【综述与专论】
基于PROTACs技术的表观遗传抗肿瘤药物研究进展
吕倩倩，梁嘉杰，季红*
(广州医科大学 药学院，广东 广州 511436)
摘要：蛋白水解靶向嵌合体（Proteolysis Targeting Chimeras，PROTACs）是异型双功能分子，可通过天然泛素蛋白酶体系统选择性地降解目标蛋白质。这种化学诱导蛋白质降解的新策略为药物发现提供了新的可能性，因此已被应用于各种靶标，包括（核）受体，激酶和转录因子等。表观遗传蛋白在肿瘤的发生、发展、转移和侵袭中发挥着重要作用，被认为是抗肿瘤药物研发的重要靶点。由于其小分子抑制剂易产生脱靶效应和耐药性，而PROTACs技术为解决这些问题提供了一种全新的策略，在表观遗传抗肿瘤药物研发中具有重要意义。介绍了PROTACs的原理及优势，系统综述了采用该技术靶向降解表观遗传蛋白的最新研究进展，并展望了基于PROTACs技术的表观遗传靶向抗肿瘤药物的发展前景。
关键词：蛋白水解靶向嵌合体；表观遗传；抗肿瘤药物；研究进展
中图分类号：R914 文献标识码：A 文章编号：0258-3283（2024）05-0001-09
DOI：10.13822/j.cnki.hxsj.2023.0790
Recent Advances in Epigenetic Antitumor Drugs Based on Proteolysis Targeting Chimeras LV qian-qian, LIANG jia-jie, JI Hong* (School of Pharmaceutical Sciences, Guangzhou Medical University, Guangzhou, 511436, China)
Abstract：Proteolysis Targeting Chimeras (PROTACs) are heteromorphic bifunctional molecules designed to selectively degrade target proteins through the natural ubiquitin-proteasome system. This novel strategy of chemically induced protein degradation has offered exciting avenues for drug discovery, with applications across various targets, including nuclear receptors, kinases, and transcription factors. Epigenetic proteins play an important role in tumor initiation, progression, metastasis, and invasion, making them promisingtargets for the development of anti-tumor drugs. Given that conventional small molecule inhibitors directed at epigenetic targets may lead to off-target effects and drug resistance, PROTACs technology provides a promising solution to these challenges. Therefore, it holds significant promise for advancing the field of epigenetic anti-tumor therapy. Herein, This discussion will delve into the principles and advantages of PROTACs, providing comprehensive overview of the recent research progress of epigenetic protein degradation using PROTACs technology, and offer insights into the future prospects of epigenetic targeted anti-tumor drugs based on PROTACs technology.
Keyword：proteolysis targeting chimeras; epigenetics; antitumor drugs; research progress
引用本文：吕倩倩，梁嘉杰，季红. 基于PROTACs技术的表观遗传抗肿瘤药物研究进展[J].化学试剂，2024,46（5）：1-9.
靶向细胞器的过氧亚硝酸盐荧光探针研究进展
潘淑芬，马晓，蓝庆春，吴勇权*
（赣南师范大学 化学化工学院,江西 赣州 341000）
摘要：过氧亚硝酸盐(ONOO−)作为氧代谢的重要产物，在免疫应答、细胞信号转导等许多生理活动中起着重要作用。然而，ONOO−的水平异常会损伤细胞生物分子，与许多疾病密切相关。因此，迫切需要监测活细胞中ONOO−的含量变化，而ONOO−的功能很大程度上依赖于亚细胞区，所以开发亚细胞的ONOO−水平变化的监测手段更有研究价值。为此，多种具有靶向细胞器的ONOO−荧光探针被设计、开发和应用。重点介绍了近6年来具有线粒体、溶酶体和内质网靶向能力的ONOO−荧光探针的代表性例子。综述了这些荧光探针的细胞器靶向策略、结构、荧光行为和生物学应用。
关键词：过氧亚硝酸盐；亚细胞水平；荧光探针；荧光检测；荧光成像
中图分类号： O65 文献标识码：A 文章编号：0258-3283（2024）05-0010-10
DOI：10.13822/j.cnki.hxsj.2023.0749
Research Progress on Fluorescent Probes of Peroxynitrite for Targeting Organelles PAN Shu-fen, MA Xiao, LAN Qing-chun, WU Yong-quan * (College of Chemistry and Chemical Engineering, Gannan Normal University, Ganzhou 341000)
Abstract：As an essential product of oxygen metabolism, peroxynitrite (ONOO−) plays an important role in various biological processes, including immune response and cell signal transduction. However, excessive ONOO− production can lead to cellular biomolecule damage and is closely associated with numerous diseases. Therefore, there is an urgent need to monitor the level changes of ONOO− in living cells. Given that the function of ONOO− largely depends on subcellular compartments, it is particularly significant to develop probes capable of monitoring subcellular ONOO− levels. To this end, a variety of ONOO− fluorescent probes, specifically targeting organelles, have been designed, developed, and successfully employed. In this review, we highlight representative cases of ONOO− fluorescent probes with targeted capabilities for mitochondrial, lysosome, and endoplasmic reticulum (ER) from the last six years. The organelle-targeting strategy, structure, fluorescence behavior, and biological application of these probes are reviewed as well.
Key Words: peroxynitrite; subcellular level; fluorescence probes; fluorescence detection; fluorescence imaging
引用本文：潘淑芬，马晓，蓝庆春，等.靶向细胞器的过氧亚硝酸盐荧光探针研究进展[J].化学试剂，2024,45（5）：10-19..
悬浮液显现技术应用于潜手印的研究进展
李泽莹，姚坤满*，武晓琳，张鸿雁
(广东警官学院 警务实验实训中心，广州 510440)
摘要：潜手印显现技术对案件侦破和司法鉴定起着重要的作用。根据客体表面的潜手印特点，需使用不同的显现技术，如悬浮液显现技术主要用于陈旧、潮湿或粘性的客体表面，而基于新兴纳米颗粒的悬浮液显现技术还因具备优异的灵敏度、信噪比、选择性等显现性能，日益受到重视。简要介绍了目前普遍使用的传统小颗粒悬浮液显现技术，较为详细地综述了近十几年来新兴纳米颗粒 (如量子点、碳纳米点、稀土发光材料、纳米氧化物等)在手印显现的应用进展，并概述了悬浮液显现技术的操作方法，最后分析了该技术目前所面临的挑战和未来发展方向，为其在法庭科学、公安教育等领域的应用提供参考。
关键词：悬浮液；潜手印显现；纳米颗粒；浸显法；滴显法；喷显法
中图分类号：DF794.1 文献标识码：A 文章编号：0258-3283（2024）05-0020-10
DOI：10.13822/j.cnki.hxsj.2023.0792
Research Progress on Latent Fingerprint Development Based on Suspension Method LI Ze-ying, YAO Kun-man*, WU Xiao-lin, ZHANG Hong-yan (Police Experimental Training Center, Guangdong Police College, Guangzhou 510440, China)
Abstract：Latent fingerprint development plays a crucial role in case detection and forensic identification. Different techniques should be utilized based on the characteristic of latent fingerprints on object surfaces. Suspension-based developing technology is primarily suitable for old, wet or sticky surfaces. However, the emerging nanoparticle suspension is gain increasing attention due to its excellent sensitivity, signal-to-noise ratio, selectivity, and other properties. This review systematically examines the application of both traditional small particle suspension widely used in latent fingerprint development and the new nanoparticle suspension, including quantum dots, carbon nanodots, rare-earth luminescence, and nano-oxides over the past decade. Additionally, the operating methods of suspension-based developing technology are summarized. Lastly, the existing challenges and future development direction of the techniques in latent fingerprint detection are analyzed, providing a valuable reference for the fields of forensic science and police education.
Key words：suspension; latent fingerprint development; nanoparticles; immersion; dropping; spray
引用本文：李泽莹，姚坤满，武晓琳. 颗粒悬浮液显现技术应用于潜指纹的研究进展[J]. 化学试剂，2024，46（5）：20-29.
【功能材料】
活化蟹壳生物质炭的制备及其在VOCs吸附中的应用
陈蓉a，彭枢璇b，张海龙*b,c
(浙江海洋大学 a. 船舶与海运学院，b. 石油化工与环境学院，
c. 港口油气储运技术国家地方联合工程实验室,浙江 舟山 316022)
摘要：针对大气中由挥发性有机化合物不可控释放引起的环境和健康问题，开发新的吸附技术和材料是重要的解决途径之一。通过热处理廉价、无毒、可再生的蟹壳废弃物，并通过KOH活化制备了可对VOCs高效吸附的蟹壳生物质炭。以炭壳为原料制备了碳化蟹壳(CS)和蟹壳活性炭(KCS)，并采用SEM、BET、FTIR、XRD对其进行了表征，系统考察了温度对VOCs(二甲苯和正己烷)的影响，分析结果表明，制备的蟹壳生物质炭是一种具有介孔结构的多孔材料，其比表面积高达2098 m2/g，平均孔径约为1.98 nm，孔体积为1.16 cm3 /g。最后，对制备的CSK-800℃进行了动态吸附实验，得到的二甲苯和正己烷的总吸附量分别为557.98、585.19 mg/g。吸附动力学研究结果表明，其吸附过程与准一级和Bangham模型拟合结果高度吻合，较好地诠释了蟹壳活性炭对VOCs吸附主要是以物理吸附为主的孔道扩散。
关键词：蟹壳生物质炭；热解；活化剂；挥发性有机物；吸附行为；
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2024）05-0030-09
DOI：10.13822/j.cnki.hxsj.2024.0042
Preparation and Application of Activated Crab Shell Biochar in VOCs Adsorption CHEN Ronga, PENG Shu-Xuanb, ZHANG Hai-Long*b,c ( a. School of Naval Architecture and Maritime; b. School of Petrochemical Engineering and Environment; c. National‑Local Joint Engineering Laboratory of Harbor Oil and Gas Storage and Transportation Technology, Zhejiang Ocean University, Zhoushan 316022, China)
Abstract：Address the environmental and health concerns arising from uncontrolled volatile organic compound (VOC) emissions into the atmosphere necessitates the development of novel adsorption technologies and materials. In this study, we have successfully produced high-efficiency biochar derived from crab shell (CS) through a process involving heat treatment of inexpensive, non-toxic, and renewable crab shell waste, followed by KOH activation. Carbonized CS and crab shell activated carbon (CSK) were meticulously prepared from the crab shell and subsequently characterized using by SEM, BET, FTIR, XRD, and TEM techniques. A comprehensive investigation was conducted to evaluate the impact of temperature on the adsorption of VOCs (specifically xylene and n-hexane). The analysis results indicated that the produced crab shell biochar exhibted a mesoporous structure with exceptional properties, including a specific surface area of 2098 m2/g, an average pore size of 1.98 nm, and a pore volume of 1.16 cm3/g. Furthermore, dynamic adsorption experiments were conducted on CSK-800℃, demonstrating impressive total adsorption capacities of 557.98 mg/g and 585.19 mg/g for xylene and n-hexane, respectively. Additionaly, the adsorption kinetics analysis indicated that the adsorption process was highly consistent with both the quasi-first-order and Bangham model fitting results, emphasizing the role of physical adsorption and pore diffusion in VOCs adsorption by CS biochars.
Key words：crab shell biochar; pyrolysis; activator; volatile organic compounds; adsorption behavior
引用本文：陈蓉，彭枢璇，张海龙.活化蟹壳生物质炭的制备及其在VOCs吸附中的应用[J].化学试剂，2024,46（5）：30-38.
棉秆和油页岩共热解生物炭的氨氮吸附性能研究
亚力昆江·吐尔逊*，张凯悦，高志伟，王珂，钟梅，代正华，李建，刘洋
（新疆大学 化工学院 新疆煤炭清洁转化与化工过程实验室，新疆 乌鲁木齐 830046）
摘要：使用棉秆（CS）和油页岩（OS）为原料，采用共热解的方式制备了共热解生物炭，探究了对氨氮的吸附性能。考察了不同热解时间、CS和OS比例、热解温度、CS的粒径对共热解生物炭对氨氮吸附量的影响规律，确定了最佳制备条件，并研究了吸附动力学和吸附等温线模型。研究表明，棉秆和油页岩共热解后生物炭的结构特性和表面形貌有较大改善，对氨氮的吸附能力有明显的提高。最佳的制备条件是热解温度为500 °C、m(棉秆) : m(油页岩)=3 : 1、热解时间为30 min和CS的粒径为0.20~0.30 mm。在投加量为10.0 g/L、pH 9.0时，最佳制备条件所制备的炭的吸附量为4.89 mg/g，是棉秆生物炭的2.2倍。吸附过程以准二级动力学和Langmuir等温吸附模型描述。吸附机制主要包括为离子交换、静电吸附和络合作用。
关键词：生物炭；共热解；油页岩；氨氮吸附
中图分类号: X703 文献标识码: A 文章编号: 0258-3283（2024）05-0039-08
DOI：10.13822/j.cnki.hxsj.2023.0817
Investigation of the Ammonia Nitrogen Adsorption Properties of co-Pyrolysis Biochar Derived from Cotton Stalk and Oil Shale YALKUNJAN Tursun *, ZHANG Kai-yue, GAO Zhi-wei, WANG Ke, ZHONG Mei, DAI Zheng-hua, LI Jian, LIU Yang ( College of Chemical Engineering Xinjiang University, Xinjiang Key Laboratory of Coal Clean Conversion & Chemical Engineering Process, Urumqi 830046, China)
Abstract: By utilizing cotton stalk (CS) and oil shale (OS) as raw materials, co-pyrolysis biochar was prepared by co-pyrolysis, followed by an investigation into its ammonia nitrogen. Various factors such as pyrolysis time, CS and OS ratio, pyrolysis temperature, and CS particle size were examined to optimize the adsorption capacity of the co-pyrolysis biochar for ammonia nitrogen. Additionally, the adsorption kinetics and adsorption isotherm models were also analyzed. The results revealed a significant enhancement in the structural and surface morphology of co-pyrolysis biochar derived from cotton stalks and oil shale, thereby increasing its adsorption capacity for ammonia nitrogen. The optimal preparation conditions included a pyrolysis temperature of 500 °C, a mass ratio of cotton stalk to oil shale of 3:1, a pyrolysis time of 30 min, and a CS particle size of 0.20~0.30 mm. Under the conditions of 10.0 g/L adsorbent dosage and pH 9.0, the adsorption capacity of the biochar prepared under the optimal conditions reached 4.89 mg/g, which was 2.2 times higher than that of cotton stalk biochar. The adsorption process followed pseudo-second-order kinetics and Langmuir isotherm adsorption model. The primary mechanism involved in the adsorption process were ion exchange, electrostatic adsorption, and complexation.
Keywords: biochar; co-pyrolysis; oil shale; ammonia nitrogen adsorption
引用本文：亚力昆江·吐尔逊，张凯悦，高志伟，等.棉秆和油页岩共热解生物炭的氨氮吸附性能研究[J].化学试剂，2024,46（5）：39-46.
轴向配体对铁卟啉催化氧化环己烷和苯C—H键的影响
张玉静，宋旭锋，马欣宇，于艳敏*
(北京工业大学 化学工程与技术系 绿色催化与分离北京市重点实验室，北京 100124)
摘要：采用密度泛函理论方法系统研究了带有不同轴向配体（F-、Cl-、CH3COO-、SCH3-）的铁卟啉作为仿生催化剂催化氧化环己烷和苯C—H键的反应，重点考察了轴向配体对高价铁-氧卟啉几何结构和电子结构的影响，以及轴向配体影响高价铁-氧卟啉氧化环己烷和苯C—H键反应活性的本质差异。相较于其他轴向配体，F-作为轴向配体使高价铁-氧卟啉具有更高的活性，更易于氧化环己烷和苯的C—H键。与苯环C—H键氧化反应相比，改变轴向配体对环己烷C—H键氧化反应的活性影响更大，且轴向配体主要通过影响过渡态结构中环己烷的形变能来改变环己烷C—H键氧化反应的活化能。而在苯环C—H键氧化反应中，轴向配体主要影响过渡态结构中高价铁-氧卟啉与苯的相互作用能以及苯分子的形变能。
关键词：铁卟啉；轴向配体；环己烷；苯；密度泛函理论
中图分类号：O64 文献标识码：A 文章编号：0258-3283（2024）05-0047-06
DOI：10.13822/j.cnki.hxsj.2023.0815
The Effect of Axial Ligands on the Catalytic Oxidation of Cyclohexane and Benzene C—H Bonds by Iron Porphyrins ZHANG Yu-jing, SONG Xu-Feng, MA Xin-yu, YU Yan-Min* (Department of Chemical Engineering, Beijing Key Laboratory for Green Catalysis and Separation, Beijing University of Technology, Beijing 100124, China)
Abstract：The present strudy focuses on the systematic investigation of C—H bond oxidation in cyclohexane and benzene, catalyzed by iron porphyrins with various axial ligands (F-, Cl-, CH3COO-, SCH3-), serving as biomimetic catalysts. Density functional theory was employed to examine the effect of axial ligands on the geometric and electronic structures of high-valent iron-oxygen porphyrin. Detailed analysis was performed to elucidate the inherent vatiations in reactivity caused by different axial ligands in the catalytic oxidation of cyclohexane and benzene C—H bonds by high-valent iron-oxygen porphyrin. Compared with other axial ligands, F- exhibited enhanced reactivity, facilitating the C—H bond oxidation of cyclohexane and benzene. Moreover, it was observed that axial ligands had a more significant impact on the reactivity of cyclohexane C—H bond oxidation. The axial ligand primarily influenced the activation energy of the cyclohexane C—H bond oxidation reaction by altering the distortion energy of cyclohexane in the transition state. Conversely, in the benzene C—H bond oxidation reaction, the axial ligand simultaneously affected the interaction energy between the high-valent iron-oxygen porphyrin and benzene, as well as the distortion energy of benzene in the transition state.
Key words：iron porphyrin; axial ligand; cyclohexane; benzene; density functional theory
引用本文：张玉静，宋旭锋，马欣宇，等. 轴向配体对铁卟啉催化氧化环己烷和苯C—H键的影响[J]. 化学试剂，2024，46（5）：47-52。
【电化学和新能源】
生物炭/光催化复合材料去除水环境有机污染物研究进展
周通1，任旭阳2，王晨阳2，李发站*1，郭翔*2，吴俊峰2，Fedorov Svyatoslav V3
（1. 华北水利水电大学 环境与市政工程学院，河南 郑州 450040；
2. 河南城建学院 河南省水体污染防治与修复重点实验室，河南 平顶山 467036；
3. 圣彼得堡国立建筑工程大学 环境与市政工程学院，俄罗斯 圣彼得堡 190005）
摘要：以光催化材料为基础的高级氧化处理技术被公认为是处理水环境中有机污染物最具潜力的绿色方法之一。同时，“以废治废”逐渐成为“碳中和”背景下对污染治理的新要求，为提高环境治理水平和社会可持续发展能力，利用生物废弃物等资源转化为生物炭已成为当前研究热点。利用生物炭比表面积易调控、导电性能好以及表面官能团丰富等优势，将光催化氧化与生物炭吸附进行功能协同是一种极具发展前景的有机污染物去除研究体系。概括了生物炭/光催化复合材料的制备方法与工艺，分析了复合材料中生物炭和光催化材料二者功能间的相互影响。此外，通过阐述生物炭/光催化复合材料对污染物的去除过程，深入探讨了吸附-光降解的整体作用机制，并梳理了国内外针对最新重点管控新污染物清单的相关研究进展。最后针对复合材料界面关系、电子迁移性质、综合水体应用等方面，对生物炭/光催化复合材料提出了相关讨论和未来建议。
关键词：生物炭；光催化；吸附-降解；机制；新污染物; 碳中和
中图分类号：TB33;O643.37 文献标识码：A 文章编号：0258-3283（2024）05-0053-10
DOI：10.13822/j.cnki.hxsj.2023.0771
Progress on the Removal of Organic Pollutants from Aquatic Environment by Biochar/Photocatalytic Materials ZHOU Tong 1,REN Xu-yang2,WANG Chen-yang2,LI fa-zhan*1,GUO xiang*2,WU Jun-feng2,Fedorov Svyatoslav V3 (1. Henan Key Laboratory of Water Pollution Control and Rehabilitation, Henan University of Urban Construction, Pingdingshan,467036, China; 2. College of Environmental and Municipal Engineering, North China University of Water Resources and Electric Power，Zhengzhou,450040,China; 3.College of Environmental and Municipal Engineering, SaintPetersburg State University of Architecture and Engineering, St.Petersburg, 190005,Russia)
Abstract：Advanced oxidation technology based on photocatalytic materials is widely recognized as a leading green method for effectively treating organic pollutants in aquatic environments. In the current era of “carbon neutrality,” the concept of "waste for waste" has emerged as a new imperative in pollution management. This trend underscores the importance of leveraging resources like bio-waste to produce biochar, thereby enhancing environmental management standards and promoting sustainable societal development. The integration of biochar’s unique surface modification capabilities, excellent electrical conductivity, and abundant surface functional groups with photocatalytic oxidation represents a promising strategy for organic pollutant removal. This article provides an overview of the preparation methods and processes involved in biochar/photocatalytic composite production, examining the functional interplay between biochar and photocatalytic materials within the composites. In addition, the paper delves into the adsorption-photodegradation mechanism, elucidating the pollutant removal process facilitated by biochar/photocatalytic composites and summarizing the latest domestic and international research advancements in managing emerging pollutants. Finally, the study offers relevant insights, discussions, and future suggestions regarding the interface dynamics, electron migration properties, and integrated water treatment applications of biochar/photocatalytic composites, outlining directions for future research and development.
Key words：biochar; photocatalytic; adsorption-degradation; mechanism; emerging contaminants; carbon neutrality
引用本文：周通，任旭阳，王晨阳，等.生物炭/光催化复合材料去除水环境有机污染物研究进展[J]. 化学试剂，2024,46（5）：53-62.
绿色纳米吸附剂去除水中药物污染物的研究进展
王子宜*,马国秀,张昭,唐燕娇
(兰州文理学院 化工学院,甘肃 兰州 730000）
摘要：药物污染物（PhCs）作为一类新兴的有机污染物，会对人类健康和生态环境造成潜在威胁。近年来，纳米吸附剂作为一种有效的碳捕集材料，因其生产成本低、可持续性好、理化性好、去除率高等优点，使废水处理吸附技术得到了快速发展。总结了近年来可持续绿色纳米吸附剂修复污染水体的研究现状，重点阐述了可持续绿色纳米吸附剂的形式、相互作用机制以及可持续绿色纳米材料在药物吸附去除方面的应用进展。最后，结合已有研究现状，对可持续绿色纳米吸附技术的研究方向进行了展望。
关键词：纳米吸附剂；药物污染物；吸附；废水处理；碳中和
中图分类号：O6-33 文献标识码：A 文章编号：0258-3283（2024）05-0063-08
DOI：10.13822/j.cnki.hxsj.2023.0720
Research Progress in the Removal of Drugs from Water using Green Nanoadsorbents WANG Zi-yi*, MA Guo-xiu, ZHANG Zhao, TANG Yan-jiao（School of Chemical Engineering, Lanzhou University of Arts and Science, Lanzhou 730000, China）
Abstract: Pharmaceutical Contaminants（PhCs）, an emerging class of organic pollutants, pose potential threats to human health and ecological environments. In recent years, the application of nanoadsorbents for wastewater treatment has seen significantly advancements due to their low production costs, sustainability, superior physicochemical properties, and high removal performance for pharmaceuticals. This review critically evaluates the progress made in the application of sustainable green nanoadsorbents for the removal of pharmaceuticals. It is also discussed the influential sorption parameters and interaction mechanisms. Furthermorey, the current challenges associated with nanoadsorbents for the remediation of pharmaceuticalsas well as their vast potential for application, are prospectively explored.
Key words: nanoadsorbents; pharmaceutical pollutants; adsorbents; wastewater treat；carbon neutrality
引用本文：王子宜,马国秀,张昭,等.绿色纳米吸附剂去除水中药物污染物的研究进展[J].化学试剂，2024,46（5）:63-70.
建筑物、室内空气中挥发性羰基化合物检测的研究进展
宋词*
(中国刑事警察学院，辽宁 沈阳 110854)
摘要：建筑物、室内空气中甲醛和乙醛等物质被归类为致癌物，并受到严格的监管，测定室内空气中羰基化合物的质量和数量是重要和必要的。重点阐述与建筑物、室内环境有关的挥发性羰基化合物的经典和现代的分析方法，并详细介绍了各种分析方法的适用目标。比色法操作简单，是目前使用最多的检测方法；许多小分子首先需要进行衍生化，然后利用气相色谱-质谱联用法或高效液相色谱-质谱联用法进行分析；光声光谱法和在线质谱法尽管有一些限制，但鉴定多组分混合物中的羰基化合物是目前最有效的方法。
关键词：挥发性羰基化合物；检测方法；室内空气；建筑物；实时监测；碳中和
中图分类号：R122.1 文献标识码：A 文章编号：0258-3283（2024）05-0071-07
DOI：10.13822/j.cnki.hxsj.2023.0714
Research Progress on the Detection of Volatile Carbonyl Compounds in Buildings and Indoor Air SONG Ci* (Criminal Investigation Police University of China, Liaoning, Shenyang, 110854, China)
Abstract：Formaldehyde and acetaldehyde, which are classified as carcinogens and strictly regulated, pose a significant concern in buildings and indoor air quality. It is crucial and imperative to assess both the presence and quantity of volatile carbonyl compounds in indoor air. This article focuses on exploring classical and modern analytical methods for detecting volatile carbonyl compounds related to buildings and indoor environments, providing a comprehensive elucidation of the objectives and applicability of these methods. The colorimetric method, being user-friendly, is currently the most widely utilized detection technique. However, the analysis of many smaller molecules necessitates a preliminary derivatization step, followed by gas chromatography-mass spectrometry or high-performance liquid chromatography-mass spectrometry. Although photoacoustic spectroscopy and online mass spectrometry possess certain limitations, they remain the most effective approach for identifying carbonyl compounds within complex mixtures.
Key words：volatile base compounds; detection methods; indoor air; buildings; real-time monitoring；carbon neutrality
引用本文：宋词.建筑物、室内空气中挥发性羰基化合物检测的研究进展[J].化学试剂，2024,46（5）：71-77.
【分析与测试】
基于多元统计分析泉州不同品种姜黄的品质
张玲玲，张文州，蔡聪艺，黄幼霞*
（泉州医学高等专科学校，福建 泉州 362000）
摘要：基于多元统计分析泉州不同品种姜黄的品质，分析不同品种姜黄的感官品质和营养物质，结合主成分分析和多元线性回归分析得出综合排名，再利用UPLC-MS/MS对姜黄有效成分进行含量测定以验证多元统计方法的准确性，最后通过聚类分析探索不同品种姜黄之间的相似性和差异性。主成分分析结果表明，前3个主成分的累积贡献率为85.039%，构建评价模型得到分数前4的品种：广西防城港的A2，越南的A3，泉州本地种a的A6和四川内江的A4。以感官评价总分和营养物质含量为对象进行多元线性回归分析，得到回归方程为：Y=67.256+3.483x1+0.662x2，此方法得到排名前4的品种与主成分分析高度一致。UPLC-MS/MS结果表明11个品种中测出姜黄素类有效成分含量前三为：A2>A3>A6，该结果与多元统计中所得的优质品种相符合，证实多元统计法在筛选优质姜黄品种方面的应用价值。聚类分析结果表明，A2、A3、A6聚为一类，具有色泽鲜黄等相同特点。这为今后姜黄品种的选育和质量控制提供了新的思路和方法。
关键词：姜黄；主成分分析；多元线性回归分析；超高效液相色谱-串联质谱法(UPLC-MS/MS)； 聚类分析
中图分类号：R284.1 文献标识码：A 文章编号：0258-3283（2024）05-0078-09
DOI：10.13822/j.cnki.hxsj.2023.0805
Multivariate Statistical Analysis-based Assessment of Turmeric Varieties Quality in Quanzhou ZHANG Ling-ling, ZHANG Wen-zhou, CAI Cong-yi, HUANG You-xia* (Quanzhou Medical College,Quanzhou 362000,China)
Abstract: The quality analysis of different turmeric varieties in Quanzhou involved a comprehensive approach combining sensory evaluation, nutrient analysis, principal component analysis (PCA), multiple linear regression (MLR), UPLC-MS/MS verification, and cluster analysis. The PCA results indicated that the first three principal components contributed to an 85.039% cumulative variation. Based on the evaluation model, the top 4 varieties, in terms of scores, were identified as A2 from Fangchenggang, Guangxi; A3 from Vietnam; A6 from Quanzhou, a local species; and A4 from Neijiang, Sichuan, China. The MLR analysis, performed on the total sensory evaluation scores and nutrient content, yielded a regression equation of y = 67.256 + 3.483x1+0.662x2. The top 4 varieties obtained from this method were highly consistent with the PCA results. UPLC-MS/MS measurements revealed that the 11 varieties had varying levels of curcumin-like active ingredients, with A2, A3, and A6 exhibiting the highest content, consistent with the high-quality varieties identified by the multivariate statistical method. Cluster analysis grouped A2, A3, and A6 together, highlighting their shared traits such as bright yellow color. These findings provide novel insights and methodologies for the future selection and quality control of turmeric varieties.
Key words:turmeric; principal component analysis; multiple linear regression analysis; ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS); cluster analysis
引用本文：张玲玲，张文州，蔡聪艺，等.基于多元统计分析泉州不同品种姜黄的品质[J].化学试剂，2024,46（5）：78-86.
烟草中甲霜灵的手性分离方法差异研究
王维刚1，陈志燕1，唐石云2，周芸1，朱丽2，洪玮*3，杨飞*4
(1.广西中烟工业有限责任公司，广西 南宁 530001；2.云南中烟工业有限责任公司，云南 昆明650000；
3. 江西中烟工业有限责任公司，江西 南昌330096；4.国家烟草质量监督检验中心，河南 郑州 450001)
摘要:对比反相液相色谱-串联质谱(RPLC-MS/MS)和超临界流体色谱-串联质谱(SFC-MS/MS)手性分离烟草中甲霜灵的差异。烟草样品经乙腈提取、盐析分层、快速滤过型净化(multi-Plug Filtration Cleanup, m-PFC)柱净化后，分别采用RPLC-MS/MS和SFC-MS/MS进行手性分离。从多个性能参数（分离效率、线性、选择性、回收率、重复性、灵敏度、基质效应等）对两种方法进行了全面比较。采用不同的分离方法，在10～500 ng/mL范围内，甲霜灵的不同异构体均可呈现良好的线性关系 （R2≥0.9993）。在各异构体加标浓度为0.1、0.5、2.0 mg/kg水平下，采用不同的分离方法均可获得满意的回收率（88.7%~96.2%）和良好的重复性(RSD<7.0%)。结果表明：RPLC-MS/MS和SFC-MS/MS具有互补性，均适用于手性分离和测定烟草基质中的甲霜灵。
关键词：反相液相色谱-串联质谱；超临界流体色谱-串联质谱；快速滤过型净化；烟草；甲霜灵；手性分离
中图分类号：TS411 文献标识码：A 文章编号：0258-3283（2024）05-0087-06
DOI：10.13822/j.cnki.hxsj.2023.0770
Investigation of Chiral Separation Methods for Metalaxyl in Tobacco WANG Wei-gang1, CHEN Zhi-yan1, TANG Shi-yun2, ZHOU Yun1, ZHU Li2, Hong Wei*3, YANG Fei*4 (1.Guangxi Tobacco Industry Co. Ltd., Nanning 530001, China; 2. Yunnan Tobacco Industry Co. Ltd., Kunming 650000, China; 3. Jiangxi Tobacco Industry Co. Ltd., Nanchang 330096, China; 4. China National Tobacco Quality Supervision&Test Center, Zhengzhou 450001, China)
Abstract: To investigate the differences in chiral separation of metalaxyl in tobacco, we utilize reverse phase liquid chromatography tandem mass spectrometry (RPLC-MS/MS) and supercritical fluid chromatography tandem mass spectrometry (SFC-MS/MS). Tobacco was extracted with acetonitrile, followed by salt-out with anhydrous magnesium sulfate, and purification using m-PFC (multi plug filtration cleaning) columns. Chiral separation was performed separately using RPLC-MS/MS and SFC-MS/MS. A comprehensive comparison oftwo methodologies was conducted based on multiple performance parameters such as separation efficiency, linearity, selectivity, recovery rate, repeatability, sensitivity, and matrix effect. The results revealed that different enantiomers of metalaxyl exhibited excellent linear relationships within the range of 10～500 ng/mL (R2≥0.9993) using both separation methods. Addtionally, satisfactory recoveries (88.7%~96.2%) and good repeatability (RSD<7.0%) were achieved at levels of 0.1, 0.5, and 2.0 mg/kg for each isomer when employing the different separation methods. These findings indicate that RPLC-MS/MS and SFC-MS/MS are complementary and suitable for chiral separation and determination of metalaxyl in tobacco substrates.
Key words：Reversed-phase liquid chromatography-tandem mass spectrometry;supercritical fluid chromatography-tandem mass spectrometry; multi-plug filtration cleanup; tobacco; metalaxyl; chiral separation
引用本文：王维刚，陈志燕，唐石云，等.烟草中甲霜灵的手性分离方法差异研究[J].化学试剂，2024，46（5）：87-92.
【标准物质与标准品】
牛肉粉中恩诺沙星和磺胺嘧啶高准确度分析方法研究与标准物质研制
李瑶瑶1,2，杨吉双3，李秀琴1，时玲1，高燕*1，张庆合*1
(1. 中国计量科学研究院 化学计量与分析科学研究所，北京 100029；
2.中国石油大学(北京) 化学工程与环境学院；北京 102249；3.中国信息通信研究院，北京 100191)
摘要：建立了基于液相色谱-同位素稀释质谱法（LC-IDMS）的牛肉粉中恩诺沙星和磺胺嘧啶残留测定的高准确度分析方法，采用同位素稀释单点校准定量，恩诺沙星和磺胺嘧啶的加标回收率分别为（99.0±0.8）%和（100.4±1.2）%，基质效应因子分别为0.9991和1.0119。采用添加法制备牛肉粉中恩诺沙星和磺胺嘧啶标准物质候选物，进行了标准物质均匀性检验、稳定性检验和定值，评定了不确定度。标准物质均匀性、稳定性良好，恩诺沙星特性量值为729 ng/g，扩展不确定度为42 ng/g（k=2），磺胺嘧啶特性量值为413 ng/g，扩展不确定度为31 ng/g（k=2）。该标准物质的研制能够应用于食品中恩诺沙星和磺胺嘧啶等相关兽药残留检测的质量控制、方法开发和验证等领域，进而保障相关检测结果的准确、可比。
关键词：牛肉粉；恩诺沙星；磺胺嘧啶；同位素稀释质谱法；标准物质
中图分类号：TS210.7 文献标识码：A 文章编号：0258-3283（2024）05-0093-07
DOI：10.13822/j.cnki.hxsj.2023.0814
Development of an Accurate Determination Method and Reference Material for Enrofloxacin and Sulfadiazine in Bovine Powder LI Yao-yao1,2, YANG Ji-shuang3, LI Xiu-qin1, SHI Ling1, GAO Yan*1, ZHANG Qing-he*1(1. Division of Chemical Metrology and Analytical Science, National Institute of Metrology, Beijing 100029, China; 2. State Key Laboratory of Heavy Oil Processing, College of Chemical Engineering and Environment, China University of Petroleum（Beijing）, Beijing 102249, China; 3. China Academy of Information and Communications Technology, Beijing, 100191, China)
Abstract：A liquid chromatography - isotope dilution mass spectrometry (LC-IDMS) method was established for the precise determination of enrofloxacin and sulfadiazine in bovine powder. Isotope dilution single point calibration method was applied for quantification. The matrix spiked recoveries of enrofloxacin and sulfadiazine were found to be（99.1±0.8）% and（100.4±1.2）%, respectively, with corresponding matrix effect factors of 0.9991 and 1.0119. To prepare the reference material, enrofloxacin and sulfadiazine standard solution were spiked into bovine muscle samples. Subsequently, the developed LC-IDMS method was utilized in homogeneity testing, stability testing, and value assignment.With an evaluation of the uncertainty of the reference material. The results indicated remarkable homogeneity and stability of enrofloxacin and sulfadiazine in bovine powder, characterized by values of 729 ng/g and 413 ng/g, respectively. This reference material can paly a pivotal role in quality control, method development, and validation of veterinary drug residue detection in food, thereby ensuring the accuracy and comparability in related detection outcomes.
Key words：bovine powder; enrofloxacin; sulfadiazine; isotope dilution mass spectrometry; reference material
引用本文：李瑶瑶, 杨吉双, 李秀琴, 等. 牛肉粉中恩诺沙星和磺胺嘧啶高准确度分析方法研究与标准物质研制[J]. 化学试剂，2024，46（5）：93-99.
【合成与工艺技术】
磺酸化β-环糊精催化合成二苯并[b,i]氧杂蒽四酮
李文欢，王英磊*，曹春，田野
(南阳理工学院 生物与化学工程学院，河南 南阳 473004)
摘要：β-环糊精是一种由微生物发酵所生产的环状低聚糖，具有廉价易得、无毒无害、可生物降解等特点。通过β-环糊精和氯磺酸的反应，制备了磺酸化β-环糊精（β-CD-SO3H）。在无溶剂条件下，β-CD-SO3H催化不同取代基的芳香醛与2-羟基-1,4-萘醌反应，以85% ~ 95%的产率合成了一系列13-芳基-5H-二苯并[b,i]氧杂蒽-5,7,12,14(13H)-四酮衍生物。β-CD-SO3H具有制备方法简单、生物相容性优良、回收利用便捷等优点，符合绿色化学的发展方向，具有较好的工业应用前景。
关键词：磺酸化β-环糊精；氧杂蒽；绿色化学；重复使用
中图分类号：O626.3 文献标识码：A 文章编号：0258-3283（2024）05-0100-06
DOI：10.13822/j.cnki.hxsj.2023.0744
Synthesis of Dibenzo[b,i]xanthene-tetraones Catalyzed by β-Cyclodextrin-SO3H LI Wen-huan, WANG Ying-lei*, CAO Chun, TIAN Ye (School of Biological and Chemical Engineering, Nanyang Institute of Technology, Nanyang 473004, China)
Abstract：β-Cyclodextrin is a cyclic oligosaccharide produced by microbial fermentation. It is well known for its low cost, easily availability, non-toxicity, harmlessness, and biodegradability. β-cyclodextrin-SO3H (β-CD-SO3H) was obtained by reacting β-cyclodextrin withchlorosulfonic acid. Under solvent-free conditions, β-CD-SO3H catalyzed the reaction between various substituted aromatic aldehyde and 2-hydroxy-1,4-naphthoquinone. This resulted in the synthesis of a series of 13-aryl-5H-dibenzo[b,i]xanthene-5,7,12,14(13H)-tetraone derivatives with yields ranging from 86% to 95%. The advantages of β-CD-SO3H include its simple preparation method, excellent biocompatibility, and convenient recyclability. These properties align with the principles of green chemistry and offer promising prospects for industrial applications.
Key words：β-cyclodextrin-SO3H; xanthene; green chemistry; reuse
引用本文：李文欢，王英磊，曹春，等. 磺酸化β-环糊精催化二苯并[b,i]氧杂蒽四酮的绿色合成 [J]. 化学试剂，2024，46(5)：100-105.
7-甲基鸟嘌呤的高效合成工艺研究
陆宗焕1,3，黎明杨2，张念椿*2,3，刘平*1，张逸伟1
（1. 华南理工大学 材料科学与工程学院，广东 广州 510641；
2. 达高工业技术研究院(广州)有限公司，广东 广州 510535；
3. 西陇科学股份有限公司，广东 广州 510535）
摘要：7-甲基鸟嘌呤（7-MG）是一种抑制DNA修复酶的天然化合物，被认为是潜在的抗癌候选药物。选用廉价易得的商业化试剂鸟苷和硫酸二甲酯为原料，连续进行两步实验制备7-甲基鸟嘌呤。第一步反应首先比较了碘甲烷、碳酸二甲酯和硫酸二甲酯的甲基化效果，结果表明硫酸二甲酯具有更好的反应效果，甲基化所需的反应条件温和，反应速率快且转化率高。优化了反应溶剂、原料比例、反应的pH值、反应温度和反应时间等实验条件，提高了反应效率和产率。对最终产品重结晶提纯的方法也进行了深入研究，优化筛选了几种常见的重结晶溶剂。结果表明当溶剂为水，pH 9时重结晶效果最佳，重结晶产率为78%，产品纯度可达99.6%。
关键词：7-甲基鸟嘌呤；鸟苷；硫酸二甲酯；重结晶；有机合成
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2024）05-0106-06
DOI：10.13822/j.cnki.hxsj.2024.0008
Research on the Efficient Synthesis of 7-Methylguanine LU Zong-huan1,3, LI Ming-yang2, ZHANG Nian-chun*2,3, LIU Ping*1, ZHANG Yi-wei1 (1.School of Material Science and Engineering，South China University of Technology, Guangzhou 510641, China; 2. Dagao Industrial Technology Research Institute (Guangzhou) Co., Ltd., Guangzhou 510535, China; 3. Xilong Scientific Co., Ltd., Guangzhou 510535, China)
Abstract: 7-Methylguanine(7-MG) is a naturally occurring compound that exhibits inhibitory effects on DNA repair enzyme, making it a promising candidate for anti-cancer drug development. The synthesis of 7-methylguanine from guanosine and dimethyl sulfate involves a two-step process. In the first step, the methylation effects of iodomethane, dimethyl carbonate, and dimethyl sulfate were compared. The results showed that dimethyl sulfate exhibited superior methylation efficiency, with mild reaction conditions, fast reaction rate, and high conversion rate. Furthermore, the experimental conditions including reaction solvent, raw material ratio, pH value, reaction temperature, and reaction time were optimized to enhance reaction efficiency and yield. Additionally, the purification of the final product was also investigated through recrystallization, and various common solvents were tested and screened. The findings revealed that using water as the solvent with a pH value of 9 achieved the highest recrystallization yieldthe of 78% and a product purity of 99.8%.
Key words: 7-methylguanine; guanosine; dimethyl sulfate; recrystallization; organic synthesis
引用本文：陆宗焕，黎明杨，张念椿，等.7-甲基鸟嘌呤的高效合成工艺研究[J].化学试剂，2024,46（5）：106-111.
点击化学制备AChE/MAO-B双抑制剂及活性评价
贾朝*1 ，梁旭华1，周伟2，潘婷婷1，李世玺1
(1. 商洛学院 生物医药与食品工程学院，陕西 商洛 726000；2. 陕西香菊药业集团有限公司，陕西 商洛 726000)
摘要：通过点击化学（CuAAC反应）设计、合成了22个香豆素衍生物。多数化合物在微摩尔范围内表现出良好的AChE和MAO-B双抑制活性，具有良好的生物相容性。尤其是一种名为A2H5的化合物，对AChE和MAO-B的IC50分别为（0.23±0.02、（0.31± 0.03）μmol/L，是最佳的AChE/MAO-B双抑制剂。实验结果表明香豆素基团是一类有效的AChE和MAO-B双抑制活性基团，羟基取代苯环的存在能够增强抑制活性。分子对接研究发现A2H5是双位点抑制剂，苯基部分结合到AChE的CAS位点，香豆素结合到PAS位点，三氮唑环占据两个活性位点的中间峡谷。A2H5的香豆素部分结合到MAO-B的入口空腔，苯基部分结合到底物空腔，并嵌入到Tyr435、Tyr398 和FAD形成的“芳香笼”。总之，香豆素C7位置取代衍生物可以被开发为AChE/MAO-B双抑制剂，为进一步开发抗AD的双靶点药物提供一个新的起点。
关键词：AD; 点击化学; 香豆素; AChE/MAO-B双抑制剂; 分子对接; 生物相容性
中图分类号：TQ46 文献标识码：A 文章编号：0258-3283（2024）05-0112-09
DOI：10.13822/j.cnki.hxsj.2023.0818
Preparation and the Activity Evaluation of AChE/MAO-B Dual Inhibitors Using "Click" JIA Zhao*1,LIANG Xu-hua 1 , ZHOU Wei 2, PAN Ting-ting 1, LI Shi-xi 1( 1. College of Biology Pharmacy and Food Engineering, Shangluo University, Shangluo 726000, China；2. Shaanxi Xiangju Pharmaceutical Group Real Estate Co., Ltd., Shaanxi Shangluo 726000, China)
Abstract：The “Click” chemistry approach(CuAAC reaction) was utilized to design and manufacture 22 coumarin derivatives. In the micromolar range, the majority of these compounds exhibite potent dual inhibitory activity against AChE and MAO-B, suggesting favorable biocompatibility. Among these derivatives, A2H5 emerged as the most effective AChE/MAO-B dual inhibitor, with IC50 values of（0.23 ± 0.02）μmol/L for AChE and （0.31 ± 0.03) μmol/L for MAO-B, respectively. Experimental results highlight, coumarin groups as robust dual inhibitory functional groups for MAO-B and AChE, with enhanced inhibitory activity observed in the presence of hydroxyl substituted benzene rings. Molecular docking studies revealed that A2H5 functions as a dual-site inhibitor, with the triazole moiety binding to the center canyon of the active sites and the phenyl and the coumarin units attaching to the CAS site of AChE and the the PAS site of MAO-B, respectivley. Specially, the phenyl component of A2H5 links to the substrate cavity, forming interactions within the "aromatic cage" created by Tyr435, Tyr398, and FAD, while the coumarin portion binds to the entrance cavity of MAO-B. In conclusion, the development of coumarin C7 substituted compounds as AChE/MAO-B dual inhibitors presents a promising approach for advancing research and development efforts focused on dual-target medications for Alzheimer’s disease.
Key words：Alzheimer’s disease; click on chemistry; coumarin; AChE/MAO-B dual inhibitors; molecular docking; biocompatibility
引用本文：贾朝，梁旭华，周伟，等.点击化学制备AChE/MAO-B双抑制剂及活性评价[J].化学试剂，2024，46（5）：112-120.
