【特约专稿】

UHPLC-HRMS结合AntDAS剖析不同产地金银花特征物质

及产地溯源研究

白莲¹，周婕婕²，余海花¹，王龙鹤¹，李淑芳³，刘文斌³，樊亚玲⁴，韩璐¹，于永杰^*1

(1.宁夏医科大学 药学院，宁夏银川 750004；2. 青岛大学附属青岛市口腔医院，山东青岛 266001；3. 河南省农业科学院 农产品质量安全研究所，河南郑州 450002；4. 陕西中烟工业有限责任公司，陕西 西安 721000)

摘要：剖析河南封丘、河南新密、山东平邑、宁夏中卫4个产区的金银花样本中化合物构成，并建立产地溯源模型，为金银花道地性鉴别及产业规范化发展提供技术支撑；超高效液相色谱-高分辨质谱联用技术（UHPLC-HRMS）结合色质谱数据分析软件AntDAS-DDA进行化合物信息提取、对齐、差异性成分筛查以及化合物鉴定，基于筛选的差异性代谢物评价4种经典化学计量学方法构建的产地判别模型；最终筛选并鉴定出11种类别共62个差异代谢物，涵盖黄酮类、香豆素类、酚酸类等。基于上述差异代谢物构建PLS-DA模型拟合度及预测能力良好（R²>0.9, Q²>0.8），可准确区分4个产区的金银花样本，模型准确率为98.60％；不同产区金银花的差异代谢物存在显著差异，其中新密产区黄酮类化合物含量较高，封丘产区中萜类成分更为丰富，所建立的产地判别模型能够有效区分样本来源。研究结果有望为我国金银花产业规范化发展提供支持。

关键词：金银花；产地判别；超高效液相色谱-高分辨质谱联用技术（UHPLC-HRMS）；AntDAS-DDA；化学计量学

中图分类号：O657.3      文献标识码：A      文章编号：0258-3283（2026）--

DOI：10.13822/j.cnki.hxsj.2026.0094 

Analysis of Characteristic Components and Geographical Origin Traceability of Lonicerae Japonicae Flos from Different Producing Areas by UHPLC-HRMS Combined with AntDAS BAI Lian¹, ZHOU Jie-jie², YU Hai-hua¹,WANG Long-he¹, LI Shu-fang³, LIU Wen-bin, FAN Ya-ling, HAN Lu¹, YU Yong-jie^*1 (1. College of Pharmacy, Ningxia Medical University, Yinchuan 750004,China; 2. Qingdao Stomatological Hospital Affiliated to Qingdao University, Qingdao 266001, China; 3. Institute of Quality and Safety for Agro-products, Henan Academy of Agricultural Science, Zhengzhou 450002, China; 4. China Tobacco Shaanxi Industrial Co., Ltd., Xi’an 721000, China)

Abstract: The chemical compositions of Lonicerae japonicae Flos samples from four producing areas―Fengqiu, Henan; Xinmi, Henan; Pingyi, Shandong and Zhongwei, Ningxia―were analyzed, and a geographic origin traceability model was established to provide technical support for the authentic identification of Lonicerae japonicae Flos and the standardized development of the Lonicerae japonicae Flos industry. Ultrahigh-performance liquid chromatography?high-resolution mass spectrometry (UHPLC-HRMS) and the data analysis software AntDAS-DDA were used for compound data extraction, alignment, screening of differential components, and compound identification. Geographic origin discrimination models constructed using four classical chemometric methods were evaluated based on the screened differential metabolites. A total of 62 differential metabolites belonging to 11 categories, including flavonoids, coumarins, and phenolic acids, were screened and identified. The partial least-squares discriminant analysis model, constructed based on the differential metabolites, exhibited excellent goodness of fit and predictive ability (R² > 0.9, Q² > 0.8) and accurately distinguished Lonicerae japonicae Flos samples from the four producing areas, with a model accuracy of 98.60%. Significant differences were found in differential metabolites of Loniceras japonicas Flos from different producing regions. Lonicerae japonicae Flos from Xinmi area had higher flavonoid contents, while Fengqiu-derived samples were richer in terpenoids. The established origin discrimination model could effectively differentiate sample origins. These results are expected to facilitate the standardized development of the Loniceras japonicas Flos industry in China.

Key words: Lonicerae japonicae Flos; geographical origin discrimination; UHPLC-HRMS; AntDAS-DDA; chemometrics

叶酸修饰的hBN(Ni)NS靶向递送卡莫司汀的DFT研究

许志鹏，任婷，孙国辉，张娜，钟儒刚，赵丽娇^*

(北京工业大学化学与生命科学学院环境与病毒肿瘤学北京市重点实验室，北京  100124） 

摘要：针对抗癌药物卡莫司汀（BCNU）稳定性差和缺乏靶向性等问题，设计了一种能够靶向叶酸（FA）受体的金属掺杂氮化硼纳米载体，用于BCNU的靶向递送，并探究了该FA修饰的羟基化镍掺杂氮化硼纳米片（FA-hBN(Ni)NS）对BCNU的靶向递送机制。采用密度泛函理论（DFT）在B3LYP/6-31+G(d,p)水平下，对FA-hBN(Ni)NS与BCNU相互作用的几何结构、吸附能、电子性质、电荷转移以及QTAIM拓扑性质进行了分析，并与未经FA修饰的hBN(Ni)NS进行了比较。结果表明，FA修饰不但提高了载体对药物的负载能力，而且BCNU/FA-hBN(Ni)NS复合物体系的偶极矩显著提升，使其能有效避免在液相生理系统中产生团聚现象。QTAIM分析表明载体与药物间相互作用均为闭壳层相互作用，且载体中的Ni原子与卡莫司汀（BCNU）药物分子形成了部分共价的强相互作用。此外，吸附过程伴随着从载体向药物的电荷转移，导致体系能隙发生改变，形成的复合物具有更高的反应活性。不仅证实了改性氮化硼纳米材料在抗肿瘤药物靶向递送领域的可行性，也为新型无机纳米药物载体的设计提供了新思路。

关键词：氮化硼纳米片；卡莫司汀；叶酸修饰；密度泛函理论；药物递送

中图分类号：O62      文献标识码：A      文章编号：0258-3283（2026）-- 

DOI：10.13822/j.cnki.hxsj.2026.0080

DFT Study on Targeted Delivery of Carmustine by Folate-Modified Ni-Doped Boron Nitride Nanosheets  XU Zhi-peng, REN Ting, SUN Guo-hui, ZHANG Na, ZHONG Ru-gang, ZHAO Li-jiao^* (Beijing Key Laboratory of Environmental and Viral Oncology, College of Chemistry and Life Science, Beijing University of Technology, Beijing 100124, China)

Abstract：To address the issues of poor stability and lack of targeting capability of the anticancer drug carmustine (BCNU), a metal-doped boron nitride nanocarrier targeting folate (FA) receptor was designed for the targeted delivery of BCNU. Furthermore, the targeted delivery mechanism of BCNU using FA-modified hydroxylated nickel-doped boron nitride nanosheets (FA-hBN(Ni)NS) was investigated. Using density functional theory (DFT) at the B3LYP/6-31+G(d,p) level, the geometric structures, adsorption energies, electronic properties, charge transfer, and QTAIM topological properties of the interaction between the FA-hBN(Ni)NS and BCNU were analyzed and compared with those of the unmodified hBN(Ni)NS. The results demonstrated that FA modification enhanced the drug-loading capacity of the carrier and significantly increased the dipole moment of the BCNU/FA-hBN(Ni)NS complex system, which effectively prevented agglomeration in liquid physiological environments. QTAIM analysis indicated that the interactions between the nanocarrier and the drug were exclusively closed-shell interactions, and that the Ni atom in the carrier formed a strong partially covalent interaction with the BCNU molecule. Furthermore, the adsorption process was accompanied by charge transfer from the carrier to the drug, leading to an alteration in the energy gap of the system and higher reactivity of the complex. This study confirms the feasibility of modified boron nitride nanomaterials for the targeted delivery of antitumor drugs and provides new insights into the design of novel inorganic nanodrug carriers.

Key words：BN nanosheet; carmustine; folic acid modification; density functional theory; drug delivery

【生化与药用试剂】

苯并噻二唑类化合物的高效合成与脂滴的荧光成像应用

杨莉，颜家宇，李静璨，张益蓉，任常?h^*，李新民^*

（遵义医科大学药学院，贵州遵义  563000）

摘要：苯并噻二唑类化合物因其优异的光物理性质和化学稳定性，在荧光探针、生物成像等领域具有重要应用价值。但现有合成方法需使用昂贵膦配体、有毒溶剂，且普遍存在反应时间长、需要高温等严苛反应条件，严重制约其实际应用。针对上述问题开发了一种无配体、绿色高效的Suzuki偶联体系，以醋酸钯为催化剂、碳酸钾为碱，乙醇和水混合溶液为反应介质，实现了4,7-二溴-2,1,3-苯并噻二唑与不同取代芳基硼酸的偶联，成功合成12个苯并噻二唑类化合物，最高收率达97%。光物理测试表明，12个化合物多为极性响应型分子，随着溶剂极性增强，化合物的发射波长发生红移；其中BTD-6的极性响应性能最佳，并且其荧光特性在复杂生物环境中保持稳定，不受pH、粘度、温度等因素的干扰。MTT细胞毒性实验证明BTD-6具有良好的生物相容性，无明显细胞毒性。激光共聚焦成像结果显示，BTD-6在HeLa细胞和HT-1080细胞中均能特异性靶向脂滴，可实时检测细胞内脂滴含量的动态变化，为脂滴相关生物成像领域提供了性能优良的荧光探针。本文为苯并噻二唑类化合物的绿色合成提供了一种新策略，BTD-6探针在脂滴靶向成像中展现出优异性能，为相关疾病诊断与机制研究奠定了重要基础。

关键词：苯并噻二唑；Suzuki反应；无配体；绿色合成；脂滴；荧光成像；极性响应

中图分类号：O62      文献标识码：A      文章编号：0258-3283（2026）--

DOI：10.13822/j.cnki.hxsj.2026.0020

Efficient Synthesis of Benzothiadiazole Compounds and Their Application in Fluorescent Imaging of Lipid Droplets YANG Li, YAN Jia-yu, LI Jing-can, ZHANG Yi-rong, REN Chang-yue^*, LI Xin-min^* (College of Pharmacy, Zunyi Medical University, Zunyi 563000, China) 

Abstract: Owing to their outstanding photophysical properties, robust chemical stability, and facile structural modifications, benzothiadiazole derivatives have important applications in the fields of fluorescent probes, biological imaging, and related interdisciplinary research. However, the currently reported synthetic routes for these functional compounds are plagued by prominent limitations, such as the reliance on costly phosphine ligands, use of toxic volatile organic solvents, and harsh reaction conditions, including prolonged reaction duration and elevated temperatures, which greatly restrict their large-scale preparation and practical application. To overcome these limitations, we developed a highly efficient ligand-free and eco-friendly Suzuki coupling reaction. This system uses palladium acetate as the catalyst, potassium carbonate as the base, and an ethanol?water solution as the green reaction medium to realize efficient coupling between 4,7-dibromo-2,1,3-benzothiadiazole and arylboronic acids bearing diverse substituents. Using this optimized protocol, 12 benzothiadiazole compounds were synthesized in isolated product yields of up to 97%. Photophysical property tests demonstrated that nearly all 12 target compounds were polarity-responsive molecules whose emission wavelengths exhibited a significant redshift with increasing solvent polarity. Among them, BTD-6 displays optimal polarity-responsive performance, and its fluorescence characteristics remain highly stable in complex biological environments without interference from microenvironmental factors, such as pH, viscosity, or temperature. MTT assays confirmed that BTD-6 possesses favorable biocompatibility without obvious cytotoxicity. Laser confocal microscopy imaging demonstrated that BTD-6 has a specific lipid droplet?targeting capability in both HeLa and HT-1080 cells, enabling real-time detection of dynamic changes in intracellular lipid droplet content, thus serving as a high-performance fluorescent probe for lipid droplet?related biological imaging. This study provides a novel green synthetic strategy for benzothiadiazole-based compounds, and the developed BTD-6 probe shows excellent performance in lipid droplet-targeted imaging and dynamic monitoring, laying an important foundation for the diagnosis of related diseases and mechanistic research.

Key words：benzothiadiazole; Suzuki reaction; ligand-free; green synthesis; lipid droplet; fluorescence imaging; polarity response

【化学品与环境】

高效液相法测定颜料中氯己定等3种防腐剂的含量

邵秋凤^*，蒋莹，张慧

（上海市质量监督检验技术研究院有限公司，上海  201114）

摘要：颜料在工业和日常生活中运用广泛，常应用于绘画、涂料等，根据颜料的特性，除了颜填料或染料外，存在大量天然成分和水等溶剂，存在滋生微生物和霉菌的营养成分和条件，都不可避免使用防腐剂延长使用期限。氯己定、氯二甲酚和己脒定二（羟基磺酸）盐是较为常见的防腐剂，但其仍为有害物质。因此，需要建立相应的防腐剂检测方法控制防腐剂的限量。以甲醇作为提取溶剂，通过超声提取2次后，离心并过滤，滤液通过高效液相色谱进行梯度分离，二级阵列检测器检测，用外标法定量。3种防腐剂在0.50 ~50.0 mg/L范围内线性关系良好，相关系数均大于0.995。检出限分别为氯己定0.05 mgL、己脒定二（羟基磺酸）盐0.05 mg/L和氯二甲酚0.1 mg/L，平均加标回收率为95%~110%，重复性RSD均小于1%。方法简便、快速、准确、可靠，适用于颜料中氯己定、氯二甲酚和己脒定二（羟基磺酸）盐的含量测定。 

关键词：氯己定；氯二甲酚；己脒定二（羟基磺酸）盐；颜料；高效液相色谱法

中图分类号：O65      文献标识码：A      文章编号：0258-3283（2026）--

DOI: 10.13822/j.cnki.hxsj.2026.0045

Method for Determining the Content of Three Preservatives including Chlorhexidine in Pigments by High-Performance Liquid Chromatography SHAO Qiu-feng*, JIANG Ying, ZHANG Hui (Shanghai Institute of Quality Inspection and Technical Research, Shanghai 201114, China)

Abstract：Pigments are widely used in industry and daily life, particularly in applications such as painting and coatings. Due to their composition, which includes pigments, fillers, dyes, natural components, and solvents (e.g., water), these materials provide an environment conducive to the growth of microorganisms and molds. Therefore, preservatives are inevitably used to extend their service life. Common preservatives such as chlorhexidine, chlorhexylphenol, and hexamidine diisethionate are effective but may pose potential health risks. Therefore, it is necessary to establish reliable detection methods for preservatives to monitor and control their limits. In this study, a new analytical method was developed for the determination of chlorhexidine, chloroxylenol, and hexamidine diisethionate in paints using high-performance liquid chromatography. Methanol was employed as the extraction solvent in combination with ultrasonic extraction, and quantification was performed using an external standard.

A linear correlation was observed between peak area and analyte concentrations over the range of 0.50 ～ 50.0 mg/L, with the correlation coefficients exceeding 0.995 for all compounds. The limits of determination (LOD) were 0.05 mg/L for chlorhexidine, 0.05 mg/L for hexamidine diisethionate, and 0.1 mg/L for chlorhexylphenol. The average spiked recoveries were 95%～110%, and the repeatability for all analytes was below 1% (RSD, n = 7). This method is simple, rapid, accurate, reliable, and suitable for the determination of chlorhexidine, chlorodicresol, and hexamidine diisethionate in pigments-based materials.

Key words: chlorhexidine; cloroxylenol; hexamidine diisethionate; pigments; HPLC

双模板分子印迹聚合物制备及其对有机磷农药选择性识别

王斌^1,2，肖怀秋*²，廖红光^1,2，李玉珍²，廖琼^1,2，王维¹

（1. 湖南化工职业技术学院制药与生物工程学院，湖南株洲  412000；2. 天然产物活性成分研究与利用湖南省高等职业学校应用技术创新中心，湖南株洲  412000）

摘要：针对传统双模板分子印迹聚合物中不同模板分子竞争同一识别位点所导致的吸附效率与选择性下降的关键难题，提出了一种空间隔离识别位点的构建策略。以毒死蜱（CPF）和甲基对硫磷（MP）为双模板分子，分别采用聚苯乙烯-b-聚丙烯酸（PS-b-PAA）和β-环糊精（β-CD）作为介孔与微孔致孔剂，通过分步印迹策略成功制备了具有分级孔道结构的双模板分子印迹聚合物（HpDt-MIPs）。采用透射电子显微镜（TEM）、比表面积分析（BET）及傅里叶变换红外光谱（FT-IR）等手段对材料的形貌、孔道结构及化学组成进行了系统表征。结果表明，HpDt-MIPs呈现出0.7和2.1 nm的双峰孔径分布，比表面积高达387.2 m²/g。吸附性能测试显示，在318 K条件下，HpDt-MIPs对CPF和MP的平衡吸附量分别达到230.29和222.39 mg/g，对应的印迹因子分别为12.32和10.74，表现出优异的特异性识别与吸附能力。研究为复杂基质中多目标污染物的高效富集与分离提供了一种新型材料设计思路。

关键词：毒死蜱；甲基对硫磷；双模板分子印迹；分级孔道；空间隔离识别位点

中图分类号：O62   文献标识码：A             文章编号：0258-3283（2026）

DOI: 10.13822/j.cnki.hxsj.2026.0084

Construction of Hierarchical Porous Dual-template Molecularly Imprinted Polymers for Selective Recognition of Chlorpyrifos and Methyl Parathion WANG Bin^1,2, XIAO Huai-qiu^*2, LIAO Hong-guang^1,2 LI Yu-zhen², LIAO Qiong^1,2, WANG Wei¹(1.College of Pharmaceutical and Bioengineering, Hunan Chemical Vocational Technology College, Zhuzhou 412000, China; 2. Hunan Vocational Applied Tech Innovation Center for Natural Product Active Ingredients Research & Utilization, Zhuzhou 412000, China)

Abstract: The simultaneous recognition and adsorption of multiple target pollutants by conventional dual-template molecularly imprinted polymers (MIPs) is often severely compromised by competition between different template molecules for the same recognition sites, yielding reduced adsorption efficiency and poor selectivity. To address this critical issue, this study proposed a novel strategy based on spatially isolated recognition sites. Using chlorpyrifos (CPF) and methyl parathion (MP) as dual templates, along with polystyrene-b-polyacrylic acid and β-cyclodextrin as mesoporous and microporous porogens, respectively, a hierarchically porous dual-template molecularly imprinted polymer (HpDt-MIPs) was fabricated via a stepwise imprinting method. The morphology, porous structure, and chemical composition of the resulting polymer were thoroughly characterized via transmission electron microscopy, Brunauer?Emmett?Teller surface area analysis, and Fourier-transform infrared spectroscopy. The characterization results revealed that the HpDt-MIPs possessed a bimodal pore size distribution with distinct peaks at 0.7 and 2.1 nm, and exhibited a high specific surface area of 387.2 m²/g. The adsorption performance was systematically evaluated under various conditions. Equilibrium adsorption experiments conducted at 318 K demonstrated that the HpDt-MIPs achieved outstanding adsorption capacities of 230.29 and 222.39 mg/g for CPF and MP, respectively. Moreover, the CPF and MP imprinting factors were as high as 12.32 and 10.74, respectively, indicating exceptional specific recognition ability for both target molecules. This remarkable adsorption selectivity was attributed to the spatially separated imprinting sites, which were derived from the distinct pore-forming agents, and the stepwise imprinting strategy, which effectively eliminated mutual interference between the two templates. These results demonstrated that the proposed hierarchically porous architecture with spatially isolated recognition sites not only resolved the long-standing competition problem for dual-template MIPs but also significantly enhanced their binding capacity and selectivity. This study provides a promising material design paradigm for the efficient enrichment and separation of multiple target pollutants in complex environmental and food matrices, which may be widely applied in sample pretreatment and sensing.

Key words: chlorpyrifos; methyl parathion; dual-template molecular imprinting; hierarchical pores; site spatial isolation

LC-QTOF-MS测定生活饮用水中的27种PFAS化合物

王玮^*，邢玉瑾

（默克化工技术（上海）有限公司，上海  200120）

摘要：建立了液相色谱-四极杆-飞行时间质谱联用方法（Liquid chromatography quadrupole time-of-flight mass spectrometry method，LC-QTOF-MS），可同时对生活饮用水中27种全氟和多氟烷基物质（PFAS）进行定性与定量分析，旨在应对PFAS这类作为“永久化学品”对饮用水安全带来的潜在健康风险。样品经过固相萃取（SPE）前处理技术完成富集与净化处理，可有效消除基质干扰，显著提升检测灵敏度。质谱分析采用FullMS-ddMS²模式进行定性分析；外标法进行定量分析。方法学验证结果表明，27种PFAS化合物在0.005 ～ 0.2 mg/L线性浓度范围内具有良好的线性响应，相关系数R²均大于0.9980。加标回收率为82.9 %～108 %，相对标准偏差为1.2 % ～ 8.6 %，27种PFAS化合物的定量限为0.01～0.05 ng/mL。各项指标均满足痕量分析要求。方法可实现生活饮用水中PFAS的检测和分析，具有较高的准确性和可靠性。为市场监管部门开展饮用水质量监督抽查提供核心技术支撑，同时也为饮用水PFAS污染溯源、风险评估提供科学依据。

关键词：液相色谱-四极杆-飞行时间质谱；全氟和多氟烷基物质（PFAS）；固相萃取；生活饮用水；痕量分析

中图分类号：O657.3      文献标识码：A      文章编号：0258-3283（2026）--

DOI：10.13822/j.cnki.hxsj.2026.0097

Determination of 27 PFAS in Drinking Water by Liquid Chromatography-Quadrupole Time-of-Flight Mass Spectrometry (LC-QTOF-MS) WANG Wei^*, XING Yu-jin (Merck Chemical Technology (Shanghai) Co., LTD, Shanghai 200120, China)

Abstract: A liquid chromatography?quadrupole time-of-flight mass spectrometry (LC-QTOF-MS) method was established for the simultaneous qualitative and quantitative determination of 27 per- and polyfluoroalkyl substances (PFAS) in drinking water, aiming to address the potential health hazards posed by PFAS, commonly dubbed “forever chemicals.”Solid phase extraction was integrated into the sample pretreatment workflow to achieve target enrichment and matrix purification, which effectively mitigated matrix interference and drastically improved the analytical system’s detection sensitivity. The full-scan MS with data-dependent MS² (Full MS-ddMS²) acquisition mode was deployed for precise qualitative screening of target PFAS contaminants. External standard calibration was applied for the quantitative analysis, and method validation was systematically implemented to assess the overall analytical performance. The 27 PFAS exhibited excellent linear fitting results within the concentration range of 0.005～0.2 mg/L, with all coefficients of determination (R²) exceeding 0.9980. The spiked recoveries ranged from 82.9% to 108%, and the relative standard deviations (RSD) ranged from 1.2% to 8.6%. The limits of quantification for all 27 target PFAS were in the range of 0.01～0.05 ng/mL. All validation indicators fully complied with the technical specifications for trace-level contaminant analysis in aqueous matrices. With its demonstrated high accuracy and robust stability, this approach is promising for the routine detection and comprehensive analysis of PFAS residues in drinking water. It provides crucial technical support for market supervision authorities conducting random inspection programs on drinking water quality, as well as reliable scientific references for pollution source tracing and health risk assessment of PFAS contamination in drinking water supply systems.

Key words: liquid chromatography quadrupole time-of-flight mass spectrometry; perfluorinated and polyfluoroalkyl substances (PFAS); solid-phase extraction; drinking water; trace analysis

【分析与测试】

金丹附延颗粒挥发油化学成分鉴定及5个主要成分含量测定

朱良辉¹，刘德鸿¹，吴倩颖^1,2，陈伟康^*1，朱作为¹，陈希¹，缪贵忠³

（1. 江西省药品检验检测研究院 江西省药品医疗器械质量工程研究中心，江西南昌  330029；2. 江西中医药大学 药学院，江西南昌  330004；3.江西华太药业有限公司，江西宜丰  336300）

摘要：建立金丹附延颗粒挥发油中间体中化学成分的成分解析与定量测定方法，完善该制剂质量控制体系。采用气相色谱-质谱联用（Gas Chromatography-Mass Spectrometry，GC-MS）技术及NIST谱库对挥发油中间体中的化学成分进行成分解析。通过解析结果，优化气相色谱-氢火焰离子化检测器（Gas Chromatography-Flame Ionization Detector，GC-FID）色谱条件，同时测定挥发油中间体中的α-蒎烯、D-柠檬烯、α-榄香烯、β-榄香烯、桂皮醛5种代表性成分含量，并开展系统方法学验证与17批样品含量测定。结果显示，从挥发油中间体中共鉴定出21个挥发性成分并完成挥发油药材来源归属；5种目标成分在各自浓度范围内线性关系良好（R²≥0.9972），仪器精密度、样品稳定性、方法重复性的相对标准偏差（RSD）均小于2.2%，加样回收率为99.27%~103.00%，RSD均小于3%；17批样品中5种成分含量分别为15.75~24.35、25.12~37.86、33.26~39.54、24.02~28.06、58.57~66.72 mg/g，上述成分在挥发油中间体中含量存在一定波动，分析原因为原料饮片质量波动及提取工艺存在细化不足。方法操作简便、专属性强、准确度高，可用于金丹附延颗粒挥发油的成分鉴别与含量测定，填补了该制剂挥发油质量控制研究的空白，为其质量评价、生产工艺优化及全过程质量管控提供科学依据。

关键词：金丹附延颗粒；挥发油；气相色谱-质谱联用；气相色谱法；成分鉴定；含量测定

中图分类号：O657                文献标识码：A              文章编号：0258-3283(2026)--

DOI：10.13822/j.cnki.hxsj.2026.0100

Identification of Chemical Constituents and Quantitative Determination of Five Major Components in Volatile Oil from Jindan Fuyan Granules ZHU Liang-hui¹, LIU De-hong¹, WU Qian-ying^1,2, CHEN Wei-kang^*1, ZHU Zuo-Wei¹, CHEN Xi¹, MIAO Gui-zhong³（1. Jiangxi Province Engineering Research Center of Drug and Medical Device Quality, Jiangxi Institute for Drug Control, Nanchang 330029, China; 2. School of Pharmacy, Jiangxi University of Traditional Chinese Medicine, Nanchang 330004, China; 3. Jiangxi Huatai Pharmaceutical Co., LTD, Yifeng 336300, China）

Abstract: A method for the identification and quantitative determination of chemical components in the volatile oil intermediate of Jindan Fuyan Granules was established to improve preparation quality control. Gas chromatography?mass spectrometry (GC?MS) combined with the NIST spectral library was used to characterize the chemical components of the volatile oil intermediate. Based on the analytical results, the chromatographic conditions for gas chromatography with flame ionization detection (GC?FID) were optimized. The contents of five representative components, namely α-pinene, D-limonene, α-elemene, β-elemene, and cinnamaldehyde, were simultaneously determined, and the method was systematically validated using 17 sample batches. A total of 21 volatile components were identified in the volatile oil intermediate, providing insight into the material basis underlying the efficacy of this traditional Chinese medicine preparation. The five target components exhibited good linear relationships within their respective concentration ranges (R² ≥ 0.9972). The relative standard deviations (RSDs) for instrument precision, sample stability, and method repeatability were all below 2.2%, whereas spike recovery rates ranged from 99.27% to 103.00% with RSDs below 3%. The concentrations of the five components in the 17 sample batches ranged from 15.75 to 24.35, 25.12 to 37.86, 33.26 to 39.54, 24.02 to 28.06, and 58.57 to 66.72 mg/g, respectively. Variations in the contents of these components were mainly attributed to differences in the quality of raw herbal materials and insufficient refinement of the extraction process. The established method demonstrated simple operation, favorable specificity, and high accuracy for the identification and quantitative determination of volatile oil components in Jindan Fuyan Granules. This method fills a gap in the quality control of volatile oil in this preparation and provides a scientific basis for quality evaluation, production process optimization, and whole-process quality control.

Key words：Jindan Fuyan Granules; volatile oil; GC-MS; GC; constituent identification; content determination

基于科瓦茨保留指数的同分异构体气相色谱分析

王兴宏¹，全灿^*2

（1. 河南省延津县公共检验检测中心，河南 新乡  453200；2. 中国计量科学研究院，北京  100029）

摘要：同分异构体因分子组成相同、结构差异微小，在气相色谱分析中易出现分离困难与定性误差，科瓦茨保留指数（Kovats Retention Index，KRI）作为无量纲的色谱定性参数，可有效消除色谱条件波动对保留时间的影响，成为同分异构体定性与分离的重要依据。本文以二甲苯、二异丙苯同分异构体为研究对象，系统阐述科瓦茨保留指数的计算原理与预测方法，探究不同色谱柱固定相、升温程序对同分异构体保留指数的影响规律，实验结果表明：在极性柱（DB-FFAP）上，二甲苯同分异构体的KRI差值达17~35，二异丙苯同分异构体的KRI差值达31~68，显著大于非极性柱（分别为13、14和9~19），极性柱通过偶极矩与氢键相互作用有效放大保留差异，可实现基线分离。研究明确基于保留指数的同分异构体出峰顺序判定与分离优化策略，为有机同分异构体的气相色谱定性分析提供标准化指导，可推广至石化、医药、环境等领域。

中图分类号：O657.3      文献标识码：A      文章编号：0258-3283（2026）--

关键词：科瓦茨保留指数；同分异构体；气相色谱；定性分析；分离优化

DOI：10.13822/j.cnki.hxsj.2026.0072

Gas Chromatographic Analysis of Isomers Based on Kovats Retention Index Wang Xing-hong¹，QUAN Can^*2 (1. Henan Province Yanjin County Public Inspection and Testing Center, Xinxiang 453200, China；2. National Institute of Metrology, Beijing 100029, China)

Abstract: Due to their identical molecular compositions and slight structural differences, isomers often face separation difficulties and qualitative errors in gas chromatographic (GC) analysis. The Kovats Retention Index (KRI), a dimensionless chromatographic qualitative parameter, can effectively eliminate the influence of fluctuations in chromatographic conditions on retention time, thus becoming an important basis for the qualitative analysis and separation of isomers. In this study, the calculation principles and prediction methods of KRI, as well as the influence of different chromatographic column stationary phases and temperature programming on the retention index of xylene and diisopropylbenzene isomers, were systematically investigated . The experimental results showed that on the polar column (DB-FFAP), the KRI differences of the xylene isomers ranged 17~35, whereas those of the diisopropylbenzene isomers ranged 31~68. These differences were significantly larger than those observed on the non-polar column (13, 14, and 9~19, respectively). The polar column effectively amplified the retention differences through dipole?dipole and hydrogen bonding interactions, enabling baseline separation. This study clarified the peak order determination and separation optimization strategies for isomers based on the retention index and provided standardized guidance for the qualitative GC analysis of organic isomers.

Key words: Kovats Retention Index (KRI); isomers; gas chromatography; qualitative analysis; separation optimization

席夫碱探针可视化淬灭识别铜离子和铁离子

曹旭旭¹，郑国彪¹，郭素琴¹，李杰森²，李红光^*1，刘文锋^*1

（1. 五邑大学 药学与食品工程学院，广东 江门  529020；2. 佛山大学 环境与化学工程学院，广东 佛山  528000）

摘要：为实现在复杂环境中快速、特异性检测Cu²⁺和Fe³⁺，设计并合成了一种基于2-呋喃甲酰肼的新型席夫碱荧光探针。通过在2-呋喃甲酰肼的氨基位点引入4-二甲基氨基肉桂醛，成功获得目标探针1，并利用核磁共振氢谱、碳谱及红外光谱对其结构进行了全面表征。采用紫外-可见吸收光谱和荧光光谱考察了探针1对多种金属离子的识别性能。结果表明，在多种阳离子共存体系中，探针1能对Cu²⁺和Fe³⁺实现快速、高灵敏度的淬灭型识别，选择性良好。Job’s plot曲线显示，探针1与两种离子的配合比均为1:1。结合核磁滴定与密度泛函理论计算，阐明了探针与离子的结合位点及荧光淬灭机理。在此基础上，将探针1与便携式365 nm紫外灯结合，开发出简易试纸传感平台。该平台可在紫外灯照射下通过裸眼观察荧光淬灭程度，实现Cu²⁺和Fe³⁺的快速现场识别。综上，获得的新型席夫碱荧光探针对Cu²⁺和Fe³⁺具有高选择性与灵敏度，结合便携式试纸平台，为金属离子的现场快速检测提供了可行方案。

关键词：席夫碱；2-呋喃甲酰肼；荧光探针；金属离子；机制研究

中图分类号：O657.3      文献标识码：A      文章编号：0258-3283（2026）--

DOI：10.13822/j.cnki.hxsj.2026.0090

Quenching of Schiff Base Probe for Recognition of Copper and Iron Ions CAO Xu-xu¹, ZHENG Guo-biao¹, GUO Su-qin¹, LI Jie-sen², LI Hong-guang^*1, LIU Wen-feng^*1 (1. School of Pharmacy and Food Engineering, Wuyi University, Jiangmen 529020, China; 2. School of Environmental and Chemistry Engineering, Foshan University, Foshan 528000, China) 

Abstract：To achieve rapid and specific detection of Cu²⁺ and Fe³⁺ in complex environments, we designed and synthesized a novel Schiff base fluorescent probe based on 2-furancarboxyhydrazide. Target probe 1 was successfully obtained by introducing 4-dimethylaminocinnamaldehyde into the amino site of 2-furancarboxaldehyde hydrazide, and its structure was comprehensively characterized using ¹H and ¹³C nuclear magnetic resonance (NMR) spectroscopy and infrared spectroscopy. The recognition performance of probe 1 for various metal ions was investigated using UV-visible absorption spectroscopy and fluorescence spectroscopy. The results showed that in a system with multiple cations, probe 1 achieved rapid and highly sensitive quenching recognition of Cu²⁺ and Fe³⁺ with good selectivity. Job's plot indicated that the complexation ratio of probe 1 with both ions was 1:1. By combining NMR titration with density functional theory calculations, the binding sites of the probe and ions, as well as the fluorescence quenching mechanism, were elucidated. Based on this, probe 1 was combined with a portable 365 nm ultraviolet lamp to develop a simple strip-based platform for ion sensing. This platform enables the rapid on-site identification of Cu²⁺ and Fe³⁺ by observing the degree of fluorescence quenching with the naked eye. In summary, the novel Schiff base fluorescent probe obtained in this study exhibits high selectivity and sensitivity towards Cu²⁺ and Fe³⁺. Combined with a portable test strip platform, the probe provides a feasible solution for rapid on-site detection of metal ions.

Key words：Schiff base; 2-furoic hydrazide; fluorescent probe; metal ion; mechanism

高效液相色谱法同时测定地氯雷他定口服溶液中的5种主要杂质含量

胡燕^*1，项玮²，於为红³

(1. 黄山市知识产权公共服务中心，安徽黄山  245000；2. 黄山市产品质量检验研究院，安徽黄山  245000；

3. 黄山精制药业有限公司，安徽黄山  245000)

摘要：为了实现对地氯雷他定口服溶液中5种主要杂质成分地氯雷他定吡啶氮氧化物、氯雷他定杂质Ⅰ、氨甲酰化氯雷他定、异地氯雷他定、氯雷他定的含量的有效检出，根据各杂质的极性和疏水性差异，优化梯度洗脱程序进行分离，从而建立一种高效液相色谱法（High Performance Liquid Chromatography，HPLC）以实现5种杂质的同时测定。采用GL Sciences C18（250 mm×4.6 mm,5 μm）色谱柱，以0.25%（质量分数）十二烷基硫酸钠溶液作为流动相A，乙腈作为流动相B，进行梯度洗脱，洗脱程序为：0～20 min，60%流动相A；20～25 min，60%～50%流动相A；25～50min，60%流动相A；50～51 min，60%～50%流动相A；51～60 min，50%流动相A，设定流速为1.0 mL/min，设定柱温为35℃，检测波长设置为280 nm，进样量设置为100 μL。5种主要杂质峰形良好，且质量浓度在其范围内分别与色谱峰面积呈现良好的线性关系，5个相关系数均大于0.999，定量限在0.01～0.02 μg/mL范围内，平均回收率范围在94.7%～103.3%之间，测定结果的相对标准偏差（Relative standard deviation，RSD）均小于3.0%（n=9）。所建立的高效液相色谱法高效、稳健且准确，可成功应用于地氯雷他定口服溶液中5种主要杂质成分的同时定量测定，为该制剂的质量控制提供可靠技术支撑。

关键词：高效液相色谱法；梯度洗脱；地氯雷他定口服溶液；杂质检测；质量控制

中图分类号：O65      文献标识码：A      文章编号：0258-3283（2026）-- 

DOI：10.13822/j.cnki.hxsj.2026.0051

Simultaneous Determination of Five Impurities in Desloratadine Oral Solution by High Performance Liquid Chromatography Hu-Yan^*1, Xiang-Wei², Yu-Weihong³ (1. Huangshan City Intellectual Property Public Service Center, Huangshan 245000, China; 2. Huangshan City Product Quality Inspection Institute, Huangshan 245000, China; 3. Huangshan Refined Pharmaceutical Co., Ltd., Huangshan 245000, China) 

Abstract：To effectively detect the five main impurity components―Desloratadine Pyridine N-Oxide, Desloratadine Impurity I, Formyl Desloratadine, Iso Desloratadine, and Loratadine―in Desloratadine oral solution, a reliable and efficient high-performance liquid chromatography (HPLC) method was developed and fully validated. Due to significant differences in polarity and hydrophobicity among these impurities, the gradient elution procedure was systematically optimized to achieve complete baseline separation and accurate simultaneous quantification without interference from the main drug component or formulation excipients. Chromatographic separation was performed on a GL Sciences C18 column (250 mm × 4.6 mm, 5 μm). Mobile phase was A consisted of 0.25% mass fraction sodium dodecyl sulfate aqueous solution, and mobile phase B was acetonitrile. The optimized gradient elution program was as follows: 0~20 min, 60% A; 20~25 min, 60%~50% A; 25~50 min, 60% A; 50~51 min, 60%~50% A; 51~60 min, 50% A. The flow rate was maintained at 1.0 mL/min, the column temperature was set at 35℃, the detection wavelength was 280 nm, and the injection volume was 100 μL. Under these conditions, all five impurities exhibited sharp, symmetrical peaks with resolution values greater than 1.5 between adjacent peaks. The mass concentrations of the five main impurities showed good linear relationships with the corresponding peak areas within their respective ranges, with correlation coefficients all above 0.999. The limits of quantification ranged from 0.01 to 0.02 μg/mL,demonstrating high sensitivity suitable for trace impurity analysis in complex pharmaceutical matrices. Accuracy was evaluated through spike recovery experiments at three concentration levels (low, medium, and high). The average recoveries ranged from 94.7% to 103.3%, indicating good accuracy. Precision was confirmed by relative standard deviations of less than 3.0% (n = 9), demonstrating excellent repeatability and intermediate precision. System suitability parameters, including theoretical plate numbers, tailing factors, and retention time stability, were all within acceptable limits. In conclusion, the established HPLC method is efficient, stable, accurate, and robust. It enables the simultaneous quantitative determination of the five major impurity components in Desloratadine oral solution. This method provides reliable and practical technical support for routine quality control, long-term stability studies, and regulatory compliance assessment of Desloratadine oral solution in pharmaceutical manufacturing and quality assurance environments.

Key words：HPLC; gradient elution, Desloratadine oral solution; impurity testing, quality control

【合成与应用】

一种贝诺酯连续流合成方法研究

周泳磊¹，陈念²，凌芳^*1，秦建国¹，周少方^*1，查晓明²

（1.上海沃凯生物技术有限公司，上海  201507；2. 中国药科大学 工学院，江苏 南京  211198）

摘要：贝诺酯作为一种通过对阿司匹林与扑热息痛进行酯化结构修饰得到的非甾体类解热镇痛药，在临床上展现出良好的药效。迄今为止，尽管对于贝诺酯的制备方法均较为成熟，但高效实用的方法仍相对有限。现有的一些方法往往存在生产过程长期面临能耗偏高、反应周期长以及收率低等问题。因此，开发一种高效、操作简单的合成方法是非常有必要的。基于连续流反应器技术，设计以水杨酸和对氨基酚为原料，在温和条件下成功实现了一种贝诺酯的新型连续流合成工艺。其中，乙酰水杨酸的制备、乙酰水杨酰氯的制备、对乙酰氨基酚的制备以及贝诺酯的合成4步生产流程均改造为连续流工艺，各步反应时间被大幅压缩至数分钟甚至数十秒级别，目标产物的分离收率可高达98.25%。该工艺路线不仅在反应效率和产品的纯度上实现了显著提升，还通过对工艺条件的精确控制，有效促进了产物的稳定生成，同时显著降低了能耗与安全风险。研究结果为连续流技术在实现绿色、高效药物合成中的应用提供了有力支撑。

关键词：贝诺酯；连续流合成；微通道反应；乙酰水杨酸；乙酰水杨酰氯；对乙酰氨基酚

中图分类号：O62      文献标识码：A      文章编号：0258-3283（2026）--

DOI：10.13822/j.cnki.hxsj.2026.0065

A Continuous Flow Synthesis Method for Benorilate ZHOU Yong-lei¹, CHEN Nian², LING Fang^*1, QIN Jian-guo¹, ZHOU Shao-fang^*1, ZHA Xiao-ming² (1. Shanghai Our ChemBio-Technology Co., Ltd., Shanghai 201507, China; 2. School of Engineering, China Pharmaceutical University, Nanjing 211198, China)

Abstract: Benorilate, a non-steroidal antipyretic and analgesic drug derived from the esterification of aspirin and paracetamol, has demonstrated favorable clinical efficacy. Although existing preparation methods for benorilate are well established, efficient and practical synthetic routes remain limited. Many current approaches suffer from drawbacks such as high energy consumption, prolonged reaction times, and low yields. Therefore, the development of efficient and operationally simple synthetic methods is of considerable importance. In this study, a novel continuous-flow synthesis process for benorilate was developed using salicylic acid and 4-aminophenol as starting materials under mild conditions. Based on continuous-flow reactor technology, the four-step sequence involving the synthesis of acetylsalicylic acid, acetylsalicyloyl chloride, acetaminophen, and benorilate was transformed into a continuous-flow process. The reaction time for each step was significantly reduced to several minutes or even tens of seconds. The isolated yield of the target product reached as high as 98.25%. This process not only significantly improves the reaction efficiency and product purity but also ensures stable product formation through precise control of process parameters, while markedly reducing energy consumption and safety risks. These findings strongly support the application of continuous-flow technology for the green and efficient synthesis of pharmaceutical compounds.

Key words: benorilate; continuous-flow synthesis; microchannel reaction; acetylsalicylic acid; acetylsalicyloyl chloride; acetaminophen

【电子化学品】

ICP-MS技术在电子化学品痕量金属杂质分析中的应用进展

焦永杰^*，吴朝阳，黄爱平

（河南应用技术职业学院  绿色化工与新材料学院，河南郑州 450042）

摘要：随着半导体集成电路制程工艺向纳米级微缩，电子化学品的纯度水平成为决定器件性能和良率的重要因素。湿电子化学品、电子特气、封装材料等核心辅料中痕量金属杂质即使在10⁻¹⁵级浓度，也足以诱发栅氧化层缺陷或电迁移失效，对器件性能产生灾难性影响。传统光谱技术因检测限不足，难以满足多元素同步分析的高通量质控需求。而在电子级分析体系中，电感耦合等离子体-质谱法（ICP-MS）技术因具有极低的检测限、多元素同时测定等特点而显示出巨大的应用前景。对近几年国内外ICP-MS在电子化学品痕量分析上的研究进展进行综述，介绍了ICP-MS的技术优势、针对复杂电子级基体的质谱干扰消除机制、高洁净度进样和前处理系统等，分析了该技术在湿电子化学品、电子特气和硅基前驱体、封装材料及固体材料表面分析等领域的具体应用。最后，对于未来ICP-MS在在线监控、形态分析等方面的挑战和机遇进行了展望。

关键词：ICP-MS技术；电子化学品；痕量金属；杂质分析；质谱干扰消除

中图分类号：O657.63, O611.4   文献标识码：A     文章编号：0258-3283(2026)--

DOI：10.13822/j.cnki.hxsj.2026.0026

Advances in ICP-MS Technology for Trace Metal Impurity Analysis in Electronic Chemicals JIAO Yong-jie*, WU Zhao-yang, HUANG Ai-ping (Green Chemical and New Materials Faculty, Henan Technical Institute, Zhengzhou 450042, China)

Abstract: As semiconductor integrated-circuit manufacturing processes continue to scale down to the nanometer level, the purity of chemicals used in electronics has become a critical factor in determining device performance and yield. Even trace metal impurities at concentrations as low as 10⁻¹⁵ in core auxiliary materials―such as wet electronic chemicals, specialty gases, and packaging materials―are sufficient to induce gate oxide defects or electromigration failure, with catastrophic consequences for device performance. Owing to their suboptimal detection limits, traditional spectroscopic techniques struggle to meet high-throughput quality control requirements for the simultaneous analysis of multiple elements. Within the electronic-grade analytical framework, inductively coupled plasma mass spectrometry (ICP-MS) has demonstrated significant application potential owing to its extremely low detection limits and capability for simultaneous multi-element determination. This paper reviewed recent advances in domestic and international research on ICP-MS for the trace analysis of electronic chemicals, covering the technical advantages of ICP-MS, mechanisms for eliminating MS interference in complex electronic-grade matrices, and high-purity sample analysis and pretreatment systems. The specific applications of this technology have been analyzed across various fields like wet electronic chemicals, electronic specialty gases, silicon-based precursors, packaging materials, and solid material surfaces. Finally, future challenges and opportunities for ICP-MS in online monitoring and speciation analyses were explored.

Key words: ICP-MS technology; electronic chemicals; trace metals; impurity analysis; Mass spectrometry interference suppression