【特约专题】

硼亲和分子印迹聚合物对水中土霉素的吸附

张愈惠^1,2,3，王凤杰^1,2,3，罗莎^1,2,3，王怡雪^1,2,3，卫潇^*1,2,3

（1. 长安大学 水利与环境学院，陕西 西安  710054；2. 旱区地下水文与生态效应教育部重点实验室，陕西 西安  710054；3. 水利部旱区生态水文与水安全重点实验室，陕西 西安  710054）

摘要：为提高分子印迹体系的特异选择性吸附能力，解决功能单体和模板分子之间仅依靠氢键作用而造成的特异性不足以及分子印迹聚合物活性位点内嵌导致吸附容量低的问题，研究基于硼酸基与土霉素（OTC）所含有的顺式邻二羟基结构之间的特殊作用以及电子转移-原子自由基聚合(ARGET ATRP)活性可控的特点，选取4-乙烯基苯硼酸（VPBA）作为分子印迹体系的功能单体，通过精准调控反应条件，利用ARGET ATRP成功制备出对OTC具有特异选择性的硼酸基共价印迹聚合物（MIPs）。系统研究各因素对MIPs性能的影响，优选预聚合体系中OTC与VPBA的最佳物质的量比为1:1，吸附剂的最佳投加量为5.0 mg；以80 mg/L的OTC为目标污染物时，MIPs的最大吸附容量达51.44 mg/g，其吸附过程符合Temkin模型和拟二级动力学模型。选择性实验及模拟废水实验表明，MIPs对OTC有较强的特异选择性，能有效克服实际水体环境中的复杂干扰，具有良好的适用性。通过材料表征、吸附模型拟合和Scatchard分析可知，MIPs的吸附过程是由非共价作用与共价键作用共同作用。研究为水体中有机污染物的高效去除提供了新思路，在水污染治理领域具有潜在应用价值。

关键词：吸附；土霉素；分子印迹聚合物；硼亲和；电子转移-原子自由基聚合

中图分类号：O647.3；X52              文献标识码：A              文章编号：0258-3283（2025）

DOI：10.13822/j.cnki.hxsj.2025.0023

Adsorption of Oxytetracycline in Water by Boron-affinity Molecularly Imprinted Polymers ZHANG Yu-Hui^1,2,3, WANG Feng-Jie^1,2,3, LUO Sha^1,2,3, WANG Yi-Xue^1,2,3, WEI Xiao^*1,2,3 (1. School of Water and Environment, Chang′an University, Xi′an 710054, China; 2. Key Laboratory of Subsurface Hydrology and Ecological Effect in Arid Region of the Ministry of Education, Xi′an 710054, China; 3. Key Laboratory of Eco-hydrology and Water Security in Arid and Semi-arid Regions of Ministry of Water Resources, Xi′an 710054, China) 

Abstract：To enhance the specific selective adsorption capacity of the molecularly imprinted system and address the issues of insufficient specificity caused by the sole reliance on hydrogen-bond interactions between the functional monomer and the template molecule, as well as the low adsorption capacity resulting from the embedding of active sites in the molecularly imprinted polymer, this study was carried out. Based on the special interaction between the boronic acid group and the cis-diol structure contained in oxytetracycline (OTC), and the controllable activity of activators regenerated by electron transfer for atom transfer radical polymerization (ARGET ATRP), 4-vinylphenylboronic acid (VPBA) was selected as the functional monomer of the molecularly imprinted system. Boric acid-based covalently imprinted polymers (MIPs) with specific selectivity for OTC were successfully prepared by using ARGET ATRP through precise regulation of reaction conditions. Systematic investigations on performance influencing factors revealed optimal conditions: the optimal ratio of OTC to VPBA in the pre-polymerization system was preferably selected as 1:1, and the optimal dosage of the adsorbent was 5.0 mg. When the target pollutant is 80 mg/L OTC, the maximum adsorption capacity of MIPs reached 51.44 mg/g, and its adsorption process conformed to the Temkin model and the pseudo-second-order kinetic model. Selectivity experiments and simulated wastewater tests demonstrated that MIPs possessed strong specific selectivity for OTC, could effectively overcome complex interferences in real water environments and had excellent applicability. Through material characterization, adsorption model fitting, and Scatchard analysis, it was found that the adsorption process of MIPs was the results from the combined action of non-covalent and covalent bond interactions. This study provides a new idea for the efficient removal of organic pollutants in water bodies and has potential application value in the field of water pollution control.

Key words：adsorption; oxytetracycline; molecularly imprinted polymers; boronate affinity; activators regenerated by electron transfer for atom transfer radical polymerization

近红外荧光探针在活性氧检测中的研究进展

张奥金¹，弓韬²，于保锋²，文朝朝^*1，梁文婷^*1

(1. 山西大学 化学化工学院，山西 太原  030006; 2. 山西医科大学 生物化学与分子生物学教研室，山西 太原  030001)

摘要：活性氧（ROS）在细胞的生命活动中扮演着重要角色。它不仅参与细胞信号传导、调控细胞生长和分化，还能抵御病原体的侵袭，因此，与衰老、心血管疾病、糖尿病及癌症以及很多的并发症有密切的联系。近年来，荧光成像由于其众多优点，在监测细胞内ROS水平变化的研究方面得到了广泛应用。近红外（NIR）发射或激发技术凭借其强的组织穿透性、高分辨率、优越的光稳定性等优势，逐渐成为荧光成像ROS的首选技术。目前，尽管众多研究者致力于近红外ROS荧光探针的开发工作，但相关研究的系统性综述仍较为缺乏。系统梳理了近5年来基于不同识别机制的近红外ROS响应型荧光探针的研究进展，重点对每一类探针的检测机制进行了综述，同时对其生物应用进行了简要说明，为开发具有更高选择性、更低毒性、更好生物相容性的新型NIR探针，满足基础研究和临床应用的多样化需求提供帮助。特别提出了以DeepSeek 为代表的先进人工智能技术与科研相结合来进行优化分子设计和性能预测，以期提升NIR荧光探针开发效率，为ROS的高效检测、精准调控及疾病诊疗开辟新途径。

关键词：近红外荧光探针；检测机制；活性氧；生物成像；研究进展

中图分类号: O657.3             文献标识码：A                文章编号：0258-3283（2025）

DOI：10.13822/j.cnki.hxsj.2025.0051

Research Progress of Small Molecule Fluorescent Probes for the Detection of Reactive Oxygen Species ZHANG Ao-jin¹，GONG Tao², YU Bao-feng², WEN Chao-chao^*1, LIANG Wen-ting^*1(1. College of chemistry and chemical engineering, Shanxi University, Taiyuan 030006, China;2. Department of Biochemistry and Molecular Biology, Shanxi Medical University, Taiyuan 030001, China)

Abstract: Reactive oxygen species (ROS) play a significant role in the life activities of cells. They not only participate in cell signaling, regulate cell growth and differentiation, but also resist pathogen invasion. Hence, they are closely associated with aging, cardiovascular diseases, diabetes, cancer, and numerous complications. In recent years, fluorescence imaging has been extensively applied in the research of monitoring intracellular ROS level variations due to its numerous merits. Near-infrared (NIR) emission or excitation technology, with its strong tissue penetrability, high resolution, and superior photostability, has gradually emerged as the preferred technique for fluorescence imaging of ROS. Currently, although numerous researchers are committed to the development of near-infrared ROS fluorescent probes, systematic overviews of related studies remain relatively scarce. This article systematically reviews the research advancements of near-infrared ROS-responsive fluorescent probes based on different recognition mechanisms over the past five years, with a focus on elaborating the detection mechanisms of each type of probe and providing a brief account of their biological applications. We anticipate that this review can offer assistance in the development of novel NIR probes with higher selectivity, lower toxicity, and better biocompatibility to meet the diverse requirements of fundamental research and clinical applications. Specifically, it is proposed that advanced artificial intelligence technologies represented by DeepSeek be integrated with scientific research for optimizing molecular design and performance prediction, with the aim of enhancing the development efficiency of NIR fluorescent probes and opening up new pathways for the efficient detection, precise regulation, and diagnosis and treatment of diseases related to ROS.

Key words: NIR fluorescent probes; detection mechanism; reactive oxygen species; biological imaging; research progress

人血清淀粉样蛋白A纯品含量的同位素稀释质谱方法研究

朱天翼，李兰英，孟娇然，王乐乐^*，李杰，刘刚

（上海市计量测试技术研究院 国家市场监管重点实验室（生物分析计量溯源），上海  201203）

摘要：建立了人血清淀粉样蛋白A（SAA）纯品的液相色谱-同位素稀释串联质谱检测方法。首先采用凝胶电泳和液相色谱法对SAA的纯度进行了表征，然后采用飞行时间质谱对SAA的相对分子量和肽图进行了测定，最后利用氨基酸水解-同位素稀释串联质谱方法对SAA含量进行了准确测定。结果表明，SAA样品纯度为99.39%，实测相对分子质量为11678.73 Da，与理论分子量11682.7 Da高度一致，氨基酸序列覆盖率99.04%，氨基酸水解-同位素稀释串联质谱法的定量结果为80.9 μg/g，扩展不确定度为2.0 μg/g （k=2）。该方法具有较高的精密度和准确度，测量结果可溯源至SI单位，为SAA蛋白标准物质的研制奠定了基础。

关键词：血清淀粉样蛋白A；同位素稀释质谱法；氨基酸；标准物质；不确定度

中图分类号：O655              文献标识码：A              文章编号：0258-3283（2025）

DOI：10.13822/j.cnki.hxsj.2024.0498

Analysis of Content of Human Serum Amyloid A by Isotope Dilution Mass Spectrometry Method ZHU Tian-yi, LI Lan-ying, MENG Jiao-ran, WANG Le-le^*, LI Jie, LIU Gang (Key Laboratory of Bioanalysis and Metrology for State Market Regulation, Shanghai Institute of Measurement and Testing Technology, Shanghai 201203, China) 

Abstract：A liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for the detection of pure human serum amyloid A (SAA) was established. The purity of SAA was initially characterized using sodium dodecyl sulfate polyacrylamide gel electrophoresis and liquid chromatography. Subsequently, the relative molecular weight and peptide map of SAA were determined using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. The SAA content was then accurately quantified using an amino acid hydrolysis-isotope dilution LC-MS/MS method. The results demonstrated that the purity of the SAA sample was 99.39%, and the measured relative molecular weight was 11,678.73 Da, which was consistent with the theoretical value of 11682.7 Da. Furthermore, the amino acid sequence coverage rate was found to be 99.04%. The quantitative result of the amino acid hydrolysis-isotope dilution LC-MS/MS method was 80.9 μg/g, with an uncertainty of 2.0 μg/g (k=2). This method exhibits high precision and accuracy, with measurement results traceable to the International System of Units (SI units), laying a solid foundation for the development of SAA protein reference materials.

Key words：serum amyloid A; isotope dilution mass spectrometry; amino acid; certified reference materials; uncertainty

【生化与药用试剂】

ROS响应型荧光传感器阵列构建及其鉴别肿瘤

刘倩¹，陶新怡¹，万宇²，张苗苗¹，卢海峰^*1

(1. 安徽医科大学 药学院 炎症与免疫性疾病安徽省重点实验室，安徽 合肥  230032；

2. 安徽化工研究院检测评价科技有限公司，安徽 合肥  230041)

摘要：细胞内的活性氧（ROS）种类和含量与肿瘤类型密切相关，但基于ROS的模式识别用于癌症的精准诊断尚未见报道。在此，提出了一种基于pH调控多色金纳米簇的ROS响应荧光传感器阵列，用于区分肿瘤细胞类型及其增殖状态。该策略通过调控pH合成了三色荧光的组氨酸模版金纳米团簇（AuNCs @ His），响应细胞内ROS而导致不同程度的荧光猝灭，从而形成独特的光学“指纹”，通过主成分分析（PCA）可以很好地聚为几个分离的基团，互不重叠。通过流式细胞术( FCM )检测发现，3种AuNCs @ His被多种癌细胞内化后，对细胞内的ROS表现出不同程度的荧光淬灭。利用传感器阵列提供的信息，细胞内ROS种类和水平的差异形成了独特的光学"指纹"，通过PCA可用于区分各种癌细胞，且具有良好的重现性和准确性。更重要的是，所提出的ROS响应的荧光传感器阵列在区分肿瘤的增殖状态方面也表现出优异的性能。ROS响应的荧光传感器阵列可以作为一种有前途的工具用于癌症的精确诊断，显示出巨大的临床应用潜力。

关键词：金纳米团簇；活性氧; 模式识别；主成分分析；癌症精准诊断 

中图分类号：O631；R917              文献标识码：A              文章编号：0258-3283（2025）

DOI：10.13822/j.cnki.hxsj.2025.0007

Construction of ROS-Responsive Fluorescent Sensor Array for Tumor Differentiation LIU Qian¹, TAO Xin-yi¹, WAN Yu², ZHANG Miao-miao¹, LU Hai-feng^*1 （1. Inflammation and Immune Mediated Diseases Laboratory of Anhui Province, School of Pharmacy, Anhui Medical University, Hefei 230032, China；2. Anhui Chemical Research Institute Testing and Evaluation Technology Co., Ltd. Hefei 230041, China）

Abstract: Intracellular reactive oxygen species (ROS) are closely associated with the types of tumors, but ROS-based pattern recognition for precise diagnosis of cancer has never been reported yet. Herein, we proposed an ROS-responsive fluorescent sensor array based on pH-controlled multicolor gold nanoclusters to distinguish tumor cell types and their proliferation states. This strategy involves the synthesis of three types of histidine-templated gold nanoclusters AuNCs@His with different fluorescence profiles by adjusting the pH value. The response to intracellular ROS leads to varying degrees of fluorescence quenching, thereby forming unique optical "fingerprints", which were well-clustered into several separated groups without overlap by principal component analysis (PCA). After being internalized by various cancer cells, three types of AuNCs@His exhibited different fluorescent quenching degrees in response to the intracellular ROS, as revealed by flow cytometry (FCM). Utilizing the information provided by the sensor array, the differences in types and levels of intracellular ROS formed unique optical “fingerprints”, which could be used to differentiate various cancer cells with excellent reproducibility and accuracy by PCA. More importantly, the proposed ROS-responsive fluorescent sensor array also exhibited excellent performance in differentiating the proliferation states of cancer. Overall, our study provides a promising tool for precise diagnosis of cancer, holding great potential for clinical application

Key words: gold nanoclusters; reactive oxygen species; pattern recognition; principal component; precise cancer diagnosis

SOD纳米类酶的分类及其疾病治疗应用

张思嘉，刘鑫欣，崔岱宗^*

（东北林业大学 生命科学学院，黑龙江省酶与类酶工程重点实验室，黑龙江 哈尔滨 150040）

摘要：超氧化物歧化酶（SOD）作为机体内酶抗氧化系统的组分，在消除多余的活性氧（ROS），应对氧化应激，维持氧化还原平衡，使机体处于健康稳定状态发挥重要作用，同时，SOD在疾病治疗，食品，化妆品等方面有着广泛的应用。然而天然SOD存在提取困难，成本高，易失活，以及分子量大，细胞透过性弱等缺点严重限制了其应用。因此近年来，具有替代天然SOD发挥作用的潜力的SOD纳米类酶的研究较为活跃。综述了SOD纳米类酶优势，分类，活性调控，论述了SOD纳米类酶在疾病治疗上应用，总结了SOD纳米类酶面临的挑战和未来的发展方向。SOD纳米类酶在疾病治疗上具有较大的前景，但其发挥作用的机理日趋复杂，需要更深一步的研究。

关键词：超氧化物歧化酶；SOD；纳米类酶；疾病治疗；活性调控  

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.2024.0301

Classification and Therapeutic Applications of SOD Nanoenzymes ZHANG Si-jia, LIU Xin-xin, CUI Dai-zong^* (Key Laboratory of Enzyme and Enzyme Engineering of Heilongjiang Province, College of Life Sciences, Northeast Forestry University, Harbin 150040, China)

Abstract：Superoxide dismutase (SOD), as a component of the body's antioxidant enzyme system, plays an important role in eliminating excess reactive oxygen species (ROS), combating oxidative stress, and maintaining redox balance to keep the body in a healthy and stable state. Additionally, SOD enzymes have been widely applied in disease treatment, food, cosmetics, and other fields. However, natural SOD faces limitations such as difficult extraction, high cost, easy inactivation, large molecular weight, and weak cell permeability, which severely restrict its application. Therefore, in recent years, research on SOD nanoenzymes, which have the potential to replace natural SOD and perform similar functions, has been active. This review summarizes the advantages, classification, activity regulation, and application of SOD nanoenzymes in disease treatment, and also highlights the challenges and future development directions of SOD nanoenzymes. SOD nanoenzymes have great prospects in disease treatment, but their mechanisms of action are becoming increasingly complex and require further research.

Key words：superoxide dismutase; SOD; nanoenzymes; therapeutic applications; activity regulation

用于光热/光动力治疗的BODIPY衍生物合成及性能研究

谢煜琦，姜渊，张蒙，刘晓婷，吴清华，李丽^*

(安徽中医药大学 药学院，安徽 合肥  230012)

摘要：开发一种兼具光热治疗（PTT）与光动力治疗（PDT）协同效应的新型光敏分子。通过分子工程策略设计并合成了双三苯胺（TPA）取代的BODIPY二聚体，采用核磁共振（NMR）和高分辨质谱（HRMS）对目标化合物的分子结构进行确证。通过系统光物理性质发现，该分子在近红外区域（780 ~ 800 nm）展现出显著红移的特征吸收，较传统BODIPY单体（500 nm）红移了近400 nm，为深层组织光疗提供了有利条件。该化合物在808 nm激光激发下展现出双重治疗特性：一方面通过能量转移途径产生单线态氧（¹O₂）；另一方面表现出优异的光热转换效率（η = 60.6%），其光热转换效率是临床常用光敏剂吲哚菁绿（ICG）的两倍。值得关注的是，其光热稳定性经连续6次激光循环后仍保持90%以上性能，显著优于ICG的快速光漂白特性。体外实验证实，该化合物对4T1乳腺癌细胞具有显著杀伤效果，优于市售光敏剂ICG，展现出更高的生物相容度与稳定性，在深层组织治疗应用中显示出重要潜力，为开发高效近红外光疗试剂提供了新的参考策略。

关键词：氟硼二吡咯；光动力疗法；光热疗法；活性氧；二聚体

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.2025.0066

Synthesis and Properties Study of BODIPY Dimer Derivatives for Combinational Phototherapy XIE Yu-qi, JIANG Yuan, ZHANG Meng, LIU Xiao-ting, WU Qing-hua, LI Li^* (School of Pharmacy, Anhui University of Chinese Medicine, Hefei 230012, China) 

Abstract：This study aims to develop a novel photosensitizer integrating synergistic photothermal therapy (PTT) and photodynamic therapy (PDT). A molecular engineering strategy was employed to design and synthesize a bis-triphenylamine (TPA)-substituted BODIPY dimer, with its molecular structure unambiguously confirmed by nuclear magnetic resonance and high-resolution mass spectrometry. Systematic photophysical characterization of the target compound revealed a remarkably red-shifted absorption band in the near-infrared region (780~800 nm), achieving a bathochromic shift of ~400 nm compared to conventional BODIPY monomers (λ_max ≈ 500 nm), which favors deep-tissue phototherapeutic applications. Under 808 nm laser irradiation, the target compound exhibited dual therapeutic functionalities: generation of singlet oxygen (¹O₂) via energy transfer pathways, and exceptional photothermal conversion efficiency (η = 60.6%), doubling that of the clinically used photosensitizer indocyanine green (ICG). Notably, the material retained over 90% of its photothermal performance after six consecutive laser cycles, demonstrating superior photostability compared to ICG rapid photobleaching behavior. In vitro experiments confirm significant tumor-killing effects against 4T1 cells, outperforming commercial photosensitizer ICG. The compound also displays enhanced biocompatibility and stability, showing important potential for deep-tissue therapeutic applications. This work provides a novel reference strategy for developing high-efficiency near-infrared phototherapeutic agents.

Key words：Fluoroboron dipyrrole; photothermal therapy；photodynamic therapy；active oxygen; dimer 

【电化学和新能源】

电化学传感器检测果蔬中农用杀菌剂的研究进展

赵锦瑶，王悦琪，惠怡帆，邱旭，顾菲菲，马廷梅，纳森巴特，杜海军^*

(伊犁师范大学 化学化工学院，新疆生物质资源清洁转化和高值化利用重点实验室，新疆 伊宁  835000）

摘要：果蔬表面残留的杀菌剂严重影响食用安全性和危害人体健康，因而引起了人们的高度关注。近年来，电化学传感器由于制备过程简单、响应速度快、灵敏度高等优点，构建电化学传感器快速检测杀菌剂依然是国内外研究的热点。鉴于此，归纳总结了不同类型的电化学杀菌剂传感器，重点突出了当前探索的主要电极材料包括有机框架（金属有机框架和共价有机框架）、金属和金属衍生物、碳材料（碳纳米管、石墨烯、g-C₃N₄）、MXene等在制备传感器的核心功能。这些纳米材料在电化学传感器中发挥着重要的作用，包括作为促进氧化还原的电催化剂、作为负载识别元件或催化剂的载体、作为识别目标的识别器。此外，还进一步分析了基于不同纳米材料电化学传感器的检测性能以及面临的挑战，为电化学传感器的进一步发展和应用以及真实样品中杀菌剂的检测提供理论参考和新的见解。

关键词：果蔬；农用杀菌剂；电化学传感器；纳米材料

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

DOI：10.13822/j.cnki.hxsj.2024.0486

Advances in the Detection of Agricultural Fungicides in Fruits and Vegetables Using Electrochemical Sensors ZHAO Jin-yao, WANG Yue-qi, HUI Yi-fan, QIU Xu, GU Fei-fei, MA Ting-mei, Nathan Bart, DU Hai-jun^* (Xinjiang Key Laboratory of Clean Conversion and High Value Utilization of Biomass Resources, College of Chemistry and Chemical Engineering, Yili Normal University, Yining 835000, PR China)

Abstract: The residual fungicides on fruits and vegetables seriously affect food safety and endanger human health, and the issue of pesticide residues exceeding the standard has attracted high attention from people. In recent years, due to the advantages of simple preparation process, fast response speed, and high sensitivity of electrochemical sensors, using electrochemical sensors as a sensing platform for rapid detection of fungicides remains a hot research topic both domestically and internationally. In view of this, this paper summarized the different types of electrochemical fungicides sensors, highlighting the central functions of the main electrode materials currently explored involving organic frameworks (metal-organic and covalent organic frameworks), metals and metal derivatives, carbon materials (carbon nanotubes, graphene, g-C₃N₄), MXene, etc. in the preparation of sensors. These nanomaterials play important roles in electrochemical sensors, including: (1) acting as electrocatalysts to promote redox, (2) serving as carriers for loaded identifying components or catalysts, (3) functioning as a recognizer for identifying targets. In addition, the detection performance of electrochemical sensors based on different nanomaterials and the challenges faced were further analysed, for the purpose of providing theoretical references and new insights for the further development as well as application of electrochemical sensors for the detection of fungicides in real samples.

Key Words: fruits and vegetables; agricultural fungicides; electrochemical sensors; construction; nanomaterials

氮碳掺杂NiCoO₂@N-C-X电极材料的制备及其超级电容器性能研究

张曼^*，王盈雪，王蕊，陈俞霖，任立新

（赤峰学院 化学与生命科学学院，内蒙古 赤峰  024000）

摘要：在全球能源转型和环境保护的大背景下，深入探讨了氮碳掺杂对镍钴基电极材料电化学性能及储能效果的影响机制。选取六水合硝酸钴与六水合硝酸镍作为主要前驱体，通过精细调控水热反应条件及退火处理工艺，成功制备了一系列氮碳掺杂比例不同的NiCoO₂@N-C-X电极材料。借助傅里叶红外光谱(FT-IR)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射仪(XRD)及X射线光电子能谱(XPS)等先进表征技术，系统分析了掺杂前后电极材料的微观形貌、晶体结构、元素组成及化学状态的变化。研究揭示，氮碳掺杂有效促进了电极材料形成中空海胆状纳米球结构，显著增加了比表面积和活性位点数量，进而提升了电极材料的导电性、电化学活性及循环稳定性。特别地，当氮碳掺杂比例为1时，NiCoO₂@N-C-1电极材料展现出最优的电化学性能，其比电容、电流密度及能量密度均显著高于未掺杂的NiCoO₂电极材料。此外，研究还进一步阐明了氮碳掺杂对电极材料电荷转移动力学及储能机制的影响，为高性能超级电容器电极材料的设计与制备提供了重要的理论依据和技术支撑。

关键词：超级电容器；镍钴基氧化物；电极材料；海胆状；氮碳掺杂

中图分类号：O646          文献标识码：A                        文章编号：0258-3283（2025）

DOI：10.13822/j.cnki.hxsj.2024.0223

Preparation of Nitrogen - Carbon Doped NiCoO₂@N - C - X Electrode Materials and Study on Their Supercapacitor Performance ZHANG Man^*, WANG Ying-xue, WANG Rui, CHEN Yu-lin, REN Li-xin (School of Chemistry and Life Sciences, Chifeng University, Chifeng 024000, China)

Abstract: In the backdrop of global energy transition and environmental conservation, this study delved deeply into the mechanism underlying the influence of nitrogen and carbon doping on the electrochemical performance and energy storage efficacy of nickel-cobalt-based electrode materials. Cobalt nitrate hexahydrate and nickel nitrate hexahydrate were chosen as the principal precursors. Through meticulous manipulation of the hydrothermal reaction conditions and annealing treatment processes, a series of NiCoO₂@N-C-X electrode materials with varying nitrogen and carbon doping ratios were successfully fabricated. Advanced characterization techniques, including Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffractometry (XRD), and X-ray photoelectron spectroscopy (XPS), were employed to systematically analyze the variations in the microscopic morphology, crystal structure, elemental composition, and chemical states of the electrode materials before and after doping. The findings demonstrated that nitrogen and carbon doping effectively facilitated the formation of a hollow sea urchin-like nanosphere structure in the electrode materials, remarkably augmenting the specific surface area and the quantity of active sites. This, in turn, enhanced the conductivity, electrochemical activity, and cycling stability of the electrode materials. Notably, when the nitrogen and carbon doping ratio was 1, the NiCoO₂@N-C-1 electrode material exhibited the most favorable electrochemical performance, with its specific capacitance, current density, and energy density being significantly higher than those of the undoped NiCoO₂ electrode material. Furthermore, this study further elucidated the impact of nitrogen and carbon doping on the charge transfer kinetics and energy storage mechanism of the electrode materials, thereby providing crucial theoretical foundations and technical support for the design and preparation of high-performance supercapacitor electrode materials.

Key words: supercapacitors; nickel cobalt based oxide; electrode materials; urchin-like; nitrogen-carbon doped

【化学品与环境】

陶瓷膜负载ZIF-67活化PMS降解染料废水的研究

罗顺，高常飞^*

（烟台大学 环境与材料工程学院，山东 烟台 264005）

摘要：随着纺织印染、造纸等行业染料废水排放量激增，其高色度、难降解特性对水生态系统构成严重威胁。传统硫酸根自由基高级氧化技术受限于均相催化剂金属浸出（如Co²⁺>1 mg/L）和非均相体系回收困难，而金属有机骨架材料ZIF-67虽具有高比表面积和优异过一硫酸盐（PMS）活化性能，但其粉末形态在连续流系统中易流失。针对上述问题，创新性开发多孔陶瓷膜原位负载ZIF-67的催化-分离一体化工艺：通过水热合成法在多孔陶瓷膜孔道内原位生长ZIF-67晶体，构建ZIF-67-CM复合催化膜，其比表面积显著提升。实验表明，在25℃、pH 7、跨膜压差0.1MPa、负载量0.032wt%条件下，ZIF-67-CM耦合0.9 mmol/L PMS对40 mg/L茜素红（ARS）和亚甲基蓝（MB）在30 min内去除率分别达99.2%与99.4%，较未负载膜提升>60%。机理研究表明，ZIF-67中Co²⁺通过界面电子转移活化PMS，同步产生单线态氧（¹O₂）、超氧自由基（）、硫酸根自由基（）和羟基自由基（·OH），其中为主要自由基主导ARS与MB的降解。该系统在pH 4 ~ 10范围内保持>95%去除率，证实了催化膜在宽pH范围下的稳定性与工程应用潜力，为工业废水处理提供了高效可靠的技术方案。

关键词：膜分离技术；亚甲基蓝；茜素红；ZIF-67；PMS

中图分类号：O643.3；X522             文献标识码:A          文章编号：0258-3283（2025）

DOI：10.13822/j.cnki.hxsj.2025.0068

Study on Degradation of Dye Wastewater by Activating PMS Loaded with ZIF-67 Ceramic Membrane LUO Shun, GAO Chang-fei^* (School of Environmental and Materials Engineering, Yantai University, Yantai 264005, China)

Abstract: With the rapid discharge of dye wastewater from textile printing and dyeing, papermaking, and other industries, its high chroma and recalcitrant characteristics pose a significant threat to aquatic ecosystems. Traditional sulfate radical-based advanced oxidation processes (SR-AOPs) are limited by metal leaching from homogeneous catalysts (e.g., Co²⁺ > 1 mg/L) and the recovery challenges of heterogeneous systems. Although the metal-organic framework material ZIF-67 exhibits a high specific surface area and excellent peroxymonosulfate (PMS) activation capability, its powdered form is prone to loss in continuous flow systems. To address these issues, this study innovatively developed an integrated catalytic separation process involving the in-situ loading of ZIF-67 onto a porous ceramic membrane. Using a hydrothermal synthesis method, ZIF-67 crystals were grown in situ within the pores of the ceramic membrane, thereby constructing a ZIF-67-CM composite catalytic membrane with a significantly enhanced specific surface area. Experimental results demonstrated that under conditions of 25°C, pH 7, transmembrane pressure difference of 0.1MPa, and a loading rate of 0.032wt%, the removal efficiencies of 40 mg/L alizarin red (ARS) and methylene blue (MB) achieved by coupling ZIF-67-CM with 0.9 mmol/L PMS reached 99.2% and 99.4%, respectively, within 30 minutes, representing an improvement of over 60% compared to the unloaded membrane. Mechanistic studies revealed that Co²⁺ in ZIF-67 activates PMS via interfacial electron transfer, simultaneously generating singlet oxygen (¹O₂), superoxide radicals (), sulfate radicals (), and hydroxyl radicals (·OH). Among these,  was identified as the dominant radical responsible for the degradation of ARS and MB. The system maintained a removal efficiency exceeding 95% across the pH range of 4?10, confirming the stability and engineering application potential of the catalytic membrane in a wide pH range and providing an efficient and reliable technical solution for industrial wastewater treatment.

Key words: membrane separation technology; methylene blue; alizarin red; ZIF-67; PMS

【分析与测试】

无需净化气相色谱质谱联用法测定奶制品中的三聚氰胺

肖雪¹，洪亮¹，陈华国^*2

(1.贵州师范大学 分析测试中心，贵州 贵阳  550001; 2. 贵州师范大学 山地环境与信息系统重点实验室，贵州 贵阳  550001）

摘要：针对现行《原料乳与乳制品中三聚氰胺检测方法》国家标准（GB/T 22388-2008）中气相色谱-质谱联用法在样品处理环节存在无法获取上清液进而无法开展后续净化与衍生化处理等弊端，旨在优化处理流程，构建一种无需净化步骤的气相色谱串联质谱法，以实现对奶粉中三聚氰胺的快速精准测定，为奶粉及其制品中三聚氰胺的高效检测及相关标准修订提供参考依据。分别以不同浓度的甲醇和乙腈溶液作为提取剂，在超声条件下提取样品中的三聚氰胺，无需净化直接衍生化后结合气相色谱串联质谱法检测，外标法对其进行定量分析。结果表明：50%乙腈作为提取剂，其蛋白沉淀及提取效果显著优于现行国家标准方法。样品经50%乙腈水溶液超声后，在分流比为1:10，多反应监测模式(MRM)， m/z：342>327（定量离子）, m/z：342>327、342>171（定性离子）的质谱条件下，在0～40 mg/kg呈现良好的线性关系，检出限为0.0007 mg/kg，定量限为0.002 mg/kg，平均回收率为96.33%～103.33%，相对标准偏差为1.86%～2.61%。该方法通过对提取试剂和检测条件进行改进，有效解决了无法获得上清液所带来的困扰，前处理简单、重复性好、结果准确可靠,能够对批量奶粉及奶制品中的三聚氰胺进行快速、有效测定。

关键词 奶粉；三聚氰胺；无需净化；乙腈；气相色谱-质谱/质谱法

中图分类号：O652.1              文献标识码：A              文章编号：0258-3283（2025）

DOI：10.13822/j.cnki.hxsj.2025.0012

Determination of Melamine in Milk Powder by Gas Chromatography-Mass Spectrometry without Purification XIAO Xue¹，HONG Liang¹,CHEN Hua-guo^*2 (1. Analysis and Testing center of Guizhou Normal University, Guiyang 550001, China; 2. Key Laboratory of Mountain Environment and Information System of Guizhou Normal University, Guiyang 550001, China)

Abstract: In view of the drawbacks of the gas chromatography-mass spectrometry (GC-MS/MS) method in the current national standard "Determination of Melamine in Raw Milk and Dairy Products" (GB/T 22388-2008) in the sample processing stage, such as the inability to obtain the supernatant, which makes it impossible to carry out subsequent purification and derivatization processes, this study aims to optimize the processing workflow and establish a gas chromatography-tandem mass spectrometry method that does not require a purification step. In this way, the rapid and accurate determination of melamine in milk powder can be achieved, and a reference basis can be provided for the efficient detection of melamine in milk powder and its products, as well as the revision of relevant standards. In this study, methanol and acetonitrile solutions at different concentrations were used as extractants respectively. Melamine in the samples was extracted under ultrasonic conditions. After direct derivatization without purification, the samples were detected by GC-MS/MS,

Key words: milk powder; melamine; without purification; acetonitrile; gas chromatography-mass spectrometry

固相萃取-高效液相色谱法测定亚麻油中酚类抗氧化剂的不确定度评定

蔡林森^*，马占花，宋宇杰，马洪英

（青海省产品质量检验检测院，青海 西宁  810008)

摘 要：采用固相萃取-高效液相色谱法（SPE-HPLC）测定亚麻油中特丁基对苯二酚（TBHQ）、叔丁基茴香醚（BHA）和2,6－二叔丁基对甲酚（BHT）3种抗氧化剂，并建立该方法的不确定度评定模型，以进一步提高亚麻油中抗氧化剂检测结果的准确性。采用固相萃取法对亚麻油样品进行预处理以去除杂质并富集目标抗氧化剂。使用高效液相色谱法对预处理后的样品中的3种抗氧化剂进行定量分析。根据CNAS-CL-01：2021《测量不确定度的要求》、JJF1059.1 -2012《测定不确定评定与表示》和RB/T 214-2017《检验检测机构资质认定能力评价检验检测机构通用要求》分析亚麻油中抗氧化剂测定方法的不确定度来源。通过对样品前处理、标准物质不确定度、标准物质配制过程、固相萃取过程、标准曲线拟合、仪器设备精密度和样品测定结果重复性等因素进行分析，量化各个分量建立合理的数学模型。亚麻油中3种抗氧化剂TBHQ、BHA和BHT的扩展不确定度分别为4.63%、4.61%、4.65%，测定结果表示为：X_TBHQ=(19.47±1.80)mg/kg、X_BHA=(19.65±1.81)mg/kg、X_BHT=(19.21± 1.79)mg/kg（k=2，P=95%）。建立方法对3种抗氧化剂测定结果的相对不确定度均小于5%，展现出良好的准确性和可靠性。影响方法不确定度的主要因素包括标准物质配制过程、SPE处理过程和仪器设备精密度。

关键词：不确定度；亚麻油；抗氧化剂；固相萃取；高效液相色谱法（HPLC）

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.2025.0006

Evaluation of Uncertainty in the Determination of Phenolic Antioxidants in Linseed Oil by Solid-Phase Extraction-High Performance Liquid Chromatography CAI Lin-sen^*，MA Zhan-hua， SONG Yu-jie，MA Hong-ying（Qinghai Product Quality Inspection and Testing Institute, Xining, Qinghai, 810008）

Abstract: To determine the three antioxidants tert-butylhydroquinone (TBHQ), butylated hydroxya- nisole (BHA), and 2,6-di-tert-butyl-4-methylphenol (BHT) in flaxseed oil using solid-phase extraction coupled with high-performance liquid chromatography (SPE-HPLC). An uncertainty evaluation model for this method was established to further improve the accuracy of antioxidant detection results in flaxseed oil. Flaxseed oil samples were pretreated using solid-phase extraction to remove impurities and enrich the target antioxidants. High-performance liquid chromatography was used for quantitative analysis of the three antioxidants in the pretreated samples. According to CNAS-CL-01:2021 "Requirements for Measurement Uncertainty", JJF1059.1 -2012 "Evaluation and Expression of Measurement Uncertainty", and RB/T 214-2017 "General Requirements for the Competence Evaluation and Accreditation of Testing and Inspection Laboratories", the sources of uncertainty in the determination method of antioxidants in flaxseed oil were analyzed. By analyzing factors such as sample pretreatment, uncertainty of standard materials, preparation process of standard materials, solid-phase extraction process, calibration curve fitting, precision of instruments and equipment, and the repeatability of measurement results, a reasonable mathematical model was established to quantify each uncertainty component. The expanded uncertainties for the three antioxidants TBHQ, BHA, and BHT in flaxseed oil were 4.63%, 4.61%, and 4.65%, respectively. The measurement results were expressed as: X_TBHQ = (19.47 ± 1.80) mg/kg, X_BHA = (19.65 ± 1.81) mg/kg, and X_BHT = (19.21 ± 1.79) mg/kg (k = 2, P = 95%). The established method demonstrated good accuracy and reliability with relative uncertainties for the determination results of the three antioxidants all being less than 5%. The main factors affecting the method's uncertainty included the preparation process of standard materials, the SPE process, and the precision of instruments and equipment.

Key words: uncertainty; flaxseed oil; antioxidants; solid-phase extraction; high-performance liquid chromato- graphy (HPLC)

HPLC-DAD检测胡豆莲多种有效成分

杨浩然，秦学^*

（重庆大学附属三峡医院，重庆  404000）

摘要：旨在建立一种高效液相色谱-二极管阵列检测法（HPLC-DAD），用于同时测定胡豆莲（Euchresta japonica）中7种主要有效成分的含量，包括金雀花碱、氧化苦参碱、牡荆素、毛蕊异黄酮、苦参碱、N-甲基金雀花碱和芒柄花素。采用迪马Platisil ODS色谱柱（250 mm × 4.6 mm, 5 μm），以0.1%甲酸（pH 1.9）-乙腈为流动相进行梯度洗脱，流速为1.0 mL/min，柱温为30 ℃，进样量为20 mL。根据各成分的最大吸收波长，分别设置检测波长。通过优化提取和色谱条件，7种成分在各自线性范围内（金雀花碱：7.27 ~ 72.74 mg/mL；氧化苦参碱：37.05 ~ 370.52 mg/mL；牡荆素：0.93 ~ 9.30 mg/mL；毛蕊异黄酮：0.64 ~ 6.44 mg/mL；苦参碱：34.04 ~ 340.44 mg/mL；N-甲基金雀花碱：3.51 ~ 35.08 mg/mL；芒柄花素：1.59 ~ 15.85 mg/mL）均表现出良好的线性关系（R² > 0.9980）。方法的平均加样回收率为95.70% ~ 103.99%，相对标准偏差（RSD）在2.44% ~ 5.10%之间，表明方法具有较高的准确度和精密度。对不同产地的胡豆莲样品进行分析，结果显示7种成分的含量差异较大，其中氧化苦参碱和苦参碱的含量较高，分别为5.21 ~ 11.75和3.62 ~ 9.57 mg/g。该方法操作简便、准确可靠，适用于胡豆莲药材的质量控制，为其临床应用和进一步研究提供了科学依据。

关键词: 胡豆莲；化学成分；高效液相色谱-二极管阵列检测法；质量控制；同一色谱条件

中图分类号：O657；R284.1      文献标识码：A      文章编号：0258-3283（2025）--

DOI：10.13822/j.cnki.hxsj.2024.0459

HPLC-DAD Detection of Multiple Active Components in Euchresta Japonica of Chinese Herbal Medicines with Local Characteristic YANG Hao-ran, QIN Xue^* (Chongqing University Three Gorges Hospital, Chongqing 404000, China)

ABSTRACT：This study aimed to establish a high-performance liquid chromatography-diode array detection (HPLC-DAD) method for the simultaneous determination of seven major active components in Euchresta japonica, including cytisine, oxymatrine, vitexin, calycosin, matrine, N-methylcytisine, and formononetin. A Dikma Platisil ODS column (250 mm × 4.6 mm, 5 μm) was used for the analysis. The mobile phase consisted of 0.1% formic acid (pH 1.9) and acetonitrile, which was applied in a gradient elution mode. The flow rate was set at 1.0 mL/min, the column temperature was maintained at 30 ℃, and the injection volume was 20 mL. The detection wavelengths were set according to the maximum absorption wavelengths of the respective components. Through the optimization of extraction and chromatographic conditions, the seven components exhibit good linear relationships within their respective linear ranges (cytisine: 7.27 ~ 72.74 μg/mL; oxymatrine: 37.05 ~ 370.52 μg/mL; vitexin: 0.93 ~ 9.30 μg/mL; calycosin: 0.64 ~ 6.44 μg/mL; matrine: 34.04 ~ 340.44 μg/mL; N-methylcytisine: 3.51 ~ 35.08 μg/mL; formononetin: 1.59 ~ 15.85 μg/mL), with determination coefficients (R²) over 0.9980. The method demonstrates high accuracy and precision, with average recovery rates ranging from 95.70% to 103.99% and relative standard deviations (RSD) between 2.44% and 5.10%. Analysis of Euchresta japonica samples from different regions reveals significant variations in the content of the seven components, among them, the contents of oxymatrine and matrine were relatively high, being 5.21 ~ 11.75 mg/g and 3.62 ~ 9.57 mg/g, respectively. This method is simple, accurate, and reliable, making it suitable for the quality control of Euchresta japonica and providing a scientific basis for its clinical application and further research.

Key Words: Euchresta japonica; chemical constituents; HPLC-DAD；quality control；same chromatographic conditions

快速微波消解结合电感耦合等离子体发射光谱法（ICP-OES）测定枸杞中金属元素研究

高绪安^*1，李胜生¹，谢飞²

(1. 安徽省地质实验研究所，安徽 合肥  230001；2. 安徽省建设工程测试研究院，安徽 合肥  230051)

摘要：为了实现对中药枸杞（Lycium barbarum）中的矿物元素进行快速、准确测定，有效解决传统消解方法存在的效率低、分解不完全等问题；建立了快速微波消解前处理结合电感耦合等离子体发射光谱法（ICP-OES）技术测定枸杞中的15种金属元素的方法。采用密闭式微波消解前处理实现对枸杞样品的快速、完全分解。通过正交实验优化微波消解参数，建立高效样品前处理体系。利用ICP-OES的高精度和宽线性范围特性，成功检测了枸杞中的15种矿物元素，包括Na、K、S、Mg、P、Si、Ca、Fe、Al、Ti、Zn、Mn、Cu、Ba和Cr；通过测定不同实验条件下的加标回收率，对建立方法消解温度、消解时间、消解压力进行优化，确定了最佳的实验条件为200 ℃下，采用HNO₃/H₂O₂混合消解体系在最终消解压力为3.5MPa下消解10分钟，枸杞中15种元素的加标回收率均在90 %以上；结论：本研究建立的方法体系灵敏度高（多数元素LOD<1 mg/L）、精密度好（RSD<3.5%）、线性范围宽（0.025-50 mg/L），实验结果为开展枸杞的药理学研究提供了重要的基础数据。

关键词：枸杞；微波消解；ICP-OES；金属元素分析；加标回收；准确度；精密度

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.2025.0003

Study on the Determination of Metal Elements in Lycium barbarum by Rapid Microwave Digestion Combined with Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) GAO Xu-an¹, LI Sheng-sheng¹, XIE Fei^*2 (1. Anhui Provincial Institute of Geological Experiment, Hefei, 230001 China; 2. Anhui Construction Engineering Testing and Research Institute Co. Ltd., Hefei 230051, China)

Abstract： To achieve rapid and accurate determination of mineral elements in the traditional Chinese herb Lycium barbarum (wolfberry), addressing the inefficiency and incomplete decomposition of conventional digestion methods, a method integrating rapid microwave digestion pretreatment with inductively coupled plasma optical emission spectrometry (ICP-OES) was developed to quantify 15 metallic elements (Na, K, S, Mg, P, Si, Ca, Fe, Al, Ti, Zn, Mn, Cu, Ba, and Cr) in wolfberry. Closed-vessel microwave digestion ensured complete sample decomposition. Orthogonal experiments optimized key parameters (temperature, time, pressure) to establish an efficient pretreatment system. ICP-OES leveraged its high precision and broad linear range for multi-element detection. Optimal digestion conditions (200°C, 3.5 MPa, 10 min with HNO₃/H₂O₂) yielded spiked recoveries >90% for all elements. The method demonstrated high sensitivity (detection limits: 0.002 mg/L for Ba to 2.44 mg/L for Na), excellent precision (RSD <3.5%), and a wide linear range (0.025-50 mg/L). This robust analytical system provides reliable foundational data for pharmacological research on wolfberry, supporting quality evaluation and mechanistic studies on its health benefits.

Key words：lycium barbarum; microwave digestion; ICP-OES; metal element analysis; spiked recovery; accuracy; precision

【合成与应用】

高效芳甲硫醚化反应合成光引发剂TPMK

罗勇波¹，程格^*2

(1. 台州科技职业学院，浙江 台州  318020；2. 台州生物医化产业研究院，浙江 台州318000)

摘要：四丁基溴化铵相转移催化中间体2-甲基-2-(4-吗啉基)-1-(4-氯苯基)-1-丙酮(IV) 与质量分数为20%的甲硫醇钠水溶液的芳甲硫醚化反应合成光引发剂2-甲基-1-[4-(甲硫基)苯基)-2-(4-吗啉基)-1-丙酮(TPMK) 是目前TPMK合成工艺中的关键反应步骤，但在该反应中存在相转移催化效率不稳定、四丁基溴化铵耗量大、后处理中因四丁基溴化铵回收难度大导致的生产废水中含大量季铵盐类有机污染物、废水处理费用增加以及对TPMK产品纯度的影响等问题；为了克服这些弊端，偶极非质子溶剂N ̶ 甲基吡咯烷酮（NMP）和二甲亚砜（DMSO）被筛选出来取代四丁基溴化铵而介入该反应中，增强反应介质对阴离子CH₃S ^̶ 亲核试剂的去溶剂化效应、促成中间体IV分别在NMP-H₂O和DMSO-H₂O中与甲硫醇钠的高效芳甲硫醚化反应合成光引发剂TPMK；在优化反应条件基础上，获得了不采用催化剂、中间体IV与甲硫醇钠芳甲硫醚化反应的最佳反应条件及结果参数为：水在反应介质NMP-H₂O和DMSO-H₂O中的体积分数j(%)为28%、甲硫醇钠相对于中间体IV的摩尔分数c(%)为64%、反应温度为116 ~ 120 ^oC，反应转化率在2 h内达100%，产物光引发剂TPMK的收率达97 %，GC纯度达98.9 %，为避免使用四丁基溴化铵、改进目前光引发剂TPMK合成工艺提供了科学依据。 

关键词：甲硫醇钠；N ̶ 甲基吡咯烷酮（NMP）；二甲亚砜（DMSO）；偶极非质子溶剂；2-甲基-1-(4-氯苯基)-2-吗啉基-1-丙酮；芳甲硫醚化反应；2-甲基-1-[4-(甲硫基)苯基)-2-(4-吗啉基)-1-丙酮；光引发剂TPMK
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.2025.0010

Synthesis of Photoinitiator TPMK by Highly Efficient Aryl Methylthiolation Luo Yong-bo¹，Cheng Ge*² (1. Taizhou Vocational College of Science & Technology，Taizhou 318020， China；2. Taizhou Bio-medical Industry Research Institute，Taizhou 318000， China) 

Abstract: The key step in the current synthesis process of the photoinitiator, 1-(4-methylthiophenyl)-2-methyl-2 -morpholinopropan-1-one (TPMK), is the aryl-methylthiolation of 1-(4-chlorophenyl)-2-methyl-2- morpholinopropan-1-one (IV) with aqueous solution of sodium methanethiolate with a mass fraction of 20% under liquid-liquid phase-transfer catalysis (PTC) catalyzed by tetrabutylammonium bromide. However, in this reaction, there are problems, such as the unstable phase transfer catalysis efficiency, the high consumption of tetrabutylammonium bromide with its difficulty in recovery , which lead to a large amount of quaternary ammonium salt as organic pollutants in the production wastewater with wastewater treatment costs increased as well as the side-effect on the purity of TPMK. In order to overcome these disadvantages, dipolar aprotic solvents, N-methylpyrrolidone (NMP) and dimethyl sulfoxide (DMSO) were selected to replace tetrabutylammonium bromide and introduced into in the reaction to enhance the desolvation effect of the reaction medium on anionic nucleophile CH₃S^- for prompting the higly efficient aryl-methylthiolation of intermediate IV with sodium methanethiolate in NMP-H₂O and DMSO-H₂O, respectively. Based on optimizing the reaction conditions, the reaction parameters for the higly efficient aryl-methylthiolation of intermediate IV with sodium methanethiolate without any catalyst were obtained as follows: the volume fraction of water in NMP-H₂O and DMSO-H₂O j (%) as 28%, the molar fraction of sodium methanethiolate relative to intermediate IV c(%) is 64%, the reaction temperature is 116 ~ 120 ^oC, and the conversion of intermediate IV reaches 100% within 2 hours with the yield of the photoinitiator TPMK is 97% and the GC purity is 98.9%. It provided a scientific basis for avoiding the use of tetrabutylammonium bromide and improving the synthesis process of TPMK.

Key words：sodium methanethiolate; N-methylpyrrolidone (NMP); dimethyl sulfoxide (DMSO); dipolar aprotic solvents; 1-(4-chlorophenyl)-2-methyl-2-morpholinopropan-1-one; aryl-methylthiolation; 1-(4-methylthiophenyl)- 2-methyl -2- morpholinopropan-1-one; photoinitiator TPMK