基于Co₃O₄@CNTs信号放大的有机磷与葡萄糖酶基传感器

李杰，张捷，王康康，董社英^*

（西安建筑科技大学化学与化工学院，西安 710055）

摘要：利用六水合硝酸钴（Co（NO₃）₂·6H₂O）与对苯二甲酸（HOOC-C₆H₄-COOH）合成MOF-71前驱体，将其与双氰胺（C₂H₄N₄）混合热解，得到在Co₃O₄上生长碳纳米管（CNTs）的Co₃O₄@CNTs电极修饰材料。采用扫描电子显微镜（SEM）、N₂吸附-脱附曲线（BET）、X射线衍射（XRD）、X射线能谱分析（EDS）对材料进行表征。结果表明，该纳米复合材料具有丰富的孔隙结构和较大的比表面积，可增大乙酰胆碱酯酶（AChE）和葡萄糖氧化酶（GOD）的负载量，起到信号放大的作用。电化学研究表明：MOF-71的热解及其与CNTs的复合使Co₃O₄@CNTs具有优良的导电性，也有利于信号的提升。将其分别固定AChE和GOD，构建酶基传感器用于检测有机磷农药和葡萄糖（Glu）。检测甲基对硫磷时，其线性范围为1.0×10^-3~1.0 ng/mL，检出限低至0.31 pg/mL；检测对氧磷时，其线性范围为1.0×10^-3~1.0 ng/mL，检出限低至0.34 pg/mL；检测Glu时，其线性范围为0.1~5 μmol/L和10~200 μmol/L，检出限为0.04 μmol/L。

关键词：Co₃O₄@CNTs；甲基对硫磷；对氧磷；葡萄糖；电化学生物酶传感器

中图分类号：O646    文献标识码：A    文章编号：1000-0720（2024）04-0455-08

Organophosphorus and glucose enzyme-based sensors based on Co₃O₄@CNTs signal amplification

LI Jie，ZHANG Jie，WANG Kangkang，DONG Sheying^*

School of Chemistry and Chemical Engineering，Xi'an University of Architecture and Technology，Xi'an 710055，China）

Abstract：Co₃O₄@CNTs electrode modification materials were obtained by mixed pyrolysis of dicyandiamide （C₂H₄N₄） and MOF-71 precursors synthesized by cobalt nitrate hexahydrate （Co（NO₃）₂·6H₂O） and pure terephthalic acid（HOOC-C₆H₄-COOH）. The materials were characterized by scanning electron microscope （SEM），Brunner-Emmet-Teller measurement （BET），X-ray diffraction （XRD），and energy dispersive spectroscopy （EDS）. The results showed that the nanocomposites had rich pore structures and large surface area，which could increase the loading of acetylcholinesterase （AChE） and glucose oxidase （GOD） for signal amplification. Meanwhile，the electrochemical performance study showed that Co₃O₄@CNTs had excellent conductivity and elevated signal due to the pyrolysis of MOF-71 and its combination with CNTs. AChE and GOD were further immobilized onto the Co₃O₄@CNTs to construct enzyme-based sensors for the detection of organophosphorus pesticides and glucose （Glu）. The linear concentration ranges were 1.0×10^-3-1.0 ng/mL，1.0×10^-3-1.0 ng/mL and 0.1-5 μmol/L as well as10-200 μmol/L for methyl parathion detection，paraoxon detection and Glu detection，respectively，accompanied by low detection limit of 0.31 pg/mL，0.34 pg/mL and 0.04 μmol/L.

Keywords：Co₃O₄@CNTs；methyl parathion；paraoxon；glucose；electrochemical biological enzyme sensor

气相色谱-质谱法测定食品接触材料及制品中4种柠檬酸酯类化合物的迁移量

刘仕途，曾铭，陈湘颖，李丹^*，董犇，阿文伟，钟怀宁

（广州海关技术中心，广州 510070）

摘要：建立了测定食品接触材料及制品中柠檬酸三乙酯（TEC）、乙酰柠檬酸三乙酯（ATEC）、柠檬酸三丁酯（TBC）和乙酰柠檬酸三丁酯（ATBC）迁移量的气相色谱-质谱（GC-MS）法。食品接触材料样品经迁移试验后，所得水基浸泡液和橄榄油浸泡液分别经正己烷和乙腈萃取后测定，95%乙醇浸泡液和异辛烷浸泡液直接测定。结果表明，4种目标化合物的标准工作曲线在0.2~2.0 mg/L浓度范围内线性关系良好，相关系数（r²）大于0.995；4种柠檬酸酯类化合物在4%乙酸、10%乙醇、20%乙醇、50%乙醇、95%乙醇、异辛烷、橄榄油等模拟物中的检出限为0.05~0.11 mg/L，定量限为0.15~0.30 mg/L。对基质空白浸泡液进行低、中、高3个浓度水平添加实验，加标回收率在90.6%~110%之间，相对标准偏差（RSD）为0.9%~8.6%。该方法能够满足食品接触材料及制品中4种柠檬酸酯类化合物迁移量检测的需求。

关键词：柠檬酸三乙酯（TEC）；乙酰柠檬酸三乙酯（ATEC）；柠檬酸三丁酯（TBC）；乙酰柠檬酸三丁酯（ATBC）；食品接触材料；气相色谱-质谱法（GC-MS）

中图分类号：O657.71；O622.3    文献标识码：A    文章编号：1000-0720（2024）04-0463-06

Determination of migration of four citrate compounds in food contact materials and products by gas chromatography-mass spectrometry method

LIU Shitu，ZENG Ming，CHEN Xiangying，LI Dan^*，DONG Ben，A Wenwei，ZHONG Huaining

Guangzhou Customs Technical Center，Guangzhou 510070，China）

Abstract：A gas chromatography-mass spectrometry （GC-MS） method was established to determine the migration of triethyl citrate （TEC），acetyl triethyl citrate （ATEC），tributyl citrate （TBC），and acetyl tributyl citrate （ATBC） in food contact materials and products. After the migration test of food contact material samples，the obtained water-based soaking solution and the olive oil soaking solution were extracted with n-hexane and acetonitrile respectively，and then determined by GC-MS，while the 95% ethanol soaking solution and isooctane soaking solution were directly determined by GC-MS. The results showed that the method had correlation coefficients （r²） greater than 0.995. The detection limits of four citrate compounds in 4% acetic acid，10% ethanol，20% ethanol，50% ethanol，95% ethanol，isooctane，and olive oil simulants were 0.05-0.11 mg/L，the limits of quantification were 0.15-0.30 mg/L，and the linear ranges were 0.2-2.0 mg/L. The average spiked recoveries of this method at low，medium，and high levels were 90.6%-110%，and the relative standard deviations （RSDs） were 0.9%-8.6%. This method can meet the requirements for determination of the migration amounts of four citrate compounds in food contact materials and their products.

Keywords：triethyl citrate （TEC）；acetylcitrate triethyl ester （ATEC）；tributyl citrate （TBC）；acetyl tributyl citrate （ATBC）；food contact materials；gas chromatography-mass spectrometry（GC-MS）

基于紫外光谱研究溶解性黑炭质子化

张竑^1，2，3，穆玉宁^1，2，杨晨宇¹，苏友波^1，2，蒋明¹，张继来^*1，2，傅开道³，张乃明^1，2，陈文华⁴

（1. 云南农业大学资源与环境学院，昆明 650500；2. 云南省土壤培肥与污染修复工程实验室，昆明 650201；3. 云南大学国际河流与生态安全研究院，昆明 650091；4. 保山学院资源与环境学院，保山 678000）

摘要：运用紫外光谱滴定技术结合差分光谱与二维相关光谱分析，对溶解性黑炭（DBC）的质子化过程进行定性和定量研究。结果发现：热解温度为280，360，440 ℃的DBC在消光光谱200~250 nm间有特征吸收峰，但DBC特征峰并未随pH变化出现发色团去质子化和结构改变；运用差分光谱分析发现，3个热解温度下DBC均于波长280，355，385 nm处形成特征差分吸收峰，且吸收峰强度与H⁺浓度成正相关（p＜0.05）；二维紫外相关光谱分析表明，DBC的质子化主要发生于羧基及含酚官能团上。以上结果表明，紫外差分光谱滴定法可以定量分析DBC的质子化，DBC发生质子化的主要位点与腐殖酸类似，均为羧基及酚羟基。

关键词：生物碳；溶解性黑炭；质子化；紫外吸收光谱

中图分类号：O657.3    文献标识码：A    文章编号：1000-0720（2024）04-0469-07

Study of dissolved black carbon protonation based on ultraviolet spectroscopy

ZHANG Hong^1，2，3，MU Yuning^1，2，YANG Chenyu¹，SU Youbo^1，2，JIANG Ming¹，ZHANG Jilai^*1，2，FU Kaidao³，ZHANG Naiming^1，2，CHEN Wenhua⁴

1. College of Resources and Environment，Yunnan Agricultural University，Kunming 650500，China；2. Lab of Soil Fertilization and Pollution Remediation Engineering，Yunnan Province，Kunming 650201，China；3. Institute of International Rivers and Ecological Security，Yunnan University，Kunming 650091，China；4. School of Resources and Environment，Baoshan University，Baoshan 678000，China）

Abstract：The quantitative and qualitative study of the protonation process of dissolved black carbon （DBC） were carried out by combining ultraviolet （UV） spectral titration technique combining with differential spectroscopy and two-dimensional correlation spectroscopy analysis. It was found that DBC with pyrolysis temperatures of 280，360 and 440 ℃ had characteristic absorption peaks in the extinction spectral range of 200-250 nm，but the characteristic peaks of DBC did not show deprotonation of chromophores and structural changes with pH changes. Differential spectroscopy analysis revealed that the DBC at the three pyrolysis temperatures formed characteristic differential absorption peaks at 280，355 and 385 nm，and the intensity of the absorption peaks was positively correlated with the H⁺ concentration （p<0.05）. Two-dimensional UV correlation spectroscopy showed that the protonation of DBC mainly occurred at the carboxyl group and phenol-containing functional groups. The above results indicated that the UV differential spectroscopy titration method could quantitatively analyze the protonation of DBC，and the main sites of protonation of DBC were carboxyl and phenolic hydroxyl groups，where were similar to those of humic acid.

Keywords：biochar；dissolved black carbon；protonation；ultraviolet absorption spectrum

基于磁性金属有机骨架材料的固相萃取电感耦合等离子体质谱法测定环境水中的重金属元素

王意^*1，邹昊彤²，薛涛¹，刘洋¹，林奎¹，李方²，邓小娟¹

（1. 天津大学分析测试中心，天津 300072；2. 天津大学材料学院，天津 300072）

摘要：利用水热反应，成功合成了一种功能化的金属有机骨架材料，磁性MIL-101（Fe），并将其用作磁性固相萃取（MSPE）吸附剂，与电感耦合等离子体质谱（ICP-MS）联用，实现高效、灵敏的痕量重金属离子测定。利用扫描电子显微镜、透射电子显微镜、X射线衍射和X射线光电子能谱对磁性MIL-101（Fe）进行了表征，并通过间歇吸附实验优化了溶液pH、吸附时间和解吸时间等萃取参数。结果表明，所合成的MIL-101（Fe）磁性固相萃取剂具有良好的晶体结构和表面功能化纳米颗粒。在优化实验条件下，所建立的MSPE-ICP-MS方法线性范围为0.5~500 μg/L，As（III），Pb（II）和Cu（II）的检出限为0.177~0.301 μg/L，相对标准偏差为1.7%~3.2%，在连续7次循环使用后回收率仍可达82%。该方法用于环境水样中痕量重金属离子的测定，加标回收率为90.0%~113.2%，可用于环境水样中痕量重金属检测。

关键词：磁性固相萃取；电感耦合等离子体质谱；金属有机骨架材料；重金属离子

中图分类号：O657.63    文献标识码：A    文章编号：1000-0720（2024）04-0476-06

Determination of heavy metals in environmental water by magnetic solid phase extraction-inductively coupled plasma mass spectrometry based on magneticmetal-organic framework materials

WANG Yi^*1，ZOU Haotong²，XUE Tao¹，LIU Yang¹，LIN Kui¹，LI Fang²，DENG Xiaojuan¹

1. Analysis and Testing Center，Tianjin University，Tianjin 300072，China；2. College of Materials Science and Engineering，Tianjin University，Tianjin 300072，China）

Abstract：A functionalized metal-organic framework material，magnetic MIL-101（Fe） composite，was successfully synthesized through hydrothermal reaction. MIL-101 （Fe） composite was used as a magnetic solid phase extraction （MSPE） agent，which was coupled with inductively coupled plasma mass spectrometry （ICP-MS） to realize the efficient and sensitive analysis of trace heavy metal ions. The synthesized magnetic MIL-101（Fe） composite was characterized by scanning electron microscopy，transmission electron microscopy，X-ray diffraction and X-ray photoelectron spectroscopy. The extraction parameters including solution pH，adsorption time and desorption time，were optimized by batch adsorption experiments. The experimental results showed that the MSPE agent was nanoparticles with good crystal structure and surface functionality. Under the optimized experimental conditions，the established MSPE-ICP-MS method had a linear range of 0.5-500 μg/L，the detection limits of As（III），Pb（II） and Cu（II） ions were 0.177-0.301 μg/L，and the relative standard deviations were 1.7%-3.2%. The recycled magnetic MIL-101 （Fe） composite exhibited good reusability，and the recovery was higher than 82% after seven adsorption-desorption cycles. The method was successfully applied to the determination of trace heavy metal ions in environmental water samples. The recoveries of arsenic，lead and copper ions in seawater and lake water samples ranged from 90.0% to 113.2%. This method can be used for the determination of trace heavy metals in environmental water samples.

Keywords：magnetic solid phase extraction；inductively coupled plasma mass spectrometry；metal-organic framework；heavy metal ions

钠离子促进消解-电感耦合等离子体质谱法测定植物中的硅

孙文军^1，2，刘向磊^*1，2，蔡焕花¹，张宏丽^3，4，文田耀^1，2，王腾飞¹

（1. 河南省地质矿产勘查开发局第一地质矿产调查院，洛阳 471023；2. 河南省金银多金属成矿系列与深部预测重点实验室，洛阳 471023；3. 中国地质科学院郑州矿产利用研究所，郑州 450006；4. 国家非金属资源综合利用工程技术中心，郑州 450006）

摘要：植物中的硅因具有含量低、难消解、用含氟酸处理易损失等特点，一直是湿法处理的难点。本研究选择硝酸+氢氟酸+氯化钠混合消解液和高通量微波密闭消解植物样品，通过优化消解液配比、消解温度和消解时间、碰撞气体流量，建立了钠离子促进消解-电感耦合等离子体质谱法测定植物中硅的方法。结果表明，使用硝酸+氢氟酸混合消解溶液，可有效消解植物样品基体及基体中的硅元素；向消解液中加入一定量的钠离子和使用微波密闭消解法，能够促进试样中二氧化硅消解完全，提高消解效率及避免氟硅化合物的挥发损失。使用聚四氟乙烯同心圆雾化器、聚四氟乙烯旋流雾化室和蓝宝石中心管，可有效降低由溶液中氢氟酸介质腐蚀石英进样系统引入的仪器本底值；选择氦气作为碰撞气并控制氦气流量，可以有效消除氮、碳、铝、硼、氢、氧等元素的多原子离子对²⁸Si的质谱干扰，提高方法的灵敏度。硅的方法检出限为0.001%，相对标准偏差（RSD）和误差（RE）分别在1.8%~7.7%和-1.8%~4.5%之间。方法适合于植物样品中硅的准确、快速测定，也可为农业考古和植物碳汇潜力研究中硅的总量分析提供技术支撑。

关键词：硅；钠离子；植物样品；微波消解；电感耦合等离子体质谱

中图分类号：O652.4；O657.63    文献标识码：A    文章编号：1000-0720（2024）04-0482-06

Determination of silicon in plants by sodium ion promoted digestion-inductively coupled plasma mass spectrometry

SUN Wenjun^1，2，LIU Xianglei^*1，2，CAI Huanhua¹，ZHANG Hongli^3，4，WEN Tianyao^1，2，WANG Tengfei¹

1. No.1 Institute of Geological and Mineral Resources Survey，Henan Bureau of Geoexploration and Mineral Development，Luoyang 471023，China；2. Key Laboratory of Au-Ag-Polymetallic Deposit Series and Deep-seated Metallogenic Prognosis of Henan Province，Luoyang 471023，China；3. Zhengzhou Institute of Multipurpose Utilization of Mineral Resources，Chinese Academy of Geological Sciences，Zhengzhou 450006，China；4. China National Engineering Research Center for Utilization of Industrial Minerals，Zhengzhou 450006，China）

Abstract：Silicon in plants has always been one of the difficulties in wet treatment because of its low content，difficult digestion，and easy loss of fluorine-containing acid treatment. In this study，HNO₃+HF+NaCl mixed digestion solution and high-throughput microwave closed digestion for plant samples were selected. By optimizing the ratio of digestion solution，digestion temperature and digestion time，collision gas flow，a method for the determination of silicon in plants by inductively coupled plasma mass spectrometry with sodium ion promoted digestion was established. The results showed that the use of HNO₃-HF mixed digestion solution could effectively digest the plant sample matrix and the silicon element in the matrix. The addition of a certain amount of sodium ions to the digestion solution and the use of microwave closed digestion method could promote the complete digestion of silica in the sample，improve the digestion efficiency and avoid the volatilization loss of fluorosilicone compounds. The use of polytetrafluoroethylene concentric atomizer，polytetrafluoroethylene swirl atomizing chamber and sapphire central tube can effectively reduce the instrument background value introduced by the hydrofluoric acid medium corrosion quartz injection system in the solution. Choosing helium （He） as collision gas and controlling the flow rate of helium can effectively eliminate the mass spectral interference of polyatomic ions of nitrogen，carbon，aluminum，boron，hydrogen，oxygen and other elements on ²⁸Si，and improve the sensitivity of the method. The detection limit of silicon was 0.001%，and the relative standard deviations （RSDs） and error （RE） of the method were 1.8%-7.7% and -1.8%-4.5%，respectively. The method is suitable for the accurate and rapid determination of silicon in plant samples，and can also provide technical support for the total amount analysis of silicon in agricultural archaeology and plant carbon sink potential research.

Keywords：silicon；sodium ion；plant samples；microwave digestion；inductively coupled plasma-mass spectrometry

基于Hg/Au基纳米酶过氧化物酶活性比色/SERS双模式检测烟碱

张海¹，何彬¹，高宪辉¹，周渭皓¹，刘磊¹，李秋兰²，吴伟²，杨德志^*2，杨亚玲^*2

（1. 云南省烟草烟叶公司，昆明 650218；2. 昆明理工大学生命科学与技术学院，昆明 650500）

摘要：利用Hg²⁺与Au基纳米材料形成金汞齐制备Hg/Au基纳米酶（AuNPs@Hg）。基于纳米酶表面增强拉曼光谱（SERS）活性和模拟酶催化活性，建立了比色/SERS双模式检测烟碱的方法。结果表明，AuNPs@Hg可以模拟过氧化物酶，催化过氧化氢氧化无色的3，3'，5，5'-四甲基联苯胺（TMB），同时也可以作为SERS底物，检测TMB氧化产物（oxTMB）的SERS信号，而烟碱则可以显著增加AuNPs@Hg的过氧化物酶活性。基于比色法，在烟碱浓度1.25~375 μg/mL范围内呈良好的线性关系，检出限（LOD）为0.34 μg/mL。基于SERS法，烟碱浓度在6.25×10^-3~1.25 mg/mL范围内有较好的线性校准曲线，LOD为1.80 μg/mL。实际样品中烟碱的回收率在96.1%~105.3%范围内，相对标准偏差（RSD）为2.4%~4.7%，且实际样品中存在的共存物质对所建立的方法几乎无干扰作用，检测结果与行业标准方法测定结果一致。本研究可为多功能传感器的设计及SERS在烟草行业中的应用提供新的策略和途径。

关键词：烟碱；纳米酶；表面增强拉曼光谱；过氧化物酶；金汞齐

中图分类号：O657.37    文献标识码：A    文章编号：1000-0720（2024）04-0488-09

Colorimetric/SERS dual-mode detection of nicotine based on the peroxidase-like activity of Hg/Au-nanozyme

ZHANG Hai¹，HE Bin¹，GAO Xianhui¹，ZHOU Weihao¹，LIU Lei¹，LI Qiulan²，WU Wei²，YANG Dezhi^*2，YANG Yaling^*2

1. Yunnan Tobacco Leaf Company，Kunming 650218，China；2. Faculty of Life Science and Technology，Kunming University of Science and Technology，Kunming 650500，China）

Abstract：The preparation of Hg/Au-based nanozyme （AuNPs@Hg） by the formation of gold amalgam between Hg²⁺ and Au-based nanomaterials was proposed. Based on the enhanced SERS activity and simulated catalytic activity of the nanozyme，a colorimetric/SERS dual-mode method was established for the detection of nicotine. The results showed that AuNPs@Hg could simulate peroxidase to catalyze the oxidation of colorless 3，3'，5，5'- tetramethylbenzidine （TMB） by hydrogen peroxide （H₂O₂）. Meanwhile，it could also be used as SERS substrate to detect the SERS signal of TMB oxidation products （oxTMB）. Nicotine can significantly increase the peroxidase activity of AuNPs@Hg. Based on TMB colorimetric assay，nicotine showed good linearity in the range of 1.25-375 μg/mL with the limit of detection （LOD） of 0.34 μg/mL. Based on the SERS method，the nicotine concentration in the range of 6.25×10^-3-1.25 mg/mL had a good linear calibration curve，and the LOD was 1.80 μg/mL. The recoveries of nicotine in the real e-cigarette liquid samples were in the range of 96.1%-105.3% with the relative standard deviations （RSDs） of 2.4%-4.7%. The coexisting substances in the actual samples had almost no interference，and the detection results were consistent with that of the industry standard method. This research can provide a new strategy and approach for the design of multi-functional sensor and SERS application in the tobacco industry.

Keywords：nicotine；nanozyme；surface-enhanced Raman spectroscopy；peroxidase；Au-Hg amalgam

聚多巴胺涂覆的磺丁基醚-β-环糊精开管毛细管电色谱柱的制备及应用

黄子为，霍虹懿，龙科，石爽，关瑾^*

（沈阳化工大学理学院，沈阳 110142）

摘要：制备了以聚多巴胺/磺丁基醚-β-环糊精（PDA/SBE-β-CD）为手性固定相的开管毛细管电色谱柱。最佳制备条件为：SBE-β-CD浓度10.0 mg/mL，多巴胺浓度5.0 mg/mL，涂覆时间2 h。通过红外光谱和扫描电镜对制备的色谱柱进行了表征，并将其应用于奥美拉唑对映体的毛细管电色谱（CEC）分离分析。在110 mmol/L Tris-H₃PO₄（pH 6.0）缓冲溶液和外加电压15 kV条件下，奥美拉唑对映体在13 min内成功分离，分离度为5.82。对映异构体质量浓度在50~600 μg/mL 范围内线性关系良好（r²=0.9958），迁移时间和峰面积的相对标准偏差（RSD）分别小于2.8%和4.8%。PDA/SBE-β-CD固定相在毛细管电色谱（CEC）手性分离中具有良好的应用潜力。

关键词：毛细管电色谱；手性分离；开管柱；磺丁基醚-β-环糊精；聚多巴胺

中图分类号：O657.8    文献标识码：A    文章编号：1000-0720（2024）04-0497-05

Preparation and application of polydopamine/sulfobutyl ether-β-cyclodextrin coated open tube capillary electrochromatographic column

HUANG Ziwei，HUO Hongyi，LONG Ke，SHI Shuang，GUAN Jin^*

College of Science，Shenyang University of Chemical Technology，Shenyang 110142，China）

Abstract：An open tube capillary electrochromatographic column was prepared using polydopamine/sulfobutyl ether-β-Cyclodextrin （PDA/SBE-β-CD） as chiral stationary phase. The optimal conditions of fabricated capillary column were as follows：SBE-β-CD concentration of 10.0 mg/mL，dopamine concentration of 5.0 mg/mL，and coating time of 2 h. The fabricated capillary column was characterized by scanning electron microscopy and Fourier transform infrared spectroscopy. Furthermore，the chiral separation effectiveness of the fabricated capillary column was evaluated by capillary electrochromatography （CEC） using enantiomers of omeprazole as model analyte. The enantiomers of omeprazole were resolved within 13 min with high resolution of 5.82 using 110 mmol/L Tris-H₃PO₄ buffer （pH 6.0） at an applied voltage of 15 kV. Good linearities were obtained in the concentration range of 50-600 μg/mL with the correlation coefficients of r²=0.9958 for the enantiomers of omeprazole. And for the migrated time and peak areas，the relative standard deviations （RSDs） were below 2.8% and 4.8%，respectively. The results reveal that PDA/SBE-β-CD has great potential as chiral stationary phases for enantio separation in CEC.

Keywords：capillary electrochromatography；chiral separation；open tubular column；sulfobutyl ether-β-cyclodextrin；polydopamine

基于直接标准化与分段直接标准化联用的木质素近红外模型传递方法研究

刘智健¹，熊智新^*1，胡云超¹，汪莹¹，黄浩冉¹，王红鸿¹，梁龙²

（1. 南京林业大学轻工与食品学院，南京 210037；2. 中国林业科学研究院林产化学工业研究所，南京 210042）

摘要：为了提高木质素近红外分析模型转移的质量，提出了将直接标准化（DS）与分段直接标准化（PDS）联用的DS-PDS方法，即利用PDS算法校正使用DS方法全局校正后仪器之间仍然存在的局部差异，并以3台光谱仪（棱光为主机、Si-ware和Insion为从机）测得的81个样品木质素光谱数据为研究对象，验证该方法的可行性。结果表明，该联用算法能充分发挥DS算法与PDS算法各自的优点，与单独使用DS的最优结果相比，标样集并未增加，PDS算法的窗口宽度、偏最小二乘回归（PLSR）模型的主因子数均减小，对从机样品的预测精度进一步提高。对Si-Ware而言，相对标准偏差（RPD）值由DS方法的3.3853提高到4.0335，Insion的RPD值则从2.8600提高到3.4462。DS-PDS联用算法除了使用更少的参数，还能减弱模型转移中光谱不连续现象，弥补了单独使用DS和PDS算法的缺点，为近红外光谱的模型转移提供了一种新的解决方案。

关键词：木质素；近红外光谱；模型传递；DS-PDS

中图分类号：O657.63    文献标识码：A    文章编号：1000-0720（2024）04-0502-09

Research on near-infrared model transfer for lignin based on the combined direct standardization-piecewise direct standardization method

LIU Zhijian¹，XIONG Zhixin^*1，HU Yunchao¹，WANG Ying¹，HUANG Haoran¹，WANG Honghong¹，Liang long²

1. College of Light Industry and Food，Nanjing Forestry University，Nanjing 210037，China；2. Institute of Chemical Industry of Forest Products，Chinese Academy of Forestry，Nanjing 210042，China）

Abstract：In order to improve the transfer performance of the lignin near-infrared analysis model，a method combining direct standardization （DS） and piecewise direct standardization （PDS），named DS-PDS，was proposed. The PDS algorithm was used to correct the local differences between instruments still existed after the global correction using the DS method. The lignin spectral data of 81 samples measured by three spectrometers （Lengguang as master instrument，and Si-Ware and Insion as target instruments，respectively） were used to verify the feasibility of the new method. The experimental results showed that the combined algorithm can exploit the advantages of DS algorithm and PDS algorithm respectively. Compared with the optimal results of using DS algorithm alone，the standard sample set did not increase. For PDS algorithm，the window width，and the number of principal factors of the partial least square regression （PLSR） model were reduced，while the prediction accuracy of the target instruments was further improved. The ratio of prediction to deviation （RPD） value for Si-Ware increased from 3.3853 to 4.0335 comparing to the previous DS method，and the RPD value for Insion increased from 2.8600 to 3.4462. In addition to using fewer parameters，the combined DS-PDS algorithm can also reduce the phenomenon of spectral discontinuity in model transfer，which makes up for the shortcomings of using DS and PDS algorithms alone，and provides a new solution to the model transfer strategy of near-infrared spectroscopy.

Keywords：lignin；near-infrared spectroscopy；model transfer；DS-PDS

基于四氧化三铁/聚（苯乙烯-4-乙烯吡啶）的食品中四环素残留的快速筛选

沈唐文¹，折欢欢¹，张毅¹，严恒²，谢卫红^*1

（1. 湖北工业大学生物工程与食品学院，武汉 430068；2. 湖北省食品质量安全监督检验研究院，武汉 430075）

摘要：基于四环素对四氧化三铁（Fe₃O₄）/聚（苯乙烯-4-乙烯吡啶）（Fe₃O₄/P（st-4vp））的过氧化物酶活性的抑制作用，建立了一种快速筛选牛奶和蜂蜜中四环素残留的方法。酸性条件下，所制备的Fe₃O₄/P（st-4vp）能够催化H₂O₂氧化3，3，5，5’-四甲基联苯胺（TMB）生成蓝色的氧化TMB（oxTMB），在652 nm处出现可见吸收特征峰。四环素对该反应产生抑制作用，在pH 5.0、50 ℃水浴、反应时间20 min、H₂O₂浓度10 mmol/L、Fe₃O₄/P（st-4vp）浓度1.0 mg/mL、TMB浓度0.36 mmol/L条件下，四环素对Fe₃O₄/P（st-4vp）酶活性的抑制作用最强。根据四环素浓度与酶抑制率的关系曲线，对牛奶和蜂蜜中的加标四环素进行了筛查。结果表明，Fe₃O₄/P（st-4vp）对四环素加标量范围5~197.5 μg/kg的牛奶和蜂蜜的筛查准确度分别为94.4%和96.3%。

关键词：四氧化三铁；聚（苯乙烯-4-乙烯吡啶）；纳米酶；四环素残留；快检

中图分类号：TS207.3    文献标识码：A    文章编号：1000-0720（2024）04-0511-06

Rapid screening of tetracycline residues in food based on Fe₃O₄/poly（styrene-4-vinyl pyridine） nanocomposites

SHEN Tangwen¹，SHE Huanhuan¹，ZHANG Yi¹，YAN Heng¹，XIE Weihong^*2

1. College of Biotechnology and Food，Hubei University of Technology，Wuhan 430068，China；2. Hubei Provincial Institute for Food Supervision and Test，Wuhan 430075，China）

Abstract：A rapid screening method for tetracycline residues in milk and honey samples was developed based on the inhibitory effect of tetracycline on the peroxidase activity of Fe₃O₄/poly（styrene-4-vinylpyridine） （Fe₃O₄/P（st-4vp））. Under acidic conditions，the prepared Fe₃O₄/P（st-4vp） was able to catalyze the oxidation of 3，3，5，5'- tetramethylbenzidine （TMB） by H₂O₂ to produce blue oxidized TMB （oxTMB），with a characteristic absorption peak at 652 nm. The reaction was inhibited by tetracycline，which showed the strongest inhibition of Fe₃O₄/P （st-4vp） enzyme activity under conditions of pH 5.0，50 ℃ of water bath，20 min of reaction time，10 mmol/L of H₂O₂，1.0 mg/mL of Fe₃O₄/P（st-4vp），and 0.36 mmol/L of TMB. Based on the relationship curve between tetracycline concentration and enzyme inhibition rate，the spiked tetracycline in milk and honey samples was screened，and the results showed that the screening range of Fe₃O₄/P（st-4vp） for tetracycline spiked in milk and honey was 5-197.5 μg/kg，and the relative accuracy were 94.4% and 96.3%，respectively.

Keywords：Fe₃O₄；poly（styrene-4-vinylpyridine）；nanozyme；tetracycline residue；quick test

十六烷基三甲基溴化铵增敏化学发光法测定东莨菪内酯

赵悦¹，张罗一览³，程轲¹，向警¹，吴文婕²，王琴²，张雨润²，黄文静²，孙建敏⁴，杨宪^*1，郑红^*2

（1. 重庆师范大学生命科学学院，活性物质生物技术教育部工程研究中心，重庆 401331；2. 重庆师范大学化学学院，活性物质生物技术教育部工程研究中心，重庆 401331；3. 重庆市水利投资（集团）有限公司中心实验室，重庆 401100；4. 重庆师范大学科研处，重庆 401331）

摘要：本文提供了一种新的测定东莨菪内酯的化学发光方法。酸性条件下，十六烷基三甲基溴化铵（CTAB）可增强东莨菪内酯在高锰酸钾（K₂MnO₄）-甲醛体系中的发光强度，因此以CTAB作为增敏剂和助溶剂，联合流动注射法对东莨菪内酯进行测定。在优化条件下，相对发光强度与东莨菪内酯浓度在0.1~26.0 μmol/L范围内有良好的线性关系，检出限（3σ）达1.40 nmol/L。对2.0 μmol/L东莨菪内酯连续测定11次，相对标准偏差（RSD）为1.1%。本方法可用于测定样品中东莨菪内酯的含量。

关键词：东莨菪内酯；增敏；十六烷基三甲基溴化铵；流动注射；化学发光

中图分类号：O657.3；R284.1    文献标识码：A    文章编号：1000-0720（2024）04-0517-05

Determination of scopoletin by chemiluminescence with cetyltrimethylammonium bromide as sensitizer

ZHAO Yue¹，ZHANG Luoyilan³，CHENG Ke¹，XIANG Jing¹，WU Wenjie²，WANG Qin²，ZHANG Yurun²，HUANG Wenjing²，SUN Jianmin⁴，YANG Xian^*1，ZHENG Hong^*2

1. College of Life Sciences，Chongqing Normal University，Engineering Research Center of Active Matter Biotechnology，Ministry of Education，Chongqing 401331，China；2. College of Chemistry，Chongqing Normal University，Engineering Research Center of Active Matter Biotechnology，Ministry of Education，Chongqing 401331，China；3. Central Laboratory of Chongqing Water Conservancy Investment （Group） Company Limited，Chongqing 401100，China；4. Scientific Research Department of Chongqing Normal University，Chongqing 401100，China）

Abstract：A new chemiluminescence method for the determination of scopoletin was developed. Under acidic conditions，cetyltrimethylammonium bromide （CTAB） can enhance the luminescence intensity of scopoletin in the potassium permanganate-formaldehyde system. Therefore，using CTAB as sensitizer and co-solvent，scopoletin could be measured by combining chemiluminescence with flow injection method. Under the optimized conditions，the relative luminescence intensities showed good linearity with scopoletin concentrations in the range of 0.1-26.0 μmol/L，and the detection limit （3σ） was 1.40 nmol/L. In addition，the relative standard deviation （RSD） was 1.1% for 11 consecutive determinations of 2.0 μmol/L of scopoletin. The developed method can be applied to the determination of scopoletin in samples with satisfactory results.

Keywords：scopoletin；sensitization；cetyltrimethylammoniumbromide （CTAB）；flow injection；chemiluminescence

液相色谱-串联质谱法测定植物源驱蚊防蚊产品中11种致敏芳香剂和3种化学驱避剂

胡玉霞^1，2，李红艳¹，陈德文^*3

（1. 浙江省产品质量安全科学研究院，杭州310018；2. 浙江经贸职业技术学院，杭州310018；3. 杭州职业技术学院生态健康学院，杭州 310018）

摘要：建立了植物源驱蚊防蚊产品中11种致敏性芳香剂和3种化学驱避剂同时测定的液相色谱-串联质谱方法。样品用二氯甲烷超声提取，在电喷雾离子源（ESI）正负离子多反应监测模式下同时采集，以乙腈-水为流动相梯度洗脱，采用Fastcore C₁₈色谱柱进行分离，外标法定量。结果表明，该方法可以有效分离同分异构体6-甲基香豆素和7-甲基香豆素，14种目标化合物在0.4 ~20000 μg/L范围内线性关系良好，相关系数R²>0.99，方法定量限为0.001~1.0 mg/kg。以定量限、4倍定量限和10倍定量限3个水平进行加标实验，回收率为80.6%~118%，相对标准偏差（RSD）为1.1%~7.4%。采用本方法对30批驱蚊产品进行检测，检出香兰素、香豆素、避蚊胺和丁香酚4种目标物。该方法适用于同时检测植物源驱蚊产品中致敏性芳香剂和化学驱避剂。

关键词：液相色谱-串联质谱法（LC-MS/MS）；致敏性芳香剂；化学驱避剂；驱蚊

中图分类号：O657.63    文献标识码：A    文章编号：1000-0720（2024）04-0522-06

Determination of 11 allergic fragrances and 3 chemical repellents in plant derived mosquito repellent and anti-mosquito products by liquid chromatography-tandem mass spectrometry

HU Yuxia^1，2，LI Hongyan¹，CHEN Dewen^*3

1. Zhejiang Institute of Product Quality and Safety Science，Hangzhou 310018，China；2. Zhejiang Institute of Economics and Trade，Hangzhou 310018，China；3. Hangzhou Vocational & Technical College，Ecology and Health Institute，Hangzhou 310018，China）

Abstract：A liquid chromatography-tandem mass spectrometry （LC-MS/MS） method was developed for the simultanous determination of 11 allergic fragrances and 3 chemical repellents in plant derived mosquito repellent and anti mosquito products. After ultrasonic extraction with dichloromethane，the samples were analyzed simultaneously under electric spray ion source （ESI） positive and negative ion multi reaction monitoring mode （MRM）. Chromatographic separation of the migration solution was performed on a Fastcore C₁₈ chromatographic column by a gradient elution of acetonitrile and water. The external standard method was used for the quantitative analysis. The results showed that the isomers 6-methylcoumarin and 7-methylcoumarinthe could be separated efficiently. There were good linear relationships for the14 targets in the concentration range of 0.4-20000 μg/L，with the correlation coefficients higher than 0.99，and the method limits of quantification （LOQs） were 0.001-4.0 mg/kg. The recoveries of the targets were 80.6%-118% at three spiked levels of LOQ，4×LOQ and 10×LOQ. The relative standard deviations （RSDs） were 1.1%-7.4%. This method was used to detect 30 mosquito repellent products，and 4 targets including vanillin，coumarin，N，N-diethyl-meta-toluamide （DEET） and eugenol were detected. This method could be applied for the determination of allergenic fragrances and chemical repellents in plant derived mosquito repellent and anti-mosquito products.

Keywords：liquid chromatography-tandem mass spectrometry （LC-MS/MS）；allergic fragrance；chemical repellent；mosquito repellent

高效液相色谱-串联质谱法测定化妆品中12种N-亚硝胺类物质

李静，周智明^*，陈张好，陆土柳

（国家药品监督管理局化妆品风险评估重点实验室（广东省药品检验所），广州 510525）

摘要：建立了化妆品中12种N-亚硝胺类物质的高效液相色谱-串联三重四极杆质谱（HPLC-MS/MS）检测方法。0.5 g样品用25 mL 50%（V/V）甲醇水溶液溶解后，冰浴超声提取5 min，10000 r/min离心5 min净化，以PFP 色谱柱为分析柱，5 mmol/L甲酸胺（含0.1%甲酸）水溶液-甲醇为流动相梯度洗脱，大气压化学电离源电离后正离子、多反应监测模式测定，外标法定量。12种亚硝胺类物质在5~200 μg/L范围内线性良好（r²＞0.99），检出限为5~50 μg/kg。膏霜、乳液和水剂3种基质的平均回收率为78.9%~119.7% ，相对标准偏差为0.71%~8.8%。本方法能够为化妆品中12种亚硝胺类物质的监测评估提供技术手段。

关键词：N-亚硝胺类物质；高效液相色谱-串联质谱法；化妆品

中图分类号：O657.7；TQ651.2    文献标识码：A    文章编号：1000-0720（2024）04-0528-07

Determination of 12 N-nitrosamines in cosmetics by high performance liquid chromatography-triple quadrupole mass spectrometry

LI Jing，ZHOU Zhiming^*，CHEN Zhanghao，LU Tuliu

National Medical Products Administration Key Laboratory for Safety Risk Assesment of Cosmetics （Guangdong Institute for Drug Control），Guangzhou 510525，China）

Abstract：The method for the simultaneous determination of twelve N-nitrosamines from cosmetics by high performance liquid chromatography-triple quadrupole mass spectrometry （HPLC-MS/MS） was developed. 0.5 g of sample was dissolved in 25 mL of 50% （V/V） methanol solution，then the 12 kinds of N-nitrosamines were extracted from cosmetics by ice bath supersonic extraction for 5 min，and the extracts were purified by centrifugation with 10000 r/min for 5 min. The chromatographic separation was performed on PFP column by gradient elution，with 5 mmol/L formic acid amine （containing 0.1% formic acid） aqueous solution-methanol as mobile phase at a flow rate of 0.3 mL/min．The 12 kinds of N-nitrosamines were analyzed in positive ions mode under multiple reaction monitoring （MRM） mode，after ionization by atmospheric pressure chemical ionization source，and quantified by external standard method. Results showed that there were good linear relationships for the 12 kinds of N-nitrosamines in the range of 5-200 μg/L，with their correlation coefficients （r²） more than 0.99. The limits of detection were 5-50 μg/kg. The average recoveries of the 12 kinds of N-nitrosamines in cream，emulsion and water ranged from 78.9% to 119.7%，with the relative standard deviations （RSDs） of 0.71%-8.8%. The method can be used for monitoring and evaluation of 12 kinds of N-nitrosamines in cosmetics.

Keywords：N-nitrosamine；high performance liquid chromatography-triple quadrupole mass spectrometry；cosmetics

棉签固相微萃取结合高效液相色谱-串联质谱法检测蜂蜜中9种大环内酯类抗生素

宫小明，李凯^*，许文娟，王洪涛，刘孟孝，孔彩霞

（潍坊海关综合技术服务中心，潍坊 261041）

摘要：通过“dip-coating”法制备了一种表面覆盖聚丙烯腈（PAN）/亲水-疏水平衡颗粒（HLB）涂层的棉签固相微萃取（SPME）。该棉签SPME制作方法简便、成本低廉（1元/支）、可重复使用，并可实现样品前处理的半自动化。通过优化PAN和HLB的组成比例，使棉签SPME对9种大环内酯类抗生素标准品的吸附率达到80%以上，解吸率达到99%以上。使用棉签SPME结合高效液相色谱-串联质谱法（HPLC-MS/MS），同时检测蜂蜜中9种大环内酯类抗生素（MACs）。9种MACs在1~20 μg/L浓度范围内呈良好线性关系，线性相关系数（R²）均大于0.9978。9种MACs在1，5，10 μg/kg 3个标准添加浓度下的平均回收率为71.8%~86.4%，相对标准偏差（RSD）为2.2%~5.3%，检出限（LOD）为0.24~1.35 μg/kg，定量限（LOQ）为1.02~4.62 μg/kg。

关键词：大环内酯类抗生素；固相微萃取；蜂蜜；高效液相色谱-串联质谱

中图分类号：O657.31；X832    文献标识码：A    文章编号：1000-0720（2024）04-0535-06

Quantification of macrolide antibiotics in honey by using cotton swab based solid-phase microextraction combined with high performance liquid chromatography-tandem mass spectrometry

GONG Xiaoming，LI Kai^*，XU Wenjuan，WANG Hongtao，LIU Mengxiao，KONG Caixia

Comprehensive Technical Service Center of Weifang Customs，Weifang 261041，China）

Abstract：A cotton swab based solid-phase microextraction （SPME） covered with polyacrylonitrile （PAN）/hydrophilic-hydrophobic balance （HLB） particles，which is simple，inexpensive，reusable，and semi-automated for sample pretreatment，was prepared by the dip-coating method. By optimizing the composition ratio of PAN to HLB，the adsorption rate of swab SPME for nine macrolide antibiotic standards reached more than 80% and the desorption rates were more than 99%. Detection of 9 macrolide antibiotics （MACs） in honey was performed using this SPME in combination with HPLC-MS/MS. The nine MACs showed good linearity in the concentration range of 1-20 μg/L，with linear correlation coefficients （R²） greater than 0.9978. The average recoveries of the nine MACs at three spiked standard concentrations of 1，5 and 10 μg/kg ranged from 71.8% to 86.4%，with the relative standard deviations （RSDs） of 2.2%-5.3%. The limits of detection （LODs） were 0.24-1.35 μg/kg and the limits of quantification （LOQs） were 1.02-4.62 μg/kg.

Keywords：macrolide antibiotics；solid-phase microextraction；honey；high performance liquid chromatography-tandem mass spectrometry （HPLC-MS/MS）

基于荧光共轭聚合物和氧化石墨烯的核酸外切酶I检测

程昆淇¹，高梦莹¹，邢佳贝¹，赵一帆¹，卢宏飞¹，刘学国^*2，邢小静^*1

（1. 南阳师范学院化学与制药工程学院，南阳 473061；2. 南阳理工学院生物与化学工程学院，南阳 473004）

摘要：核酸外切酶I（Exo I）作为一种重要的核酶参与了许多生物学过程，具有维持遗传信息稳定性的功能，因此建立有效检测Exo I活性的方法具有重要的研究价值。基于聚芴类荧光共轭聚合物-poly［（9，9-bis（6′-N，N，N-trimethyl-ammonium）hexyl）-fluorenylene phenylene dibromide］（PFP）不能与吸附在氧化石墨烯（GO）表面的单链DNA结合的实验发现，借助GO对单链DNA和双链DNA作用力强度大小的差异，构建了一个背景信号低、灵敏度高的Exo I检测新方法。GO和PFP的最适浓度分别为2.5和7.2 mg/L。在最佳条件下，Exo I 浓度在0.5~4.0 U/mL范围内与体系的荧光强度呈良好的线性关系，线性方程为F=-0.11c+0.861，检出限为0.16 U/mL。该方法可用于血清模拟样品中Exo I活性的检测，加标回收率为103.6%~106.0%。

关键词：荧光共轭聚合物；氧化石墨烯；DNA；低背景；核酸外切酶I

中图分类号：O657.3    文献标识码：A    文章编号：1000-0720（2024）04-0541-06

Detecting exonuclease I based on fluorescent conjugated polymers and graphene oxide

CHENG Kunqi¹，GAO Mengying¹，XING Jiabei¹，ZHAO Yifan¹，LU Hongfei¹，LIU Xueguo^*2，XING Xiaojing^*1

1. College of Chemistry and Pharmaceutical Engineering，Nanyang Normal University，Nanyang 473061，China；2. Department of Biology and Chemical Engineering，Nanyang Institute of Technology，Nanyang 473004，China）

Abstract：As an important ribozyme，exonuclease I （Exo I） engages in a series of biological processes and has the capability to keep stability of genetic information. Therefore，it has great research value to establish an effective method to detect the Exo I activity. According to the finding that the polyfluorene-based fluorescent conjugated polymers-poly［（9，9-bis（6′-N，N，N-trimethyl-ammonium）hexyl）-fluorenylene phenylene dibromide］（PFP） couldn't interact with single-stranded DNA adsorbed on graphene oxide （GO） surface，a novel method with low background and high sensitivity for sensing Exo I was constructed by utilizing the difference in the interaction force of GO on single stranded DNA and double stranded DNA. The results showed the optimal concentrations of GO and PFP were 2.5 and 7.2 mg/L，respectively. Under the optimum conditions，the fluorescence intensity at 525 nm exhibited a good linearity with Exo I concentration in the range of 0.5-4.0 U/mL，where the linear equation was F=-0.11c+0.861，and the detection limit was 0.16 U/mL. The method was successfully used for the detection of Exo I in serum with recoveries of 103.6%-106.0%.

Keywords：fluorescent conjugated polymers；graphene oxide；DNA；low background；exonuclease I

QuEChERS-超高效液相色谱-串联质谱法测定牧草中氟喹诺酮类药物残留

谢敏¹，徐俊^*1，2，费丹¹，侯玉洁³，刘昌林³，俞莉³，周瑶敏¹，于翔⁴，王梦芝^*4

（1. 江西省农业科学院农产品质量安全与标准研究所，江西省农产品质量安全重点实验室，南昌 330200；2. 江西省农业科学院畜牧兽医研究所，南昌 330200；3. 南昌市农业科学院，南昌 330200；4. 扬州大学动物科学与技术学院，扬州 225009）

摘要：建立了QuEchERS-超高效液相色谱-串联质谱（UPLC-MS/MS）检测牧草中7种氟喹诺酮类药物残留的方法。样品采用0.1 mol/L Na₂EDTA-Mcllvaine 缓冲液和1%乙酸-乙腈提取，经QuEchERS净化后Agilent ZORBAX Eclipse Plus C₁₈色谱柱分离，正离子模式扫描，多反应监测模式，内标法定量。7种氟喹诺酮类药物在0.5~50 μg/L范围内线性相关系数（R²）均大于0.9955，方法检出限为0.05~0.2 μg/kg，定量限为0.1~0.5 μg/kg。平均添加回收率为79.0%~115.4%，相对标准偏差为0.20%~8.5%。该方法适用于牧草中氟喹诺酮类药物检测分析，可为牧草中氟喹诺酮类药物残留风险评估、质量安全监管、牧草品质评价等提供技术支撑。

关键词：牧草；QuEchERS；超高效液相色谱串联质谱；氟喹诺酮；残留

中图分类号：S859.84；O657.6    文献标识码：A    文章编号：1000-0720（2024）04-0547-06

Simultaneous determination of quinolones in forage grass by QuEChERS-ultra-high performance liquid chromatography-tandem mass spectrometry

XIE Min¹，XU Jun^*1，2，FEI Dan¹，HOU Yujie³，LIU Changlin³，YU Li³，ZHOU Yaomin¹，YU Xiang⁴，WANG Mengzhi^*4（1. Institute of Quality Safety and Standards of Agricultural Products，Jiangxi Academy of Agricultural Sciences，Key Laboratory of Agro-product Quality and Safety of Jiangxi Province，Nanchang 330200，China；2. Animal Husbandry and Veterinary Science of Jiangxi Academy of Agricultural Sciences，Nanchang 330200，China；3. Institute of Nanchang Agricultural Sciences Academy of Agricultural Sciences，Nanchang 330200，China；4. College of Animal Science and Technology，Yangzhou University，Yangzhou 225009，China）

Abstract：A QuEChERS-ultra-high performance liquid chromatography tandem mass spectrometry （UPLC-MS/MS） method for the simultaneous determination of 7 kinds of fluorchinolones in forage grass was developed. Forage grass sample was extracted with 0.1 mol/L Na₂EDTA-Mcllvaine buffer and 1% acid-acetonitrile solution，and purified by QuEChERS. Then the target compounds were separated by Agilent ZORBAX Eclipse Plus C18 column，analyzed by electrospray ionization in positive ion scanning under multiple reaction monitoring mode，and quantified with internal standard method. The 7 kinds of fluorchinolones displayed good linearity in the range of 0.5-50 μg/L，and the correlation coefficients （R²） were above 0.9955. The limits of detection were 0.05-0.2 μg/kg，and the limits of quantification were 0.1-0.5 μg/kg. In addition，the recoveries were 79.0%-115.4%，and the relative standard deviations （RSDs） were between 0.2% and 8.5%. The method is suitable for the simultaneous analysis of 7 kinds of fluorchinolones in forage grass，which can provide a scientific basis for fluorchinolones residues risk assessment，quality and safety supervision，and forage grass quality evaluation.

Keywords：forage grass；ultra-high performance liquid chromatography tandem mass spectrometry；QuEchERS；fluorchinolone；residuals

基于酞菁敏化CuCo₂O₄的光电化学传感器选择性检测L-半胱氨酸

岑亚来，诸葛文凤^*，彭金云，黄青，何诗诗

（广西民族师范学院化学与生物工程学院，崇左 532200）

摘要：通过水热法制备了具有3D形貌的CuCo₂O₄微米花，基于酞菁（Pc）敏化CuCo₂O₄修饰氧化铟锡（ITO）玻璃电极（Pc/CuCo₂O₄/ITO），建立了一种L-半胱氨酸（L-Cys）光电化学传感器。研究表明，Pc/CuCo₂O₄复合材料具有良好的光电化学活性，其光电流是纯CuCo₂O₄的15倍、Pc的18倍。以红光作为激发源，在偏置电压-0.05 V，电解液pH 4.0条件下，在0.25~15.0 μmol/L范围内，光电流与L-Cys浓度呈线性相关，检出限为0.0296 μmol/L。在其他氨基酸、制剂辅料和常见无机离子存在下，Pc/CuCo₂O₄/ITO检测L-Cys具有良好的专属性。该传感器已成功用于L-半胱氨酸胶囊的含量测定。

关键词：光电化学传感；Pc/CuCo₂O₄；L-半胱氨酸

中图分类号：O657.1    文献标识码：A    文章编号：1000-0720（2024）04-0553-06

A photoelectrochemical sensor based on phthalocyanine sensitized CuCo₂O₄ for selective detection of L-Cysteine

CEN Yalai，ZHUGE Wenfeng^*，PENG Jinyun，HUANG Qing，HE Shishi

College of Chemical and Biological Engineering，Guangxi Minzu Normal University，Chongzuo 532200，China）

Abstract：CuCo₂O₄ micron flowers were synthesized via hydrothermal method. An effective photoelectrochemical （PEC） sensor was established for detection of L-Cysteine （L-Cys） based on indium tin oxide （ITO） glass electrode （Pc/CuCo₂O₄/ITO） modified by phthalocyanine （Pc）-sensitized CuCo₂O₄. The result has shown that Pc/CuCo₂O₄ composite material exhibited admirable photoelectrochemical activity，its photocurrent was 15-fold and 18-fold those of pure CuCo₂O₄ micron flowers or Pc，respectively. Using red light as the excitation source，under the conditions of external bias potential of -0.05 V，the pH value of electrolyte solution at pH 4.0，the photocurrent was linearly correlated with L-Cys concentration in the range of 0.25-15.0 μmol/L，and the detection limit was 0.0296 μmol/L. The proposed sensor exhibited good selectivity for L-Cys in the presence of other amino acids，medical excipient and common inorganic ions. This PEC sensor has been successfully used for the content determination of L-Cys capsules.

Keywords：photoelectrochemmical sensor；Pc/CuCo₂O₄；L-cysteine

CRISPR/Cas12a联合催化发夹自组装的miRNA21检测

李甜^*，邹红敏，陈菲，游芸，张莉萍

（河南科技大学基础医学与法医学院，洛阳 471023）

摘要：构建了一种基于CRISPR/Cas12a和催化发夹自组装（CHA）的miRNA21检测方法。目标物miRNA21可引发CHA，产生大量的双链DNA复合物。作为Cas12a的底物，双链DNA复合物包含原型间隔序列毗邻基序（5′-TTTN-3′），可激发Cas12a的附属切割活性，剪切一端带有荧光基团、另一端带有猝灭基团的单链DNA荧光报告探针，产生可检测的荧光信号。考察了CHA反应温度、发夹探针浓度、荧光报告探针浓度和Cas12a切割时间的影响。在优化条件下，荧光信号与miRNA21浓度的对数呈良好的线性关系，线性相关系数R²=0.9924，检出限为1.1 pmol/L。利用本方法对miRNA21加标的胎牛血清样品进行分析，20 pmol/L和100 pmol/L miRNA21的回收率分别为（92.0±4.2）%和（94.1±4.7）%。CRISPR/Cas12a联合催化发夹自组装的miRNA检测方法，使miRNA检测摆脱了热循环仪器，操作简单，通用性强，具有实际应用潜力。

关键词：催化发夹自组装；CRISPR/Cas12a；miRNA21；荧光

中图分类号：O661.1    文献标识码：A    文章编号：1000-0720（2024）04-0559-05

Detection for MiRNA21 by combining CRISPR/Cas12a with catalytic hairpin assembly

LI Tian^*，ZOU Hongmin ，CHEN Fei，YOU Yun，ZHANG Liping

College of Basic Medicine and Forensic Medicine，Henan University of Science and Technology，Luoyang 471023，China）

Abstract：A detection strategy for miRNA21 based on CRISPR/Cas12a and catalytic hairpin self-assembly （CHA） was constructed. The target miRNA21 could trigger CHA and produce a large number of double-stranded DNA complexes. As the substrate of Cas12a，the double-stranded DNA complex contained a prototype spacer sequence adjacent to the motif （5'-TTTN-3'），which could stimulate the accessory cleavage activity of Cas12a. It cleaved a single-stranded DNA fluorescence reporter with a fluorescent group at one end and a quenching group at the other end，thereby leading to the generation of appreciable fluorescence signals. The effects of reaction temperature for CHA，hairpin concentration，fluorescent reporter concentration and Cas12a cleavage time were investigated. Under the optimized conditions，the fluorescence signal and the logarithm of miRNA21 concentration showed a good linear relationship，along with the correlation coefficient （R²） of 0.9924 and the detection limit of 1.1 pmol/L. The spiked recoveries of miRNA21 in fetal bovine serum were （92.0±4.2）% and （94.1±4.7）% for 20 pmol/L and 100 pmol/L of miRNA21，respectively. This strategy constructed by combining CRISPR/Cas12a and CHA，made miRNA detection simple，universal and nonuse of thermal cycling instruments，showing great potential for practical application.

Keywords：catalytic hairpin assembly；CRISPR/Cas12a；miRNA21；fluorescence

氮自掺杂碳量子点的合成及其在细胞成像中的应用

瞿金为¹，杨淑琼¹，陈盛余²，胡月芳^*1

（1. 贺州学院，广西碳酸钙资源综合利用重点实验室，材料与化学工程学院，贺州 542899；2. 百色学院，桂西区域生态环境分析与污染控制重点实验室，化学与环境工程学院，百色 533000）

摘要：以特色农产品废弃物马蹄皮为原料，通过水热法合成了氮掺杂碳量子点（N-CQDs），对温度及反应时间等合成条件进行了优化。在最佳合成条件下，得到量子产率为22%的N-CQDs，对其结构、形貌、组成、荧光及电化学性能进行分析。实验结果表明，N-CQDs稳定性良好，表现出更优异的荧光性能和电化学性能，且具有良好的生物相容性和细胞膜穿透性，可用于细胞内多色细胞成像。本研究为促进N-CQDs的绿色合成及其在生物医学领域的应用提供了新的思路。

关键词：氮自掺杂碳量子点；水热法；光学性能；电化学性能；细胞成像

中图分类号：O657.1    文献标识码：A    文章编号：1000-0720（2024）04-0564-08

Synthesis of nitrogen self-doped carbon quantum dots and their application in cell imaging

QU Jinwei¹，YANG Shuqiong¹，CHEN Shengyu²，HU Yuefang^*1

1. Guangxi Key Laboratory of Calcium Carbonate Resources Comprehensive Utilization，College of Materials and Chemical Engineering，Hezhou University，Hezhou 542899，China；2. Key Laboratory of Regional Ecological Environment Analysis and Pollution Control of West Guangxi，College Chemistry and Environment Engineering，Baise University，Baise 533000，China）

Abstract：Nitrogen-doped carbon quantum dots （N-CQDs） were synthesized by hydrothermal method using horseshoe skin as raw material. The synthesis conditions of temperature and reaction time were optimized. N-CQDs with a quantum yield of 22% were obtained under the optimal synthesis conditions. The structure，morphology，composition，fluorescence and electrochemical properties of the synthesized N-CQDs were analyzed. The experimental results showed that N-CQDs were stable and exhibited better fluorescence and electrochemical properties，and had good biocompatibility and cell membrane penetration，which could be used for intracellular multicolor cell imaging. This study provides a new way to promote the green synthesis and application of N-CQDs in the biomedical field.

Keywords：nitrogen-doped carbon quantum dots；hydrothermal synthesis method；optical performance；electrochemical properties；cell imaging

一种咪唑-香豆素类荧光探针的合成及其对Cu²⁺的选择性识别

胡浩¹，尹纪臣²，姚叶林¹，邓林龙¹，薛蕾¹，王海滨^*1

（1. 宁夏师范学院化学化工学院，固原 756000；2. 康龙化成（北京）新药技术股份有限公司，北京 102600）

摘要：以7-（二乙氨基）香豆素-3-甲醛和苯偶酰为原料，合成了一种咪唑-香豆素类荧光探针7-（二乙基氨基）-3-（4，5-二苯基-1H-咪唑-2-基）苯并吡喃-2酮（L），并表征了其结构。该探针在乙腈溶液中对Cu²⁺表现出高选择性识别，并具有较强的抗干扰能力。在Cu²⁺浓度7.5~29.5 μmol/L范围内，探针L在508 nm处的荧光强度与Cu²⁺浓度呈良好的线性关系，线性相关系数R²=0.9955。探针L与Cu²⁺的结合比是2∶1，结合常数为1.02×10² （L/mol）^1/2。探针L对Cu²⁺的检出限为0.082 μmol/L。该探针可被制成试纸用于检测Cu²⁺。

关键词：荧光探针；识别；Cu²⁺；香豆素；咪唑

中图分类号：O657.31    文献标识码：A    文章编号：1000-0720（2024）04-0572-06

Synthesis of an imidazole coumarin based fluorescent probe and its selective recognition for Cu²⁺

HU Hao¹，YIN Jichen²，YAO Yelin¹，DENG Linlong¹，XUE Lei¹，WANG Haibin^*1

1. College of Chemistry and Chemical Engineering，Ningxia Normal University，Guyuan 756000，China；2. Pharmaron Beijing Co.，Ltd.，Beijing 102600，China）

Abstract：An imidazole coumarin based fluorescent probe named 7-（diethylamino）-3-（4，5-diphenyl-1H-imidazol-2-yl）chromen-2-one （L） was synthesized using dibenzoyl and 7-diethylaminocoumarine-3-aldehyde as raw materials，and the structure of L was characterized. The probe L demonstrated high selectivity and strong anti-interference ability towards Cu²⁺ recognition in acetonitrile solution. The fluorescence intensity of probe L at 508 nm showed a linear relationship with Cu²⁺ concentration in the range of 7.5-29.5 μmol/L，with the correlation coefficient （R²） of 0.9955. The binding ratio of probe L toward Cu²⁺ was 2∶1，and the binding constant was 1.02×10² （L/mol）^1/2. The limit of detection of probe L toward Cu²⁺was 0.082 μmol/L. The probe can be made to test papers for detecting Cu²⁺.

Keywords：fluorescent probe；recognizition；Cu²⁺；coumarin；imidazole

高效液相色谱法同时检测化妆品中视黄醇及其衍生物

杨淡梅^1，2，付寒¹，王鹏¹，刘兆宾²，邬晓鸥²，邱颖姮^*2

（1. 深圳市慢性病防治中心深圳市皮肤病防治研究所，深圳 518020；2. 深圳市药品检验研究院，国家药品监督管理局化妆品监测评价重点实验室，深圳 518057）

摘要：建立了检测化妆品中视黄醇及其衍生物等16种组分含量的高效液相色谱分析方法。分离检测16种同类物质及同分异构体的优化条件为：采用Kromasil 100-5-C₁₈色谱柱（250 mm×4.6 mm，5 μm）分离，以甲醇为流动相A，四氢呋喃为流动相B，10 mmol/L磷酸二氢钠溶液为流动相C，梯度洗脱，流速为1.0 mL/min，柱温为25 ℃。使用二极管阵列检测器，标准曲线法定量。16种组分的线性相关系数均大于0.999，在3个添加水平下，16种组分的平均回收率为91.2%~107.8%，相对标准偏差为0.5%~4.0%。该方法可以为化妆品质量监督提供有效的技术支持。

关键词：视黄醇及其衍生物；化妆品；高效液相色谱法

中图分类号：O657.72；TQ047.2    文献标识码：A    文章编号：1000-0720（2024）04-0578-05

Simultaneous determination of retinol and its derivatives by high performance liquid chromatography

YANG Danmei^1，2，FU Han¹，WANG Peng¹，LIU Zhaobin²，WU Xiaoou²，QIU Yingheng^*2

1. Shenzhen Center for Chronic Disease Control，Shenzhen Institute of Dermatology，Shenzhen 518020，China；2. Shenzhen Institute for Drug Control，NMPA Key Laboratory for Monitoring and Evaluationof Cosmetics，Shenzhen 518057，China）

Abstract：A high performance liquid chromatography （HPLC） method for the determination of 16 components including retinol and its derivatives in cosmetics was established. The optimized conditions for the separation and detection of the 16 components were as follows：separated by a Kromasil 100-5-C₁₈ column （250 mm×4.6 mm，5 μm），and gradient elution with methanol as mobile phase A，tetrahydrofuran as mobile phase B and 10 mmol/L sodium dihydrogen phosphate solution as mobile phase C，with a flow rate of 1.0 mL/min and the column temperature of 25 ℃. The analysis was completed using photo-diode array detector and quantified by standard curve method. The results showed that the linear correlation coefficients of the 16 components were greater than 0.999，the average recoveries were 91.2%-107.8%，and the relative standard deviations were 0.5%-4.0% at three spiked levels. This method can provide effective technical support for cosmetics quality supervision.

Keywords：retinol and its derivatives；cosmetics；high performance liquid chromatography

新型碳材料用于固相萃取环境和食品中邻苯二甲酸酯的研究进展

陈昊翔^1，2，周远浩^1，2，李顺滢^1，2，王丹青^1，2，石胜鹏³，叶宏^*1，2

（1. 北京食品质量与安全实验室，北京工商大学轻工科学技术学院，北京 100048；2. 中国轻工业酿酒分子工程重点实验室，北京工商大学轻工科学技术学院，北京 100048；3. 中国石油化工股份有限公司北京化工研究院，北京100013）

摘要：邻苯二甲酸酯类物质（PAEs）是一类对人体健康危害严重的内分泌干扰物，当前在食品和环境中的污染问题十分突出。固相萃取技术广泛应用于针对PAEs的样品前处理过程，其分离富集的关键在于固相萃取材料。随着各种吸附材料制备技术快速发展，基于新型碳材料的固相萃取技术应用日益广泛。本文对近年来新型碳材料用于固相萃取环境和食品中PAEs的应用进行了总结分析，综述了碳纳米管、石墨烯等新型碳材料作为固相萃取材料在PAEs分析检测应用中的最新进展，为该领域固相萃取材料的开发、改性和应用提供了新的研究思路和方向。

关键词：邻苯二甲酸酯；碳材料；固相萃取

中图分类号：O652.6；TQ414.1    文献标识码：A    文章编号：1000-0720（2024）04-0583-12

Research progress of novel carbon materials for solid phase extraction of phthalate esters in environment and food

CHEN Haoxiang^1，2，ZHOU Yuanhao^1，2，LI Shunying^1，2，WANG Danqing^1，2，SHI Shengpeng³，YE Hong^*1，2

1. Beijing Laboratory of Food Quality and Safety，College of Light Industry Science and Technology，Beijing Technology and Business University，Beijing 100048，China；2. Key Laboratory of Brewing Molecular Engineering of China Light Industry，College of Light Industry Science and Technology，Beijing Technology and Business University，Beijing 100048，China；3. SINOPEC Beijing Research Institute of Chemical Industry，Beijing 100013，China）

Abstract：Phthalate esters （PAEs） are a kind of endocrine disruptors that are seriously harmful to human health，and the pollution problem in food and environment is very prominent. Solid phase extraction （SPE） technology is widely used in the sample pre-treatment process of PAEs，and the key to its separation and enrichment lies in the SPE materials. With the rapid development of various adsorption material preparation technologies，SPE technologies based on new carbon materials are increasingly widely used. In this paper，the applications of new carbon materials in SPE of PAEs in environment and food in recent years were summarized，and the latest progress of carbon nanotubes，graphene and other new carbon materials as SPE materials in PAEs detection were reviewed，providing the new research idea and direction for the development，modification and application of SPE materials in this field.

Keywords：phthalate esters；carbon materials；solid phase extraction

基于文献计量的抗生素适配体传感技术研究进展与热点分析

梁刚^1，2，高羽菲³，甄建辉⁴，巩文雯^*1，2，陈瑞春⁴，李再兴³，潘立刚^1，2

（1. 北京市农林科学院质量标准与检测技术研究所，北京 100097；2. 农业部农产品质量安全风险评估实验室（北京），北京 100097；3. 河北科技大学环境科学与工程学院，石家庄 050024；4. 石家庄海关技术中心，石家庄 050001）

摘要：适配体是经体外筛选得到的短链寡核苷酸序列，能与靶标进行高亲和力和强特异性结合，以适配体为识别元件的生物传感器被广泛用于小分子传感检测研究。近年来，抗生素作为一类新兴污染物，其在环境和食品中的出现引起了人们的广泛关注。本文采用文献计量分析可视化工具VOSviewer，以Web of Science（WoS）核心数据库的文献资料为数据源，对抗生素适配体领域研究的发展过程、主要研究力量、研究热点及前沿等进行了分析。结果表明，抗生素适配体的研究发文数量不断增长，尤其是近10年呈快速增长态势；中国的累计论文发表数量最多，为378篇，占全球总发文量的57.62%，在国际合作网络中占据重要地位，而韩国、美国等国家的发文质量更高。关键词共现分析表明，抗生素适配体研究热点主要体现在“抗生素适配体筛选及性能表征”、“适配体传感器的构建及抗生素检测研究”以及“纳米材料在适配体传感检测抗生素中的应用”等3个方面。本研究提出了抗生素适配体领域未来发展方向和研究重点，有助于推进适配体生物传感技术的产业化发展。

关键词：抗生素；适配体；文献计量；研究进展；研究热点

中图分类号：O6-04；O652.7    文献标识码：A    文章编号：1000-0720（2024）04-0595-14

Progress and hotspots analysis of antibioticaptamer-based sensing technology：A bibliometric analysis

LIANG Gang^1，2，GAO Yufei³，ZHEN Jianhui⁴，GONG Wenwen^*1，2，CHEN Ruichun⁴，LI Zaixing³，PAN Ligang^1，2

1. Institute of Quality Standard and Testing Technology，Beijing Academy of Agriculture and Forestry Sciences，Beijing 100097，China；2. Risk Assessment Lab for Agro-products （Beijing），Beijing 100097，China；3. College of Environmental Science and Engineering，Hebei University of Science and Technology，Shijiazhuang 050024，China；4. Shijiazhuang Customs Technology Center，China，Shijiazhuang 050001，China）

Abstract：Aptamers are short-chain oligonucleotide sequences screened in vitro，which can bind to the target with high affinity and strong specificity. They have been widely used as molecular recognition elements within biosensors for the detection of small molecules. In recent years，the emergence of antibiotics as a kind of new pollutants in environment and food has attracted extensive attentions. Accordingly，the development process，main researchers，research hotspots and frontiers in the field of antibiotic aptamers were analyzed by using the bibliometric analysis visualization tool VOSviewer with the Web of Science （WoS） Core Collection data as the data source. The results showed that the number of publications on antibiotic aptamers is increasing，especially in recent ten years. China has the largest cumulative number of publications （378 papers，accounting for 57.62% of the total number of published papers in the world），occupying an important position in the international cooperation network，while the United States and South Korea published higher quality papers. Keyword co-occurrence analysis showed that the research hotspots of antibiotic aptamers were mainly in three aspects："screening and characterization of antibiotic aptamers"，"construction of aptamer sensors and detection of antibiotic"，and "application of nanomaterials in antibiotics aptamer sensors". This study puts forward the future development direction and research focus in the field of antibiotic aptamers，which is helpful to promote the industrial development of aptamer biosensing technology.

Keywords：antibiotics；aptamer；bibliometric；research progress；research hotspots