化学试剂
2025年47（4）中英文摘要
【综述与专论】
荧光探针用于活性氧检测的研究进展
曹艳珍，鲁谨菡，刘润乐，刘雨，白燕玲*
(齐鲁理工学院 生物与化学工程学院，山东 济南 250200)
摘要：活性氧（ROS）作为细胞内生成的具有氧化活性的化学物质，其涵盖过氧化氢（H₂O₂）、次氯酸（HClO）、过氧亚硝酸盐（ONOO⁻）等。在正常的生理状态下，细胞会产生一定量 ROS，它们在细胞信号传导等生理过程中发挥着重要作用。然而，当 ROS 生成量过多或机体清除能力不足时，就会引发氧化应激反应，这不仅会对细胞造成损害，还与众多疾病的发生发展紧密相关，如心血管疾病、神经退行性疾病及癌症等。ROS 具有寿命短、反应活性高等显著特征，因而，对其进行检测极具挑战性。实现对 ROS 快速且精准的检测，对于深入阐明机体疾病发生的生理和病理过程至关重要，有助于为疾病的早期诊断与有效治疗提供关键依据。荧光探针检测技术凭借其灵敏度高、选择性好、操作简便、响应迅速以及适用于生物体等诸多优点，成为检测 ROS 的理想选择。结合荧光显微成像技术，利用 ROS 荧光探针能够直接获取细胞、组织和生物体内的 ROS 信息，实现对 ROS 的可视化检测。总结近年来应用于检测H₂O₂、HClO以及ONOO⁻ 的荧光探针的研究进展，重点聚焦探针设计与生物医学等领域的应用。
关键词：活性氧；荧光探针；过氧化氢；次氯酸；过氧亚硝酸盐
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2025）
DOI：10.13822/j.cnki.hxsj.2024.0473
Research progress of Fluorescent Probes for Reactive Oxygen Species Detection CAO Yan-zhen, LU Jin-han, LIU Run-le, LIU Yu, PAK Yen Leng* (College of Biological and Chemical Engineering, Qilu Institute of Technology, Jinan 250200, China)
Abstract: Reactive oxygen species (ROS) are chemically active oxidants produced within cells, including compounds such as hydrogen peroxide (H₂O₂), hypochlorous acid (HClO), and peroxynitrite (ONOO⁻). Under typical physiological conditions, cells generate a regulated amount of ROS, which are essential for various physiological functions, including cell signaling. However, excessive production of ROS or inadequate clearance by the body can lead to an oxidative stress response. This response not only causes cellular damage but is also significantly associated with the onset and progression of numerous diseases, including cardiovascular disorders, neurodegenerative conditions, and cancer. ROS has significant characteristics of short life span and high reactivity, which makes its detection extremely challenging. Therefore, rapid and accurate detection of ROS is crucial for in-depth elucidation of the physiological and pathological processes of disease occurrence in the body, providing key evidence for early diagnosis and effective treatment of diseases. The detection technology with fluorescent probe has become an ideal method for detecting ROS due to its advantages such as high sensitivity, good selectivity, simple operation, rapid response and suitability for biological applications. Combined with fluorescence microscopy imaging technology, ROS fluorescent probes can be used to directly obtain ROS information in cells, tissues and organisms, facilitating visual detection of ROS. The research progress of fluorescent probes for detection of H₂O₂, HClO and ONOO⁻ in recent years, and focusing on probe design and applications in biomedicine and other fields were summarized.
Key words：reactive oxygen species; fluorescent probe; hydrogen peroxide; hypochlorous acid; peroxynitrite
杨小娟，王雨晗，陈安洋，钟玉梅，黎茵茵，郭维，郑绿茵*
(赣南师范大学 合成药物化学江西省重点实验室，江西 赣州 341000)
摘要：为了解抗血吸虫药物研发工作进展，总结了近年来有机小分子化合物抗血吸虫活性与作用机理，以期为新型抗血吸虫药物研发提供依据。从化学合成小分子化合物和酶抑制剂两方面，对有机小分子化合物的抗血吸虫抗虫活性及作用机理的最新进展进行了评价。针对抗血吸虫活性、构效关系和对虫体的影响等方面，总结了噻唑、喹啉、咪唑类化合物以及具有抗肿瘤、抗炎、抗组胺和利尿剂等活性化合物和重要酶抑制剂的抗血吸虫活性、构效关系和对虫体的影响，指出了抗虫活性最佳的先导化合物。利用现代生物技术，发现血吸虫生长、发育和繁殖相关的重要酶、蛋白抑制剂是今后抗血吸虫药物研发的重要途径。
关键词：抗血吸虫活性；化学合成小分子化合物；酶抑制剂；作用机理
中图分类号：R383.24 文献标识码：A 文章编号：0258-3283（2025）
DOI：10.13822/j.cnki.hxsj.2024.0488
Recent Progress in Anti-Schistosoma Activity and Mechanism of Small Molecule Organic Compounds YANG Xiao-juan, WANG Yu-han, CHENG An-xiang, ZHONG Yu-mei, LI Yin-yin, GUO Wei, ZHENG Lv-yin* (Jiangxi Provincial Key Laboratory of Synthetic Pharmaceutical Chemistry, Gannan Normal University, Ganzhou 341000, China)
Abstract: In order to understand the progress of research and development of anti-schistosomiasis drugs, the anti-schistosoma activity and possible mechanism of organic small molecule compounds in recent years were summarized, which aimed to provide a basis for the development of new anti-schistosoma drugs. The latest progress in the anti-schistosomiasis activity and mechanism of organic small molecule compounds was evaluated in two aspects: chemical synthetic small molecule compounds and enzyme inhibitors. The anti-schistosomiasis activity, structure-activity relationship, and effects on the schistosoma of thiazoles, quinolines, imidazoles, and some bioactive compounds with anti-tumor, anti-inflammatory, antihistamine, and diuretic properties, as well as important enzyme inhibitors were summarized. The lead compounds with the best insecticidal activity were also identified. In the future, the application of modern biotechnology to discover important enzyme and protein inhibitors related to the growth, development, and reproduction of schistosoma is an important strategy for the development of anti-schistosoma drugs.
Key words: anti-schistosoma activity; chemical synthetic small molecule compounds; enzyme inhibitors; mechanism
大麻二酚增溶技术进展
刘佳莹
(黑龙江省科学院 高技术研究院，黑龙江 哈尔滨 150000)
摘要：大麻二酚（CBD）具有广阔生物及药理活性，能够治疗癫痫，还可缓解焦虑和抑郁症状，在一些实验模型中，CBD表现出对精神分裂症症状的改善作用，对阿尔茨海默病也有潜在的治疗作用。CBD还具有镇痛、抗炎等医疗用途，在食品及保健品领域也具有探索性。但因其脂溶性强、水溶性差，限制了其在食品、化妆品、生物医药及农业等相关领域的应用。近年来，众多增溶技术被广泛研究用于改善CBD的溶解性。通过查阅大量国内外相关文献，对CBD 增溶技术的研究进展为其更广泛的应用提供了可能，总结出可通过成盐法、改变晶型、减小粒径、固体分散体、溶剂体系、环糊精包合、微乳及脂质体8种技术来改善CBD的水溶性，提高生物利用度，但各技术仍面临诸多挑战，未来需进一步优化以推动CBD相关产品的开发与利用。
关键词：大麻二酚；增溶技术；生物利用度；药理活性；成盐法；减小粒径；固体分散体
中图分类号：O629.9 文献标识码：A 文章编号：0258-3283（2025）--
DOI：10.13822/j.cnki.hxsj.2024.0487
Progress of Cannabidiol Solubilization Technology LIU Jia-ying (Institute of High Technology, Heilongjiang Academy of Sciences, Harbin 150000, China)
Abstract: Cannabidiol (CBD) has a wide range of biological and pharmacological activities, can treat epilepsy, can also relieve anxiety and depression symptoms, in some experimental models, CBD has shown improvement in schizophrenia symptoms, and has potential therapeutic effects on Alzheimer's disease. CBD also has analgesic, anti-inflammatory and other medical uses, and is also exploratory in the field of food and health products. However, due to its strong fat solubility and poor water solubility, its application in food, cosmetics, biomedicine, agriculture and other related fields is limited. In recent years, many solubilization techniques have been widely studied to improve the solubility of CBD. By referring to a large number of relevant literatures at home and abroad, the research progress of CBD solubility enhancement technology provides a possibility for its wider application, and summarizes eight technologies that can improve the water solubility and bioavailability of CBD through salting, changing crystal shape, reducing particle size, solid dispersion, solvent system, cyclodextrin inclusion, microemulsion and liposome. However, various technologies still face many challenges and need to be further optimized in the future to promote the development and utilization of CBD-related products.
Key words: cannabidiol; solubilization technology; bioavailability; pharmacological activity;salt-forming process; reduce the particle size; solid dispersion
【生化与药用试剂】
(2. 凯里学院 大健康学院 黔东南苗侗药现代化研究重点实验室，贵州 凯里 556011)
摘要：近年来，靶向蛋白降解技术蓬勃发展，其能够选择性且有效地触发目标蛋白质的降解，有望克服传统药物研发技术的瓶颈问题，挑战“难成药”靶点，为靶向药物领域提供新的治疗策略。这种新颖的方法相比常规小分子抑制剂具有多种优势，如低剂量，高选择性，克服耐药性等优点。靶向蛋白质降解策略包括分子胶，蛋白水解靶向嵌合体和基于疏水标签的降解剂等。与其他的靶向蛋白降解剂相比，疏水标签蛋白降解剂是通过模拟蛋白错误折叠而被蛋白酶体识别并降解，但是具体的降解机制还有待进一步研究。目前不同结构的疏水标签被报道，例如金刚烷、Boc3Arg、降冰片烯、芘、芴、碳硼烷等，而且疏水标签降解剂优异的成药性与可设计性，已广泛应用于多个研究领域。但现有的疏水标签在诸多方面存在的问题，仍存在理化性质差、易被消除、生物利用度较低、降解效率不高等缺点，对疏水标签降解剂的发展形成了一定阻碍。因此主要介绍了近年来疏水标签降解剂在药物研发领域中的应用进展，希望为未来靶向蛋白降解剂的研发提供有价值的参考。
关键词：疏水标签；靶向蛋白降解；靶向药物；药物研发
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2025）
DOI：10.13822/j.cnki.hxsj.2024.0490
Advances in the application of hydrophobic label-targeted protein degradation agents YU Si-qi1, WANG Jing2, WANG Qin2, ZHANG Lei*1,2 (1. School of Pharmacy, Zunyi Medical University, Zunyi 563006, China; 2. Key Laboratory for Modernization of Qiandongnan Miao & Dong Medicine, School of Life and Health Science, Kaili University, Kaili 556011, China.)
Abstract：In recent years, targeted protein degradation technology has developed vigorously, which can selectively and effectively trigger the degradation of target proteins. It is expected to overcome the bottleneck of traditional drug development technology, challenge "undruggable" targets, and provide new therapeutic strategies for the field of targeted drugs. This novel approach has several advantages over conventional small molecule inhibitors, such as low dose, high selectivity, and overcoming drug resistance. Targeted protein degradation strategies include molecular glues, proteolytic targeting chimeras, and hydrophobic tag degraders. Compared with other targeted protein degraders, hydrophobic tag protein degraders are recognized and degraded by the proteasome by mimicking protein misfolding, but the specific degradation mechanism needs to be further studied. At present, hydrophobic tags with different structures have been reported, such as adamantane, Boc3Arg, norbornene, pyrene, fluorene, carborane, etc. Among them, hydrophobic tag has various applications due to its druggability and designability compared with other targeted protein degradation molecules. However, the existing hydrophobic labels still have the shortcomings of poor physical and chemical properties, easy elimination, low bioavailability, and low degradation efficiency, which hinder the development of hydrophobic label degraders. This review highlights the recent applications of hydrophobic tag degraders in drug development, which might provide valuable information for the future research and development of targeted protein degraders.
Key words: hydrophobic tag; targeted protein degradation; targeted drug; drug discovery
【分离提取技术】
当归中活性成分提取方法及药理作用的研究进展
王庆彦1，毕映燕2，徐生杰1，韩子豪1，刘珂*1
（1. 兰州石化职业技术大学 应用化学工程学院，甘肃 兰州 730060；2.甘肃省中医院 药剂科，甘肃 兰州 730050）
摘要：当归是传统的药食同源植物，蕴含着众多的生物活性物质与组分。当归中的活性成分包含挥发油类、有机酸类、多糖类、黄酮类以及其他元素等。当归具有广泛的药理作用，在血液系统方面，既能抗血小板聚集，又能促进造血补血；还具有抗氧化、抗菌、抗肿瘤等功效，例如阿魏酸钠可抑制血小板聚集，当归多糖能促进造血、抗氧化，蒿本内酯能抗菌等，可通过多种机制发挥对人体的保健与治疗功效。目前，当归单方药品剂型丰富，如片剂、胶囊剂、丸剂、口服液、注射剂等，可满足不同患者需求。其不同部位成分和功效存在差异，如当归尾，侧重于活血；当归身，侧重养血等。当归的生物活性成分常见的提取方法包括传统的溶剂提取法、水蒸气蒸馏法，以及新兴的超声辅助提取技术、微波辅助提取技术、红外辐射提取技术、CO2超临界萃取技术等。针对不同提取方法的实例予以分析，就当归中活性成分及提取方法、药理作用的研究进展及未来提取技术展望和临床应用拓展展开综述，旨在为当归提取工艺的抉择和优化提供全面的参照，为该药材的进一步深入研究和临床应用奠定基础。
关键词：当归；生物活性成分；提取方法；药理作用；临床应用
中图分类号：S853.75 文献标识码：A 文章编号：0258-3283（2025）
DOI：10.13822/j.cnki.hxsj.2024.0455
Progress of Extraction Methods and Pharmacological Effects of active Components in Angelica Sinensis WANG Qing-yan1, BI Ying-yan2, XU Sheng-jie1, HAN Zi-hao1, LIU Ke*1 (1. College of Applied Chemical Engineering, Lanzhou Petrochemical University of Vocational Technology, Lanzhou 730060, China; 2.Department of Pharmacy, Gansu Provincial Hospital of TCM, Lanzhou 730050,China)
Abstracts: Angelica sinensis is a traditional medicinal and food homologous plant, which contains numerous bioactive substances and components. The active components in angelica sinensis include volatile oils, organic acids, polysaccharides, flavonoids and other elements. Angelica has a wide range of pharmacological effects, such as anti-thrombosis in the blood system, hematopoietic and supplemental function, good effect on cardiovascular and cerebrovascular. In addition, angelica possessed anti-oxidation, antibacterial, anti-tumor, treatment of Alzheimer's disease, liver protection, anti-inflammatory analgesia and other effects. In brief, angelica can prevent and treat related diseases for human. Currently, diverse drug forms (including tablets, hard capsules, pills, oral liquids, injection, etc.) could satisfy the needs of different patients. For different parts of angelica, differences in the components and effects could be observed; for example, angelica tail focuses on promoting blood activating, while its body focuses on blood nourishing, etc. Nowadays, the methods for angelica's bioactive ingredient extraction are diverse. Traditional methods include solvent extraction and water vapor distillation. Emerging technologies include enzyme decomposition, ultrasound assisted extraction, microwave assisted extraction, infrared assisted extraction, and supercritical fluid extraction. The examples of different extraction methods and provides a comprehensive reference for the selection and optimization of angelica extraction process was analyzed. Furthermore, different extraction methods and progress of pharmacologic action for angelica were reviewed and outlooked, and finally aims at laying the foundations for its further investigation and clinical application.
Key words: angelica sinensis; bio-active components; extraction methods; pharmacological effects; chinese medicinal herb
【电化学和新能源】
富氢气氛中CO优先氧化反应催化剂的研究进展
胡子圆，宁静*
（西部金属材料股份有限公司，陕西 西安 710201）
摘要：氢气作为清洁、高效的二次能源具有越来越广泛的用途，当被用作质子交换膜燃料电池的原料时，其中微量的CO会毒害燃料电池的Pt电极，从而导致严重的极化现象。CO优先氧化法（CO preferential oxidation，CO-PROX）可选择性的氧化痕量的CO同时保持H2不被氧化，从而实现氢气的纯化。催化剂在CO优先氧化反应中发挥着重要作用，已被广泛研究。总结了CO优先氧化方法中涉及的催化剂的研究进展，重点讨论了Pt族催化剂（platinium group metal，PGM）催化剂、Au基催化剂、双金属催化剂、非贵金属催化剂的研究现状，并对其反应活性和反应机理进行了阐述。
关键词：CO优先氧化；PGM催化剂；Au基催化剂；双金属催化剂；非贵金属催化剂
中图分类号：O614.1 文献标识码：A 文章编号：0258-3283（2025）
DOI：10.13822/j.cnki.hxsj.2024.0484
Advances in Catalysts for Preferential Oxidation of CO in Hydrogen-rich Gas Streams HU Zi-yuan, NING Jing*(Western Meta Materials Co.,Ltd., Xi’an 710201, China)
Abstract：Hydrogen has an increasingly widespread use as a clean and efficient secondary energy source. When H2-rich gas streams are used as feedstock for proton exchange membrane fuel cells, trace amounts of CO in them can poison the platinum electrodes. Preferential oxidation of CO (CO-PROX) is a promising method to selectively oxidize trace amounts of CO while keeping H2 unoxidized. Catalysts play an important role in PROX. To date, a large number of catalysts have been developed for PROX. The current status of catalysts used in the preferential oxidation method of CO (including platinum group metal catalysts, gold-based catalysts, bimetallic catalysts, and nonmetallic catalysts), and their reactivity and reaction mechanisms were reviewed.
Key words：CO preferential oxidation; PGM catalyst; Au catalyst; bimetallic catalyst; non-precious metal catalyst
紫外光辐照构建含氧空位Bi/(BiO)2CO3增强光催化还原CO2
何欣阳1，孙志飞2，邓良广2，郭靖3，崔文昊3，吕英*1
(1. 西安石油大学 材料科学与工程学院，陕西 西安 710065；2. 中国石油天然气股份有限公司 长庆油田分公司 第十一采油厂，甘肃 庆阳 745099；3. 西安长庆同欣石油科技有限公司，陕西 西安 710000)
摘要：以BiOCOOH为前驱体，使用绿色、温和的紫外光诱导法制备具有氧空位的Bi/(BiO)2CO3。对紫外光辐照不同时间的样品进行光催化还原CO2性能测试，光催化活性高度依赖于制备过程的光照时间。在所制备的样品中，光辐照时间为50 min时的样品（B-50）表现出最高的光催化活性，其在CO2还原6 h后的CO累计产量高达88.84 μmol/g，为BiOCOOH的4倍。与此同时，CO选择性为100%。通过电化学测试表明，光催化性能的提高可归因于氧空位缺陷能级和Bi纳米颗粒的等离子体共振效应（SPR）的协同作用，调节了能带结构、提高了可见光的吸收范围、促进了光生载流子的分离。这一领域的研究不仅提供了一种简便、低成本的方法同时将氧空位和Bi纳米颗粒引入材料中，而且证实了紫外光辐照是调节材料光催化性能的有效方法，为开发高效光催化剂和还原CO2提供了见解。
关键词：BiOCOOH；紫外光辐照；氧空位；光催化还原CO2；Bi纳米颗粒
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2025）
DOI：10.13822/j.cnki.hxsj.2024.0481
Constructed Oxygen Vacancy in Bi/(BiO)₂CO₃ by UV Irradiation to Enhance photocatalytic CO₂ Reduction HE Xin-yang1, SUN Zhi-fei2, DENG Liang-guang2, GUO Jing3, CUI Wen-hao3, LV Ying*1 (1. College of Materials Science and Engineering, Xi'an Petroleum University, Xi'an 710065, China; 2. Eleventh Oil Production Plant, PetroChina Changqing Oilfield Branch, Qingyang 745099, China; 3. Xi'an Changqing Tongxin Petroleum Technology Co., Ltd., Xi'an 710000, China)
Abstract：Bi/(BiO)2CO3 with oxygen vacancies was prepared using a green and mild UV-induced method by utilizing BiOCOOH as a precursor. Samples irradiated with UV light for different times were tested for photocatalytic reduction of CO2, and the photocatalytic activity was highly dependent on the time of light irradiation of the preparation process. Among the prepared samples, the sample with a light irradiation time of 50 min (B-50) exhibited the highest photocatalytic activity, with a cumulative CO yield as high as 88.84 μmol/g after 6 h of CO2 reduction, which is four times that of BiOCOOH. Meanwhile, the CO selectivity was 100%. The improved photocatalytic performance can be attributed to the synergistic effect of the oxygen vacancy defect energy levels and the plasmon resonance effect (SPR) of the Bi nanoparticles, which modulated the energy band structure, improved the absorption range of the visible light, and facilitated the separation of photogenerated carriers, as shown by electrochemical tests. Research in this area not only provides a facile and low-cost method to simultaneously introduce oxygen vacancies and Bi nanoparticles into materials, but also confirms that UV irradiation is an effective method to modulate the photocatalytic properties of materials, providing insights into the development of highly efficient photocatalysts and the reduction of CO2.
Key words：BiOCOOH; ultraviolet irradiation; oxygen vacancies; photocatalytic reduction of CO2; Bi nanoparticles
Mo-Cu共掺RuO2电催化剂的制备及酸性析氧性能研究
邓连江1,2，周俊杰*2，朱银安*2，林贻超2
（1. 宁波大学 材料科学与化学工程学院，浙江 宁波 315211；2. 中国科学院宁波材料技术与工程研究所 全省先进燃料电池与电解池技术重点实验室，浙江 宁波 315201）
摘要：质子交换膜（PEM）电解槽中，受限于强酸腐蚀以及高氧化电位的工作环境，开发用于酸性析氧反应（OER）的高性能、高耐久的Ru基催化剂是一个巨大的挑战。为此，将不同浓度的RuCl3和Mo/Cu-MOFs结构进行离子交换，经煅烧后制备了一系列Mo和Cu共掺RuO2电催化剂。结果表明，(Mo,Cu)-RuO2-7催化剂在酸性电解质中表现出优异OER性能，其在10 mA/cm2电流密度下过电位仅为214 mV，且经20 h连续工作后稳定性大幅优于商业RuO2。研究为设计高性能PEM电解水阳极催化剂提供了新思路，有望推动PEM电解槽技术及其工业应用的发展。
关键词：电解水；析氧反应；二氧化钌；共掺杂；酸性介质
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2025）
DOI：10.13822/j.cnki.hxsj.2024.0476
Preparation and Acidic Oxygen Evolution Performance of Mo-Cu Co-doped RuO2 Electrocatalysts DENG Lian-jiang1,2, ZHOU Jun-jie2*, ZHU Yin-an2*, LIN Yi-chao2 （1. School of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, China; 2. Zhejiang Key Laboratory of Advanced Fuel Cells and Electrolyzers Technology, Ningbo Institute of Materials Technology & Engineering, Chinese Academy of Sciences, Ningbo 315201, China）
Abstract：The development of high-performance and durable Ru-based electrocatalysts in proton exchange membrane （PEM） water electrolyzers for the oxygen evolution reaction （OER） remains a huge challenge due to the severe catalyst’s corrosion and high reaction overpotential in acid media. A series of Mo and Cu co-doped RuO2 electrocatalysts were prepared by exchanging different concentrations of RuCl3 into the Mo/Cu-MOFs structure. The results demonstrated that the (Mo,Cu)-RuO2-7 catalyst exhibited excellent OER performance under acidic conditions. The overpotential is only 214 mV at a current density of 10 mA/cm2, and the stability after 20 hours of continuous operation is significantly better than that of commercial RuO2. This work provides a new idea for the development of high-performance anode catalysts for PEM water splitting, which is expected to promote the development and industrial application of PEM electrolyzer technology.
Key words：water splitting ; oxygen evolution reaction ; ruthenium dioxide ; co-doped; acid media
低共熔溶剂一步原位浸出钴酸锂中有价金属的研究
付飞娥，张正惠*
(云南开放大学/云南国防工业职业技术学院 化学工程学院，云南 昆明 650500）
摘要：随着锂离子电池产业的快速发展，高效的回收技术应对资源浪费和环境污染至关重要，然而，同时实现绿色、温和、高效回收仍然具有挑战性。提出了一种基于乙二醇-草酸的新型低共熔溶剂，用于在温和条件下从 LiCoO2 中一步选择性提取有价金属。采用单因素实验考察了关键浸出参数（温度、物质的量比、时间、液料比）对浸出率的影响，系统测试了低共熔溶剂的热稳定性和结构特征并探究了浸出机制。结果表明，在最佳浸出条件下（温度90 ℃、乙二醇-草酸的物质的量比6:1、浸出时间12 h、液料比50 g/g、搅速400 r/min），锂全部浸出到滤液中，钴以CoC2O4·2H2O纳米棒状的沉淀形式析出。乙二醇和草酸结合形成分子间氢键，温度对低共熔溶剂的热稳定性影响明显。方法操作简单，不涉及额外沉淀剂及还原剂，为低共熔溶剂快速、短流程回收废旧电池材料奠定理论基础。
关键词：废旧锂离子电池；钴酸锂；低共熔溶剂；原位浸出；机制
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2025）
DOI：10.13822/j.cnki.hxsj.2024.0440
One-step in-situ Leaching of Valuable Metals from Lithium Cobalt Oxide Using Deep Eutectic Solvents FU Fei-e, ZHANG Zheng-hui*（College of Chemical Engineering, Yunnan Open University/Yunnan Vocation and Technical College National Defense Industry, Kunming 650500, China）
Abstract：Efficient recycling technology for the rapid growth of spent lithium-ion batteries is essential to tackle the resources and environmental crisis. However, the simultaneous realization of green, efficient recovery at mild temperature is still challenging. A novel deep eutectic solvent based on ethylene glycol(EG)-oxalic acid(OA) was designed for one-step and selective extraction of valuable metals from LiCoO2 under mild conditions. Single-factor experiments were used to investigate the effects of key leaching parameters (temperature, materal ratio, time, liquid-to-solid ratio) on the leaching rate. The thermal stability and structural characteristics of the deep eutectic solvent were systematically tested and the leaching mechanism was explored. The results indicate that lithium is completely ached into the filtrate, and cobalt is precipitated in the form of CoC2O4·2H2O nanorods under the optimal leaching conditions, the temperature is 90 °C, EG-OA material ratio is 6:1, leaching time is 12 h, liquid-solid ratio is 50 g/g, stirring speed is 400 r/min. Intermolecular hydrogen bonds are formed between ethylene glycol and oxalic acid. Temperature has a significant effect on the thermal stability of deep eutectic solvents. This method is simple to operate and does not involve additional precipitants, laying a theoretical foundation for the rapid and short-process recovery of waste battery materials using deep eutectic solvents.
Key words：waste lithium-ion batteries; lithium cobal; deep eutectic solvent; in-situ leaching; mechanism
催化效果研究
黄礼智1，邹子墨2，段百超2，曹忠2，刘亚丽1，王路辉*1, 3
（1. 浙江海洋大学 浙江省石油化工环境污染控制重点实验室，浙江 舟山 316022；
2. 浙江石油化工有限公司，浙江 舟山 316299;
3. 浙江海洋大学 临港石油天然气储运技术国家地方联合工程研究中心，浙江 舟山 316022）
摘要： 聚丙烯（PP）废弃物的大量堆积已对环境造成严重威胁，开发绿色高效的解聚技术成为实现资源化利用的关键。旨在探索NiO/Al₂O₃催化剂在温和常压条件下对PP解聚反应的催化性能及其结构特性的影响，为高效处理聚丙烯废弃物提供理论依据与技术支持。采用浸渍法制备NiO/Al₂O₃催化剂，通过TEM、XRD、NH₃-TPD、H₂-TPR和XPS等表征手段分析催化剂的物理化学性质，并进行PP解聚反应测试，系统评估液相产物收率、产物分布以及催化稳定性，重点研究表面酸性分布和金属氧化态的调控作用。实验结果表明，1%NiO/Al₂O₃催化剂在340 °C下液相产物收率高达35%，显著优于1%Ni/Al₂O₃和纯Al₂O₃催化剂，且液相中C5～C12低碳数烃类比例达到80%，显示出优异的选择性。此外，表面酸性分析表明，NiO/Al₂O₃具有优化的酸性位点分布，中强酸性区域增强，显著促进了PP的解聚反应。还原行为测试进一步表明，NiO颗粒与载体间的强相互作用提升了活性金属的分散性和稳定性，从而改善了催化性能。1%NiO/Al₂O₃催化剂在温和常压条件下表现出高效的催化性能，优化的表面酸性分布和金属氧化态调控是其高效性能的关键。为实现PP废弃物的高值化利用提供新思路，同时推动了绿色可持续解聚技术的发展。
关键词：聚丙烯；解聚反应；NiO/Al₂O₃催化剂；表面酸性调控；金属氧化态；液相产物选择性
中图分类号：X705 文献标识码：A 文章编号：0258-3283（2025）
DOI：10.13822/j.cnki.hxsj.2024.0493
Catalytic Performance of NiO/Al₂O₃ Catalyst in Polypropylene Depolymerization under Atmospheric Pressure HUANG Li-zhi1，ZOU Zi-mo2，DUAN Bai-chao2，CAO Zhong2，LIU Ya-li1，WANG Lu-hui*1,3(1. Zhejiang Key Laboratory of Petrochemical Pollution Control, Zhejiang Ocean University, Zhoushan 316022, China; 2. Zhejiang Petroleum&Chemical Co.,Ltd., Zhoushan 316299, China; 3. National-Local Joint Engineering Laboratory of Harbor Oil & Gas Storage and Transportation Technology, Zhejiang Ocean University, Zhoushan 316022, China)
Abstract：The large accumulation of polypropylene (PP) waste has posed a serious threat to the environment. Thus, the development of green and efficient depolymerization technologies has been a key approach for resource utilization. We aimed to explore the catalytic performance of NiO/Al₂O₃ catalysts for PP depolymerization under mild and atmospheric pressure conditions, as well as the impact of their structural characteristics. It provides a theoretical basis and technical support for the efficient treatment of polypropylene waste. The NiO/Al₂O₃ catalysts were prepared by impregnation. Then, the physical and chemical properties of the catalysts were analyzed using characterization techniques such as TEM, XRD, NH₃-TPD, H₂-TPR, and XPS. PP depolymerization reactions were conducted to systematically evaluate the liquid-phase product yield, product distribution, and catalytic stability, with a focus on studying the role of surface acidity distribution and the regulation of metal oxidation states. Experimental results indicated that the 1%NiO/Al₂O₃ catalyst achieved a liquid-phase product yield of up to 35% at 340°C, significantly outperforming the 1%Ni/Al₂O₃ and pure Al₂O₃ catalysts. Furthermore, the proportion of C5～C12 low-carbon hydrocarbons in the liquid phase reached 80%, demonstrating excellent selectivity. Surface acidity analysis revealed that NiO/Al₂O₃ had an optimized distribution of acidic sites, with an enhanced medium-strength acidic region, which significantly promoted PP depolymerization. Reduction behavior tests further indicated that the strong interaction between NiO particles and the support improved the dispersion and stability of the active metal, thus enhancing the catalytic performance. The 1%NiO/Al₂O₃ catalyst demonstrated high catalytic efficiency under mild, atmospheric conditions, with optimized surface acidity distribution and regulation of metal oxidation states being key to its excellent performance. This study will provide new insights for the high-value utilization of PP waste, and promote the development of green and sustainable depolymerization technologies.
Key words：polyolefin; depolymerization reaction; NiO/Al₂O₃ catalyst; surface acidity; metal oxidation state; liquid-phase product selectivity
基于UPLC-Q-Exactive-Plus-Orbitrap-MS技术的
木贼化学成分分析
张宝1,2,3，李悦1，蒋礼2,3，刘佳1，马晓1，赵珊1，孙绪*4
（1.贵阳市妇幼保健院/贵阳市儿童医院 药学部，贵州 贵阳 550003；2. 贵州医科大学 贵州省药物制剂重点实验室，贵州 贵阳 550004；3. 贵州医科大学 药学院，贵州 贵阳 551113；4. 贵州省食品药品检验所，贵州 贵阳 550004）
摘要：采用超高效液相色谱-四极杆-静电场轨道阱高分辨质谱（UPLC-Q-Exactive-Plus-Orbitrap-MS）技术快速鉴定木贼的化学成分。色谱采用赛默飞公司Hypersil GOLD C18（100 mm×2.1 mm，1.9 μm）型色谱柱，0.1%甲酸-水溶液为流动相A，乙腈为流动相B，设置流速、柱温和进样量分别为0.3 mL/min、40℃和1 μL；质谱采用电喷雾离子源（ESI），正、负离子模式扫描。将化合物的保留时间、准分子离子和特征碎片离子与标准品或文献报道的化合物进行对比，共鉴定化合物70个，包括22个有机酸类、15个氨基酸类、12个生物碱类、7个核苷类、4个糖类、3个黄酮类、2个芳香醛及5个其他成分。UPLC-Q-Exactive-Orbitrap-MS技术具有快速、准确、灵敏的优势，采用该方法可快速分析鉴定木贼的化学成分，为进一步研究其药效物质基础、作用机制及产品开发提供参考依据。
关键词：UPLC-Q-Exactive-Plus-Orbitrap-MS；木贼；化学成分；有机酸；生物碱
中图分类号：R282 文献标识码: A 文章编号：0258-3283（2025）
DOI: 10.13822/j.cnki.hxsj.2024.0431
Identification of Chemical Constituents in Equisetum hyemale L. Based on UPLC-Q-Exactive-Plus-Orbitrap-MS ZHANG Bao1,2,3, LI Yue1, JIANG Li2,3, LIU Jia1, MA Xiao1, ZHAO Shan1, SUN Xu*4 (1. Department of Pharmacy, Guiyang Maternal and Child Healthcare Hospital/Guiyang Children’s Hospital, Guiyang 550003, China; 2. Guizhou Provincial Key Laboratory of Pharmaceutics, Guizhou Medical University, Guiyang 550004, China; 3. School of Pharmacy, Guizhou Medical University, Guiyang 551113, China; 4. Guizhou Provincial Institute for Food and Drug Control, Guiyang 550004, China)
Abstract: UPLC-Q-Exactive-Plus-Orbitrap-MS was used to rapidly identify the chemical constituents in Equisetum hyemale. A Hypersil GOLD C18 column (100 mm×2.1 mm, 1.9 μm) was used for gradient elution using acetonitrile (B)-0.1% formic acid solution (A) as mobile phase. The flow rate of 0.3 mL/min, column temperature was 40℃, and sample size was 1 μL. The electrospray ionization (ESI) source was adopted for the analysis in positive/negative ion mode. The retention time, quasi-molecular ions, and MS/MS characteristic fragment ions of the chemical constituents of Equisetum hyemale were compared with those of standards or or previously reported compounds. A total of 70 compounds were identified from Equisetum hyemale, including 22 organic acids, 15 amino acids, 12 alkaloids, 7 nucleosides, 4 carbohydrates, 3 flavonoids, 2 aromatic aldehydes and 5 other constituents. UPLC-Q-Exactive-Plus-Orbitrap-MS method is rapid, accurate and sensitive, and quickly elucidates the chemical compositions of Equisetum hyemale, which provide reference for further pharmacodynamic material basis, mechanisms of action and product development study of the crude medicine.
Key words: UPLC-Q-Exactive-Plus-Orbitrap-MS; Equisetum hyemale L.; chemical constituents; organic acids; alkaloids
【合成与应用】
选择性JAK2&JAK3双重抑制剂的设计和合成
凌珍，张洁，黄艳琴，张敏，韦理莎，罗佳媛，何林洪*
（广西医科大学 药学院，广西 南宁 530021）
摘要：为了探索选择性JAK1&JAK3或JAK2&JAK3双重抑制剂的设计，采用不同的非亲电碎片替换高效共价选择性JAK3抑制剂（R） -5-（苯并[d][1,3]二氧杂环戊烯-5-基）-4-（（1-（乙烯基磺酰基）哌啶-3-基）氧基）-7H-吡咯并[2,3-d]嘧啶的亲电碎片，共合成16个目标化合物（A1～A16），并经核磁共振波谱和质谱鉴定结构正确。体外活性研究表明，碎片为短链的酰基（A2～A4）和砜基取代基（A5）的化合物可获得JAK3抑制活性，当替换为大体积的基团如苯基酰基（A9～A12）或苯基砜基（A13、A14），化合物活性将下降或完全失去。其中，最优JAK3抑制剂A3（IC50 = 178.7 ± 23.6 nmol/L）还能选择性抑制JAK2（IC50 = 4.2 ± 0.6 µmol/L）而非JAK1（IC50 > 25 µmol/L），而且在10 µmol/L浓度下有效抑制小鼠脾脏淋巴细胞的增殖（54.9 %± 6.1%）。因此，A3可作为研发该系列骨架选择性JAK2&JAK3双重抑制剂的先导化合物，为自身免疫性疾病的安全治疗提供更多选择。
关键字： JAK2；JAK3；抑制剂；非亲电碎片；选择性
中图分类号：R914 文献标识码：A 文章编号：0258-3283(2025)--
DOI：10.13822/j.cnki.hxsj.2024.0467
Design and synthesis of selective JAK2&JAK3 dual inhibitors LING Zhen, ZHANG Jie, Huang Yan-qin, ZHANG Min, WEI Li-sha, LUO jia-yuan, HE Lin-hong* (Pharmaceutical College, Guangxi Medical University, Nanning 530021, China)
Abstract: To explore the design of selective JAK1&JAK3 or JAK2&JAK3 dual inhibitors, the electrophilic group on the highly potent and selective JAK3 inhibitor (R) 5- (benzo [d] [1,3] dioxolan-5-yl) -4- ((1- (vinylsulfonyl) piperidin-3-yl) oxy) -7H-pyrrolo [2,3-d] pyrimidine was replaced with different non-electrophilic fragments leading to the obtaining 16 targeted compounds（A1～A16）, whose structures were verified by nuclear magnetic resonance spectrum and mass spectrum. Results of in vitro assays revealed that compounds introduced with short chains including acyl (A2～A4) and sulfone (A5) substituents as the fragments could achieve enzymatic activity towards JAK3, while replaced with large volume groups such as phenylacyl (A9～A12) or phenysulfone (A13, A14), activity of the compounds could be decreased or totally lost. Among them, the optimal JAK3 inhibitor A3 (IC50 = 178.7 ± 23.6 nmol/L) not only selectively suppress JAK2 (IC50 = 4.2 ± 0.6 µmol/L) rather than JAK1 (IC50 > 25 µmol/L), but also effectively inhibit the proliferation of mice spleen lymphocytes (54.9%± 6.1%) at the concentration of 10 µmol/L. Therefore, A3 could be regarded as a potent lead compound to develop selective JAK2&JAK3 dual inhibitors bearing this scaffold, which maybe provide more safe options for the treatment of autoimmune diseases.
Key words: Janus kinase 2 (JAK2); JAK3; inhibitors; non-electrophilic fragments; selectivity
稳定同位素标记苯胺-D5的交换合成研究
李豹，王伟，雷雯*，许森，范若宁，解龙，喻静兰
（上海化工研究院有限公司，上海 200062）
摘要：氘元素作为稳定同位素中研究最多的核素之一，其标记的化合物广泛应用于创新药物、新型显示材料、临床诊断、含能材料表征等学科领域。稳定同位素标记苯胺-D5不仅可以作为核磁检测技术的溶剂，也可以作为稳定同位素氘标记试剂合成过程中的基础原料，在氘代材料、氘代药物分子的制备合成中的应用尤为广泛，目前，苯胺-D5的制备方法主要包括化学合成法和氢氘交换法（HIE），为解决环上氘标记苯胺-D5的工业级放大生产问题，设计了以氢氘交换法制备稳定同位素氘标记苯胺-D5的合成路线，考察了苯胺与重水在不同催化剂条件下的一次交换效果，并通过控制变量法和单因素优化的方法考察了催化剂用量、反应时间、反应温度、氘原子与氢原子的物质的量之比对苯胺氢氘交换反应的影响。结果表明，产物苯胺-D5的氘同位素丰度平衡最优工艺条件为：反应时间24 h，反应温度90 ℃，催化剂用量1∶1，氘原子与氢原子的物质的量之比为100∶1。最终经3次氢氘交换反应，产物苯胺-D5丰度≥98.2 atom%D，纯度99.1%，单次交换收率＞80%。
关键词：苯胺-D5；氘；氢氘交换；丰度；单因素
中图分类号：O60 文献标识码：A 文章编号：0258-3283（2025）
DOI：10.13822/j.cnki.hxsj.2024.0464
Investigation on Exchange Synthesis of Stable Isotope Labeled Aniline-D5 Li Bao, Wang Wei, Lei Wen*, Xu Sen, Fan Ruo-ning, Xie Long, Yu Jing-lan (Shanghai Research Institute of Chemical Industry, Shanghai 200062, China)
Abstract: Deuterium has received the most attentions among stable isotopes, and its labeled compounds have been widely applied in diverse fields including innovative drugs, new display materials, clinical diagnosis, characterization of energetic materials, etc.. Stable isotope-labeled aniline-D5 can not only be used as a solvent for nuclear magnetic detection technology, but also as a basic raw material in the synthesis of stable isotope deuterium-labeled reagents. Particularly, it is widely used in the preparation and synthesis of deuterated materials and deuterated drug molecules. Up to now, for aniline-D5 preparation, chemical synthesis and hydrogen-deuterium exchange (HIE) are the mainly used approaches. In order to solve the problem of industrial scale-up production of deuterium-labeled aniline-D5 on the ring, hydrogen-deuterium exchange method was designed for the preparation of stable isotope deuterium-labeled aniline-D5. In this investigation, the primary exchange effect of aniline and heavy water under different catalyst conditions was investigated. In the process, the effects of catalyst dosage, reaction time, reaction temperature, and the ratio of deuterium atoms to hydrogen atoms on the hydrogen-deuterium exchange reaction of aniline were meticulously studied, through the control variable method and the single-factor optimization method. The results suggested that the optimal process conditions for the deuterium isotope abundance balance of the product aniline-D5 was as following: reaction time of 24 h; reaction temperature of 90℃, the catalyst dosage of 1:1. And the ratio of deuterium atoms to hydrogen atoms was 100:1. Finally, after three hydrogen-deuterium exchange reactions, the product aniline-D5 has an abundance of ≥98.2 atom%D, a purity of 99.1%, and a single exchange yield greater than 80%.
Key words: aniline-D5; deuterium; hydrogen-deuterium exchange; abundance; single factor
双（叔丁胺基）硅烷合成方法的研究
刘成1,3，许振良*1,2，周晓兵3，程亮1,2
（1. 华东理工大学 化学工程联合国家重点实验室，化学工程研究所，膜科学与工程研发中心，上海 200237；2. 上海电子化学品创新研究院，上海 200237；3. 江苏南大光电材料股份有限公司，江苏 苏州 215126）
摘要：以价廉易得的叔丁胺（BTA）与硅烷（SiH4）为原料，在二丁基镁（DBM）催化下发生脱氢偶联反应合成了双（叔丁胺基）硅烷(BTBAS)，一步合成产率可达60%以上，精馏后产品纯度达98.72%。通过核磁共振氢谱（1HNMR）、气相色谱（GC）和气相色谱-质谱联用技术（GC-MS）对产物进行定性定量分析。讨论了脱氢偶联法合成BTBAS工艺中投料比、压力、反应温度和催化剂的影响，优化了工艺参数。实验结果表明，当投料时硅烷过量、m（催化剂）：m（叔丁胺）≈1:30、反应温度为15 ℃和反应压力为0.8~1.5 MPa时，可得到高产率、高纯度的BTBAS。
关键词：双（叔丁胺基）硅烷；叔丁胺；硅烷；脱氢偶联；合成
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2025）--
DOI：10.13822/j.cnki.hxsj.2024.0485
Study on Bis (tert-butylamine) Silane Synthetic Method LIU Cheng1,3, XU Zhen-liang*1,2, ZHOU Xiao-bing3, CHENG Liang1,2 （1. Membrane Science and Engineering R&D Center, Institute of Chemical Engineering, State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China; 2. Shanghai Innovation Institute of Electronic Chemicals, Shanghai 200237, China; 3. Jiangsu Nata Opto-electronic Material Co., Ltd., Suzhou 215126, China）
Abstract：Bis (tert-butylamine) silane (BTBAS) was synthesized by dehydrogenation coupling reaction from readily available materials including tert-butylamine (BTA) and silane (SiH4) under the catalysis of dibutyl magnesium (DBM). The one-step synthetic yield can reach over 60%, and the purity of BTBAS reached 98.72% after vacuum distillation. Qualitative and quantitative analysis of intermediate & final products was conducted by nuclear magnetic resonance hydrogen spectrum (1HNMR), gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS). The effects of the ratio of reaction raw materials, pressure & temperature of reactor and catalyst using were discussed while the process parameters were optimized after experiment. The experimental results showed that when the reaction conditions were as follows: feeding excessive silane, adding catalyst at about 1/30 (mass ratio) of BTA, the setting temperature of reactor at 15 ℃ and the pressure between 0.8 and 1.5 MPa, BTBAS with high yield and purity can be obtained.
Key words：bis (tert-butylamine) silane; tert-butylamine; silane; dehydrogenation coupling; synthesis
