【综述与专论】

Daphenylline的全合成研究进展

刘钊，何述钟^*

（贵州大学 药学院，贵州 贵阳  550000）

摘要：虎皮楠生物碱是一类重要的天然产物，具有多种药理活性。Daphenylline是该类生物碱家族中唯一拥有苯环结构的成员，具有6/6/6/5/7/5六环笼状骨架，6个手性中心。因其独特的结构，自分离报道以来，受到国内外有机合成化学家的密切关注。利用了6π电开环/芳构化、氧化去芳构化环化、Robinson环化/芳构化、Diels?Alder/芳构化、Cope 重排等反应，完成了daphenylline的全合成。基于近年来的合成研究，对daphenylline的合成路线和合成策略进行归纳总结，为今后此类生物碱分子的合成研究提供参考。

关键词：daphenylline; 虎皮楠生物碱; 串联环化反应; 氮杂[3.3.1]桥环; 全合成

中图分类号: O629.3              文献标识码: A                   文章编号: 0258-3283(2025)

DOI：10.13822/j.cnki.hxsj.2024.0462

Research Progress in Total Synthesis of Daphenylline LIU Zhao, HE Shu-zhong^* (School of Pharmaceutical Sciences, Guizhou University, Guiyang, 550000 China)

Abstract：Daphniphyllum alkaloids are an important class of natural products with a variety of pharmacological activities. Daphenylline is the only member with a benzene ring structure in the alkaloid family, possessing a 6/6/6/5/7/5 six-ring cage skeleton and six chiral centers. Daphenylline has attracted great attention owing to its unique chemical structure from chemist in organic synthesis both at home and abroad since its first isolation. They have implemented the total synthesis of the daphenylline by 6π electrocyclic ring opening/aromatization, oxidative dearomatization cyclization, Robinson cyclization/aromatization, Diels?Alder/aromatization, and Cope rearrangement. Based on the synthetic research in recent years, the synthetic route and strategy of daphenylline is summarized to provide a reference for the future synthesis of this type of alkaloid molecules.

Key words：daphenylline; daphniphyllum alkaloids; tandem cyclization reaction; aza[3.3.1] bridged ring; total synthesis

二氧化碳固体吸附剂材料改性研究进展

刘智勇^1,2，周枫然^1,2，张体强^1,2，王德发^*1,2，宋小平^*1

(1. 中国计量科学研究院，北京  100029； 2. 国家气体产品质量检验检测中心，北京  100029) 

摘要：碳捕集、利用与封存（Carbon capture, utilization and storage，CCUS）是实现“双碳”目标的有效途径，捕集二氧化碳并将其转化为更具经济价值的产品是当前研究热点。二氧化碳捕集的效率、成本对后续大规模工业化利用影响巨大，而二氧化碳捕集效率和成本主要受限于吸附材料的吸附性能。二氧化碳固体吸附技术高效简单、综合成本相对液体吸收技术较低，具有更大的应用潜能研究较为广泛，但还存在吸附剂吸附效率有待提升、吸附性能受环境温度湿度影响较大等问题。因此调研了近几年胺类固体吸附剂、金属有机框架固体吸附剂、碱金属固体吸附剂、沸石类吸附剂等新型吸附剂最新的改性研究现状并对其改性途径进行分类总结，为二氧化碳固体吸附剂相关工作提供参考，进而促进二氧化碳捕集技术的发展。

关键词：CCUS；二氧化碳捕集；固体吸附剂；吸附性能；改性

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.2024.0492

Research Progress on Modification of Solid Adsorbents for Carbon Dioxide LIU Zhi-yong^1,2, ZHOU Feng-ran^1,2, ZHANG Ti-qiang^1,2, WANG De-fa^*1,2, SONG Xiao-ping^*1(1. National Institute of Metrology, Beijing, 100029, China; 2. National Quality Inspection and Testing Center for Gas Products, Beijing 100029, China)

Abstract：Carbon Capture, Utilization and Storage (CCUS), which is an effective way to achieve the “dual carbon” goals, and capturing carbon dioxide and converting it into more economically valuable products, is one of the hot research topics currently. The efficiency and cost of carbon dioxide capture have a significant impact on the subsequent large-scale industrial utilization, and are mainly limited by the adsorption performance of the adsorbent materials. The solid adsorption technology of carbon dioxide is efficient, simple, and cost-effective compared to liquid absorption technology, with greater potential for application. However, there are still problems such as it still to improve the adsorption efficiency and environmental temperature and humidity have significant influence on adsorption performance. Therefore, the latest modification research status of new adsorbents such as amine solid adsorbents, metal organic framework solid adsorbents, alkali metal solid adsorbents and zeolite-based adsorbent was investigated, and their modification pathways were classified and summarized, in order to provide references for the related work of carbon dioxide solid adsorbents to promote the development of carbon dioxide capture technology.

Key words：CCUS; carbon dioxide capture; solid adsorbent; adsorption performance; modification 

低价硒代葡萄糖及其衍生物: 一种工业硒源与新试剂

肖欣蕊^1a，钱蓉蓉²，张旭^1b，曹洪恩^*1a，俞磊^*1b

（1. 扬州大学 a. 植物保护学院, b. 化学化工学院, 江苏 扬州  225002；2. 江苏旅游职业学院, 江苏 扬州  225127)

摘要：硒是生命必需的微量元素，硒缺乏会导致各种健康问题。然而，我国约70%面积的国土是缺硒地区，约有10亿以上居民需要补硒。发展富硒农业，是实现大规模补硒的有效途径。低价硒代葡萄糖是近年来刚刚发展起来的有机硒源，可用于生产叶面硒肥与富硒饲料添加剂。最近的研究表明，低价硒代葡萄糖及其衍生物，还具有一定的生物活性，有望应用于植物病虫害防治及医疗领域。此外，低价硒带葡萄糖合成工艺简便，成本低廉，可以作为一种-2价硒源用于制备含硒材料，有着很好的工业应用价值。

关键词：硒；葡萄糖；肥料；农药；医药

中图分类号：O69            文献标识码：A         文章编号：0258-3283（2025）--

DOI：10.13822/j.cnki.hxsj.2024.0453

Low-Valent-Selenium-Substituted Glucose and the Derivative: An Industrial Selenium Source and New Reagent XIAO Xin-rui^1a, QIAN Rong-rong², ZHANG Xu^1b, CAO Hong-en^*1a, YU Lei^*1b (1a.College of Plant Protection, 1b.School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, 225002; 2. Jiangsu Vocational College of Tourism, Yangzhou, 225127 )

Abstract：Selenium is an essential trace element for life. The deficiency of selenium may lead to various health problems. However, about 70% of China's territory is selenium-deficient area and over 1 billion residents need to supplement selenium. The development of selenium-rich agriculture is an effective strategy to achieve large-scale selenium supplementation. Low-valent selenium-substituted glucose is an organic selenium source that has been developed over recent years. It can be used to produce foliar selenium fertilizers and selenium-rich feed additives. Recent studies have shown that low-valent selenium-substituted glucose and its derivatives also have biological activities, which can be applied in disease/pest control and medical fields. In addition, the synthesis process of low-valent selenium-substituted glucose is simple and low-cost, and can be used as a -2 valent selenium source for the preparation of selenium-containing materials, which has promising industrial application.

Key words：selenium; glucose; fertilizer; pesticide; medicine

【生化与药用试剂】

cGAS蛋白的翻译后修饰及其在药物研发中的意义

杨琳¹，王京²，赵剑男³，陈明杰³，张磊^*1,2

(1.遵义医科大学 药学院，贵州 遵义  563006；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；3. 上海交通大学 药学院，上海  201240)

摘要：cGAS是细胞中重要的模式识别受体蛋白，可以识别胞质中的双链DNA，并通过cGAS-STING信号通路介导体内的一系列免疫反应。近年来，众多研究表明cGAS蛋白在病毒、细菌感染，自身免疫性疾病和细胞衰老等过程中发挥重要作用。翻译后修饰是体内调控蛋白质功能的主要过程，研究翻译后修饰对cGAS生物学功能的影响可以揭示cGAS在体内的调控机制，加深对cGAS-STING通路的了解。本文综述了cGAS蛋白翻译后修饰的研究进展及在药物研发中的重要意义。

关键词：cGAS；cGAS-STING信号通路；翻译后修饰；泛素化；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.2024.0447

Post-translational Modifications of cGAS Proteins and Their Significance in Drug Discovery and Development YANG Lin¹, WANG Jing², ZHAO Jian-nan³, CHEN Ming-jie³, 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; 3. School of Pharmacy, Shanghai Jiao Tong University, Shanghai 201240, China.)

Abstract：cGAS is an important pattern recognition receptor protein in cells that recognizes double-stranded DNA in the cytoplasm and mediates a series of immune responses in vivo through the cGAS-STING signaling pathway. In recent years, numerous studies have demonstrated that cGAS protein has played crucial roles in viral and bacterial infections, autoimmune diseases, and cellular aging. Post-translational modification is a major procedure that regulates protein function in vivo. Studying the effects of post-translational modification on the biological function can reveal the regulatory mechanism of cGAS in vivo and deepen the understanding of the cGAS-STING pathway. This research summarizes the progress on post-translational modification of cGAS proteins and their significance in drug discovery and development. 

Key words: GAS; cGAS-STING signaling pathway; post-translational modifications; ubiquitination; drug discovery

【分离提取技术】

响应面法优化新疆紫草萘醌类成分提取工艺及抑菌活性研究

章斌¹，梁林辉¹，梁大伟^*1，胡盛琳²

(1. 雅安职业技术学院 药学与检验学院，四川 雅安  625100；2. 雅安市人民医院 护理部，四川 雅安  625000)

摘要：采用单因素实验和响应面法优化新疆紫草萘醌类成分的超声辅助离子液体提取工艺，并研究其体外抑菌活性。结果表明，在以浓度为0.10 mol/L的1-己基-3-甲基咪唑四氟硼酸盐（[C₆mim]BF₄）无水乙醇溶液为提取溶剂、超声温度50 ℃、超声时间85 min、料液比1:82 g/mL的最佳条件下6种萘醌类成分提取总量为（18.08±0.21）mg/g。新疆紫草萘醌类成分对革兰阳性菌金黄色葡萄球菌的最小抑菌浓度（MIC）和最小杀菌浓度（MBC）分别为128和256 μg/mL，对革兰阴性菌大肠埃希菌分别为256和512 μg/mL。杀菌曲线实验分析显示，新疆紫草萘醌类成分的抗菌活性呈剂量-效应关系。

关键词：新疆紫草；离子液体；萘醌；响应面法；抑菌活性

中图分类号：R284.2              文献标识码：A              文章编号：0258-3283（2025）

DOI：10.13822/j.cnki.hxsj.2024.0446

Optimization in Extraction Process of Naphthoquinones from Arnebia euchroma and Their Antibacterial Activities  ZHANG Bin¹, LIANG Lin-hui¹, LIANG Da-wei^*1, HU Sheng-lin²  (1.School of Pharmacy and Medical Laboratory Science, Ya’an Polytechnic College, Ya’an 625100, China; 2. Department of Nursing, Ya’an People’s Hospital, Ya’an 625000, China) 

Abstract：The ultrasound-assisted ionic liquid extraction of naphthoquinones from Arnebia euchroma was optimized by single factor experiment and response surface methodology, and in vitro antibacterial activities were investigated. The results indicated that the total amount of six kinds of naphthoquinones was (18.08±0.21) mg/g under the optimal conditions of 1-hexyl-3-methylimidazolium tetrafluoroborate ([C₆mim]BF₄) ethanol solution as the extraction solvent with concentration of 0.10 mol/L, ultrasonic temperature of 50 °C, ultrasonic time of 85 min, and solid to liquid ratio of 1:82 g/mL. The antibacterial activity showed that the minimum inhibitory concentration (MIC) of the naphthoquinones against Staphylococcus aureus (Gram-positive bacteria) and Escherichia coli (Gram-negative bacteria) was 128 and 256 μg/mL, and the minimum bactericidal concentration (MBC) was 256 and 512 μg/mL, respectively. The analysis of the sterilization curve revealed a dose- dependent relationship in the antibacterial activity of the naphthoquinones.

Key words：Arnebia euchroma; ionic liquid; naphthoquinone; response surface methodology; antibacterial activity

澳洲檀香精油工艺提取及其成分分析的研究

涂永元

(1.国家燃香类产品质量监督检验中心（福建），福建 泉州  362600；2.福建省香产品质量检验中心，福建 泉州  362600；3.永春县产品质量检验所，福建 泉州  362600)

摘要：采用水蒸气蒸馏法、超临界CO₂提取法提取澳洲檀香精油，利用气相色谱-质谱结合解卷积和保留指数技术分析鉴定澳洲檀香精油成分，并用峰面积归一化法确定精油成分相对含量，同时结合其对DPPH自由基清除能力，比较不同精油之间的抗氧化活性区别。结果显示，与传统水蒸气蒸馏法相比，超临界法提取获得的澳洲檀香精油得油率更高、提取时间更短，其最优工艺提取条件为萃取压力25 MPa、萃取温度75 ℃、萃取时间4 h，得油率达到2.23%；从水蒸气蒸馏法、超临界提取法所得精油中共鉴定出33种化合物，其主要化学成分基本相同，并均含有较高含量的香榧醇、Z-α-檀香醇、反式，反式-金合欢醇、α-红没药醇、Z-β-檀香醇、澳白檀醇、反式-α-香柠檬醇、β-红没药醇等醇类成分；超临界法提取的精油清除DPPH自由基能力优于水蒸气蒸馏法提取的精油，并具备一定的抗氧化能力。研究结果可为澳洲檀香的高效提取及其精深加工利用提供了理论支持和技术参考。

关键词：澳洲檀香精油；超临界提取；气相色谱-质谱法；抗氧化；工艺优化；成分分析

中图分类号：O657.7              文献标识码：A              文章编号：0258-3283（2025）

DOI：10.13822/j.cnki.hxsj.2024.0471

Study on Technological Extraction and Composition Analysis of Australian Sandalwood Essential Oil TU Yong-yuan^1,2,3(1.National Quality Inspection and Testing Center for Incense Products(Fujian), Quanzhou 362600, China; 2. Yongchun Product Quality Inspection Institute, Quanzhou 362600, China; 3.Fujian Quality Inspection Center of Incense Products, Quanzhou 362600, China) 

Abstract：The essential oil of Australian sandalwood was extracted using hydrodistillation and supercritical CO₂ fluid extraction methods. The components of the Australian sandalwood essential oil were analyzed and identified by GC-MS combined with deconvolution and retention index techniques, and the relative contents of the oil components were determined by normalizing the peak areas. Additionally, the antioxidant activity differences between different oils were compared based on their DPPH radical scavenging abilities. The results showed that, compared to the traditional hydrodistillation method, the supercritical fluid extraction yielded a higher amount of Australian sandalwood essential oil in a shorter period. The optimal conditions for this process were as follows: extraction pressure at 25 MPa, extraction temperature at 75°C, and an extraction duration of 4 hours, resulting in an extraction rate of 2.23%. A total of 33 compounds were identified from the oils obtained through both hydrodistillation and supercritical extraction methods. The primary chemical components measured by these two extraction methods were essentially identical, containing high levels of alcohols such as nuciferol, Z-α-santalol, trans-farnesol, α-bisabolol, Z-β-santalol, cis-lanceol, Z-α-trans-Bergamotol, and β-bisabolol. The oil extracted via the supercritical method exhibited superior DPPH radical scavenging ability compared to that extracted by hydrodistillation and demonstrated notable antioxidant capacity. This study provides theoretical support and technical reference for the efficient extraction and deep processing of Australian sandalwood.

Key words：Australian sandalwood essential oil; supercritical extraction; GC-MS; antioxidation; process optimization; component analysis

【电化学和新能源】

碳纳米纤维在铝离子电池中的应用研究

杨文文^*1，刘建学²

(1. 北京工业职业技术学院 基础教育学院，北京  100042；2. 航天材料及工艺研究所，北京  100076)

摘要：碳纳米纤维作为一种三维碳纳米材料，可作为铝离子电池正极活性材料的载体形成柔性自支撑复合结构，兼具生长模板、导电基体以及缓冲支撑三重作用，以改善正极活性材料在储铝过程中存在的循环稳定性差、比容量不足以及倍率性能低下等问题。以聚丙烯腈为前驱体制备了氮掺杂碳纳米纤维，分别在700、800和900 ℃进行热处理。TEM、Raman和ICP-OES结果表明，高碳化温度会增加碳纳米纤维的石墨化程度提高其导电性，但能作为电化学活性位点的缺陷含量也会随之降低。结合EIS测试结果分析表明，900 ℃碳化的碳纳米纤维由于具有更高的石墨化程度而具有更小的电荷转移阻抗，而800℃碳化的碳纳米纤维由于具有更多的吡啶氮和吡咯氮等缺陷位点而具有更小的扩散阻抗。循环充放电结果显示，800℃碳化的碳纳米纤维在铝离子电池中表现出了最佳的储能性能，这是碳纳米纤维的微观结构、石墨化程度、缺陷浓度等因素共同作用的结果。这一研究成果为铝离子电池正极的设计提供了理论基础和设计依据。

关键词：碳纳米纤维；铝离子电池；氮掺杂，碳化温度；石墨化、缺陷位点

中图分类号：TM911.4              文献标识码：A              文章编号：0258-3283（2025）

DOI：10.13822/j.cnki.hxsj.2024.0479

Application Research of Carbon Nanofibers in Aluminum-ion Batteries Yang Wen-wen^*1, Liu Jian-xue²(1. School of Basic Education, Beijing Polytechnic College, Beijing 100042, China; 2. Aerospace Research Institute of Materials & Processing Technology, Beijing 100076, China)

Abstract： As a three-dimensional carbon nanomaterial, carbon nanofibers can act as substrates for the cathode active materials of Aluminum ion batteries to form free-standing composite structures, in which carbon nanofibers act as conductive substrate, growth template and buffer support, which can improve the aluminum storage performance including rate performance, cycle stability and specific capacity. Polyacrylonitrile was used as the precursor to prepare N-doped carbon nanofibers, which were thermal treated at 700, 800 and 900℃. TEM, Raman and ICP-OES results show that the graphitization of carbon nanofibers increases with the increase of carbonization temperature, while the defects that can act as electrochemical active sites decreases. EIS results indicate that the carbon nanofibers carbonized at 900 ℃ exhibits lower charge transfer impedance due to the graphitization, while the carbon nanofibers carbonized at 800 ℃ have lower diffusion impedance due to the defect sites such as pyridine nitrogen and pyrrole nitrogen. As a result of microstructure, graphitization degree and defect concentration, the carbon nanofibers carbonized at 800 ℃ exhibits the best energy storage performance in galvanostatic charge-discharge tests. The research results provide a theoretical basis and design basis for the design of the cathode materials of aluminum ion batteries.

Key words：carbon nanofibers; aluminum ion batteries; nitrogen doping, carbonization temperature, graphitization, defect sites

【化学品与环境】

宁夏引黄灌区水稻种植区土壤重金属污染特征及风险评价

李谦，王泽岚^*，孙少忆，张学玲，杨建兴

（宁夏回族自治区食品检测研究院 国家市场监督管理总局重点实验室（枸杞及葡萄酒质量安全），宁夏 银川  750000）

摘要：采用单因子污染指数法、内梅罗综合污染指数法、污染物分担率对宁夏引黄灌区水稻种植区土壤重金属Pb、Cd、Cr、As和Hg的污染状况及人体健康风险进行分析评价。Pb、Cd、Cr、As和Hg的含量分别高于宁夏土壤背景值1.20、1.16、1.30、1.12、1.38倍，表明存在不同程度的累积富集效应，均远低于农用地土壤污染风险筛选值与管制值，无一例超标样品点。单因子污染指数评价结果显示采样点位单因子污染指数P_i均小于1.0，等级为一级，均未超标。内梅罗综合污染指数评价结果表明污染程度最高为平罗，最低为青铜峡。宁夏引黄灌区水稻重金属污染物主要为砷，与我国土壤相关标准相比，宁夏引黄灌区土壤5种重金属含量处于较低水平。健康风险评价结果表明，As与Cd为主要的非致癌因子与致癌因子，对人体健康具有一定的负面影响，需引起关注，进行严格管控。

关键词：宁夏引黄灌区；水稻土壤污染；重金属；污染特征；风险评价

中图分类号：X5              文献标识码：A              文章编号：0258-3283（2025）

DOI：10.13822/j.cnki.hxsj.2024.0450

Characteristics and Risk Assessment of Heavy Metal Pollution in Paddy Soil in Ningxia Yellow River Irrigation Area LI Qian, WANG Ze-lan^*，SUN Shao-yi, ZHANG Xue-ling, YANG Jian-xing (Key Laboratory of Quality State Administration for Market Regulation(Safety of Chinese wolfberry and wine), Ningxia Hui Autonomous Region Food Inspection and Research Institute, Yinchuan 750000, China)

Abstract：The pollution status and health risk of heavy metals (such as Pb, Cd, Cr, As and Hg) in the soil of rice planting area at Ningxia Yellow River Diversion Irrigation Area were analyzed by single factor pollution index, Nemero comprehensive pollution index and pollutant sharing rate. The average content of Pb, Cd, Cr, As and Hg were respectively 1.20, 1.16, 1.30, 1.12 and 1.38 times higher than the background values of Ningxia soil, indicating an accumulation and enrichment with different degrees. However, the content of heavy metals were far below the screening and control value for pollution risk of agricultural soil, and no sample point exceeded the standard. The evaluation showed that the single-factor pollution index P_i at the sampling point was lower than 1.0, which was classified as Grade I (not beyond the standard). The most and least polluted region was respectively Pingluo and Qingtongxia by the evaluation of Nemero comprehensive pollution index. Arsenic (As) was the main heavy metal pollutant in Ningxia Yellow River irrigation area. Compared with the relevant soil standards in China, the contents of the five heavy metals in soil of Ningxia Yellow River Irrigation Area were at a lower level. The assessment of health risk showed that arsenic and cadmium were the main non-carcinogenic and carcinogenic factors, which had a negative impact on human health and needed more attention and strict control.

Key words: Ningxia Yellow river diversion irrigation Area; rice soil pollution; heavy metal; pollution characteristics; risk evaluation

基于羊肝胆碱酯酶抑制检测有机磷农药的潜力

刘昊¹，李珏^1,2，王仕红¹，玛依拉·阿不力木克¹，袁浩然²，何庆峰^*1,2

（1.和田职业技术学院 农业科技系，新疆 和田  848000；2.天津农学院 食品科学与生物工程学院，天津  300392）

摘要：酶抑制法是有机磷农药残留检测常用的方法之一，检测用酶的研发将会促进该法的应用。通过硫酸铵盐析、sephadex G-200凝胶过滤层析、依酚氯铵-琼脂糖4B亲和层析纯化等步骤，分离纯化了一种羊肝胆碱酯酶(Sheep liver cholinesterase, sChE)。纯化的sChE酶活为0.25 U，酶比活力约为1.59 U/mg，蛋白回收率为0.08%，酶活回收率为5.00%，纯化倍数约为61倍。SDS-PAGE鉴定其分子质量为63.67 kDa。该酶对3种底物碘化乙酰硫代胆碱（acetylthiocholine iodide，ATChI）、碘化丁酰硫代胆碱、碘化丙酰硫代胆碱酶促反应动力学模型均符合典型Michalis-Menten方程，米氏常数（K_m）分别为0.27、0.79、0.88 mmol/L ，最适底物为ATChI。该酶最适温度为40℃，最适pH为8.0。在较低温度（低于45℃），近似弱碱性（pH 7.0～8.0）条件下酶储存稳定性较好。在0.1～10 mg/L范围，金属离子（Ca²⁺、Zn²⁺、Mn²⁺、Cd²⁺）对该酶活力有剂量依赖性的抑制作用，而低浓度（0.1～1 mg/L）Mg²⁺ 可促进酶活。4种有机磷农药（辛硫磷、敌百虫、敌敌畏、乐果）对sChE的抑制反应的半数抑制浓度（IC₅₀）分别为5.47×10^-5、1.35×10^-5 、2.16×10^-6和3.13×10^-5 mol/L，与商业电鳗乙酰胆碱酯酶的敏感性接近。为 sChE作为酶源的酶抑制-比色法，检测有机磷农药提供了理论依据。

关键词：酶抑制；胆碱酯酶；有机磷农药；农药检测；比色法

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.2024.0392

Potential of Organophosphorus Pesticides Detection Based on Sheep Liver Cholinesterase Inhibition LIU Hao¹，LI Jue^1,2，WANG Shi-hong¹，Mayila·Abulikemu¹，YUAN Hao-ran²，HE Qing-feng^*1,2（1.Department of Agricultural Science and Technology, Hetian Polytechnic, Hetian 848000, China;2.College of Food Science and Bioengineering, Tianjin Agriculture University, Tianjin 300392, China）

Abstract: The enzyme inhibition colorimetry is one of commonly used methods for the detection of organophosphorus pesticides (OPs) residues. The research and development of enzymes would further promote their application. This research aimed to detect OPs by enzyme inhibition colorimetry using sheep liver cholinesterase (sChE) as an enzyme source. Firstly, sChE was isolated and purified from sheep liver by salting out effect of ammonium sulfate, filtration chromatography by Sephadex G-200 gel, and affinity chromatography by edrophonium chloride-agarose 4B . The purified sChE was obtained with enzyme activity of 0.25 U, specific activity of 1.59 U/mg, protein recovery of 0.08%, enzyme activity recovery of 5.00%, and the purification fold of about 61 times. The molecular weight of purified enzyme was 63.67 kDa by SDS-PAGE. The enzyme catalyzed the enzymatic reaction of three kinds of choline substrates (including acetylthiocholine iodide, butyrylthiocholine iodide, and propionyl thiocholine iodide) in the manner of the typical Michalis Menten equation, with K_m values of 0.27, 0.79, and 0.88 mmol/L , respectively. The optimal substrate was acetylthiocholine iodide. The most suitable temperature of the enzyme was  40℃ with a most suitable pH of 8.0. The enzyme had good stability in weak alkaline environments (pH of 7.0～8.0) below 45℃. In the range of 0.1～10 mg/L, metal ions (Ca²⁺, Zn²⁺, Mn2⁺, and Cd²⁺) have a dose-dependent inhibitory effect on enzyme activity; while enzyme activity can be promoted at low concentrations (0.1～1 mg/L) of Mg²⁺. The IC₅₀ values of four kinds of organophosphorus pesticides (such as phoxim, dichlorvos, dichlorvos, and dimethoate) for inhibiting sChE were 5.47 × 10^-5 mol/L, 1.35 × 10^-5 mol/L, 2.16 × 10^-6 mol/L, and 3.13 × 10^-5 mol/L, respectively, which were similar to those of commercial electric eel acetylcholinesterase. This study would provide a theoretical basis for sChE as an alternative enzyme source for detecting OPs by enzyme inhibition colorimetry.

Key words: enzyme inhibition；cholinesterase；organophosphorus pesticides；pesticide detection；colorimetric method

【分析与测试】

基于水解氨基酸-同位素稀释质谱法的酪蛋白磷酸肽特征肽段纯度定值研究

徐琪，李玲，杨梦瑞^*，周剑，李付凯，李亮

（中国农业科学院农业质量标准与检测技术研究所 农业农村部农产品质量安全重点实验室，北京  100081）

摘要：针对酪蛋白磷酸肽特征肽段YKVPQLEIVPNpSAEER，建立了基于水解氨基酸-同位素稀释质谱法（AA⁃LC-IDMS/MS）的纯度定值方法。重点表征了特征肽段原料分子量、氨基酸序列等结构信息，优化了肽段氨基酸水解条件，讨论了空间位阻对水解效率的影响。选取脯氨酸、缬氨酸、亮氨酸以及异亮氨酸这4种氨基酸，运用建立的 AA⁃LC-IDMS/MS 方法，对酪蛋白磷酸肽特征肽段原料展开纯度定值。结果表明，基于4种不同氨基酸的肽段定值结果一致性良好，定值准确可靠，最终肽段的定值结果为（0.916±0.016）g/g。该方法的建立，为下一步特征肽段标准物质研制及酪蛋白磷酸肽的准确测量奠定了基础。

关键词：酪蛋白磷酸肽；特征肽段；水解氨基酸同位素稀释质谱法；纯度；定值

中图分类号: O657.63              文献标识码: A                   文章编号: 0258-3283(2025)

DOI：10.13822/j.cnki.hxsj.2024.0427

Purity Measurement of Specific Peptide Segment of Casein Phosphopeptides Using Amino Acid-Based Isotope Dilution Mass Spectrometry Xu Qi, Li Ling, Yang Meng-rui ^*, Zhou Jian, Li Fu-kai, Li Liang(Key Laboratory of Agro-food Safety and Quality, Ministry of Agriculture and Rural Affairs, Institute of Quality Standard and Testing Technology for Agro-Products, Chinese Academy of Agricultural Sciences, Beijing 100081, China)

Abstract：A determination method of purity based on hydrolysed amino acid-isotope dilution mass spectrometry (AA⁃LC-IDMS/MS) was established for the casein phosphopeptide with specific peptide segment of YKVPQLEIVPNpSAEER. The structural information, such as molecular weight and amino acid sequence of the specific peptide segment of raw materials was focused. The hydrolysis conditions of peptide segment amino acids were further optimized, and the influence of spatial resistance on the hydrolysis efficiency was also discussed. Four kinds of amino acids, including proline, valine, leucine, and isoleucine, were selected to determine the purity of the casein phosphopeptide with specific peptide segment by the established AA-LC-IDMS/MS. The results showed that the accurate and reliable determinations of peptide segment based on four different amino acids were obtained with a good consistency, and the value was ultimately assigned to be (0.916 ± 0.016) g/g. The determination method would lay a foundation for the preparation of certified reference of the specific peptide segment and the accurate measurement of casein phosphopeptides.

Key words：casein phosphopeptides; specific peptide segment; hydrolyzed amino acid isotope dilution mass spectrometry; purity; characterization

高效液相色谱法同时测定葵花盘粉提取物中的东莨菪素、芦丁、槲皮素和木樨草素

巩润梓¹，吴大刚²，邢小霞¹，李平亮^*1

（1.青岛农业大学 植物医学学院，山东 青岛  266109；2.山东牧香生物科技有限公司,山东 青岛  266199）

摘要：选择东莨菪素、芦丁、槲皮素和木樨草素作为葵花盘粉提取物抗痛风活性成分的代表，通过优化QuEChERS前处理方法的提取液、净化剂组成，以及色谱流动相组成、梯度洗脱程序、检测定量波长，建立了同时测定葵花盘粉提取物样品中4种成分的高效液相色谱分析方法。4种化合物的定量限和检出限范围分别为0.08~0.15 mg/L和0.02~0.06 mg/L，添加回收率范围为87%~97%，相对标准偏差范围1.1%~5.2%。采用该方法检测了3种葵花盘粉样品，结果表明东莨菪素、芦丁、槲皮素和木樨草素的含量范围分别为68.75~179.41、48.52~232.35、20.45~32.47和0.34~1.10 mg/kg。本研究为葵花盘粉相关产品的活性成分检测与质量控制提供了方法学参考。

关键词：葵花盘粉；高效液相色谱；东莨菪素；芦丁；槲皮素；木樨草素

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.2024.0463

Determination of Scopoletin, Rutin, Quercetin and Luteolin in Sunflower Calathide Powder Extractions by Using HPLC GONG Run-zi¹, WU Da-gang², XING Xiao-xia¹, LI Ping-liang^*1 (1. College of Plant Health and Medicine, Qingdao Agricultural University, Qingdao 266109, China; 2. Shandong Muxiang Biotechnology Co., Ltd, Qingdao 266199, China) 

Abstract: In this study, scopoletin, rutin, quercetin and luteolin were selected as the representatives of the active ingredients of sunflower calathide powder extraction against hyperuricemia. A method based on high-performance liquid chromatography (HPLC) for simultaneous determination of four compounds in sunflower calathide was developed by optimizing the extraction solution by QuEChERS method, constituent of purification agents and mobile phases, procedure of gradient elution, and detection wavelength. The limit of detection and limit of quantification were in the range of 0.08-0.15 mg/L and 0.02-0.06 mg/L, respectively. The recovery of four compounds from real samples was in the range of 87%-97% with relative standard deviation (RSD) of 1.1%~5.2%. Then this method was applied to detect four compounds in products of three sunflower calathide powder. The results showed that the concentrations of scopoletin, rutin, quercetin and luteolin were in the range of 68.75~179.41, 48.52~232.35, 20.45~32.47 and 0.34~1.10 mg/kg. This research would provide a methodology for quality control of active components in sunflower calathide-based products.

Key words: sunflower calathide powder; high-performance liquid chromatography (HPLC); scopoletin; rutin; quercetin; luteolin

顶空-气相色谱-质谱法对参鹿补片中32种残留溶剂的筛查测定

张若良¹，汪元亮²，许江红¹，朱良辉^*2，肖小武^*2

（1. 赣州市综合检验检测院，江西 赣州  341001；2. 江西省药品检验检测研究院 a. 江西省药品与医疗器械质量工程技术研究中心，b. 国家药品监督管理局中成药质量评价重点实验室，江西 南昌  330029)

摘要:建立了同时测定参鹿补片及对应原辅料包中的32种残留溶剂的筛查测定方法，确定了残留溶剂的主要来源。采用顶空-气相色谱-质谱法（HS-GC-MS）法，以Agilent HP-INNOWAX(60 m×0.32 mm×0.25 μm)为色谱柱进行分离，采用选择离子监测模式(SIM)进行质谱检测，外标法定量。方法学结果表明，32种残留溶剂分离良好，在相应的质量浓度范围内线性良好(R²≥0.9973)；精密度、重复性、稳定性的相对标准偏差（RSDs）均不高于3.9%，加标回收率为89.9%～115.2%，RSDs(n=9)均不高于5.3%。从参鹿补片中共筛查检测出18种溶剂，通过与对应的原辅包进行对比，确定主要来源为原药材。该方法精密度、重复性、稳定性好，准确可靠，可为参鹿补片及同类药品的实现从原料药材延伸至药包材直至成品全链条的质量把控和安全风险评估提供参考。

关键词: 参鹿补片；残留溶剂；顶空-气相色谱-质谱(HS-GC-MS)

中图分类号：R284.1      文献标识码：A               文章编号：0258-3283（2025）--

DOI：10.13822/j.cnki.hxsj.2024.0391

Screening Test of 32 Residual Solvents in Shenlubu Tablets by HS-GC-MS ZHANG Ruo-liang¹,WANG Yuan-liang²,XU Jiang-hong¹,ZHU Liang-hui^*2 ,XIAO Xiao-wu^*2 (1.Ganzhou General Inspection and Testing Institute,Ganzhou 341001，China；2a. NMPA Key Laboratory for Quality Evaluation of Traditional Chinese Medicine, 2b.Jiangxi Provincial Engineering Research Center for Drug and Medical Device QualityJiangxi Institute For Drug Control, Nanchan 330029，China)

Abstract: A method for the simultaneous determination of 32 residual solvents in Shenlu Tablets and corresponding raw materials was established. The main source of residual solvents was also determined. The separation was performed by HS-GC-MS with Agilent HP-INNOWAX (60 m×0.32 mm×0.25 μm) as the chromatographic column. And the ion monitoring mode (SIM) was used for mass spectrometry and quantitative determination by an external standard method. The methodological results showed that 32 residual solvents were successfully separated with a good linearity (R²≥0.9986) in a range of the corresponding mass concentration. Relative standard deviations (RSD_S)of precision, repeatability and stability were not higher than 3.9%, and the recoveries were 89.5%~112.72% with RSD_S (n=9) of lower than 5.3%. Eighteen solvents which mainly existed in the raw medicinal materials were detected from Shenlu Tablets by the comparison between Shenlu Tablets and raw medicinal materials. The simple, stable, and reliable method would provide a quality control and assessment of security risk, especially for the entire circulation of Shenlu Tablets and similar medicine..

Key words:Shenlubu Tablets ;Residual solvents;Head space-gas chromatography-mass spectrometry(HS- GC-MS)

【合成与应用】

7-羧酸类蛇床子素衍生物的合成及其抑制AKR1C3活性研究

李启鑫^1,2，李丽明¹，郑雪花²，姚梓青²，许志森²，孙明娜^*1,2

（1. 广州医科大学附属中医医院，广东 广州  510000；

2. 广州医科大学药学院 a.广东省分子靶标与临床药理学重点实验室, b.呼吸疾病国家重点实验室，广东 广州  511436） 

摘要：合成7-羧酸类蛇床子素衍生物，评价该类化合物对醛酮还原酶1C3（AKR1C3）催化活性的影响。蛇床子素在三溴化硼的催化下脱除甲基，生成7-羟基-8-溴代烷基香豆素中间体1。在碳酸铯的碱性条件下，中间体1的7-位羟基与不同的溴代酸酯发生Williamson醚化反应，同时，8-位溴代烷基在该碱性条件下发生消除溴化氢的反应，生成7-位酯类蛇床子素衍生物。随后，酯类衍生物在氢氧化锂的作用下水解，进而酸化后得到7-位含有羧基的蛇床子素衍生物；利用HR-MS，¹HNMR及¹³CNMR确证化合物的结构；通过中通量抑酶活性测试方法评价所合成化合物对AKR1C3催化活性的影响，并计算其IC₅₀值。以蛇床子素为起始原料，经脱甲基、取代、水解反应合成了7-羧酸类蛇床子素衍生物8个，其中，7-（8-（3-甲基丁-2-烯-1-基）-7-羟基-2H-苯并吡喃-2-酮氧基）庚酸显示出良好的AKR1C3抑制活性，可为后续研究提供一定的依据。

关键词：蛇床子素；醛酮还原酶1C3；羧酸；合成；衍生物；香豆素

中图分类号：R91              文献标识码：A              文章编号：0258-3283（2025）--

DOI：10.13822/j.cnki.hxsj.2024.0483

Synthesis and AKR1C3 Inhibitory Activity of 7-Carboxylic Acid Osthole Derivatives LI Qi-xin^1,2, LI Li-ming¹, ZHENG Xue-hua², YAO Zi-qing², XU Zhi-sen², SUN Ming-na^*1,2 (1. The Affiliated TCM Hospital of Guangzhou Medical University, Guangzhou 510000, China; 2a. Key Laboratory of Molecular Target & Clinical Pharmacology, 2b. the State Key Laboratory of Respiratory Disease, School of Pharmaceutical Sciences, Guangzhou Medical University, Guangzhou 511436, China) 

Abstract：7-carboxylic acid derivatives of osthole were synthesized and their inhibitory effect on the catalytic activity of aldo-keto reductase 1C3 (AKR1C3) was evaluated. The demethylation of osthole was catalyzed by boron tribromide to produce the 7-hydroxyl-8-bromoalkylcoumarin intermediate 1. Then, under a basic condition in the presence of cesium carbonate, the 7-hydroxyl group of intermediate 1 reacted with various bromo acid esters via the Williamson etherification, while the 8-bromoalkyl group underwent elimination of hydrogen bromide, finally yielding 7-ester derivatives of osthole. These ester derivatives were subsequently hydrolyzed in the presence of lithium hydroxide, followed by acidification to obtain osthole derivatives containing a carboxyl group at the 7-position. The chemical structures of target compounds were confirmed by HR-MS, ¹HNMR and ¹³CNMR. The effects of the compounds on the catalytic activity of AKR1C3 were evaluated using the medium flux enzyme activity inhibition tests, and the IC₅₀ values were calculated. Eight of 7-carboxylic acid derivatives of osthole were synthesized through demethylation, substitution, and hydrolysis, using osthole as the starting material. Among them, 7-((8-(3-methylbut-2-en-1-yl)-2-oxo-2H-chromen-7-yl)oxy)heptanoic acid exhibited good inhibitory activity against AKR1C3, which could provide some basis for subsequent research.

Key words：osthole; aldo-keto reductase 1C3; carboxylic acid; synthesis; derivative; coumarin

4-苯氧基喹啉衍生物的合成及抗肿瘤活性

李雯，陈佳妍，顾珍珍，汪海峰，刘丹^*

（沈阳化工大学 化学工程学院，辽宁 沈阳  110142）

摘要：以7-氟-4-氯喹啉、7-甲氧基-4-氯喹啉为原料，分别与不同的取代苯酚通过亲核取代反应得到12个4-苯氧基喹啉衍生物（3a~3l）。目标化合物的结构经ESI-MS及¹HNMR确证。利用MTT法，采用人非小细胞肺癌A549细胞和人肝癌HepG2细胞对目标化合物进行体外抑制肿瘤细胞增殖活性研究。结果显示，大部分化合物展现出和阳性对照物相当或更好的抑制能力。其中7-氟-4-（3,4-二甲基苯氧基）喹啉（3d, IC₅₀=38.82 μmol/L）和7-甲氧基-4-（4-溴-2-甲氧基苯氧基）喹啉（3f, IC₅₀=25.40 μmol/L）对HepG2细胞表现出显著的抑制活性，7-甲氧基-4-（4-溴-3-甲基苯氧基）喹啉（3g, IC₅₀=24.81 μmol/L）对A549细胞表现出显著的抑制活性，均优于阳性对照物吉非替尼和乐伐替尼。通过虚拟筛选预测出目标化合物治疗肝癌的7个潜在靶点，并将3f与预测出的EGFR蛋白进行对接，对接结果表明3f和EGFR可以通过氢键和疏水等作用结合。该研究为酪氨酸激酶抑制剂的开发奠定了基础。
关键词：喹啉衍生物；苯酚；抗肿瘤活性；分子对接；酪氨酸激酶抑制剂
中图分类号：O626  文献标识码：A     文章编号：0258-3283（2025）03--06

DOI：10.13822/j.cnki.hxsj.2024.0441

Synthesis and Antitumor Activity of 4- Phenoxy Quinoline Derivatives LI Wen, CHEN Jia-yan, GU Zhen-zhen, WANG Hai-feng, LIU Dan^* (College of Chemical Engineering, Shenyang University of Chemical Technology, Shenyang, Liaoning, 110142）

Abstract: Twelve of 4- phenoxyquinoline derivatives (3a~3l) were synthesized by nucleophilic substitution of 7-fluoro-4-chloroquinoline and 7-methoxy-4-chloroquinoline with different substituted phenols. The chemical structure of the target compound was confirmed by ESI-MS and ¹H-NMR. By MTT assay, the in vitro inhibitory activity of the compound on tumor cell (human non-small cell lung cancer A549 cells and human hepatocellular carcinoma HepG2 cells) proliferation was studied by MTT assay. Most of the compounds showed the comparable or even better inhibitory ability with the positive control. Among them, 7-fluoro-4-(3,4-dimethylphenoxy)quinoline (3d, IC₅₀ = 38.82 μmol/L) and 7-methoxy-4-(4-bromo-2-methoxyphenoxy)quinoline (3f, IC₅₀ = 25.40 μmol/L) showed significant inhibitory activity against HepG2 cells, and 7-methoxy-4-(4-bromo-3-methylphenoxy)quinoline (3g, IC₅₀ = 24.81 μmol/L) showed significant inhibitory activity against A549 cells, all of which were superior to the positive control drugs Gefitinib and Lenvatinib. Seven potential targets for the treatment of liver cancer with target compounds were predicted through virtual screening, and 3f was docked with the predicted EGFR protein. The docking results showed that 3f and EGFR can bind through hydrogen bonding and hydrophobic interactions. This study would lay the foundation of the exploitation of tyrosine kinase inhibitors.

Key words: quinoline derivatives; phenol; antitumor activity; molecular dockng; tyrosine kinase inhibitors