ZrO₂/PPy@玉米芯多孔碳材料的制备及用于检测稻谷中草甘膦残留

王惠，何利^*，潘无双，钱玟，林德贤，刘书亮，陈姝娟

（四川农业大学食品学院，雅安 625014）

摘要：通过在PPy@玉米芯多孔碳修饰的玻碳电极上沉积ZrO₂纳米粒子，制备了一种灵敏检测食品中草甘膦残留的电化学传感器电极材料。玉米芯多孔碳的平均孔径为4.07 nm。PPy@玉米芯多孔碳复合材料的高比表面积增加了ZrO₂的负载量。PPy@玉米芯多孔碳修饰电极用于草甘膦检测的线性范围为0.1~10 μg/kg和10~1000 μg/kg，检出限为24.4 ng/kg，检测稻谷中草甘膦的回收率为95.5%~99.1%。该传感器可用于实际食品样品中草甘膦残留的检测。

关键词：ZrO₂/PPy@玉米芯多孔碳；电化学检测；草甘膦

中图分类号：O657.1；TB322    文献标识码：A    文章编号：1000-0720（2023）12-1563-08

Preparation of ZrO₂/PPy@corncobs porous carbon materials for determination of glyphosate residues in rice

WANG Hui，HE Li^*，PAN Wushuang，QIAN Wen，LIN Dexian，LIU Shuliang，CHEN Shujuan

College of Food Science，Sichuan Agricultural University，Ya’an 625014，China）

Abstract：A sensing electrode material for sensitive electrochemical detection of glyphosate was prepared by depositing ZrO₂ nanoparticles on a glassy carbon electrode modified with PPy@corncob porous carbon. The average pore size of the corncob porous carbon was 4.07 nm. The load of ZrO₂ on PPy@corncob was improved due to the high specific area of PPy@corncob porous carbon composite. The linear concentration ranges of this electrode for glyphosate detection was 0.1-10 μg/kg and 10-1000 μg/kg，and the detection limit was 24.4 ng/kg. Meanwhile，the recoveries were 95.5%-99.1% in real sample tests. The electrochemical sensor was proved to be useful for the detection of glyphosate residues in actual food samples.

Keywords：ZrO₂/PPy@ corncob porous carbon；electrochemical detection；glyphosate

基于同步荧光与支持向量回归的典型蔬菜农药残留快速检测

王晓燕，蒋喆臻，冯小涛，郭鑫月，卞海溢，季仁东^*

（江苏省湖泊环境遥感技术工程实验室，淮阴工学院电子信息工程学院，淮安 223003）

摘要：采用恒波长同步荧光法结合支持向量回归（SVR）算法，对西红柿汁中的春雷霉素和多杀菌素农药残留含量进行快速检测。确定了春雷霉素和多杀菌素的最佳波长差（Δλ）分别为70，45 nm，同时得到最佳Δλ下的特征峰分别位于322，292 nm。春雷霉素样本和多杀菌素样本的建模结果显示，2种农药模型的均方误差均小于0.002，决定系数（R²）均超过0.99，平均回收率分别为99.5%和100.1%。采用同步荧光结合SVR算法可有效检测西红柿中春雷霉素和多杀菌素的含量，并为其它蔬菜中农药残留检测提供方法依据。

关键词：农药残留；快速检测；同步荧光法；支持向量回归

中图分类号：O657.3    文献标识码：A    文章编号：1000-0720（2023）12-1571-05

Rapid detection of pesticide residues in typical vegetable based on synchronous fluorescence and support vector regression

WANG Xiaoyan，JIANG Zhezhen，FENG Xiaotao，GUO Xinyue，BIAN Haiyi，JI Rendong^*

Jiangsu Laboratory of Lake Environment Remote Sensing Technologies，Faculty of Electronic Information Engineering，Huaiyin Institute of Technology，Huai’an 223003，China）

Abstract：A rapid determination method for kasugamycin and spinosad pesticide residues in tomato juice was proposed by the constant wavelength synchronous fluorescence method combined with support vector regression （SVR） algorithm. The optimum wavelength distinctions （Δλ） of kasugamycin and spinosad were 70 and 45 nm，and the optimal characteristic peaks were obtained as 322 and 292 nm，respectively. According to the modelling results of kasugamycin and spinosad samples，the mean square errors of the two pesticide models were less than 0.002，the coefficients of determination （R²） were more than 0.99，and the average recoveries were 99.5% and 100.1%，respectively. The results showed that the synchronous fluorescence combined with SVR method is capable of detecting the contents of kasugamycin and spinosad in tomatoes，and provides a support for the detection of pesticide residues in other vegetables.

Keywords：pesticide residues；rapid detection；synchronous fluorescence；support vector regression

基于摩擦纳米发电机的水质检测

冯朗，龙威^*，李萌，向琴，刘文楷

（昆明理工大学机电工程学院，昆明 650500）

摘要：基于接触起电和静电感应耦合作用，提出了一种自供电水质检测技术。通过分析不同液相和固体壁面在摩擦感应过程中电信号的形成输运机理，明确不同待测水样通过聚四氟乙烯（PTFE）管道时与壁面形成的摩擦电信号输出特征，从而实时快速检测水中无机盐浓度和杂质成份。结果表明：在摩擦起电过程中，液柱与PTFE管壁之间主要通过电子和带电粒子形成双电层的方式在液固界面完成从水相向固相的定向跃迁；随着液相无机盐浓度和杂质成份的不同，电极检测到的感应电势和电荷密度也呈现不同规律；进一步以去离子水、自来水、矿泉水、红墨水溶液、聚苯乙烯溶液和不同浓度的无机盐溶液为例，验证了其作为液相在摩擦感应过程中形成电信号的差别及其内部组分和开路电压之间的关系。

关键词：水质检测；摩擦纳米发电机；双电层；有机物检测；无机盐检测

中图分类号：X832；TH85    文献标识码：A    文章编号：1000-0720（2023）12-1576-08

Water quality detection based on triboelectric nanogenerator

FENG Lang，LONG Wei^*，LI Meng，XIANG Qin，LIU Wenkai

Faculty of Mechanical and Electrical Engineering，Kunming University of Science and Technology，Kunming 650500，China）

Abstract：A self-powered water quality detection technology was proposed by coupling contact electrification with electrostatic induction. Through the analysis of the formation and transport mechanism of contact electrification between different liquid phase and solid inner wall phase，triboelectric signal output characteristics of different water samples passed through polytetrafluoroethylene （PTFE） pipes were detected. In this way，the concentrations of inorganic salts and impurities in water can be detected in real time and quickly. The results showed that during the triboelectric process，the directional transition from water to solid phase completed at the liquid-solid interface between the liquid droplet and PTFE pipe wall was mainly through the formation of electric double layer by free electrons and other charged particles. The induced potential and charge density detected by the electrode were various at different concentrations of inorganic salt and impurity composition in the liquid phase. Furthermore，taking deionized water，tap water，mineral water，red ink solution，polystyrene solution and inorganic salt solution with different concentrations as examples，the differences of electrical signals formed in the friction induction process as liquid phase and the relationship between internal components and open-circuit voltage were verified.

Keywords：water quality detection；triboelectric nanogenerator；electric double layer；detection of organic matter；detection of inorganic salt

荧光适配体生物传感器的构建及用于检测中药饮片中的啶虫脒

张红艳，陈淑萍，范申，张淑玲，余宇燕^*，林舒^*

（福建中医药大学药学院，福州 350122）

摘要：构建了一种基于纳米金（AuNPs）和碳量子点（CQDs）的荧光适配体传感方法，并用于啶虫脒的快速检测。在优化条件下，荧光强度与啶虫脒浓度在20~100 μg/mL范围内具有良好的线性关系，相关系数为0.9972，检出限为8.31 μg/mL。应用本方法对中药饮片山药和太子参中的啶虫脒进行加标回收实验，回收率为90.8%~105.7%，相对标准偏差（RSD）为0.4%~5.8%。该方法有望用于啶虫脒现场快速定量分析。

关键词：荧光生物传感器；农药残留；啶虫脒；适配体

中图分类号：O657.31    文献标识码：A    文章编号：1000-0720（2023）12-1584-07

Fabrication of fluorescent aptamer sensor for the detection of acetamiprid in Chinese prepared slices of crude drugs

ZHANG Hongyan，CHEN Shuping，FAN Shen，ZHANG Shuling，YU Yuyan^*，LIN Shu^*

Pharmacy College of Fujian University of Traditional Chinese Medicine，Fuzhou 350122，China）

Abstract：A fluorescent aptamer biosensor based on gold nanoparticles （AuNPs） and carbon quantum dots （CQDs） for the rapid detection of acetamiprid was fabricated. Under the optimized conditions，there was a good linear relationship between the fluorescence intensity and the acetamiprid concentration in the range of 20-100 μg/mL，with a correlation coefficient of 0.9972，and the detection limit was 8.31 μg/mL. This method was applied to the spiked recovery experiment of acetamiprid in traditional Chinese medicine slices of yam and Radix Pseudostellariae，the recoveries ranged from 90.8% to 105.7%，and the relative standard deviations （RSDs） were 0.4%~5.8%. This method is expected to be used for the on site rapidly quantitative analysis of acetamiprid .

Keywords：fluorescent biosensor；pesticide residues；acetamiprid；aptamer

气相色谱-质谱法检测纺织品中28种芳香胺和4种芳香胺盐

刘金源^1，2，叶曦雯^*2，罗忻²，牛增元²，刘坤²，陈静²，李晶莹¹

（1. 青岛科技大学环境与安全工程学院，青岛 266042；2. 青岛海关技术中心，青岛 266109）

摘要：建立了同时测定纺织品中28种芳香胺和4种芳香胺盐的气相色谱-质谱方法。纺织品样品中偶氮染料和游离态的芳香胺盐在碱性的柠檬酸盐缓冲溶液中，经连二亚硫酸钠还原成芳香胺，经叔丁基甲醚溶剂提取，气相色谱-质谱法同时测定。优化条件为2 mL 质量分数40%的NaOH碱化、10 mL叔丁基甲醚提取。28种芳香胺均呈良好的线性关系，26种芳香胺线性范围为0.05~10 mg/L，2，4-二氨基苯甲醚和2，5-二氨基甲苯的线性范围为0.2~10 mg/L；相关系数为0.996~0.999；26种芳香胺检出限为0.05 mg/L，2，4-二氨基苯甲醚和2，5-二氨基甲苯的检出限为0.2 mg/L。2，4-二氨基苯甲醚硫酸盐的加标回收率为33.1%~36.0%，其余3种芳香胺盐平均加标回收率为84.5%~124.6%；2，4-二氨基苯甲醚加标回收率为43.7%~64.3%，其余27种芳香胺回收率在71.7%~119.3%之间。阳性样品检测结果表明：对于原有芳香胺化合物的检测，本方法和ISO 14362方法对比无显著差异；对新增芳香胺特别是2，5-二氨基甲苯，ISO 14362方法存在漏检风险，而本方法具有更高的回收率。本方法为OEKO-TEX新增的芳香胺及芳香胺盐的检测提供了参考。

关键词：气相色谱-质谱法；芳香胺；芳香胺盐；纺织品

中图分类号：O657.63；X832    文献标识码：A    文章编号：1000-0720（2023）12-1591-08

Determination of 28 aromatic amines and 4 aromatic amine salts in textiles by gas chromatography-mass spectrometry

LIU Jinyuan^1，2，YE Xiwen^*2，LUO Xin²，NIU Zengyuan²，LIU Kun²，CHEN Jing²，LI Jingying¹

1. College of Environmental and Safety Engineering，Qingdao University of Science and Technology，Qingdao 266042，China；2. Technology Center of Qingdao Customs，Qingdao 266109，China）

Abstract：A method for the detection of 28 aromatic amines and 4 aromatic amine salts in textiles by gas chromatography-mass spectrometry was established. Azo dyes and free aromatic amine salts in textiles were reduced to aromatic amines by sodium dithionite in alkaline citrate buffer solution，extracted by tert-butyl methyl ether solvent，and then determined simultaneously by gas chromatography-mass spectrometry. The optimized pretreatment conditions were alkalized by 2 mL of 40% NaOH and extracted by 10 mL of tert butyl methyl ether. 28 aromatic amines showed good linear relationships，the linear ranges were 0.05-10 mg/L for 26 aromatic amines，and 0.2-10 mg/L for 2，4-diaminoanisole and 2，5-diaminotoluene，with the correlation coefficients of 0.996-0.999. The detection limits were 0.05 mg/L for 26 aromatic amines，and 0.2 mg/L for 2，4 diaminoanisole and 2，5-diaminotoluene. The standard adding recovery experiments showed that the recoveries of 2，4-diaminoanisole sulfate were 33.1%-36.0%，and that of the other three aromatic amine salts were 84.5%- 124.6%. The recoveries of 2，4-diaminoanisole were 43.7%-64.3%，and that of the other 27 aromatic amine were 71.7%-119.3%. The test results of positive samples showed that there was no significant difference between this method and ISO 14362 method for the detection of original aromatic amine compounds. For newly added aromatic amines，especially 2，5-diaminotoluene，the ISO 14362 method has the risk of missing detection，while this method has a higher recovery rate，and can provide a reference for the detection of newly added aromatic amines and aromatic amine salts in OEKO-TEX.

Keywords：gas chromatography-mass spectrometry；aromatic amines；aromatic amine salts；textiles

基于双频超声辅助酶解结合EDTA法快速高效提取水产品中的铅

朱念辛，郝丽玲，刘馨娜，黄椿华，颜会铭，诸子蘅，蔡欣怡，徐斐^*

（上海理工大学健康科学与工程学院，上海 200093）

摘要：建立了一种基于双频超声辅助酶解（DUED）结合乙二胺四乙酸二钠盐（EDTA）提取水产品中铅的前处理方法。该方法利用超声探头的空化效应促进蛋白酶的水解进程，并结合EDTA的强络合能力，可在12 min内快速提取鱼肉粉中的铅。通过单因素实验考察料液比、酶配方、酶解时间、EDTA提取时间和EDTA浓度对铅提取率的影响。在双频超声与EDTA提取相结合的模式下，最佳提取条件为：pH 7.0的磷酸盐溶液为缓冲溶液，料液比为1∶6 （700 mg鱼肉粉样品+4.2 mL磷酸盐缓冲液），10 mg风味蛋白酶（5.5×10⁴ U/g）与70 mg中性蛋白酶（18.3×10⁵ U/g）为复配酶，超声辅助酶解时间为6 min，EDTA浓度为40 mmol/L，提取时间6 min。在最优条件下，鱼肉粉中铅的提取率可达（84.83±1.00）%。该前处理方法可实现鱼肉粉中铅的快速、高效提取，且与重金属的快速检测方法具有良好的兼容性，是一种有前景的食品安全检测前处理技术。

关键词：双频超声辅助酶解；乙二胺四乙酸二钠盐；铅；水产品；前处理

中图分类号：TS254.7    文献标识码：A    文章编号：1000-0720（2023）12-1599-07

A rapid and efficient extraction method for lead from aquatic products by dual-frequency ultrasonic-assisted enzymatic digestion combined with EDTA

ZHU Nianxin，HAO Liling，LIU Xinna，HUANG Chunhua，YAN Huiming，ZHU Ziheng，CAI Xinyi，XU Fei^*

School of Health Science and Engineering，University of Shanghai for Science and Technology，Shanghai 200093，China）

Abstract：Herein，a pretreatment method based ondual-frequency ultrasonic-assisted enzymatic digestion （DUED） combined with disodium ethylenediaminetetraacetate （EDTA） for extracting lead from aquatic products was established. In this method，the cavitation effect of ultrasonic probe was employed to promote the hydrolysis process of protease，and combined with the strong complexing ability of EDTA，the lead in fish meal was quickly extracted within 12 min. The single factor experiment was carried out to investigate the effects of solid-liquid ratio，enzyme dosage，enzymolysis time，EDTA extraction time and concentrations on the extraction efficiency of lead. Under the mode of combining dual frequency ultrasound with EDTA extraction，the optimal extraction conditions were exhibited as follows：phosphate solution （pH 7.0） as buffer solution，solid-liquid ratio of 1∶6 （700 mg of fish meal sample with 4.2 mL of phosphate buffer solution），10 mg of flavor protease （5.5×10⁴ U/g） and 70 mg of neutral protease （18.3×10⁵ U/g） as complex enzyme formula，40 mmol/L EDTA as extractant. The extraction rate of the lead from fish meal was around （84.83±1.00）% within 12 min，of which 6 min for DUED and 6 min for EDTA extraction. The results showed that the pretreatment method could achieve rapid and efficient extraction of lead from fish meal，and possesses favourable compatibility with the rapid determination of heavy metal. It can be recognized as a promising pretreatment technology for food safety detection.

Keywords：dual-frequency ultrasound-assisted enzymeextraction；ethylenediaminetetraacetic acid disodium salt；lead；aquatic products；pretreatment

基于核酸适体的试纸条检测三磷酸腺苷

任林娇¹，王朋伟¹，陈青华^*1，齐汝宾¹，闫艳霞²，张培¹，秦自瑞¹，陈高凯¹，姜利英^*1，3

（1. 郑州轻工业大学电气信息工程学院，郑州 450002；2. 郑州轻工业大学计算机与通信工程学院，郑州 450002；3. 郑州轻工业大学量子科技研究院，郑州 450002）

摘要：将核酸适体（Aptamer）的特异性与纳米金颗粒的独特光学性质相结合，制备了一种适用于小分子检测的干式试纸条。该试纸条以修饰功能化核酸适体（PloyT13-Aptamer）的纳米金为识别元件，在控制线（C）上修饰ployA13序列，与识别元件结合以判断试纸条的有效性；在测试线（T）上修饰与Aptamer部分互补的DNA序列，与待测物形成竞争关系，通过T线上纳米金显色的深浅来定性或定量分析待测物浓度。结果表明，优化实验条件下，观察T线颜色变化可实现三磷酸腺苷（ATP）的肉眼定性检测，视觉检出限为10 μmol/L。使用Image J软件进行定量分析，试纸条检测范围为10~1000 μmol/L，检出限为2.4 μmol/L。该试纸条生物传感器可以在10 min内得出检测结果且特异性良好，血清中回收率为104.4%~119.0%，为ATP的现场快速检测提供了一种经济有效的方法。

关键词：试纸条；核酸适体；纳米金颗粒；三磷酸腺苷

中图分类号：O657.3    文献标识码：A    文章编号：1000-0720（2023）12-1606-09

Determination of adenosine triphosphate by aptamer strips

REN Linjiao¹，WANG Pengwei¹，CHEN Qinghua^*1，QI Rubin¹，YAN Yanxia²，ZHANG Pei¹，QIN Zirui¹，CHEN Gaokai¹，JIANG Liying^*1，3

1. College of Electrical and Information，Zhengzhou University of Light Industry，Zhengzhou 450002，China；2. College of Computer and Communication Engineering，Zhengzhou University of Light Industry，Zhengzhou 450002，China；3. Academy for Quantum Science and Technology，Zhengzhou University of Light Industry，Zhengzhou 450002，China）

Abstract：A dry strip for small molecule detection was prepared by combining specific aptamers and gold nanoparticles （AuNPs） with unique optical properties. The ployA13 sequence was modified on the control line （C） and the PloyT13-Aptamer nanogold was used as the recognition element to judge the validity of the strip. The DNA sequence complementary to aptamer was modified on the test line （T） to form a competitive relationship with the object to be tested. The concentrations of the target is capable of being analyzed qualitatively and quantitatively by the color shade of the AuNPs on the T line. The results exhibited that the color change of the T-line can be observed under optimized conditions，and the visual detection limit of ATP was 10 μmol/L. The detection range of the strip was 10-1000 μmol/L with a detection limit of 2.4 μmol/L，when Image J software was used for quantitative analysis. The strip biosensor can produce results within 10 min with excellent specificity，and the serum recovery rates were 104.4%-119.0%，which provides an economical and effective strategy for rapid detection of ATP in relevant fields.

Keywords：test strip；aptamer；gold nanoparticles；adenosine triphosphate

水溶性糖基荧光探针用于肝癌细胞的靶向标记

谭名超，刘芳美，沈琼霞，厉凯彬^*

（台州学院医药化工学院，台州 318000）

摘要：以罗丹明荧光团作为骨架，通过点击化学的方法引入半乳糖基，设计合成了一种具备肝癌细胞靶向功能的荧光探针Glycosyl Rhodamine（GR）。糖基的引入，使得探针具有较好的水溶性和生物靶向性。在分子溶液水平测试了探针GR的紫外和荧光光谱，发现探针GR对Hg²⁺选择性良好，其它金属阳离子无干扰，并具备较好的浓度依赖关系。利用核磁滴定实验研究了探针与Hg²⁺的响应机理。细胞毒性实验表明，探针GR具有良好的生物相容性，当探针浓度高达100 μmol/L时，细胞存活率大于100%。基于探针分子内半乳糖对肝癌细胞表面糖蛋白受体的特异性识别，利用 Hg²⁺的配位作用，实现了HepG2肝癌细胞的靶向标记。

关键词：糖基荧光探针；肝癌细胞；汞离子；罗丹明

中图分类号：O657.32    文献标识码：A    文章编号：1000-0720（2023）12-1615-07

Water-soluble glycosyl fluorescent probe for targeting labelling of hepatoma cells

TAN Mingchao，LIU Fangmei，SHEN Qiongxia，LI Kaibin^*

Department of Chemistry，Taizhou University，Taizhou 318000，China）

Abstract：A fluorescence probe of Glycosyl Rhodamine （GR） with the function of liver cancer cells targeting was developed. The rhodamine fluorophore was used as the skeleton coupled，and the contained galactose group was introduced via click chemistry method. The introduction of glycogroup promoted the water solubility and biological targeting of the probe. The ultraviolet and fluorescence spectra of the probe GR were tested at the molecular level. The probe GR possessed favorable selectivity to Hg²⁺ with good concentration dependence，and the interference of other metal cations was limited to it. The response mechanism between GR and Hg²⁺ was studied by NMR titration. The cytotoxicity test showed that the probe GR owned satisfactory biocompatibility，and the cell viability was more than 100% when the probe concentration was 100 μmol/L. Based on the specific recognition of the glycoprotein receptor on the surface of hepatocellular carcinoma cells by galactose within the probe molecule，the targeted labeling of HepG2 hepatocellular carcinoma cells was realized by the coordination of Hg²⁺.

Keywords：glycosyl fluorescent probe；liver cancer cells；mercury ion；Rhodamine

酸水解-酶水解-UPLC-MS/MS测定特殊医学用途配方食品中多种氨基酸和牛磺酸

卢兰香，薛霞，张艳侠，孙立臻，程志，郑文静，郑红，宿书芳，尹丽丽，刘艳明^*，王骏，祝建华

（山东省食品药品检验研究院，山东省食品药品安全检测工程技术研究中心，山东省特殊医学用途配方食品质量控制工程技术研究中心，济南 250101）

摘要：利用酸水解与酶水解互补，采用超高效液相色谱-串联质谱法（UPLC-MS/MS），建立了特殊医学用途配方食品中22种氨基酸和牛磺酸的检测方法。样品经酸水解或酶水解提取，采用6-氨基喹啉基-N-羟基琥珀酰亚胺-氨基甲酸酯（AQC）衍生后，以乙腈-甲酸铵（10 mmol/L）为流动相梯度洗脱，通过AccQ-Tag Ultra C18色谱柱进行分离，三重四极杆质谱电喷雾多反应监测模式检测，内标法定量。结果表明：22种氨基酸和牛磺酸线性关系良好，相关系数均大于0.9956；检出限在0.0028~0.0225 g/100 g之间，定量限在0.0094~0.0751 g/100 g之间。22种氨基酸和牛磺酸的平均加标回收率在90.1%~104.7%之间，相对标准偏差在1.1%~4.3%之间。该方法实现了GB 29922-2013和GB 25596-2010中规定的22种不同性质氨基酸以及牛磺酸成分的水解提取与准确测定，适用于特殊医学用途配方食品中氨基酸和牛磺酸的准确定性、定量分析。

关键词：氨基酸；牛磺酸；水解；衍生；特殊医学用途配方食品；超高效液相色谱-串联质谱法

中图分类号：TS207.3    文献标识码：A    文章编号：1000-0720（2023）12-1622-09

Determination of amino acids and taurine in formula foods for special medical by UPLC-MS/MS with acidic hydrolysis and enzymatic hydrolysis

LU Lanxiang，XUE Xia，ZHANG Yanxia，SUN Lizhen，CHENG Zhi，ZHENG Wenjing，ZHENG Hong，SU Shufang，YIN Lili，LIU Yanming^*，WANG Jun，ZHU Jianhua

Shandong Institute for Food and Drug Control，Shandong Research Center of Engineering and Technology for Safety Inspection of Food and Drug，Shandong Research Center of Engineering and Technology for Quality Control of Food for Special Medical Purposes，Jinan 250101，China）

Abstract：A simultaneous determination method for 22 amino acids and taurine in formula foods for special medical purpose by ultra-high performance liquid chromatography-tandem mass spectrometry （UPLC-MS/MS） with the complementary technology of acidic hydrolysis and enzymatic hydrolysis was established. The samples were extracted by acidic hydrolysis or enzymatic hydrolysis，and the perpared analytes were derivatized with 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate （AQC）. The chromatographic separation was carried out using AccQ-Tag Ultra C18 column，with gradient elution using a mobile phase consisting of acetonitrile and ammonium formate （10 mmol/L）. The target compounds were detected by triple quadrupole mass spectrometry with electrospray ionization （ESI） under the multiple reaction monitoring （MRM） mode，and then quantified by an internal standard method. Calibration curves had satisfactory linearities for 22 amino acids and taurine，and the correlation coefficients were above 0.9956. The limits of detection were in the range of 0.0028-0.0225 g/100 g，and the limits of quantitation were in the range of 0.0094-0.0751 g/100 g. The average recoveries were from 90.1% to 104.7%，and the relative standard deviations ranged from 1.1% to 4.3%. The method realized the hydrolytic extraction and accurate determination of 22 amino acids and taurine in GB 29922-2013 and GB 25596-2010. This method is suitable for accurate qualitative and quantitative analysis of amino acids and taurine in formula foods for special medical purpose.

Keywords：amino acids；taurine；hydrolysis；derivatization；food for special medical purposes；ultra-high performance liquid chromatography-tandem mass spectrometry

鸡蛋中氟苯尼考时间分辨荧光快速定量检测卡的制备和应用

余文琴^*1，龚迎昆¹，李姗¹，史沁芳¹，肖昭竞¹，李明伟²，章健²

（1. 重庆市计量质量检测研究院，重庆 401123；2. 成都微瑞生物科技有限公司，成都 611731）

摘要：制备了一种可快速定量检测氟苯尼考的时间分辨荧光免疫层析卡，并建立了一种快速定量检测鸡蛋中氟苯尼考的时间分辨荧光免疫层析方法。采用时间分辨荧光微球标记氟苯尼考单抗，筛选了具有高灵敏度和特异性的氟苯尼考抗原抗体，优化了时间分辨荧光微球与氟苯尼考单抗的标记条件、氟苯尼考抗原在硝酸纤维（NC）膜上的包被浓度、稀释复溶液配方等条件。结果表明：氟苯尼考的线性范围为0.05~1.00 μg/kg，检出限为0.05 μg/kg。采用鸡蛋进行加标回收实验，氟苯尼考的回收率在85.0%~98.0%，批内相对标准偏差（RSD）为8.0%~12%，批间RSD为11%~17%。实际样品的检测结果与国标方法结果无显著性差异。方法适用于鸡蛋中氟苯尼考的现场快速定量筛查。

关键词：氟苯尼考；时间分辨；荧光免疫层析；快速定量检测

中图分类号：O657.3；TS201.6    文献标识码：A    文章编号：1000-0720（2023）12-1631-07

Preparation and application of a time-resolved fluorescence rapid quantitative detection card for the determination of florfenicol in eggs

YU Wenqin^*1，GONG Yingkun¹，LI Shan¹，SHI Qinfang¹，XIAO Zhaojing¹，LI Mingwei²，ZHANG Jian²

1. Chongqing Academy of Metrology and Quality Inspection，Chongqing 401123，China；2.Chengdu Weirui Biotechnology Co. Ltd.，Chengdu 611731，China）

Abstract：A method based on a developed time-resolved immunochromatogram card was proposed for rapid quantitative detection of flufenicol in eggs. Flufenicomumab was labeled with time-resolved fluorescent microspheres and the Fflufenicol antigens with high sensitivity and specificity were screened. The labeling conditions of time-resolved fluorescent microspheres and flufenicomumab，the coating concentrations of flufenicomumab antigen on nitrate-fiber membrane （NC），and the formulation of diluted complex solution were optimized，respectively. The results showed that the linear range for the flufenicol was 0.05-1.00 μg/kg，and the detection limit was 0.05 μg/kg. The spiked recoveries of florfenicol were 85.0%-98.0%，the intra-batch relative standard deviations （RSDs） were 8.0%-12%，and the inter-batch RSDs were 11%-17%. The difference of the test results of actual samples between this method and the national standard method is little. The developed rapid time-resolved fluorescence determination method is suitable for the rapid and quantitative screening of flurfenicol in eggs.

Keywords：flufenicol；time-resolved；fluorescence immunochromatography；rapid quantitative detection

基于SERRS法检测盐酸普鲁卡因

胡振帅¹，李文杰¹，赵超阳¹，臧佳琳²，刘婷婷¹，王慧玉¹，付双¹，黄鑫睿¹，隋会敏^*1

（1. 齐齐哈尔医学院药学院，齐齐哈尔 161000；2. 齐齐哈尔医学院附属第二医院，齐齐哈尔 161000）

摘要：结合偶氮衍生反应，建立了盐酸普鲁卡因的表面增强共振拉曼散射（SERRS）检测方法。将对巯基苯胺（PATP）重氮化，得到的重氮盐离子与盐酸普鲁卡因发生偶氮衍生反应，生成相应偶氮产物，再与银纳米粒子混合并立即进行拉曼测试，最后利用偶氮产物的SERRS响应检测盐酸普鲁卡因含量。优化实验条件为：最大吸收峰波长为442 nm的银溶胶作为增强基底，532 nm作为激发波长，偶氮衍生的最佳时间为20 min，偶氮衍生过程中最佳Na₂CO₃质量浓度为8%。在10 ng/mL~10 μg/mL范围内，得到SERRS强度比值I₁₄₃₅/I₃₈₄（y）与盐酸普鲁卡因浓度负对数（x）间的线性方程为y=78.97421-8.66853x，线性相关系数R²为0.9774，检出限（LOD）为8.196 ng/mL。方法对盐酸普鲁卡因注射液测定结果与标准值基本一致，采用标准加入法测得回收率在96.4%~103.3%之间，相对标准偏差（RSD）在3.4%~6.4%之间。将方法用于大鼠血清模拟样品测定，回收率在96.0%~103.5%之间，RSD在4.3%~7.6%之间，为监管盐酸普鲁卡因非法添加和滥用提供方便快捷且可靠的检测方法。

关键词：表面增强共振拉曼散射（SERRS）；普鲁卡因；偶氮；检测

中图分类号：O657.37    中献标识码：A    文章编号：1000-0720（2023）12-1638-06

Determination of procaine hydrochloride based on SERRS

HU Zhenshuai¹，LI Wenjie¹，ZHAO Chaoyang¹，ZANG Jialin²，LIU Tingting¹，WANG Huiyu¹，FU Shuang¹，HUANG Xinrui¹，SUI Huimin^*1

1. School of Pharmacy，Qiqihar Medical University，Qiqihar 161000，China；2. The Second Affiliated Hospital of Qiqihar Medical University，Qiqihar 161000，China）

Abstract：A simple and sensitive surface-enhanced resonant Raman scattering （SERRS）method for the determination of procaine hydrochloridewas established by combining with azo derivatization. The dizaonium ions from p-aminothiophenol （PATP） reacted with procaine hydrochloride via azo coupling reaction. Then the generated azo product was mixed with silver nanoparticles for immediate Raman measurements. The concentration of procaine hydrochloride can be determined through SERRS response of azo product. The optimum conditions of the derivatization process were as followed：silver sol with the maximum absorption of 442 nm was used as enhancing substrate，and the 532 nm utilized as excitation wavelength，the azoderivatization time was 20 min，the concentration of sodium carbonate was 8%. The linear equation between I₁₄₃₅/I₃₈₄ and the negative logarithm of procaine hydrochloride concentration was y=78.97421-8.66853x，with the correlation coefficient （R²） of 0.9774 in the range from 10 ng/mL to 10 μg/mL. The limit of detection （LOD） was 8.196 ng/mL. The determination results of procaine hydrochloride injection were basically consistent with the standard values. The recoveries were 96.4%-103.3%，and the RSDs were 3.4%-6.4% by standard addition method. The method was additionally applied to the determination of rat serum simulated samples. The recoveries were 96.0%-103.5%，and the RSDs were 4.3%-7.6%. The method is simple and sensitive，providing a convenient，fast and reliable detection way to the supervision of illegal addition and the abuse of procaine hydrochloride.

Keywords：surface-enhanced resonance Raman scattering （SERRS）；procaine；azo；detection

人体呼出气体一氧化氮的气液相化学发光检测

熊桠林¹，毛娅²，黄丹³，范力瑞¹，付大友¹，谭文渊^*1，张欢¹，吴雨燃¹

（1. 四川轻化工大学化学工程学院，自贡 643000；2. 四川化工职业技术学院药品与环境工程学院，泸州 646009；3. 泸州市应急保障中心，泸州 646000）

摘要：通过选择KMnO₄氧化剂将NO气体氧化为NO₂气体，基于鲁米诺（Luminol）化学发光检测NO₂气体的体系，采用自主研发的气液相化学发光检测仪，建立了一种化学发光检测呼吸系统疾病中痕量NO气体的方法。研究了KMnO₄浓度，pH以及Luminol检测NO₂体系中各组分浓度对化学发光强度的影响。结果表明，在KMnO₄浓度为0.15 mol/L、pH 1.7时氧化效果最好，在Luminol（5.0 mmol/L）、KOH（50 mmol/L）体系中加入Na₂SO₃（0.10 mol/L）、乙二醇（3.0%（V/V））能显著增强Luminol体系检测NO₂的化学发光信号。最优条件下，在10~250 μg/L范围内，NO浓度与发光强度呈现出良好的线性关系。

关键词：气液相化学发光；一氧化氮；鲁米诺；呼吸系统疾病

中图分类号：O659.21    文献标识码：A    文章编号：1000-0720（2023）12-1644-05

Gas-liquid phase chemiluminescence detection of human exhaled gas nitric oxide

XIONG Yalin¹，MAO Ya²，HUANG Dan³，FAN Lirui¹，FU Dayou¹，TAN Wenyuan^*1，ZHANG Huan¹，WU Yuran¹

1. School of Chemical Engineering，Sichuan University of Science and Engineering，Zigong 643000，China；2. School of Pharmaceutical Products and Environmental Engineering，Sichuan Vocational College of Chemical Technology，Luzhou 646009，China；3. Luzhou City Emergency Support Center，Luzhou 646000，China）

Abstract：A chemiluminescence method for the detection of trace level of NO gas in respiratory diseases was established by a self-developed gas-liquid chemiluminescence detector，which the main mechanism was based on KMnO₄ oxidizing NO to NO₂ and generating chemiluminescence signal. The influence of the concentration of KMnO₄，pH and Luminol on the chemiluminescence intensity in NO₂ system were investigated. The oxidation effect was optimal at the KMnO₄ concentration of 0.15 mol/L and pH value of 1.7. Meanwhile，the additions of Na₂SO₃ （0.10 mol/L） and ethylene glycol （3%） in the Luminol （5.0 mmol/L） and the KOH （50 mmol/L） can significantly enhance the intensity of luminol system. Under the optimal conditions，the NO concentration showed a favorable linear relationship with the luminescence intensity in the range of 10-250 μg/L. This method possessed multiple benefits like high accuracy，good stability，easy carrying and green environmental protection.

Keywords：gas-liquid phase chemiluminescence；nitric oxide；luminol；respiratory disease

基于智能手机检测系统的抗坏血酸电化学传感应用

汪广源¹，张兆康²，陈芳如²，李艳霞^*2

（1. 福州大学环境与安全工程学院，福州 350108；2. 闽江学院材料与化学工程学院，福州 350108）

摘要：制备了一种基于石墨烯微电极的抗坏血酸（AA）智能传感器。通过设计与U盘式电化学分析仪相兼容的直插式三电极图案，采用激光直写技术制备图案化石墨烯电极，选择AA作为目标分析物，构建了一种基于石墨烯微电极的AA便携式智能检测方法。使用PalmSens U盘式微型电化学分析仪，结合智能手机APP检测，采用循环伏安法，考察了所制备的石墨烯电极对AA的电化学响应。结果表明，pH 1时，在AA浓度0.01~0.5 mg/mL范围内，峰电流与AA浓度具有良好的线性关系。所设计的石墨烯微电极可兼容于PalmSens U盘式电化学分析仪，所构建的检测方法可用于汗液、尿液等不同生物样品的检测。

关键词：PalmSens U盘式电化学分析仪；石墨烯；激光直写；抗坏血酸

中图分类号：R857.3    文献标识码：A    文章编号：1000-0720（2023）12-1649-06

Application of ascorbic acid electrochemical sensing based on smart phone detection system

WANG Guangyuan¹，ZHANG Zhaokang²，CHEN Fangru²，LI Yanxia^*2

1. College of Environment and Safety Engineering，Fuzhou University，Fuzhou 350108，China；2. College of Materials and Chemical Engineering，Minjiang University，Fuzhou 350108，China）

Abstract：An intelligent sensor of ascorbic acid （AA） based on graphene microelectrode was constructed. By designing the pattern of a three-electrode system which is compatible with the U-disk electrochemical analyzer，a portable intelligent detection method for AA was developed based on graphene microelectrode using laser direct writing technology. The electrochemical response of the prepared graphene electrode to AA was assessed by cyclic voltammetry through smart phone detection. The results showed that the concentration of AA had a good linear relationship in the range of 0.01-0.5 mg/mL at pH 1. The designed graphene microelectrode is compatible with the PalmSens U-disk electrochemical analyzer. The prepared method can be used for the detection of sweat and urine samples.

Keywords：palmsens U-disk electrochemical analyzer；graphene；laser direct writing；ascorbic acid

分压校正顶空气相色谱法测定重晶石矿总有机质含量

刘学琰，李伟，于康，范智禹，罗迎春，戴毅^*

（贵州民族大学化学工程学院，贵阳 550025）

摘要：建立了一种分压校正顶空气相色谱测定重晶石矿中总有机质含量的新方法。酸性条件下，K₂Cr₂O₇将矿样中的有机质氧化为CO₂，通过分压校正可知顶空瓶中CO₂和O₂的信号值之比α与有机质含量呈正相关。因此可通过检测α测定重晶石样品中的有机质含量。结果表明，在120 ℃下加热10 min，重晶石矿样品与K₂Cr₂O₇溶液（0.136 mol/L）的反应达到平衡。总有机质含量与α值之间存在很好的线性关系，相关系数（R²）为0.999，相对标准偏差（RSD）<2.9%，加标回收率在95.6%~109.2%之间，定量限为0.018%。本方法适用于重晶石矿中有机质含量的批量检测。

关键词：重晶石矿；顶空气相色谱法；有机质含量

中图分类号：O657.7    文献标识码：A    文章编号：1000-0720（2023）12-1655-05

Determination of the total organic matter content in barite ore by partial- pressure-corrected headspace gas chromatography

LIU Xueyan，LI Wei，YU Kang，FAN Zhiyu，LUO Yingchun，DAI Yi^*

School of Chemical Engineering，Guizhou Minzu University，Guiyang 550025，China）

Abstract：A method for determining the total organic matter content in barite ore using partial-pressure-corrected headspace gas chromatography was constructed. The organic matter in barite ore was oxidized to CO₂ by K₂Cr₂O₇ under acidic condition，and the ratio of CO₂ and O₂ signals in headspace vial was positively correlated with the content of organic matter by partial pressure-corrected method. Therefore，the content of organic matter in barite samples can be determined by measuring α value. The results showed that barite sample could react completely with K₂Cr₂O₇ solution （0.136 mol/L） at 120 ℃ for 10 min. A good linearity between the total organic matter content and the α value was obtained （R²=0.999），with the relative standard deviation less than 2.9%，the recoveries ranged from 95.6% to 109.2%，and the limit of quantitation was 0.018%. This method can be used for batch determination of organic matter content in barite ore.

Keywords：barite ore；headspace gas chromatography；total organic matter content

基于Mn²⁺增强的氧化石墨烯荧光开关和杂交链式反应信号放大的新型纳米传感器高灵敏检测作物转基因

褚秀玲¹，梅如波¹，隋本会¹，李凯¹，张川¹，朱德颂^*2

（1. 山东省泰安生态环境监测中心，泰安 271000；2. 山东农业大学化学与材料科学学院，泰安 271018）

摘要：开发了一种新型纳米传感器，利用Mn²⁺增强的石墨烯（GO）荧光开关（Mn²⁺-GO-FS）结合杂交链式反应（HCR）进行信号放大，用于作物中Bt转基因的高灵敏检测。本传感器利用Mn²⁺-GO-FS作为HCR发夹探针载体，在Mn²⁺的辅助下快速吸附发夹探针，进而淬灭探针上标记的荧光基团（FAM），获得最低的背景信号。目标Bt转基因作为触发器，启动2种亚稳态发夹探针（H1和H2）之间的级联杂交事件，聚合成缺口长双螺旋结构（dsDNA），由于GO对dsDNA的吸附能力较弱，dsDNA脱离GO表面，产生更强的荧光。经HCR信号放大后的检测结果符合预期。最佳条件下，体系的荧光强度与Bt基因浓度在0.1 pmol/L~50 nmol/L范围内呈线性关系，检出限0.05 pmol/L。该传感器具有良好的选择性和检测实际样品的潜力。

关键词：Mn²⁺；氧化石墨烯荧光开关；杂交链式反应信号放大；高灵敏检测；Bt转基因

中图分类号：O657.3    文献标识码：A    文章编号：1000-0720（2023）12-1660-06

A novel nanosensor based on Mn²⁺-enhanced graphene oxide fluorescence switch and hybrid chain reaction signal amplification for highly sensitive detection of crop transgene

CHU Xiuling¹，MEI Rubo¹，SUI Benhui¹，LI Kai¹，ZHANG Chuan¹，ZHU Desong^*2

1. Shandong Tai'an Ecological Environment Monitoring Center，Tai'an 271000，China；2. School of Chemistry and Materials Science，Shangdong Agricultural University，Tai'an 271018，China）

Abstract：A simple，enzyme-free，and high-sensitivity novel nanosensor was developed by utilizing manganese ion （Mn²⁺）-enhanced graphene oxide （GO） fluorescence switch （Mn²⁺-GO-FS） which was combined with hybridization chain reaction （HCR） for signaling amplified and highly sensitive detection of Bt transgene in crops. This sensor utilized Mn²⁺-GO-FS as the HCR hairpin probes carrier and rapidly adsorbed the hairpin probes with the assistance of Mn²⁺，which efficiently quenched the fluorophores （FAM） labeled on the probe to obtain the lowest background signal. The target Bt transgene acted as a trigger to initiate a cascade of hybridization events between two metastable hairpin probes （H1 and H2） to aggregate into a gap-long duplex structure （dsDNA）. Because of the weak adsorption of GO to dsDNA，dsDNA detached from the GO surface，resulting in stronger fluorescence. The detection results after HCR signal amplification were encouraging. Under the optimal conditions，the fluorescence intensity was linearly related to its concentration in the range of 0.1 pmol/L-50 nmol/L，and the detection limit was 0.05 pmol/L，indicating the sensor had good selectivity and potential to detect real samples.

Keywords：Mn²⁺；Mn²⁺-GO-FS；hybrid chain reaction signal amplification；highly sensitive detection；Bt transgene

基于Fe₃O₄@SiO₂@Ag/GCE传感器检测土霉素

贾荣玲^*，裴瑞杰，李生涛，王桂桢

（河南省动物疫病防控工程技术研究中心，南阳农业职业学院牧医工程学院，南阳 473000）

摘要：合成了具有核壳结构的Fe₃O₄@SiO₂纳米复合材料，在Fe₃O₄@SiO₂表面负载银纳米离子，制备了一种新型的Fe₃O₄@SiO₂@Ag复合材料，并采用玻碳电极（GCE）构建Fe₃O₄@SiO₂@Ag/GCE传感器，对土霉素（OTC）进行定量检测。优化了电解质溶液的种类和pH，Fe₃O₄@SiO₂@Ag用量以及富集时间和富集电位等实验条件。在最佳条件下，OTC浓度（c）与峰电流（I_p）在0.01~120 μmol/L范围内呈线性关系，线性方程为I_p=0.9307c-0.0033，线性相关系数R²=0.9986，检出限为8.2 nmol/L。该传感器对牛奶中OTC的检测结果与国标法结果一致。

关键词：四氧化三铁；银；纳米复合材料；土霉素；电化学传感器

中图分类号：TS207.3    文献标识码：A    文章编号：1000-0720（2023）12-1666-07

Detection of oxytetracycline based on Fe₃O₄@SiO₂@Ag/GCE sensor

JIA Rongling^*，PEI Ruijie，LI Shengtao，WANG Guizhen

Henan Engineering and Technology Research Center for Animal Disease Prevention and Control，Nanyang Vocational College of Agriculture of Veterainary Medicine and Engineering，Nanyang 473000，China）

Abstract：The Fe₃O₄@SiO₂ nanocomposite with core-shell structure was synthesized. A new type of nanocomposite Fe₃O₄@SiO₂@Ag was prepared by loading silver nanoparticles on the surface of Fe₃O₄@SiO₂，and a  Fe₃O₄@SiO₂@Ag/GCE sensor was constructed using glassy carbon electrode （GCE） to detect oxytetracycline （OTC）. The type and pH of electrolyte solution，the amount of Fe₃O₄@SiO₂@Ag，the enrichment time and enrichment potential were optimized，respectively. Under the optimal conditions，the OTC concentration （c）and peak current （I_p） had a linear relationship in the concentration range of 0.01-120 μmol/L，and the equation was I_p=0.9307c-0.0033，with the coefficient R²=0.9986. The detection limit was 8.2 nmol/L. The detection results of OTC in milk by this method were consistent with that of national standard method.

Keywords：ferric oxide；silver；nanocomposites；oxytetracycline；electrochemistry；sensor

胶束毛细管电泳同时分离测定葛根及其制剂中的5种异黄酮

张春莉，郭爱琳，曹秋娥，李菲^*

（云南大学化学科学与工程学院，昆明 650091）

摘要：建立了一种新的胶束毛细管电泳方法，用于同时分离检测葛根素、大豆苷、3'-甲氧基葛根素、3'-羟基葛根素和4'-甲氧基葛根素5种异黄酮。优化的实验条件为：以40 mmol/LNa₂B₄O₇+4 mmol/L NaOH（pH 9.62）为运行缓冲溶液，5%（V/V）甲醇和14 mmol/L的十二烷基磺酸钠（SDS）为添加剂，分离电压22 kV，检测波长250 nm，进样时间5 s。在优化条件下，葛根素、大豆苷、3'-甲氧基葛根素、3'-羟基葛根素和4'-甲氧基葛根素5种异黄酮可在14 min内完成分离检测，各目标组分的峰面积与其浓度之间的线性关系良好。该方法用于葛根及其制剂中5种异黄酮的定量分析，加标回收率范围为95.6%~104.8%，相对标准偏差不超过4.0%。

关键词：胶束毛细管电泳；异黄酮；葛根；制剂

中图分类号：O657.7    文献标识码：A    文章编号：1000-0720（2023）12-1673-05

Simultaneous separation and determination of five isoflavones in Paeonia Lactiflora Radix and its preparations by micellar capillary electrophoresis

ZHANG Chunli，GUO Ailin，CAO Qiue，LI Fei^*

School of Chemical Science and Technology，Yunnan University，Kunming 650091，China）

Abstract：A new method of micellar capillary electrophoresis was developed for the simultaneous separation and detection of puerarin，daidzin，3'-methoxypuerarin，3'-hydroxypuerarin，and 4'-methoxypuerarin. The buffer solution consisted of 40 mmol/L Na₂B₄O₇ and 4 mmol/L NaOH （pH 9.62），with 5%（V/V） methanol and 14 mmol/L sodium dodecyl sulfate （SDS） as additives. The separation voltage was 22 kV，the detection wavelength was 250 nm，and the injection time was 5 s. Under the optimized conditions，five isoflavones could be separated and detected within 14 min，and the linear relationship between the peak area of each target component and its concentration was good. The method was applied to the quantitative analysis of five isoflavones in Pueraria lobata and its preparations. The spiked recoveries ranged from 95.6% to 104.8%，and the relative standard deviation was not more than 4.0%.

Keywords：micellar capillary electrophoresis；isoflavones；Paeonia Lactiflora Radix；preparations

气相色谱-质谱法检测葡萄酒中二甲基二碳酸盐

陈波^*，罗洁，万志刚，易冰清，涂小珂，何纯点，靳保辉

（深圳海关食品检验检疫技术中心，深圳 518067）

摘要：建立了气相色谱-质谱（GC-MS）法检测葡萄酒中二甲基二碳酸盐代谢产物碳酸甲乙酯的方法，进而建立了二甲基二碳酸盐添加量的检测方法。优化了仪器参数、色谱条件、萃取试剂种类和体积、提取时间等参数。结果表明，方法的线性范围为0.5~30 mg/L，在红葡萄酒、甜白葡萄酒、起泡葡萄酒中添加0.5，10.0，30.0 mg/L的碳酸甲乙酯，方法回收率为90.0%~110%，相对标准偏差为3.6%~6.7%，检出限为0.25 mg/L，定量限为0.5 mg/L。该方法适合于葡萄酒中碳酸甲乙酯以及二甲基二碳酸盐的检测。

关键词：葡萄酒；气相色谱-质谱法；二甲基二碳酸盐；碳酸甲乙酯

中图分类号：O657.63    文献标识码：A    文章编号：1000-0720（2023）12-1678-05

Determination of dimethyldicarbonate in wine by gas chromatography-mass spectrometry

CHEN Bo^*，LUO Jie，WAN Zhigang，YI Bingqing，TU Xiaoke，HE Chundian，JIN Baohui

Food Inspection Center of Shenzhen Custom，Shenzhen 518067，China）

Abstract：A method for the determination of methyl ethyl carbonate a metabolite of dimethyl decarbonate in wine by gas chromatography-mass spectrometry （GC-MS） was developed，and then a method for the determination of the added amount of dimethyldecarbonate was established. The analytical equipment parameters，chromatographic conditions，type and volume of extraction reagents，and extraction time were optimized. The linear range of this method was 0.5-30 mg/L. The average recoveries for methyl ethyl carbonate spiked at 0.5，10.0 and 30.0 mg/L in red wine，sweet white wine and sparkling wine ranged from 90.0% to 110%，the relative standard deviations were 3.6%-6.7%，the limit of detection was 0.25 mg/L，and the limit of quantification was 0.5 mg/L. The method is suitable for the detection of methyl ethyl carbonate and dimethyl dicarbonate in wine.

Keywords：wine；gas chromatography-mass spectrometry；dimethyl decarbonate；methyl ethyl carbonate

电感耦合等离子体发射光谱法同时测定镨钕氧化物中氯和硫含量

赵艳，谢艳艳^*，白晓艳^*，高燕，付娜，陈雄飞，胡梦桥，张力久

（国标（北京）检验认证有限公司，北京 100088）

摘要：建立了一种电感耦合等离子体发射光谱（ICP-OES）同时测定镨钕氧化物中氯（Cl）和硫（以SO₄^2-形式存在）含量的方法。读取真空紫外波段129~190 nm谱线信号，优化了测试参数。使用硝酸低温溶解样品，选择分析谱线为Cl（134.724 nm）和S（180.731 nm），标准曲线法测定。在优化条件下，Cl和S在0~10 mg/L范围内线性相关系数均为0.9999，Cl回收率为93.1%~107.2%，相对标准偏差（RSD）为4.8%；S回收率为89.9%~94.9%，RSD为3.8%。该方法可以检测镨钕氧化物材料中含量大于0.014%的Cl和含量大于0.003%的S。

关键词：电感耦合等离子体发射光谱；镨钕氧化物；氯和硫

中图分类号：O657.31    文献标识码：Ａ    文章编号：1000-0720（2023）12-1683-06

Simultaneous determination of chlorinity and sulfur in praseodymium neodymium oxides by inductively coupled plasma optical emission spectroscopy

ZHAO Yan，XIE Yanyan^*，BAI Xiaoyan^*，GAO Yan，FU Na，CHEN Xiongfei，HU Mengqiao，ZHANG Lijiu

Guobiao （Beijing） Testing & Certification Co.，Ltd.，Beijing 100088，China）

Abstract：A method for the determination of the chlorinity （Cl） and sulfur （existing as SO₄^2-） contents in praseodymium neodymium oxides by inductively coupled plasma optical emission spectroscopy （ICP-OES） was established. Spectral line signals of 129-190 nm in the vacuum ultraviolet band were recorded and the instrument parameters were optimized. The sample was fully dissolved using nitric acid at low temperatures. Under the optimized conditions，the spectral lines selected for analysis were Cl （134.724 nm） and S （180.731 nm）. There were good linear relationships for Cl and S，with the correlation coefficients （r） of 0.9999. The standard addition recoveries were 93.1%-107.2% for Cl and 89.9%-94.9% for S，the relative standard deviations （RSDs） were 4.8% for Cl and 3.8% for S. This method could be used to determine Cl content higher than 0.014% and S content higher than 0.003% in praseodymium neodymium oxide materials.

Keywords：ICP-OES；praseodymium neodymium oxides；chlorinity and sulfur

尿样中低浓度19-去甲基雄酮的来源确证

温超^*，王静竹，朱天硕，刘欣，王杉

（北京体育大学北京兴奋剂检测实验室，北京 100029）

摘要：建立了19-去甲基雄酮（19NA）的气相色谱-燃烧-同位素比质谱（GC/C/IRMS）确证方法，使用高效液相色谱（HPLC）法对尿样中低浓度的19NA进行分离富集。方法检出限可达2 ng/mL，回收率为75%，线性范围为2~15 ng/mL，19NA的测量不确定度为0.76‰。本方法可在24 h内完成19NA的溯源确证，具有高选择性和检测效率，可用于兴奋剂常规检测。

关键词：19-去甲基雄酮；兴奋剂检测；高效液相色谱；分离富集

中图分类号：O657.63；O657.7    文献标识码：A    文章编号：1000-0720（2023）12-1689-06

Source confirmation for low concentration of 19-norandrosterone in urine sample

WEN Chao^*，WANG Jingzhu，ZHU Tianshuo，LIU Xin，WANG Shan

Beijing Anti-doping Laboratory，Beijing Sport University，Beijing 100029，China）

Abstract：A method based on gas chromatography-combustion-isotope ratio mass spectrometry （CG-C-IRMS） was established for source confirmation of trace amount 19-Norandrosterone （19NA） in human urine. The HPLC was employed for the separation and enrichment of 19NA. The detection limit of 19NA was 2 ng/mL，the method linearity range was 2-15 ng/mL，and the recovery was 75%. Additionally，the measurement uncertainty of 19NA was 0.76‰. The method can complete the traceability confirmation of 19NA within 24 h，with high selectivity and efficiency，and has strong application prospects in procedures for dope testing.

Keywords：19-norandrosterone；anti-doping analysis；HPLC；isolation and enrichment

全固态离子选择性电极在金属离子检测中的应用进展

李怀松^1，3，刘海兴^2，3，张文品^*1，4，徐溢^*1，2，3

（1. 重庆大学化学化工学院，重庆 400044；2. 重庆大学光电工程学院，重庆 400044；3. 重庆大学新型微纳器件与系统技术重点学科实验室和光电技术与系统教育部重点实验室，重庆 400044；4. 重庆市特种设备检测研究院，重庆 401121）

摘要：水环境中金属离子含量是水质质量的重要指标，研发简便、灵敏和准确的新型水环境金属离子检测技术已成为人们关注的热点。基于全固态离子选择电极（ASS-ISE）的电位分析技术，能实现对特定离子的快速电位响应，可满足在环境监测等领域对金属离子的实时、快速和原位检测需求。介绍了ASS-ISE法的原理及分类，综述了赝电容型、双电层电容型ASS-ISE及集成ASS-ISE电位传感器的微流控芯片在金属离子检测中的应用进展。

关键词：全固态离子选择性电极；电位传感器；金属离子检测；微流控芯片

中图分类号：O657.1    文献标识码：A    文章编号：1000-0720（2023）12-1695-10

Application progress of all solid state ion-selective electrodes in metal ion detection

LI Huaisong^1，3，LIU Haixing^2，3，ZHANG Wenpin^*1，4，XU Yi^*1，2，3

1. School of Chemistry and Chemical Engineering，Chongqing University，Chongqing 400044，China；2. School of Optoelectronic Engineering，Chongqing University，Chongqing 400044，China；3. Key Disciplines Lab of Novel Micro-Nano Devices and System Technology & Key Laboratory of Optoelectronic Technology and Systems，Ministry of Education，Chongqing University，Chongqing 400044，China；4. Chongqing Special Equipment Inspection and Research Institute，Chongqing 401121，China）

Abstract：The content of metal ion in water environment is an important index of water quality. Much more attention has been paid on the development of simple，sensitive and accurate detecting technology for metal ions in water environment. The potential analytical methods based on all-solid-state ion selective electrode（ASS-ISE） could achieve rapid potential response to specific ions and meet the needs of real-time，rapid and in-situ detection of metal ions in environmental monitoring and other fields. In this paper，the principle and classification of ASS-ISE methods were introduced. The application progress of pseudo-capacitive ASS-ISE and double-layer capacitive ASS-ISE in metal ions detection was reviewed. In particular，microfluidic chip integrated with ASS-ISE potential sensor was concerned in the application of metal ions detection.

Keywords：all solid state ion-selective electrodes （ASS-ISE）；potential sensor；metal ions detection；microfluidic chip