounds exhibited antibacterial activity. Particularly, compound A16 showed good antibacterial activity against Candida albicans with minimum inhibitory concentration (MIC) of 3.14 mg/mL, stronger than the positive control drug fluconazole. Additionally, compounds A1, A11, A16, and A17 were docked with the Candida albicans-related protein 4WMZ. On the basis of the calculation, it was further explained that the activity of compound A16 might be attributed to the strong hydrogen bonds between the carbonyl group or carboxyl group of the compound and the protein.
Key words: tiaprofenic acid; derivative; synthesis; antibacterial; molecular docking
引用本文：卫鑫宝，李玉芳，陆思颖，等. 噻洛芬酸衍生物的合成、分子对接及其抗菌活性研究[J]. 化学试剂, 2023, 45(7):43-50。
功能型SiO2气凝胶在生物/医药领域的研究进展
吕春艳a,b,c，王文倩a,c，崔闻宇a,b,c，张文君a,b,c*，厚晓庆a,c，韩锐a,c
（哈尔滨商业大学 a. 药学院，b. 抗肿瘤天然药物教育部工程研究中心，c. 黑龙江省预防与治疗老年性疾病药物研究重点实验室，黑龙江 哈尔滨 150076）
摘要:SiO2气凝胶具有高孔隙率、高比表面积、生物相容性和生物降解性等独特的性质，使其成为生物医药领域研究的热点之一。总结了SiO2气凝胶的功能型分类、特性及其影响因素，分析了SiO2气凝胶的潜在毒性，综述了SiO2气凝胶在药物输送系统、组织工程和生物传感器等生物医药领域的应用及研究现状，最后对SiO2气凝胶在生物医药领域的发展前景进行展望，以期为SiO2气凝胶材料在生物医药领域的进一步研究和应用提供参考。
关键词:SiO2气凝胶；功能型分类；生物相容性；药物输送；生物医药领域
中图分类号:TQ4 文献标识码:A 文章编号：0258-3283（2023）
DOI：10.13822/j.cnki.hxsj.2023.0078
Application of Functionalized SiO2 Aerogels in the Field of Medicine LV Chun-yana,b,c, WANG Wen-qiana,c, CUI Wen-yua,b,c, ZHANG Wen-juna,b,c*, HOU Xiao-qinga,c, HAN Ruia,c (a. School of Harbin University of Commerce Medicine; b. Engineering Research Center, Ministry of Education; c. Key Laboratory of drug research for the prevention and treatment of senile diseases, Harbin, 150076, China)
Abstract: Due to its unique properties, such as high porosity, high specific surface area, biocompatibility, and biodegradability, SiO2 aerogels have become one of the research hotspots in the field of biomedicine. In this paper, the functional classification, characteristics and influencing factors of SiO2 aerogels were summarized, and the potential toxicity of SiO2 aerogels was analyzed, the application and research status of SiO2 aerogels in the fields of biomedicine, such as drug delivery system, tissue engineering and biosensor, were reviewed, it is expected to provide reference for further research and application of SiO2 aerogels in the field of biomedicine.
Keywords: SiO2 aerogel; functional classification; biocompatibility; drug delivery; the field of biomedicine
引用本文：吕春艳, 王文倩, 崔闻宇, 等. 功能型SiO2气凝胶在生物/医药领域的研究进展[J]. 化学试剂, 2023, 45（7）:51-56.
钌化合物抗微生物应用研究进展
聂鹏*，董睿，许波*
（贵州省食品药品检验所，贵州 贵阳 550004）
摘要：了解新报道的钌化合物抗微生物应用，探究其构效关系。分析近年来已报道的钌化合物抗微生物应用文献，总结其可能发展规律。据文献总结，钌化合物可作用于细胞外膜或者细胞内的核酸，以达到抑菌或抗菌的效果。钌化合物的脂溶性、其骨架支撑配体的电子性质和化合物整体的电荷属性都是影响其抗微生物活性的重要因素，仿生配体的配位与解离能显著提高钌化合物的生物活性和相容性，研究热点也聚焦于纳米钌粒子的绿色合成和生物活性成分应激释放。抗微生物类钌化合物的研究朝着绿色、环保、低毒、高效的方向发展，为后续的深入研究提供了一定参考。
关键词：钌化合物；抗微生物；构型；作用效果
中图分类号：O627.8+1 文献类型：A 文章编号：0258-3283（2023）
DOI:10.13822/j.cnki.hxsj.2023.0140
Research Progress on Antimicrobial Application of Ruthenium Complexes NIE Peng*, DONG Rui, XU Bo* (Guizhou institute for food and drug control, Guiyang 550004, China)
Abstract: Learning about newly reported antimicrobial applications of ruthenium compounds and exploring their intrinsic structure-activity relationship is one of the research goals. The reported literatures on antimicrobial application of ruthenium compounds in recent years were analyzed, and the possible development rule were summarized. According to the literature summary, ruthenium compounds can act on the outer membrane or intracellular nucleic acids to achieve bacteriostatic or antibacterial effects. The lipophilicity of ruthenium compounds, the electronic properties of their backbone support ligands, and the overall charge properties are all important factors affecting their antimicrobial activity. In addition, the coordination and dissociation of biomimetic ligands can significantly improve the biological activity and compatibility of ruthenium compounds, and recent research hotspots focus on the green synthesis of nanoruthenium particles and the stress release of bioactive ingredients. The research of antibacterial ruthenium compounds is developing towards the direction of green and environmentally friendliness, low toxicity and high efficiency, providing references for further research.
Key words: Ru complexes; antimicrobial; configuration; effect
引用本文：聂鹏, 董睿, 许波. 钌化合物抗微生物应用研究进展[J]. 化学试剂, 2023,45（7）：57-65.
【功能材料】
壳聚糖改性生物炭复合材料的制备及其对Pb2+的吸附性能
罗小生1，李新丽*2，杨明1，何建明1
（1. 中国安能集团第一工程局有限公司，广西 南宁 530000；2. 河北工业职业技术大学，河北 石家庄 050000）
摘要: 以城市洗衣污水中的有机污泥为原料，通过热解法制备生物炭，再以水热法与胺化后的壳聚糖形成了生物炭/改性壳聚糖吸附剂（BC/NS）。FT-IR、SEM、pHzpc以及XPS对BC/NS的形貌和结构进行表征。静态和动态吸附实验表明BC/NS吸附剂对溶液中的Pb2+具有良好的吸附性能，如平衡时间短（15 min）、吸附速率快（25 mg/(g min)）、低浓度时除去率高（99%）、静态饱和吸附容量大（391 mg/g）等。动态吸附实验表明，BC/NS吸附剂的最大吸附能力约为380 mg/g，与静态吸附基本接近，远远超过了壳聚糖吸附材料。结果显示，BC/NS吸附剂对Pb2+的吸附能力受到多种吸附机制控制，如静电吸引作用、沉淀和金属离子配合作用。此外，在pH 4时用40 mg/L的铅溶液时，BC/NS吸附剂在5次吸附-脱附实验后，仍保有75%以上的吸附性能，说明BC/NS吸附剂具有良好的循环稳定性。
关键词:污泥；生物炭；壳聚糖；铅离子；吸附剂
中图分类号：TQ3118 文献标识码：A 文章编号：0258-3283（2023）
DOI:10.13822/j.cnki.hxsj.2022.0902
Preparation of Chitosan Modified Biochar Composites and Their Adsorption Properties for Pb2+ LUO Xiao-sheng1, LI Xin-li*2, YANG Ming1, HE Jian-ming1 (1. China Aneng Group First Engineering Bureau Co., LTD., Nanning 530000, China; 2. Hebei Vocational University of Industry and Technology, Shijiazhuang 050000, China)
Abstract: Biochar/modified chitosan adsorbent (BC/NS) was prepared from organic sludge in municipal laundry sewage by the pyrolytic method, and then combined with the aminated chitosan by the hydrothermal method. The morphology and structure of BC/NS were characterized by FT-IR, SEM, pHzpc and XPS analyses. The static and dynamic adsorption experimentsverify revealed that BC/NS adsorbent had good adsorption performance for Pb2+ in solution, including short equilibrium time (15 min), fast adsorption rate (150 mg/(g min)), high removal rate (99%) at low concentration and the static saturation adsorption capacity (510 mg/g). Dynamic adsorption experiments showed that the maximum adsorption capacity of BC/NS adsorbent was about 499 mg/g, very close to that of the static adsorption and far superior to that of chitosan adsorbent material. The results illustrated that the adsorption capacity of BC/NS adsorbent for Pb2+ was controlled by a variety of adsorption mechanisms, such as the electrostatic attraction, metal ion complexation, and cation-π effect. In addition, when 40 mg/L lead solution was used at pH 4, the adsorption performance of BC/NS adsorbent was more than 75% after 5 adsorption-desorption experiments, indicating that BC/NS adsorbent had good cyclic stability.
Keywords: sludge; biocarbon; chitosan; lead-ion; adsorbent
引用本文：罗小生, 李新丽, 杨明, 等. 污泥提取生物碳复合改性壳聚糖的制备及其性能评估[J]. 化学试剂，2023，45（7）： 66-71.
荧光分子探针检测甲醛的研究进展
孙萌，马杰*
(上海理工大学 材料与化学学院，上海 200000；)
摘要：甲醛，作为重要的醛基小分子原料，被广泛应用于化工、生物医药、建材等领域。过量甲醛严重时可导致基因突变或癌变。系统地综述了近年来基于2-aza-Cope重排、肼醛缩合、胺醛缩合的反应型荧光探针分子的代表性成果。根据聚集态物质的荧光特点将其分为ACQ型、AIE型和MOF材料3类，从探针分子的设计、机制和应用的方面进行系统介绍，归纳这3种类型甲醛荧光探针的优势以及不足。对甲醛荧光探针的未来发展进行了展望，以期为设计性能更优良的荧光探针提供有益参考。
关键词：甲醛；小分子荧光探针；2-aza-Cope重排；亚胺；AIE效应
中图分类号：O625.6；TB34 文献标识码：A 文章编号：0258-3283（2023）
DOI:10.13822/j.cnki.hxsj.2023.0167
Research Progress in the Detection of Formaldehyde by Fluorescent Molecular Probe SUN Meng, MA Jie* (School of Materials and Chemistry, University of Shanghai for Science and Technology, Shanghai 200000, China)
Abstract: As an important aldehyde-based small molecule raw material, formaldehyde is widely used in chemical industry, biomedicine, building materials and other fields. Excessive formaldehyde can lead to gene mutation or cancer in severe cases. The representative results of reactive fluorescent probe molecules based on 2-aza-Cope rearrangement, hydrazine and aldehyde condensation, and amine and aldehyde condensation are reviewed in recent years. According to the fluorescence characteristics of aggregates, they are divided into ACQ, AIE and MOF materials. The advantages and disadvantages of three types of formaldehyde fluorescence probes are summarized from the aspects of the design, mechanism and application of probe molecules. The future development of formaldehyde fluorescent probes was prospected in order to provide useful reference for the design of better fluorescence probes.
Key words：formaldehyde; small molecule fluorescent probe; 2-aza-Cope rearrangement; imine; AIE effect
引用本文：孙萌，马杰.荧光分子探针检测甲醛的研究进展[J].化学试剂，2023，45（7）：72-77.
植物还原制备纳米金过程中黄酮类物质的作用、外界影响因素及其应用
刘海*，王飞，王毅敏，宋桃，柯义虎
(北方民族大学 a.化学与化学工程学院，b. 国家民委化工技术基础重点实验室，c. 宁夏太阳能化学转化技术重点实验室，宁夏 银川 750021）
摘要：植物还原法制备纳米金（Gold nanoparticles, GNPs）绿色经济、易操作、原材料可再生，避免了有毒化学试剂的使用以及物理法高成本的投入，为GNPs的制备提供了新的途径。然而，植物种类繁多且生物成分复杂，以植物提取液为整体制备GNPs不同的活性组分会互相干扰，使GNPs合成机制变得复杂。此外，提取液与金前体浓度、酸碱度、温度等外界因素也直接影响着GNPs的合成。系统的综述了黄酮类物质在合成GNPs过程中的还原与保护机理，外界因素在转化率、形貌粒径、分散性等方面的影响规律以及GNPs在抗癌，药物传递，抗菌，催化等领域的应用，最后展望了植物法制备GNPs的局限性。对调控制备GNPs活性组分的作用机制以及制备条件的优化具有指导意义。
关键词：植物还原法；纳米金；黄酮类物质；外界因素；应用
中图分类号：Q501 文献标识码：A 文章编号：0258-3283（2023）--
DOI:10.13822/j.cnki.hxsj.2023.0118
Role of Flavonoids and External Influencing Factors in the Process of Preparing Nano-gold by Plant Reduction and Its Application LIU Hai *, WANG Fei, WANG Yi-min, SONG Tao, KE Yi-hu（a.School of Chemistry and Chemical Engineering, North Minzu University, b.Key Laboratory for Chemical Engineering and Technology, State Ethnic Affairs Commission, c.Ningxia Key Laboratory of Solar Chemical Conversion Technology, Yinchuan 750021, China）
Abstract: The preparation of gold nanoparticles(GNPs) by plant reduction method is green, economical, easy to operate, and the raw materials are renewable. It avoids the use of toxic chemical reagents and the high cost of physical methods, and provides a new way for the preparation of GNPs. However, there are many kinds of plants and complex biological components. When the plant extract is used as a whole to prepare GNPs, different active components will interfere with each other, leading to the synthetic mechanism of GNPs complicated. In addition, the concentration of extract and the gold precursor, pH value, temperature and other external factors also directly affect the synthesis of GNPs. The reduction and protection mechanism of flavonoids in the process of synthesizing GNPs, the influence law of external factors in conversion rate, morphology, particle size and dispersion, and the application of GNPs in anticancer, drug delivery, antibacterial and catalysis were systematically reviewed. Finally, the limitations of preparing GNPs by plant method were prospected. It would provide significant guidance for regulating the action mechanism of active components for preparing GNPs and optimizing the preparation conditions.
Key words: plant reduction method; gold nanoparticle; flavonoid; external factor; application
引用本文：刘海，王飞，王毅敏，等. 植物还原制备纳米金过程中黄酮类物质的作用、外界影响因素及其应用[J]. 化学试剂, 2023, 45(7): 78-86。
【分离提取技术】
桉叶油的提取工艺优化及对金黄色葡萄球菌的作用
刘瑞秀1，覃英克2，齐维金1，龙利1，王鲁*1
（1. 贵州大学a. 药学院，b. 西南特色药用生物资源开发利用教育部工程研究中心，贵州 贵阳 550025；2. 贵州省荔波县农业农村局，贵州 荔波 558400）
摘要：为了评价桉叶油的抑菌作用及最佳提取工艺。通过检测最低抑菌浓度（MIC）考察桉叶油抗菌谱，采用酶标仪测定其对金黄色葡萄球菌（S. aureus）的抑菌曲线，通过检测疏水性、肽聚糖、碱性磷酸酶和b-半乳糖苷酶的含量变化，评价桉叶油对S. aureus细胞壁膜的影响，通过扫描电镜验证（SEM）；热回流提取且采用响应面法以油重为评判标准优化桉叶油的工艺条件。实验结果显示，桉叶油对S. aureus的MIC为54.69 mg/mL，抑菌效果最好；1/2 MIC的桉叶油在24 h内能抑制S. aureus的生长；1 MIC的桉叶油可引起细菌细胞集聚、显著增加S. aureus细胞表面的疏水性、使b-半乳糖苷酶发生泄漏；2 MIC可干扰肽聚糖的合成和增加碱性磷酸酶的活性，经SEM验证；桉叶采用热回流提取最佳条件为m（料）∶V（液）=1∶6，蒸馏水浸泡1 h，110 ℃热回流提取4 h，桉叶油得率为6.29%。结果表明，桉叶油通过改变细胞表面的疏水性，破坏S. aureus细胞壁膜结构的完整性，导致胞内容物外流，引起细胞集聚而抑制S. aureus的生长；优化的桉叶油提取工艺稳定可行。这将为具有良好抗S. aureus活性的桉叶油研发提供理论数据。
关键词：桉叶油；金黄色葡萄球菌；细胞壁；细胞膜；提取工艺
中图分类号：R915 文献标识码：A 文章编号：0258-3283（2023）--
DOI：10.13822/j.cnki.hxsj.2023.0193
Optimization of the Extraction Process of Eucalyptus Oil and its Effect on Staphylococcus Aureus LIU Rui-xiu1, QIN Ying-ke2 , QI Wei-jin1, LONG Li1, WANG Lu*1 (1. a. College of Pharmacy; b. Engineering Research Center of the Ministry of Education for the Development and Utilization of Southwestern Special Medicinal Biological Resources, Guizhou University, Guiyang 550025; 2. Bureau of Agriculture and Rural Affairs, Libo County, Libo 558400, Guizhou Province)
Abstract: In order to evaluate the antibacterial effect of eucalyptus oil and the optimal extraction process, the antibacterial spectrum of eucalyptus oil was investigated by detecting the minimum inhibitory concentration (MIC), and its inhibition curve against Staphylococcus aureus (S. aureus) was determined by enzyme standardization, and the effect of eucalyptus oil on the cell wall membrane of S. aureus was evaluated by detecting the changes in the content of hydrophobicity, peptidoglycan, alkaline phosphatase and b-galactosidase, verified by scanning electron microscopy (SEM). The process conditions of eucalyptus oil were optimized by hot reflux extraction and oil weight as the criterion. The experimental results showed that the MIC of eucalyptus oil on S. aureus was 54.69 mg/mL, with the best inhibition effect; 1/2 MIC of eucalyptus oil could inhibit the growth of S. aureus within 24 h; 1 MIC of eucalyptus oil could cause bacterial cell aggregation, significantly increase the hydrophobicity of S. aureus cell surface, and cause the leakage of b-galactosidase; 2MIC interfered with the synthesis of peptidoglycan and increased the activity of alkaline phosphatase through SEM verification. Eucalyptus leaves were extracted by hot reflux under the best conditions of 1:6 ratio, 1 h soaking in distilled water and 4 h hot reflux at 110 ℃ to obtain eucalyptus oil in 6.29%. The results showed that eucalyptus oil could alter the hydrophobicity of the cell surface and disrupt the membrane structure of S. aureus cell wall. The optimized eucalyptus oil extraction process is stable and feasible. This will provide theoretical data for the development of eucalyptus oil with good anti-S. aureus activity.
Key words: eucalyptus oil; staphylococcus aureus; cell wall; cell membrane; extraction process
引用本文：刘瑞秀，覃英克，齐维金，等. 桉叶油的提取工艺优化及对金黄色葡萄球菌的作用[J]. 化学试剂, 2023, 45(7): 87-93.
苦蘵化学成分及抗炎活性研究
杨丽婷，李博术，张寒翠，李琼娣，贾敬皓，邱莉，谢集照*
(广西医科大学 药学院，广西 南宁 530021)
摘要：研究苦蘵的化学成分及抗炎活性。采用硅胶、Sephadex LH-20和ODS等柱色谱分离技术对苦蘵乙酸乙酯部位进行分离纯化，通过波谱学技术鉴定化合物结构，并采用LPS诱导的RAW264.7释放NO的细胞模型，评价化合物的体外抗炎活性。从苦蘵中分得13个化合物：5,4′-二羟基-3,3′,7-三甲氧基-黄酮(1)、3β-hydroxy-5α,8α-epidioxyergosta-6,22-diene(2)、(22R)-5β,6β:14α,17:14β,26-triepoxy-2α-ethoxy-13,20,22-trihydroxy-1,15-dioxo-16α,24-cyclo-13,14-secoergosta-18,27-dioic acid 18→20,27→22-dilactone(3)、alkesterol B(4)、withaminilide F(5)、酸浆苦素B(6)、酸浆苦素D(7)、酸浆苦素U(8)、withaphysalin R(9)、rel-(18R,22R)-5β,6β:18β,20-diepoxy-3β,18α-dimethoxy-4β-hydroxy-1-oxowith-24-enolide(10)、withaphysalin P(11)、β-谷甾醇(12)、棕榈酸(13)。化合物1和2首次从酸浆属中分离得到，化合物3～5、10、11首次从该植物中得到。抗炎结果表明，化合物5、6、10、11抗炎效果显著。
关键词：苦蘵；化学成分；酸浆苦素类；醉茄内酯类；抗炎活性
中图分类号：R284 文献标识码：A 文章编号：0258-3283（2023）--
DOI:10.13822/j.cnki.hxsj.2023.0077
Chemical Constituents of Physalis angulate L and Their Anti-inflammatory Activities YANG Li-ting, LI Bo-shu, ZHANG Han-cui, LI Qiong-di, JIA Jing-hao, QIU Li, XIE Ji-zhao* (School of Pharmacy, Guangxi Medical University, Nanning 530021, China)
Abstract: The chemical constituents from Physalis angulate L and their anti-inflammatory activities were studied. The chemical constituents were isolated and purified by silica gel, Sephadex LH-20 and ODS chromatography. The structures of isolated compounds were elucidated by spectroscopic analyses. Meanwhile the anti-inflammatory activities of the chemical components against NO production from LPS stimulated RAW264.7 cells were evaluated in vitro. The structures were identified as: 5,4′-dihydroxy-3,3′,7-trimethoxy-flavone (1), 3β-hydroxy-5α, 8α-epidioxyergosta-6,22-diene (2), (22R)-5β,6β:14α,17:14β,26-triepoxy-2α-ethoxy-13,20,22-trihydroxy-1,15-dioxo-16α,24-cyclo-13,14-secoergosta-18,27-dioic acid 18→20,27→22-dilactone (3), alkesterol B (4), withaminilide F (5), physalin B (6), physalin D (7), physalin U (8), withaphysalin R (9), rel-(18R,22R)-5β,6β:18β,20-diepoxy-3β,18α-dime-thoxy-4β-hydroxy-1-oxowith-24-enolide (10), withaphysalin P (11), β-sitosterol (12), and palmitic acid (13). Compounds 1 and 2 were isolated form this genus for the first time, while compounds 3～5, 10, and 11 were obtained from this plant for the first time. Compounds 5, 6, 10, and 11 show significant anti-inflammatory activities.
Key words: Physalis angulate L; chemical constituent; physalin; withanolide; anti-inflammatory activity
引用本文：杨丽婷，李博术，张寒翠，等. 苦蘵化学成分及抗炎活性研究[J]. 化学试剂, 2023, 45(7): 94-99。
【电化学和新能源】
铁稳定的铂单原子催化选择性加氢反应
尤志鑫1，纪钰霞1，蒋妍1，郎睿*1，吴传德*1,2
（1. 广东工业大学 轻工化工学院，广东 广州 510006；2. 浙江大学 化学学院，浙江 杭州 310027）
摘要：多相催化剂常以过渡金属为活性中心，当催化活性位点呈原子级分散时，金属利用率达到最高，故具有优异的催化性能。然而，铂族金属和惰性氧化物的结合较弱，所以在Al2O3和SiO2之类的载体上，铂很难被分散成单原子的形式。使用简单的溶胶凝胶法，在惰性氧化物中掺杂铁元素可显著增强铂与载体之间的共价相互作用，从而制得单原子铂催化剂。在苯乙炔选择性加氢生成苯乙烯的反应中，0.2wt%PtFe50/Al2O3-SiO2单原子催化剂具有良好的选择性，其反应速率是0.2wt%Pt/Al2O3-SiO2纳米颗粒催化剂的1.4倍。该单原子催化剂还在循环测试中表现出高稳定性，证明了载体的掺杂改性是一种将活性金属分散在惰性氧化物上，得到高活性和高稳定性的单原子催化剂的有效策略。
关键词：铂；单原子催化剂；苯乙炔；选择性加氢；复合氧化物载体
中图分类号： 文献标识码：A 文章编号：0258-3283（2023）
DOI:10.13822/j.cnki.hxsj.2023.0128
Iron-Stabilized Pt Single-Atom Catalysis for the Selective Hydrogenation YOU Zhi-xin1, JI Yu-xia1, JIANG Yan1, LANG Rui*1, WU Chuan-de*1, 2 (1. School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, China; 2. Department of Chemistry, Zhejiang University, Hangzhou 310027, China)
Abstract：The heterogeneous catalysts with isolated active metal centers at the atomic dispersion show the highest metal utilization, leading to superior catalytic activities. However, achieving the atomic dispersion of Pt-group metals on irreducible oxides, such as Al2O3 and SiO2, is quite difficult. Consequently, the Al2O3-SiO2 support is modified by the Fe component to strengthen the interaction with Pt species. The single-atom Pt catalyst was fabricated using a simple sol-gel method, showing high selectivity for the hydrogenation of phenylacetylene to styrene. Besides, the reaction rate of 0.2wt%PtFe50/Al2O3-SiO2 single-atom catalyst is 1.4 times higher than that of 0.2wt%Pt/Al2O3-SiO2 nanoparticle analogue. Moreover, the high stability of thus synthesized single-atom catalyst is proved by the recycling tests, demonstrating an efficient method to anchor single metal atoms on the modified inert oxide supports.
Key words：platinum; single-atom catalyst; phenylacetylene; selective hydrogenation; composite oxide support
引用本文：尤志鑫，纪钰霞，蒋妍，等. 铁稳定的铂单原子催化选择性加氢反应[J]. 化学试剂，2023，45（7）：100-106.
无定型碳/g-C3N4制备及其光催化降解四环素性能
陈建军*，周诗园，黄雨晨，尤红歌，郑添详，柴柳青，赵文伯
（郑州师范学院 化学化工学院，河南 郑州 450044）
摘要：以葡萄糖和尿素为原料，通过高温煅烧的方法制备出无定形碳/g-C3N4（C/g-C3N4）复合材料，并对无定型碳的含量进行调控。采用XRD、FTIR、XPS、TEM、UV-Vis和光电流测试对样品的结构、形貌和光电性能进行分析。结果表明，与相同条件下制备的g-C3N4相比，C/g-C3N4复合材料具有更强的光吸收性能和光生电子-空穴分离效率。通过可见光下降解四环素对复合材料的催化性能和稳定性进行评价。结果发现：0.05%C/g-C3N4表现出最佳的光催化效率，其对四环素的降解速率为0.05946 min-1，为g-C3N4（0.01184 min-1）的5倍。经过5个循环实验后，复合材料的降解率没有出现明显的下降。
关键词：g-C3N4；无定型碳；可见光催化；四环素；复合材料
中图分类号：O614.1 文献标识码：A 文章编号：0258-3283（2023）
DOI：10.13822/j.cnki.hxsj.2023.0098
Preparation of Amorphous Carbon/g-C3N4 and Its Photocatalytic Degradation of Tetracycline CHEN Jian-jun*, ZHOU Shi-yuan, HUANG Yu-chen, YOU Hong-ge, ZHENG Tian-xiang, CHAI Liu-Qing, ZHAO Wen-bo (School of Chemistry and Chemical Engineering, Zhengzhou Normal University, Zhengzhou 450044, China)
Abstract: The amorphous carbon/g-C3N4 composite was prepared by calcination of glucose and urea at high temperature, and the content of amorphous carbon was regulated. The structure, morphology and photoelectric properties of the samples were analyzed by XRD, FTIR, XPS, TEM, UV-Vis and photocurrent. The results showed that, compared with g-C3N4, amorphous C/g-C3N4 composite had stronger light absorption performance and electron-hole separation efficiency. The catalytic performance and stability of the composite were evaluated by the degradation of tetracycline under visible light. The results showed that 0.05%C/g-C3N4 had the best photocatalytic efficiency. The degradation rate of 0.05% C/g-C3N4 was 0.0594 min-1, which was five time as that of g-C3N4. (0.0118 min-1). After 5 cycles, the degradation rate of composites did not change significantly.
Key words：g-C3N4; amorphous carbon; visible light catalysis; tetracycline; composite material
引用本文：陈建军, 周诗园, 黄雨晨, 等. 无定型碳/g-C3N4制备及其光催化降解四环素性能[J]. 化学试剂, 2023, 45（7）：107-112.
聚茜素红-羧基化多壁碳纳米管修饰电极测定花生壳中木犀草素的含量研究
司晓晶，杨澜，刘之进，张灵露，韩梅*
(上海商学院 食品系，上海 200235)
摘要：基于羧基化多壁碳纳米管（C-MWCNT），利用聚茜素红（PAR）的电催化特性在玻碳电极（GCE）上电聚合制备了PAR/C-MWCNT/GCE电化学修饰电极并对花生壳中木犀草素（Lut）的含量测定进行了方法建立和实际应用。采用SEM、XRD对电极表面修饰剂的形貌和组成进行表征。通过循环伏安法和差分脉冲伏安法探究了Lut在电极上的电化学行为。结果表明，pH 8.5的磷酸盐缓冲溶液中，Lut在该修饰电极上的响应电流是裸电极的3倍，具有良好的分析性能，检测Lut的线性范围为1～100 μmol/L，线性方程为y = 0.37228 x-0.01675（R2 = 0.9933）。该电极具有制备简单、选择性好和线性范围宽的特点，测得花生壳中Lut的含量为8.514 μmol/L，加标回收率为91%～98%，相对标准偏差为2.62%。
关键词：木犀草素；聚茜素红；羧基化碳纳米管；修饰电极；花生壳
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2023）
DOI:10.13822/j.cnki.hxsj.2023.0074
Determination of Luteolin in Peanut Shell by Poly Alizarin Red S-Carboxylated Multi-walled Carbon Nanotube Modified Electrode SI Xiao-jing, YANG Lan, LIU Zhi-jin, ZHANG Ling-lu, HAN Mei *（The Department of Food, Shanghai Business School, Shanghai 200235, China)
Abstract：By taking advantage of the electrocatalytic property of poly alizarin red (PAR), a poly alizarin red (PAR) / carboxylated multi-walled carbon nanotube (C-MWCNT) modified glassy carbon electrode (GCE) was fabricated for the determination of luteolin (Lut) in peanut shell. The morphology and composition of the surface of modified electrode were characterized by SEM and XRD analyses. The electrochemical behavior of Lut on the modified electrode was explored by cyclic voltammetry and differential pulse voltammetry. The results showed that the current of Lut on the modified electrode was three times as that of the bare electrode in the phosphate buffer solution with pH 8.5. Under optimized conditions, a good linear relationship (y = 0.37228 x - 0.01675, R2 = 0.9933) was established with a concentration of Lut covering from 1 to 100 μmol/L. The PAR/C-MWCNT/GCE is easy to prepare, and the as-proposed method exhibits good selectivity and broad linear range for the detection of Lut. The PAR/C-MWCNT/GCE based assay was applied for the determination of Lut with the result was 8.514 μmol/Lin peanut shells. The recoveries ranged from 91% to 98% with the relative standard deviation less than 2.62%.
Key words：luteolin; alizarin red s; carboxylated multi-walled carbon nanotube; modified electrode; peanut shell
引用本文：司晓晶，杨澜，刘之进，等. 聚茜素红-羧基化多壁碳纳米管修饰电极测定花生壳中木犀草素的含量研究[J]. 化学试剂，2023，45（7）：113-118.
【化学品与环境】
改性生物炭对水体中氮和磷共去除：改性方法和吸附机制
王硕，汪雅茹，尹通，刘慧，范子涵，范世锁*
（安徽农业大学 资源与环境学院，安徽 合肥 230036）
摘要：水体中氮和磷的共去除和资源化利用一直是研究的热点，生物炭应用为其提供了新的选择。综述了改性生物炭对氮和磷的共去除，重点聚焦在改性方法和吸附机制。生物炭改性方法主要为矿物质的负载，具体可分为镁改性、铁改性、双金属改性、其它矿物质改性等。改性目的是增加生物炭的比表面积和孔隙结构；强化静电作用；加强离子交换能力；增强配合能力；促进沉淀作用，特别是促进鸟粪石结晶反应，回收资源。改性生物炭对氮和磷共去除的机制涉及：更高比表面积和发达孔隙结构提供更多的吸附点位；表面电性和氮磷之间的静电作用；矿物质组分与氮磷之间的离子交换作用；多种官能团能与氮磷产生配合作用；矿物组分能与氨氮和磷酸盐发生沉淀作用，特别是鸟粪石化学沉淀。未来的研究方向是：创新生物炭的改性方法；借助先进的手段揭示共去除的微观机制；回收氮磷制备缓释肥；改性生物炭在实际水体中的应用。
关键词：生物炭；氮和磷；共去除；改性方法；吸附机制
DOI:10.13822/j.cnki.hxsj.2023.0136
Co-removal of Nitrogen and Phosphate from water by Modified Biochar: Modification Methods and Adsorption Mechanisms WANG Shuo，WANG Ya-ru，YIN Tong，LIU Hui，FAN Zi-han，FAN Shi-suo*（School of Resources and Environment, Anhui agricultural university, Hefei 230036, China）
Abstract：Co-removal and resource utilization of nitrogen and phosphate in water had become a research hotspot, and biochar applications provided a new options. In this study, the co-removal of nitrogen and phosphate by modified biochar was summarized, focusing on the modification methods and adsorption mechanisms. The modification methods of biochar were mainly focused on the loading of minerals, including magnesium modification, iron modification, bimetallic modification, and other mineral modification methods. The purposes of modification were increasing the specific surface area and pore structure of biochar; enhancing electrostatic action; strengthening ion exchange capacity; enhancing complexation ability; promoting precipitation, especially promoting struvite crystallization reaction to recycle resources. The co-removal mechanism of nitrogen and phosphorus from modified biochar involves: its higher specific surface area and developed pore structure which provides more adsorption sites; its surface electricity causing electrostatic interaction; its mineral components leading to ion exchange; many functional groups bringing complexation; its mineral components producing precipitates, especially struvite chemical precipitation. The future research directions are: innovating the modification methods of biochar; uncovering the microscopic mechanisms of co-removal using advanced techniques; recycling of nitrogen and phosphate to prepare slow release fertilizer; application of modified biochar in actual water.
Key words：biochar; nitrogen and phosphate; co-removal; modification method; adsorption mechanism
引用本文：王硕，汪雅茹，尹通，等. 改性生物炭对水体中氮和磷共去除：改性方法和吸附机制[J].化学试剂，2023，45（7）：119-127.
低共熔溶剂在食品质量安全检测中的研究进展
王超a，于照a，李硕a,b,c，孙鹏*a,b,c
（黑龙江八一农垦大学 a.食品学院，b.农业农村部农产品及加工品质量监督检验测试中心（大庆），c.国家杂粮工程技术中心，黑龙江 大庆 163319）
摘要：低共熔溶剂（DESs）作为一种可设计的绿色溶剂，具有取代传统萃取剂的潜力。概述了近几年DESs作为萃取剂在食品的样品前处理中的研究进展，综述了其在各类食品样品中农药残留、兽药残留、重金属、食品添加剂和合成色素分析检测中的应用，同时与其他常规方法进行比较，并且对DESs作为萃取剂在食品质量安全检测领域应用中存在的问题及今后的发展方向进行了讨论和展望。
关键词：低共熔溶剂；样品前处理；食品质量安全；检测方法；发展
中图分类号：TS251.7 文献标识码：A 文章编号：02583283（2023）
DOI:10.13822/j.cnki.hxsj.2023.0038
Research Progress of Deep Eutectic Solvents in Food Safety WANG Chaoa, YU Zhaoa, LI Shuoa,b,c, SUN Peng*a,b,c (a. College of Food Science; b. Agricultural Products and Procesed Products Supervision and Testing Center, Ministry of Agriculture; c. National Coarse Cereals Engineering Research Center, Heilongjiang Bayi Agricultural University, Daqing 163319, China)
Abstract: Deep eutectic solvents (DESs) have the potential to replace conventional extracts as a designable green solvent. The article outlines the progress of research on DESs as an extract from sample pretreatment for food products during recent years. An overview of its application for the analysis and detection of pesticide residues, veterinary drug residues, heavy metals, food additives, and synthetic pigments in various food samples. Also compared with other conventional methods. The problems with applications of DESs as the extract in the field of food quality and safety testing and its future application development are also discussed and prospected.
Key words: deep eutectic solvent; sample pretreatment; food quality and safety; testing methods; development
引用本文：王超, 于照, 李硕, 等. 低共熔溶剂在食品质量安全检测中的研究进展[J]. 化学试剂，2023，45（7）：128-135.
【分析与测试】
QuEChERS联合LC-MS/MS测定土壤及蚯蚓中吡虫啉及异丙甲草胺13种代谢产物
符芙蓉1，赵丽霞1，李晓晶1，叶会科1，孙扬*1，李永涛2
（1.农业农村部环境保护科研监测所，天津 300191；2.华南农业大学 资源环境学院，广东 广州 510642）
摘 要：建立土壤及蚯蚓基质中吡虫啉及异丙甲草胺两种农药的13种代谢产物分析测试方法。通过筛选提取溶剂的种类、净化方式，优化高效液相色谱及质谱条件建立了QuEChERS联合LC-MS/MS的处理及测定方法。该方法使用含1%甲酸的乙腈溶液提取土壤及蚯蚓中两种常见农药的13种代谢物，以稀释2倍的方式削弱土壤浸提液中的基质效应、以稀释3.2倍及添加PSA、GCB、C18的方式净化蚯蚓浸提液。在土壤介质中，方法的平均回收率为68.0% ~ 114.8%，相对标准偏差为1.3% ~ 10.7%，检出限范围为0.0086 ~ 0.40 μg/kg，定量限为0.029 ~ 2.00 μg/kg。蚯蚓介质中，方法的平均回收率为67.1% ~ 93.8%，相对标准偏差为2.0% ~ 7.8%，检出限为0.11 ~ 5.00 μg/kg，定量限为0.36 ~ 25.0 μg/kg。采用本方法测定了田间实际土壤样品以及室内控制实验蚯蚓样品，检出两种农药异丙甲草胺及吡虫啉残留的代谢产物分别为MET-D、MET-2H、MET-ESASS、MET-OA，以及IMI-DH、IMI-U、IMI-5H、IMI-O；田间土壤及室内模拟实验的蚯蚓中检出水平分别为0.4 ~ 8.6和30.7 ~ 870.1 μg/kg。本研究方法相对简便高效、检出限低、稳定性高，适于实际田间和科学实验土壤及蚯蚓样品中吡虫啉及异丙甲草胺代谢产物的定性、定量分析。
关键词：土壤；蚯蚓；吡虫啉；异丙甲草胺；代谢物；QuEChERS；LC-MS/MS
中图分类号：R917 文献标识码：A 文章编号：0258-3283（2023）
DOI:10.13822/j.cnki.hxsj.2023.0162
Determination of 13 Metabolites of Imidacloprid and Metolachlor in Soil and Earthworm by QuEChERS Combined with LC-MS/MS FU Fu-rong1, ZHAO Li-xia1, LI Xiao-jing1, YE Hui-ke1, SUN Yang*1, LI Yong-tao2 (1. Agro - Environmental Protection Institute, Ministry of Agriculture and Rural Affairs, Tianjin 300191, China; 2. College of Natural Resources and Environment, South China Agricultural University, Guangzhou 51064, China)
Abstract: To determine 13 metabolites of imidacloprid and metolachlor in soil and earthworm, a method was established by adjusting the conditions of liquid phase chromatography and mass spectrometry, optimizing the types of extraction solvents and purification methods. The method used acetonitrile containing 1% formic acid to extract 13 metabolites from soil and earthworm, weakened the matrix effect of soil extract by diluting 2 times, and purified earthworm extract by diluting 3.2 times and adding PSA, GCB and C18. In soil matrix, the average recovery of the method was 68.0% ~ 114.8% with RSD as 1.3% ~ 10.7%, the limit of detection at 0.0086 ~ 0.40 μg/kg, and the limit of quantitation at 0.029 ~ 2.0 μg/kg. In earthworm matrix, the average recovery of the method was 67.1% ~ 93.8% with RSD as 2.0% ~ 7.8%, the limit of detection ats 0.11 ~ 5.00 μg/kg, and the limit of quantitation at 0.36 ~ 25.0 μg/kg. The soil samples in the field and earthworm samples from indoor control experiments were determined by this analysis method. Metabolites MET-D, MET-2H, MET-ESASS, MET-OA of metolachlor and metabolites IMI-DH, IMI-U, IMI-5H, IMI-O of imidacloprid were detected. The levels of detected metabolites in field soil and earthworm were 0.4 ~ 8.6 μg/kg and 30.7 ~ 870.1 μg/kg, respectively. The method is simple, efficient, sensitive and stable and is suitable for the qualitative and quantitative analysis of metabolites of imidacloprid and metolachlor in soil and earthworm samples from actual field and scientific experiments.
Key words: soil; earthworm; imidacloprid; metolachlor; metabolites; QuEChERS; LC-MS/MS
引用本文：符芙蓉，赵丽霞，李晓晶，等. QuEChERS联合LC-MS/MS测定土壤及蚯蚓中吡虫啉及异丙甲草胺13种代谢产物，化学试剂，2023，45（7）：136-143.
【合成与工艺技术】
水飞蓟宾C-3位衍生物的设计、合成及抗肿瘤活性研究
刘家越，李学城，赵风菊，霍荣迪，孟艳秋*
（沈阳化工大学 制药工程教研室，辽宁 沈阳 110142）
摘要：设计并合成一系列新型水飞蓟宾衍生物，研究其抗肿瘤活性。以水飞蓟宾为起始原料，经过酰化、选择性氨解、烷基化、氧化脱氢等手段，合成目标化合物。通过MTT法测定了化合物对乳腺癌MCF-7和胃癌SGC7901两株细胞的体外抗肿瘤活性。利用分子对接技术，将目标化合物与MEK受体模拟偶联，分析其与MEK的作用方式。设计并合成12个新型水飞蓟宾衍生物，通过1HNMR、13CNMR及MS对化合物进行结构表征。细胞试验表明化合物I2和I12抗肿瘤活性明显高于母体水飞蓟宾，与阳性对照药物拉帕替尼表现相当。分子对接结果显示化合物可以与MEK的氨基酸残基通过氢键等作用稳定结合。合成的水飞蓟宾衍生物对乳腺癌MCF-7和胃癌SGC7901细胞有明显的抑制作用，C-3位羟基的选择性酰化是增强抗肿瘤活性的关键。
关键词：水飞蓟宾；MEK；分子对接；抗肿瘤
中图分类号：R914 文献标识码：A 文章编号：0258-3283（2023）
DOI:10.13822/j.cnki.hxsj.2023.0151
Design, Synthesis and Antitumor Activity of C-3 Derivatives of Silybin LIU Jia-yue, LI Xue-cheng, ZHAO Feng-ju, HUO Rong-di, MENG Yan-qiu* (Department of Pharmaceutical Engineering, Shenyang University of Chemical Technology, Shenyang, 110142, China)
Abstract: A series of novel silybin derivatives were designed and synthesized and their antitumor activities were evaluated. The target compounds were synthesized from silybin by acylation, selective ammonolysis, alkylation, and oxidative dehydrogenation. The antitumor activities of the compounds against breast cancer MCF-7 and gastric cancer SGC7901 cells in vitro were determined by the MTT assay. Using molecular docking technology, the target compounds were simulated to couple with MEK receptor, and their interaction mode with MEK was analyzed. Twelve new silybin derivatives were designed, synthesized, and characterized by 1H NMR, 13C NMR and MS analysis,. Cell tests showed that the antitumor activities of compounds I2 and I12 were significantly higher than those of silybin, and were equivalent to those of positive control drug rapatinib. The results of molecular docking showed that the compounds can stably bind with amino acid residues of MEK through hydrogen bonding and other effects. The synthesized silybin derivatives have obvious inhibitory effects on breast cancer MCF-7 and gastric cancer SGC7901 cells, and the selective acylation of C-3 hydroxyl group plays a key role to enhance the anti-tumor activity.
Key words: silybin; MEK; molecular docking; antitumor activity
引用本文：刘家越, 李学城, 赵风菊, 等. 水飞蓟宾C-3位衍生物的设计、合成及抗肿瘤活性研究[J]. 化学试剂, 2023, 45（7）：144-151.
[5+1]串联反应构建螺[环己酮-吡唑啉酮]骨架的研究
陈治明
（贵州师范大学 化学与材料科学学院 贵州省功能材料化学重点实验室，贵州 贵阳 550001）
摘要：吡唑啉酮螺环骨架的构建在新药研发领域扮演着极其重要的角色，正成为有机合成领域的研究热点之一。合成了3种具有Lewis酸和手性酰胺结构的轴手性催化剂（1a ~ 1c），并将其应用于双苄叉丙酮与吡唑啉酮的[5+1]环加成串联反应，得到的目标化合物的产率高(92%)，对映体选择性好(89% e.e.)。该方法为具有生物药理活性的螺环己酮-吡唑啉酮骨架的合成提供了重要途径。
关键词：不对称串联；[5+1]环加成；螺环己酮-吡唑啉酮
中图分类号：O626 文献标识码：A 文章编号：0258-3283（2023）
DOI:10.13822/j.cnki.hxsj.2023.0182
Asymumetric [5+1] Tandem Construction of Spiro[cyclohexanone-pyrazolone] Skeleton CHEN Zhi-ming (Guizhou Provincial Key Laboratory of Functional Materials Chemistry, School of Chemistry and Materials Science, Guizhou Normal University, Guiyang 550001, China)
Abstract: The construction of pyrazolone spiro skeleton plays an extremely important role in the field of new drug research and development, and has become a research hotspot in the field of organic synthesis. Three axial chiral catalysts (1a~1c) with acidic and chiral amide structure were synthesized and applied to the [5+1] cycloaddition reaction of bisbenzylidene acetone and pyrazolone. The target compound was obtained in high yield (92%) and good enantioselectivity (89% e.e.). This method provides an important way for the synthesis of spirocyclohexanone-pyrazolone skeleton with biological pharmacological activity.
Key words: asymmetric tandem reaction; [5+1] annulation; spirocyclohexanone-pyrazolone
引用本文：陈治明. [5+1]串联反应构建螺[环己酮-吡唑啉酮]骨架的研究[J].化学试剂，2023，45（7）：152-158.
