基于碳点的“开-关-开”型荧光探针测定蔬菜中的谷胱甘肽

韩雍^*，汪慧，杜雪蓉

（陇东学院农林科技学院，庆阳 745000）

摘要：以邻苯二胺、柠檬酸、乙醇为前体物质，采用自下而上的一步水热法，制备了一种蓝色荧光碳点（BCDs），以此构建荧光探针，用于检测蔬菜中的谷胱甘肽（GSH）。结果表明，在碳点（CDs）中加入Cu²⁺后可使BCDs荧光猝灭；在该猝灭体系中加入GSH后会使BCDs-Cu²⁺体系的荧光恢复。由此建立了一种“开-关-开”型检测GSH的新方法。在激发波长390 nm下，BCDs发射峰位于445 nm处，可以实现对GSH的检测，方法线性范围是0~80 μmol/L，检出限（LOD）为0.0368 μmol/L。该方法用于实际样品蔬菜中GSH的测定，回收率为89.6%~104.3%，相对标准偏差（RSDs）为1.2%~5.2%。

关键词：碳点；快速荧光检测；谷胱甘肽

中图分类号：O657.3；O661.1    文献标识码：A    文章编号：1000-0720（2024）05-0609-06

“On-off-on” fluorescent probe based on carbon dots for the detection of glutathione in vegetables

HAN Yong^*，WANG Hui，DU Xuerong

College of Agriculture and Forestry，Longdong University，Qingyang 745000，China）

Abstract：In this work，o-phenylenediamine，citric acid and ethanol were used as precursors to prepare blue-emissive fluorescent carbon dots（BCDs） through a bottom-up hydrothermal one-step method. Then，BCDs were employed as a fluorescent probe for rapid detection of Cu²⁺ and glutathione （GSH） in vegetables. The results showed that the fluorescence of BCDs could be quenched by copper ion，and the quenched fluorescence of BCDs-Cu²⁺ can be recovered by GSH. Based on this principle，an 'on-off-on' method for detection of GSH was established. The emission peak of BCDs-Cu²⁺ located at 445 nm under excitation wavelength of 390 nm. The linear range of the method was 0-80 μmol/L and limit of detection （LOD） was 0.0368 μmol/L. The recoveries of GSH in the actual vegetable samples were 89.6%-104.3%，with the relative standard deviations （RSDs） of 1.2%-5.2%.

Keywords：carbon dots；rapid fluorescence detection；glutathione

基于酶辅助的比率型电化学适配体传感器用于前列腺特异性抗原检测

关志敏，谢瑶瑶，马会凯，王萍^*

（河南科技大学基础医学与法医学院，洛阳 471000）

摘要：基于核酸外切酶III（Exo Ⅲ）辅助靶标循环策略，构建了比率型电化学适配体传感器，并用于前列腺特异性抗原（PSA）的检测。利用亚甲基蓝（MB）作为内置参考信号，当PSA存在时，发夹探针1（HP1）的适配体序列与PSA特异性结合，引起Exo Ⅲ的2次切割过程，从而实现2次循环扩增反应，导致电极上更多的MB标记的发夹探针3（MB-HP3）被切割；再加入二茂铁（Fc）标记的DNA链（Fc-DNA）与MB-HP3酶切后的片段进行杂交；最终，Fc的信号（I_Fc）增加，而MB的信号（I_MB）基本保持不变。在最佳条件下，I_Fc/I_MB与PSA浓度的对数值在0.001~100 ng/mL范围内呈良好的线性关系，检出限为0.24 pg/mL。该传感器在临床实际样品检测中具有较好的应用前景。

关键词：前列腺特异性抗原；核酸外切酶III；比率型电化学适配体传感器

中图分类号：O657.1    文献标识码：A    文章编号：1000-0720（2024）05-0615-06

An enzyme-assisted ratiometric electrochemical aptasensor for the detection of prostate specific antigen

GUAN Zhimin，XIE Yaoyao，MA Huikai，WANG Ping^*

College of Basic Medicine and Forensic Medicine，Henan University of Science and Technology，Luoyang 471000，China）

Abstract：A ratiometric electrochemical aptasensor based on exonuclease III（Exo III）-assisted target recycling strategy was developed for the detection of prostate specific antigen（PSA）. Methylene blue（MB）was used as a built-in reference signal.In the presence of PSA，the specific binding between the aptamer region of hairpin probe1（HP1） and PSA could trigger two cleavage processes of Exo Ⅲ，thus achieving two cyclic amplification reactions，accompanying by more MB-labeled hairpin probe 3 （MB-HP3） on the electrode to be digested. The addition of ferrocene （Fc）-labeled DNA （Fc-DNA） was hybridized with the digested fragment of MB-HP3，resulting in an enhancement of Fc signal （I_Fc），while the signal of MB （I_MB） remained basically unchanged. Under the optimal conditions，a linear relationship was obtained between the I_Fc/I_MB value and the logarithm value of PSA concentration in the range from 0.001 to 100 ng/mL，and the detection limit was 0.24 pg/mL. The sensor has a good application prospect in determination of PSA in clinical samples.

Keywords：prostate specific antigen；exonuclease III；ratiometric electrochemical aptasensor

基于脉冲加热-红外吸收/热导法测定烧结氮化硅陶瓷材料中晶格氧含量

王群¹，段于森²，钱荣^*1，卓尚军^*1，朱月琴¹

（1. 中国科学院上海硅酸盐研究所无机材料分析测试中心，上海 200050；2. 中国科学院上海硅酸盐研究所高性能陶瓷和超微结构国家重点实验室，上海 200050）

摘要：基于脉冲加热-红外吸收/热导法，比较分析了恒定式、斜线式及阶梯式3种功率控制升温模式在烧结氮化硅陶瓷材料氧氮含量测定中的特点。优化后选择阶梯式功率控制升温模式并设置合理的分析参数，获得了分离良好的氧氮分量峰。结合在脉冲加热熔融样品过程中特定点位取样的X射线衍射物相分析，确定了烧结氮化硅材料的晶格氧分量峰位置及含量。测试得出Yb₂O₃做助剂的烧结氮化硅陶瓷晶格氧含量为0.094%，相对标准偏差为1.6%，与此材料的热导率水平（88.61 W/m·K）相符合。本方法适用于多种非氧化物陶瓷材料中晶格氧含量的测定。

关键词：脉冲加热-红外吸收/热导法；烧结氮化硅陶瓷；晶格氧；热导率

中图分类号：O657.33    文献标识码：A    文章编号：1000-0720（2024）05-0621-06

Determination of lattice oxygen content in sintered silicon nitride ceramics by pulse heating-infrared absorption and thermal conductivity method

WANG Qun¹，DUAN Yusen²，QIAN Rong^*1，ZHUO Shangjun^*1，ZHU Yueqin¹

1. Analysis and Testing Center for Inorganic Material，Shanghai Institute of Ceramics，Chinese Academy of Sciences，Shanghai 200050，China；2. State Key Laboratory of High Performance Ceramics and Superfine Microstructure，Shanghai Institute of Ceramics，Chinese Academy of Sciences，Shanghai 200050，China）

Abstract：Based on the pulse heating-infrared absorption and thermal conductivity method，the characteristics of three power-controlled heating modes （constant，oblique and stepped） in the determination of oxygen and nitrogen contents in sintered silicon nitride ceramic materials were compared and analyzed. After optimization，the stepwise power control heating mode was selected and reasonable analysis parameters were set，and the oxygen and nitrogen component peaks with good separation were obtained. Furthermore，the position and content of lattice oxygen component peak of sintered silicon nitride material were determined by combining with X-ray diffraction phase analysis of some specific point samples during pulse heating and melting process. The results showed that the lattice oxygen content of sintered silicon nitride ceramics with Yb₂O₃ as additive was 0.094%，with the relative standard deviation of 1.6%，which was consistent with the thermal conductivity level of this material （88.61 W/m·K）. This method is applicable to the determination of lattice oxygen content in various non-oxide ceramic materials.

Keywords：pulse heating-infrared absorption and thermal conductivity method；sintered silicon nitride ceramics；lattice oxygen；thermal conductivity

SiO₂/MnFe₂O₄磁性固相萃取-HPLC测定水中喹诺酮类抗生素

魏霄¹，陈雨莹¹，钟佳祺¹，朱霞萍^*1，任维²，赵平²

（1. 成都理工大学材料与化学化工学院，成都 610059；2. 贵州省地质矿产勘查开发局一〇五地质大队，贵阳 550018）

摘要：通过溶胶-凝胶法制备了SiO₂/MnFe₂O₄复合材料，使用X-射线衍射仪、全自动物理吸附仪、振动样品磁强计、场发射扫描电镜和X射线光电子能谱仪对其进行了表征。将其作为磁性固相萃取材料，建立了SiO₂/MnFe₂O₄磁性固相萃取-高效液相色谱法（MSPE-HPLC）测定水中氟罗沙星（FLE）、氧氟沙星（OFX）、诺氟沙星（NOR）、环丙沙星（CIP）和恩诺沙星（ENR）的新方法。磁性固相萃取的最佳条件为：SiO₂/MnFe₂O₄用量50 mg，萃取20 min后，用4 mL氨水/甲醇（12/88，V/V）混合液洗脱4 min。最佳条件下，SiO₂/MnFe₂O₄对FLE，OFX，NOR，CIP，ENR的富集倍数分别为57.3，62.5，53.2，49.8和51.5倍。MSPE-HPLC测定5种抗生素的线性范围为0.004~1 mg/L，相对标准偏差（RSDs）为2.5%~5.3%，检出限为0.0012~0.0023 mg/L。将建立的方法应用于稻田水和鱼塘水中5种抗生素的测定，加标回收率介于78.8%~102.8%之间，RSDs为2.5%~5.3%。

关键词：铁酸锰；磁性固相萃取；喹诺酮类抗生素；地表水

中图分类号：O661.1    文献标识码：A    文章编号：1000-0720（2024）05-0627-06

Determination of quinolone antibiotics in water by SiO₂/MnFe₂O₄ magnetic solid phase extraction-high performance liquid chromatography

WEI Xiao¹，CHEN Yuying¹，ZHONG Jiaqi¹，ZHU Xiaping^*1，REN Wei²，ZHAO Ping²

1. College of Materials and Chemistry and Chemical Engineering，Chengdu University of Technology，Chengdu 610059，China；2. 105 Geological Brigade，Guizhou Bureau of Geology and Mineral Resources Exploration and Development，Guiyang 550018，China）

Abstract：SiO₂/MnFe₂O₄ composites were prepared by sol-gel method and characterized by X-ray diffraction，automatic physical adsorption，vibrating sample magnetometer，field emission scanning electron microscope and X-ray photoelectron spectroscopy. A method for the determination of fleroxacin （FLE），ofloxacin （OFX），norfloxacin （NOR），ciprofloxacin （CIP） and enrofloxacin （ENR） in water samples was established by SiO₂/MnFe₂O₄ magnetic solid phase extraction-high performance liquid chromatography （MSPE-HPLC）. The optimum conditions for magnetic solid phase extraction were as follows：the SiO₂/MnFe₂O₄ amount of 50 mg，the extraction time of 20 min，and the eluent time of 4 min with 4 mL of ammonia/methanol （12/88，V/V） mixture. Under the optimum conditions，the enrichment ratios of SiO₂/MnFe₂O₄ to FLE，OFX，NOR，CIP and ENR were 57.3，62.5，53.2，49.8 and 51.5 times，respectively. The linear ranges of MSPE-HPLC determination for five antibiotics were 0.004-1 mg/L，the relative standard deviations （RSDs） were 2.5%-5.3%，and the detection limits were 0.0012-0.0023 mg/L. The method was applied to the determination of five antibiotics in paddy field water and fish-pond water，showing the recoveries of spiked antibiotics ranged from 78.8% to 102.8%，and the RSDs were 2.5% to 5.3%.

Keywords：manganese ferrate；magnetic solid phase extraction；quinolone antibiotics；surface water

D-异抗坏血酸钠热解碳构建电化学传感器检测黄芩素和木犀草素

高仪¹，陈泇冰^1，2，刘耀鹏^1，2，储婷婷^1，2，黄文胜¹，郑寅^*1，2

（1. 湖北民族大学化学与环境工程学院，恩施 445000；2. 生物资源保护与湖北省重点实验室，湖北民族大学，恩施 445000）

摘要：以廉价易得的D-异抗坏血酸钠为前驱体，通过一步热解法制备了具有三维互连多孔结构的热解碳材料（SDAIPC），利用扫描电子显微镜（SEM）、透射电子显微镜（TEM）和X射线衍射（XRD）对材料的形貌和结构进行了表征。结果表明，制备的SDAIPC是一类具有高比表面积的碳材料。以SDAIPC为电极修饰材料，构建了用于同时检测黄芩素（BA）和木犀草素（LU）的电化学传感器。通过电化学交流阻抗谱（EIS）和循环伏安法（CV）研究了传感器的电化学性能；采用微分脉冲伏安法（DPV）研究了BA和LU在不同电极上的电化学行为。在优化条件下，SDAIPC修饰电极对BA和LU进行单独检测时的线性范围为0~8.0 μmol/L，检出限（LOD）分别为1.39×10^-9 mol/L和3.02×10^-10 mol/L；对BA和LU进行同时检测时的线性范围为0.05~2.0 μmol/L，LOD分别为3.76×10^-9 mol/L和3.78×10^-10 mol/L。该电化学传感器已成功用于BA和LU的实际样品检测。

关键词：多孔碳材料；电化学传感器；黄芩素；木犀草素

中图分类号：O657.1    文献标识码：A    文章编号：1000-0720（2024）05-0633-09

Electrochemical sensor constructed of sodium ascorbate pyrolysis carbon for the determination of baicalein and lignocaine

GAO Yi¹，CHEN Jiabing^1，2，LIU Yaopeng^1，2，CHU Tingting^1，2，HUANG Wensheng¹，ZHENG Yin^*1，2

1. College of Chemical and Environmental Engineering Hubei Minzu University，Enshi 445000，China；2. Hubei Provincial Key Labortory of Occurrence and Interervention of Rheumatic Diseases，Hubei Minzu University，Enshi 445000，China）

Abstract：Pyrolytic carbon materials with three-dimensional interconnected porous structures （SDAIPC） were prepared by one-step pyrolysis using inexpensive and readily available sodium D-isoascorbate as a precursor. The morphology and structure of the material were characterized using scanning electron microscopy （SEM），transmission electron microscopy （TEM） and X-ray diffraction （XRD）. The results showed that the prepared SDAIPC was a class of carbon materials with high specific surface area. An electrochemical sensor for the simultaneous detection of baicalein （BA） and lignocaine （LU） was constructed using SDAIPC as the electrode modification material.The electrochemical performance of the sensor was investigated by electrochemical impedance spectroscopy （EIS） and cyclic voltammetry （CV），and the electrochemical behavior of BA and LU at different electrodes was studied by differential pulse voltammetry （DPV）. Under the optimized conditions，the linear detection ranges of SDAIPC-modified electrode for BA and LU were 0-8.0 μmol/L，and the limits of detection （LODs） were 1.39×10^-9 mol/L and 3.02×10^-10 mol/L，respectively. The linear detection range for the simultaneous detection of BA and LU was 0.05-2.0 μmol/L，and the LODs were 3.76×10^-9 mol/L and 3.78×10^-10 mol/L，respectively. The electrochemical sensor could be used for the detection of BA and LU in real samples.

Keywords：porous carbon material；electrochemical sensor；baicalein；luteolin

N-羟基琥珀酰亚胺作为（pq）₂Ir（acac）共反应剂电致化学发光法检测Hg²⁺

付云峰¹，任美娟¹，吴芳辉^*1，2，叶明富^1，3，殷国霞²，王晨¹

（1. 安徽工业大学化学与化工学院，马鞍山 243000；2. 生物膜法水质净化及利用技术教育部工程研究中心，安徽工业大学建筑工程学院，马鞍山 243000；3. 信息材料及器件化应用四川省高校重点实验室，成都信息工程大学，成都 610225）

摘要：制备了（pq）₂Ir（acac）（pq=2-苯基喹啉，acac=乙酰丙酮）并对其进行表征。采用N-羟基琥珀酰亚胺（NHS）作为中性混合溶剂中（pq）₂Ir（acac）的共反应剂，获得强的电致化学发光（ECL）信号。向该体系中加入Hg²⁺后，因NHS与Hg²⁺的特异性螯合作用，阻断了NHS与（pq）₂Ir（acac）之间的共反应，使得其ECL响应显著降低，据此构建了灵敏检测Hg²⁺的方法。优化条件下，（pq）₂Ir（acac）/NHS体系ECL强度变化的对数值与Hg²⁺浓度的自然对数值在0.1~90 μmol/L范围内呈良好的线性关系，检出限达33 nmol/L。（pq）₂Ir（acac）/NHS体系对Hg²⁺具有良好的选择性和稳定性。该方法可用于测定实际水样中Hg²⁺浓度。

关键词：环金属铱配合物；N-羟基琥珀酰亚胺；电致化学发光；汞离子；检测

中图分类号：O657.3；R123.3    文献标识码：A    文章编号：1000-0720（2024）05-0642-07

N-hydroxysuccinimide as coreactant of （pq）₂Ir（acac） for the detection of Hg²⁺ by electrochemiluminescence

FU Yunfeng¹，REN Meijuan¹，WU Fanghui^*1，2，YE Mingfu^1，3，YIN Guoxia²，WANG Chen¹

1. School of Chemistry and Chemical Engineering，Anhui University of Technology，Ma’anshan 243000，China；2. Engineering Research Center of Biofilm Water Purification and Utilization Technology of Ministry of Education，Civil Engineering & Architecture，Anhui University of Technology，Ma’anshan 243000，China；3. Information Materials and Devices Applications Key Laboratory of Sichuan Provincial Universities，Chengdu University of Information Technology，Chengdu 610225，China）

Abstract：（pq）₂Ir（acac） （pq=2-phenylquinoline，acac=acetylacetone） was synthesized and characterized. A strong electrochemiluminescence （ECL） signal was obtained while N-hydroxysuccinimide （NHS） exploited as an efficient coreactant for（pq）₂Ir（acac） ECL in mixed neutral medium. Then a highly sensitive ECL assay in a “turn-off” mode for the detection of Hg²⁺ was developed based on the specific chelation of NHS and Hg²⁺，which inhibited the reaction between NHS and （pq）₂Ir（acac）. Under the optimized conditions，the logarithm of the ECL intensity change of the （pq）₂Ir（acac）/NHS system and the natural logarithm of the Hg²⁺ concentration showed a good linear relationship in the range of 0.1-90 μmol/L，and the detection limit of Hg²⁺ was 33 nmol/L.This method was applied to determine Hg²⁺ in real water samples with good recovery.

Keywords：cyclometallic iridium complex；N-hydroxysuccinimide；electrochemiluminescence；mercury ion；measurement

USB电源供电表面增强拉曼基底快速制备装置的开发及其在农药残留检测中的应用

朱津毅¹，黄天雄²，王甜¹，杜一平²，龚雪¹，彭洁¹，李炜^*3

（1. 江苏中烟工业有限责任公司，南京卷烟厂品质管理处，南京 210019；2. 上海功能性材料化学重点实验室，华东理工大学化学与分子工程学院，上海 200237；3. 江苏中烟工业有限责任公司技术中心，南京 210019）

摘要：利用现用现制的方法快速制备SERS基底，以解决基底因储藏而导致稳定性变差和使用寿命不长的问题。研制了快速制备银溶胶基底的装置，该装置以USB电源供电，带有加热控温以及搅拌功能，可在10 min内制备银溶胶基底。透射电镜（TEM）结果显示，利用该装置制备的银溶胶纳米颗粒（AgNPs）分布均匀，粒径约80 nm；用于对罗丹明6G进行检测，多批次制备基底的SERS信号较强且稳定，相对标准偏差（RSD）在5%左右。将该装置用于检测苹果汁中农药残留敌草快，检出限达5.3 μg/L，与气相色谱-质谱联用（GC-MS）和超高效液相色谱-质谱联用（UHPLC-MS）法的检出限结果相当；且1581 cm^-1处的SERS信号强度与敌草快浓度间具有良好的线性关系，相关系数（R²）为0.992，加标回收率在107%~112%之间，RSD在1.4%~3.6%之间。使用现制的银溶胶基底检测苹果汁中的敌草快残留灵敏度和准确度较高，为农残快速检测提供了一个新途径。

关键词：表面增强拉曼光谱；基底；制备装置；农药；快检

中图分类号：O657.3    文献标识码：A    文章编号：1000-0720（2024）05-0649-05

Development of fast fabrication device for surface enhanced Raman spectroscopy substrate synthesis based on USB-power supply and its application for pesticide detection

ZHU Jinyi¹，HUANG Tianxiong²，WANG Tian¹，DU Yiping²，GONG Xue¹，PENG Jie¹，LI Wei^*3

1. China Tobacco Jiangsu Industrial Co.，Ltd.，Quality Management Department of Nanjing Cigarette Factory，Nanjing 210019，China；2. Shanghai Key Laboratory of Functional Materials Chemistry，School of Chemistry & Molecular Engineering，East China University of Science and Technology，Shanghai 200237，China；3. Technology Center，China Tobacco Jiangsu Industrial Co.，Ltd.，Nanjing 210019，China）

Abstract：A method for freshly synthesized surface enhanced Raman spectroscopy （SERS） substrate was proposed to solve the problem of low stability and short life of the substrate due to aggregation of nanoparticles. Based on USB power supply，a device with functions of heating，temperature control and stirring was designed and fabricated to synthesize silver colloid. Preparation of a substrate of Ag colloid for SERS detection could be completed in about 10 min by this device. The transmission electron microscope （TEM） image revealed that Ag nanoparticles （AgNPs） in the synthesized colloid show uniform distribution，with the particle size of about 80 nm. SERS signal of R6G was strong and stable，and the relative standard deviation （RSD） for five-batch substrates was around 5%. The limit of detection （LOD） of pesticide diquat in apple juice by SERS using the  synthesized substrate was 5.3 μg/L，closing to those obtained by gas chromatography-mass spectrometry （GC-MS） and ultra-high performance liquid chromatography-mass spectrometry （UHPLC-MS） methods. There was a linear relationship between SERS signal intensity at 1581 cm^-1 and concentration of diquat，and the correlation coefficient （R²） was 0.992. The recoveries were in the range of 107%-112%，and the relative standard deviations （RSDs） were 1.4%-3.6%. The sensitivity and accuracy of detecting diquat in apple juice by using the synthesized substrate were high，supplying a new way for the rapid detection of pesticide residuals.

Keywords：surface enhanced Raman spectroscopy；substrate；fabrication device；pesticide；rapid detection

羟基磷灰石修饰碳纳米电极制备及其对抗坏血酸的测定

丰明佳¹，钱功明^*1，2，熊苓雅¹，韩荻¹

（1. 武汉科技大学资源与环境工程学院，武汉 430081；2. 冶金矿产资源高效利用与造块湖北省重点实验室，武汉 430081）

摘要：通过恒电位沉积法，将纳米羟基磷灰石（HAP）成功修饰到碳纳米电极（CNE）上，制备出一种能快速检测抗坏血酸（AA）的修饰电极（HAP-CNE）。采用循环伏安法（CV）和计时安培法（CA）研究了HAP-CNE电极对AA的检测，考察了多巴胺（DA）和模拟体液pH对电极检测AA的影响。扫描电镜（SEM）结果表明，HAP已经成功修饰于CNE尖端与外壁上。电化学实验表明，与CNE相比，HAP-CNE电极信噪比显著提高，同时AA在HAP-CNE上能发生氧化还原反应，电荷转移速率提高。AA浓度在1×10^-5~2×10^-3 mol/L范围内与响应电流呈近似线性关系，检出限为1.3×10^-7 mol/L。利用HAP-CNE检测AA具有广泛的pH适应性且对DA的抗干扰能力强。该电极是一种潜在原位探针，有望为生物医学研究提供新的检测方法，并成为一种能应用于活体实时检测生物小分子代谢过程的新型传感器。

关键词：碳纳米电极；羟基磷灰石；电化学检测；抗坏血酸

中图分类号：O657.15    文献标识码：A    文章编号：1000-0720（2024）05-0654-06

Preparation of hydroxyapatite modified carbon nanoelectrode and its application in determination of antiascorbic acid

FENG Mingjia¹，QIAN Gongming^*1，2，XIONG Lingya¹，HAN Di¹

1. School of Resources and Environmental Engineering，Wuhan University of Science and Technology，Wuhan 430081，China；2. Hubei Key Laboratory for Efficient Utilization and Agglomeration of Metallurgic Mineral Resources，Wuhan 430081，China）

Abstract：Nano-hydroxyapatite （HAP） was successfully modified onto carbon nanoelectrode （CNE） by potentiostatic deposition method，and a novel modified electrode （HAP-CNE） was prepared for rapid determination of ascorbic acid （AA）. Cyclic voltammetry （CV） and chronoamperometry （CA） were used to detect AA on HAP-CNE，and the effects of dopamine （DA） and pH were investigated. The results of scanning electron microscopy （SEM） showed that HAP had been modified successfully on the tip and outer wall of CNE. Electrochemical experiments showed that the signal-to-noise ratio of HAP-CNE electrode was significantly higher than that of CNE electrode. Meanwhile，the REDOX reaction of AA happened on HAP-CNE electrode，and the transfer rate increased. In addition，the AA concentration was approximately linear with the response current in the range of 1×10^-5-2×10^-3 mol/L，and the detection limit was1.3×10^-7 mol/L. The detection of AA by HAP-CNE had a wide range of pH adaptability and strong anti-interference ability to DA. The electrode is a potential in situ probe that is expected to provide new detection methods for biomedical research and to become a novel sensor that can be applied to the real-time detection of metabolic processes of small molecules in vivo.

Keywords：carbonnanoelectrode；hydroxyapatite；electrochemistry detection；ascorbic acid

一种含1，2，3-三氮唑席夫碱的Al³⁺荧光探针及其应用

廖元淏，王帅，冯华杰，陈光英，宋媛，吴禄勇^*，何文英^*

（热带药用资源化学教育部重点实验室，海南师范大学化学与化工学院，海口 571158）

摘要：本文设计合成了5-苯基-2-苯基-1，2，3-三唑-1-4-酰肼（PP），将其与水杨醛反应，构建了一种席夫碱荧光探针（PPS）。荧光光谱及紫外光谱测定表明，PPS能够高选择性和强抗干扰性地检测乙醇溶液中的Al³⁺，检出限为8.28 nmol/L；在紫外光下可发生明显的溶剂变色效应，在含水量大于60%的有机溶剂中存在聚集诱导发光（AIE）效应，质谱、工作曲线、核磁滴定及理论计算结果均证明，PPS和Al³⁺可以络合比1∶1进行反应，生成平面结构的化合物。该探针具有低的细胞毒性且成功用于HeLa细胞的显色成像，有望被开发利用为具有AIE聚集效应的发光材料及生物体内测定Al³⁺的荧光探针。

关键词：5-苯基-2-苯基-1，2，3-三唑-1-4-酰肼席夫碱；Al³⁺；识别机理；细胞成像

中图分类号：O657.31；X832    文献标识码：A    文章编号：1000-0720（2024）05-0660-09

A fluorescent probe of 1，2，3-triazole modified by Schiff base for detecting Al³⁺ and its application

LIAO Yuanhao，WANG Shuai，FENG Huajie，CHEN Guangying，SONG Yuan，WU Luyong^*，HE Wenying^*

Key Laboratory of Tropical Medicinal Resource Chemistry of Ministry of Education，Hainan Normal University，Haikou 571158，China）

Abstract：5-phenyl-2-phenyl-1，2，3-triazole-4-hydrazid （PP） was designed and synthesized based on “click chemistry”. The fluorescence probe PPS（5-phenyl-2-phenyl-1，2，3-triazole-4-hydrazid-O-hydroxymethylbenzene） containing Schiff base was further constructed by a chemical reaction between PP and salicylaldehyde. PPS could be used to determine Al³⁺ in ethanol solution with high sensitivity and strong anti-interference performance by fluorescence and UV-vis spectroscopic methods. The limit of detection for Al³⁺ was 8.28 nmol/L，and the probe PPS showed an obvious solvatochromic effect under ultraviolet light. The aggregation-induced emission （AIE） effect of PPS was found in organic solvent when water content was more than 60%. Furthermore，the results of mass spectrometry （MS），Job’s plot，NMR titration，and density functional theory （DFT） calculation confirmed that the probe PPS and Al³⁺ could react to form a compound with a planar structure at 1∶1 complexation ratio. The probe PPS showed less low cytotoxicity to HeLa cells，so it was successfully used for chromatic bioimaging Al³⁺ in HeLa cells. It is expected to be developed and utilized as a kind of luminous material with AIE effect and a fluorescence probe for detecting Al³⁺ in vivo.

Keywords：5-phenyl-2-phenyl-1，2，3-triazole-4-hydrazid Schiff base （PPS）；Al³⁺；recognition mechanism；living cell imaging

基于红色碳点/二氧化锰纳米探针荧光法检测果汁总抗氧化性

王幸幸^1，3，4，李景敏²，杨顺¹，周扬¹，罗林^*2，邓浩³，何镇熹²，徐振林²，贾宝珠^*1

（1. 广东第二师范学院生物与食品工程学院，广州 510303；2. 广东省食品质量安全重点实验室，华南农业大学食品学院，广州 510642；3. 海南省农业科学院农产品加工设计研究所，海南省热带果蔬冷链研究重点实验室，海口 570100；4. 深圳市通量检测科技有限公司，深圳 518038）

摘要：以红色荧光碳点（R-CDs）与二氧化锰（MnO₂）纳米片为荧光探针，构建了一种灵敏、快速、简便的荧光分析方法，并用于测定食物总抗氧化性。以抗坏血酸（AA）为模型检测靶标，采用AA当量评价食品总抗氧化性，通过单因素实验优化MnO₂纳米片浓度、R-CDs稀释倍数、MnO₂与R-CDs的作用时间及其与AA的作用时间。在最佳条件下，荧光强度与AA浓度的对数值在4.0~12 μmol/L范围内呈良好的线性关系，检出限达到0.06 μmol/L。该方法测定标准添加果汁样品的回收率在85.8%~113.0%之间，具有较好的灵敏度与准确性。

关键词：MnO₂纳米片；红色荧光碳点；荧光；抗氧化剂

中图分类号：O657.31；X832    文献标识码：A    文章编号：1000-0720（2024）05-0669-07

Fluorescent assay for the determination of total antioxidant capacity of fruit juices based on red-emitting carbon dot/MnO₂ nanoprobe

WANG Xingxing^1，3，4，LI Jingmin²，YANG Shun¹，ZHOU Yang¹，LUO Lin^*2，DENG Hao³，HE Zhenxi²，XU Zhenlin²，JIA Baozhu^*1

1. College of Biological and Food Engineering，Guangdong University of Education，Guangzhou 510303，China；2. Guangdong Key Laboratory of Food Quality and Safety，College of Food Science，South China Agricultural University，Guangzhou 510642，China；3. Key Laboratory of Tropical Fruit and Vegetable Cold-chain of Hainan Province，Institute of Agro-products Processing and Design，Hainan Academy of Agricultural Sciences，Haikou 570100，China；4. Shenzhen Total-Test Technology Co.，Ltd.，Shenzhen 518038，China）

Abstract：A fluorescent assay for the determination of total antioxidant capacity （TAC） of foods was developed by using red-emitting carbon dots （R-CDs）/manganese dioxide nanosheets （MnO₂ NSs） as nanoprobe. Ascorbic acid （AA），as a typical antioxidant，was employed as model analyte，and AA equivalents was used as the index for TAC assessment. Single-factor experiments were conducted to optimize the concentration of MnO₂ nanosheets，dilution factor of R-CDs，interaction time for MnO₂ with R-CDs and AA with the nanoprobe. Under the optimal conditions，the fluorescence intensity showed a good linear relationship with AA concentration in the range of 4.0-12 μmol/L，with the detection limit of 0.06 μmol/L. The recoveries of the standard added juice samples ranged from 85.8% to 113.0%，demonstrating the high potential detection of TAC in food.

Keywords：MnO₂ nanosheet；red-emitting carbon dots；fluorescence；antioxidant

基于双发射碳量子点的比率型荧光探针检测阿司匹林

刘荔贞^*，陈梦，袁琳，米智，李彩琴，王利刚，冯锋

（山西大同大学化学与化工学院，大同 037009）

摘要：以间苯二胺和酒石酸为原料，通过一步水热法合成了在单一激发波长下具有双发射特性的碳量子点（CQDs）。利用透射电镜（TEM）、傅里叶变换红外光谱（FTIR）、X射线光电子能谱（XPS）、紫外-可见吸收光谱（UV-vis）和荧光光谱对其结构和光学性质进行了表征。当激发波长为390 nm时，该CQDs在440和502 nm处有2个发射峰。阿司匹林能够使502 nm处的发射峰荧光强度增加，而440 nm处的发射峰强度基本不变，基于此，构建了一种CQDs比率型荧光探针检测阿司匹林的新方法。阿司匹林浓度在0.5~160 μmol/L范围内与CQDs的2个发射峰的荧光强度比（F₅₀₂/F₄₄₀）呈良好的线性关系，检出限低至0.062 μmol/L。该方法成功用于药品中阿司匹林的检测。

关键词：碳量子点；阿司匹林；比率型荧光探针

中图分类号：O657.3    文献标识码：A    文章编号：1000-0720（2024）05-0676-06

Ratiometric fluorescent sensor based on double emission carbon quantum dots for the detection of Aspirin

LIU Lizhen^*，CHEN Meng，YUAN Lin，MI Zhi，LI Caiqing，WANG Ligang，FENG Feng

College of Chemistry and Chemical Engineering，Shanxi Datong University，Datong 037009，China）

Abstract：Carbon quantum dots （CQDs） with dual emission property at a single excitation wavelength were synthesized by a one-step hydrothermal method using m-phenylenediamine and tartaric acid as raw materials. The structure and optical properties of CQDs were characterized by transmission electron microscope，Fourier transform infrared spectrometer，X-ray photoelectron spectroscopy，ultraviolet-visible absorption spectroscopy and fluorescence spectroscopy. When the excitation wavelength was 390 nm，the CQDs had two emission peaks at 440 and 502 nm. The presence of aspirin can increase the fluorescence intensity of the emission peak at 502 nm，while the intensity of the emission peak at 440 nm was basically unchanged. Based on this，a novel CQDs based ratiometric fluorescent sensor was constructed for the determination of aspirin. The concentration of aspirin in the range of 0.5-160 μmol/L had a good linear relationship with the fluorescence intensity ratio （F₅₀₂/F₄₄₀） of the two emission peaks of CQDs，and the detection limit was as low as 0.062 μmol/L. The developed method has been successfully applied to the determination of aspirin in actual drugs.

Keywords：carbon quantum dots（CQDs）；aspirin；ratio metricfluorescent sensor

液相色谱串联质谱法同时测定猪肉中氟雷拉纳和五氯酚残留量

伍华雯¹，刘正才²，马欣欣¹，韩颖¹，占春瑞¹，柯秋璇²，陈练洪²，朱立怡¹，万建春^*1

（1. 南昌海关技术中心，南昌 330038；2. 福州海关技术中心，福州 350003）

摘要：采用基质分散固相萃取净化结合液相色谱-串联三重四极杆质谱分析技术，基于待测物的油水分配系数和样品前处理正交试验设计，建立了猪肉中氟雷拉纳和五氯酚残留量的检测方法。试样采用酸化乙腈均质提取，提取液加入QuEChERS萃取净化包快速净化，过膜直接上机测定。以5 mmol/L乙酸铵溶液和乙腈为流动相，氟雷拉纳和五氯酚经C18色谱柱梯度洗脱分离后，质谱负离子模式扫描检测。猪肉样品中分别添加1.0，2.0，10.0 μg/kg 3个浓度水平待测物，氟雷拉纳和五氯酚的加标回收率分别在82.3%~104.0%和71.6%~79.8%之间，相对标准偏差（RSD）分别在3.7%~5.3%和1.2%~3.4%之间。本方法检测氟雷拉纳和五氯酚的定量限均为1.0 μg/kg，适用于猪肉中氟雷拉纳和五氯酚残留量的测定。

关键词：液相色谱串联质谱；猪肉；氟雷拉纳；五氯酚；残留检测

中图分类号：O657.63    文献标识码：A    文章编号：1000-0720（2024）05-0682-05

Simultaneous determination of fluralaner and pentachlorophenol residues in pork by liquid chromatography tandem mass spectrometry

WU Huawen¹，LIU Zhengcai²，MA Xinxin¹，HAN Ying¹，ZHAN Chunrui¹，KE Qiuxuan²，CHEN Lianhong²，ZHU Liyi¹，WAN Jianchun^*1

1. Technology Center of Nanchang Customs District，Nanchang 330038，China；2. Technology Center of Fuzhou Customs District，Fuzhou 350003，China）

Abstract：The simultaneous determination of fluralaner and pentachlorophenol residues in pork was developed by using matrix dispersion solid phase extraction to purify the sample solution and liquid chromatography-tandem triple quadrupole tandem mass spectrometry，based on the oil-water distribution coefficient of the tested substance and the orthogonal experimental design of sample pretreatment. After extracting by acidified acetonitrile，the extract was added into the QuEChERS extraction purification package for rapid purification and filtered with the membrane，then the purified liquid was analyzed by LC-MS/MS. With 5 mmol/L ammonium acetate solution and acetonitrile as the mobile phase，fluralaner and pentachlorophenol were separated by gradient elution on the C18 column，and then the negative mode scanning of mass spectrometry was performed. At three spiked concentration levels of 1.0，2.0，10.0 μg/kg in the pork，the recoveries of fluralaner and pentachlorophenol were 82.3%-104.0% and 71.6%-79.8%，respectively，and the relative standard deviations （RSDs） were 3.7%-5.3% and 1.2%-3.4%，respectively. The quantitative limits of fluralaner and pentachlorophenol were 1.0 μg/kg，which is suitable for the determination of fluralaner and pentachlorophenol residues in pork.

Keywords：LC-MS/MS；pork；fluralaner；pentachlorophenol；residue detection

直接进样-高效液相色谱-串联质谱法快速检测饮用水中草铵膦、草甘膦及其代谢物氨甲基膦酸

方力^*1，邱凤梅²

（1. 浙江省海产品健康危害因素关键技术研究重点实验室，舟山市疾病预防控制中心，舟山 316021；2. 浙江省舟山市普陀区疾病预防控制中心，舟山 316100）

摘要：建立了高效液相色谱串联三重四极杆质谱（HPLC-MS/MS）定量检测饮用水中草铵膦、草甘膦及其代谢产物氨甲基膦酸的方法。水样直接经亲水PTFE膜过滤，以50 mmol/L甲酸铵（pH 3.0）为流动相，Acclaim Trinity Q1色谱柱分离，电喷雾离子化（ESI-）、选择反应监测（SRM）模式检测，外标法定量，总运行时间仅为5 min。草甘膦、氨甲基膦酸和草铵膦在10.0~1000 μg/L浓度范围内存在较好的线性关系，相关系数大于0.999，其定量限分别为5.0，5.0和10.0 μg/L；目标化合物日内和日间加标回收率分别为92.7%~102.1%和89.3%~99.9%，日内与日间相对标准偏差（RSD）均小于7.7%。该方法能满足水源水和饮用水中草铵膦、草甘膦及其代谢物氨甲基膦酸的应急检测或日常检测要求。

关键词：草甘膦；氨甲基膦酸；草铵膦；饮用水；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）05-0687-06

Rapid determination of glufosinate ammonium，glyphosate and aminomethyl phosphonic acid in drinking water by direct injection - liquid chromatography - tandem mass spectrometry

FANG Li^*1，QIU Fengmei²

1. Key Laboratory of Health Risk Factors for Seafood of Zhejiang Province，Zhoushan Municipal District Center for Disease Control and Prevention，Zhoushan 316021，China；2. Putuo Center for Disease Control and Prevention，Zhoushan 316100，China）

Abstract：A method for quantitative analysis of glufosinate ammonium，glyphosate，and its metabolite of aminomethyl phosphonic acid in drinking water was established by utilizing liquid chromatography coupled with triple quadrupole mass spectrometry （LC-MS/MS）. The water sample was directly filtered through a 0.22 μm PTFE membrane. The analytes were separated on an Acclaim Trinity Q1 column with the mobile phase of 50 mmol/L ammonium formate （pH 3），and detected in selected reaction monitoring （SRM） mode via negative electrospray ionization （ESI-）. The external standard method was used for quantitation. There were good linearities for glufosinate ammonium，glyphosate，and aminomethyl phosphonic acid in the concentration ranges of 10.0-1000 μg/L，respectively，and the correlation coefficients were higher than 0.999. The quantification limits of glufosinate ammonium，glyphosate，and aminomethyl phosphonic acid in drinking water were 5.0，5.0 and 10.0 μg/L，respectively. The inter-day and intra-day recoveries of glufosinate ammonium，glyphosate，and aminomethyl phosphonic acid were 92.7%-102.1% and 89.3%-99.9%，respectively，with the inter-day and intra-day relative standard deviations （RSDs） lower than 7.7%. The method can satisfy the requirements of emergency testing or routine testing.

Keywords：glyphosate；aminomethyl phosphonic acid；glufosinate ammonium；drinking water；liquid chromatography-tandem mass spectrometry

基于非标记适配体结构变化荧光法检测黄曲霉毒素B1

于洁，朱科晓，王  超^*，时鹏飞^*

（临沂大学化学化工学院，临沂 276000）

摘要：构建了一种基于非标记适配体结构变化荧光检测黄曲霉毒素B1（AFB1）的方法。无AFB1时，一条非标记的AFB1适配体同时与2条短互补DNA链杂交，形成DNA双链结构，导致标记于其中一条互补DNA的3’端的荧光素（FAM）与标记于另一条互补DNA的5’端的淬灭剂（BHQ1）相邻近，发生荧光共振能量转移，FAM荧光被BHQ1淬灭。AFB1存在时，适配体与AFB1结合，而不与互补DNA发生杂交。此时，FAM与BHQ1距离较远，FAM荧光不能被淬灭。通过测量体系荧光强度变化可定量检测AFB1。方法检出限0.2 nmol/L，定量检测范围1.0 nmol/L~4.0 μmol/L。该方法无需共价标记适配体，操作简便，特异性好，能够用于检测复杂基质样品中的AFB1。

关键词：黄曲霉毒素B1；适配体；荧光淬灭；快速检测

中图分类号：O657.1    文献标识码：A    文章编号：1000-0720（2024）05-0693-06

A fluorescence method for detection of aflatoxin B1 based on structural change of unlabeled aptamer

YU Jie，ZHU Kexiao，WANG Chao^*，SHI Pengfei^*

College of Chemistry and Chemical Engineering，Linyi University，Linyi 276000，China）

Abstract：A simple method was constructed for fluorescence detection of aflatoxin B1 （AFB1） based on the structural change of an unlabeled aptamer. In the absence of AFB1，an unlabeled AFB1 aptamer simultaneously hybridized with two complementary short DNA strands，forming a DNA duplex structure. As results，the fluorescein FAM labeled at 3’ end of a complementary DNA was adjacent to the quencher BHQ1 labeled at 5’ end of the other complementary DNA. In this case，fluorescence resonance energy transfer occurred，and FAM fluorescence was quenched by BHQ1. In the presence of AFB1，the aptamer bound to AFB1 instead of hybridizing with complementary DNAs. As results，FAM and BHQ1 were far away from each other，and FAM fluorescence could not be quenched. AFB1 was quantitatively detected by measuring fluorescence intensity of the system. Detection limit of this method was 0.2 nmol/L，and quantitative detection range was 1.0 nmol/L-4.0 μmol/L. This method could be used for rapid detection of AFB1 in complex matrix samples for not requiring labeling of aptamer，easy to operate，and good specificity.

Keywords：aflatoxin B1；aptamer；fluorescence quenching；rapid detection

一锅法制备生物炭-金属有机骨架复合材料用于吸附全氟辛酸

周瑶璐^1，2，祝绍玉^1，2，刘树仁¹，钱一帆^1，2，柏珊珊^*1

（1. 浙江省污染暴露与健康干预重点实验室，浙江树人学院交叉科学研究院，杭州 310015；2. 浙江树人学院生物与环境工程学院，杭州 310015）

摘要：通过一锅法制备了一种新型生物炭-铁基金属有机骨架复合材料（MIL-101（Fe）@BC）。利用傅里叶红外光谱、扫描电镜和氮气吸附-脱附分析对材料进行表征，探究了MIL-101（Fe）@BC对全氟辛酸（PFOA）的吸附效能和作用机制，并将其与5种常用工程碳材料进行对比。结果表明，MIL-101（Fe）@BC在吸附环境pH为4，吸附时间为1 h时达到最佳吸附效果，最佳投加量为0.05 g/L。MIL-101（Fe）@BC对PFOA的吸附等温线既符合Langmuir模型又符合Freundlich模型，最大饱和吸附量为925.93 μmol/g，吸附过程符合准二级动力学方程，孔隙填充和氢键作用是吸附的主要机制。MIL-101（Fe）@BC吸附和再生效能均优于已广泛使用的工程碳材料，在新污染物治理领域具有较大的应用潜力。

关键词：生物炭；复合材料；吸附；全氟辛酸

中图分类号：X52    文献标识码：A    文章编号：1000-0720（2024）05-0699-06

Preparation of biochar-metal organic framework composite by one-pot method for the adsorption of perfluorooctanoic acid

ZHOU Yaolu^1，2，ZHU Shaoyu^1，2，LIU Shuren¹，QIAN Yifan^1，2，BAI Shanshan^*1

1. Zhejiang Provincial Key Laboratory of Pollution Exposure and Health Intervention，Interdisciplinary Research Academy，Zhejiang Shuren University，Hangzhou 310015，China；2. College of Biology and Environmental Engineering，Zhejiang Shuren University，Hangzhou 310015，China）

Abstract：A novel biochar-metal organic framework composite material （MIL-101（Fe）@BC） was prepared using the one-pot method. The material was characterized using Fourier-transform infrared spectroscopy，scanning electron microscopy，and nitrogen adsorption-desorption analysis. The adsorption efficiency and mechanism of MIL-101（Fe）@BC to perfluorooctanoic acid （PFOA） were investigated and compared with five commonly used engineering carbon materials. The results showed that MIL-101（Fe）@BC achieved optimal adsorption at pH 4，with an optimum dosage of 0.05 g/L within 1 h. The adsorption isotherm of PFOA on MIL-101（Fe）@BC followed both Langmuir and Freundlich models，with a maximum saturation adsorption capacity of 925.93 μmol/g. The adsorption process followed pseudo-second-order kinetics，and pore filling and hydrogen bonding were identified as the main adsorption mechanisms of MIL-101（Fe）@BC to PFOA. MIL-101（Fe）@BC exhibited superior adsorption and regeneration efficiency compared to widely used engineering carbon materials，indicating significant practical application potential.

Keywords：biochar；composite materials；adsorption；perfluorooctanoic acid

流动注射-串联质谱法分析污水中11种毒品

郑吴淇¹，宁弘宇²，陈昊¹，黄忠平²，范一雷^*1，柯星^*1

（1. 浙江警察学院浙江省毒品防控技术研究重点实验，杭州 310053；2. 浙江工业大学化工学院，杭州 310014）

摘要：建立了一种流动注射-串联质谱法（FIA-MS/MS）快速检测污水中11种常见毒品。样品经Oasis MCX固相萃取小柱净化和浓缩后，注入FIA-MS/MS系统进行分析。质谱采用正离子模式扫描，在多反应监测模式（MRM）下，同位素内标法定量。结果表明，11种毒品在0.16~200 ng/L范围内线性关系良好，相关系数r²≥0.9902，检出限（LOD）为0.05~0.53 ng/L，定量限（LOQ）为0.16~1.60 ng/L。11种毒品在低、中、高3种加标浓度下，方法回收率为74.5%~113.7%，日内相对标准偏差（RSD）在1.0%~6.9%之间，日间RSD在2.2%~11%之间。该方法适用于污水样品中毒品的高通量筛查和定量分析。

关键词：流动注射-串联质谱法；污水；毒品检测；高通量检测

中图分类号：O657.31；X832    文献标识码：A    文章编号：1000-0720（2024）05-0705-06

Analysis of 11 drugs in wastewater by flow injection-tandem mass spectrometry

ZHENG Wuqi¹，NING Hongyu²，CHEN Hao¹，HUANG Zhongping²，FAN Yilei^*1，KE Xing^*1

1. Key Laboratory of Drug Prevention and Control Technology of Zhejiang Province，Zhejiang Police College，Hangzhou 310053，China；2. College of Chemical Engineering，Zhejiang University of Technology，Hangzhou 310014，China）

Abstract：A flow injection tandem mass spectrometry （FIA-MS/MS） method has been developed for the rapid detection of 11 common drugs in wastewater. Samples were purified and concentrated by the Oasis MCX solid-phase extraction cartridge，followed by injection into the FIA-MS/MS system. Positive ion scanning mode was used for mass spectrometry，and isotope internal standard method in multiple reaction detection mode （MRM） was employed for quantification. The results showed that all the 11 drugs had good linear relationships in the range of 0.16-200 ng/L，with correlation coefficients of r²≥0.9902. The limits of detection （LODs） and limits of quantification （LOQs） were 0.05-0.53 ng/L and 0.16-1.60 ng/L，respectively. At low，medium，and high spiked concentrations，the recoveries of 11 drugs were 74.5%-113.7%，and the relative standard deviations （RSDs） of intra-day and inter-day were 1.0%-6.9% and 2.2%-11%，respectively. The present work provides a method suitable for high-throughput screening and quantitative analysis of toxic substances in wastewater samples.

Keywords：flow injection-tandem mass spectrometry；wastewater；drug detection；high-throughput detection

基于UHPLC-Q-Orbitrap高分辨质谱联用快速鉴定半夏中的化学成分

王静，崔洁，刘子怡，杨杨，李展，刘慧灵^*

（中国医学科学院药用植物研究所，北京 100193）

摘要：利用UHPLC-Q-Orbitrap四极杆-静电场轨道阱高分辨质谱联用技术对半夏的化学成分进行快速识别和鉴定。以80%（V/V）甲醇提取，Acquity UPLC BEH C18色谱柱（2.1 mm×100 mm，1.7 μm）分离，0.1%甲酸水（A）-0.1%甲酸的乙腈（B）溶液作为流动相进行梯度洗脱。质谱采用正、负离子监测模式，利用全扫描及自动触发二级质谱扫描，快速识别和鉴定半夏中的化学成分。根据高分辨质谱数据，从半夏中共分析鉴定出111个化合物，包括生物碱类37个、氨基酸及其衍生物20个、黄酮类17个、萜类12个、有机酸及其衍生物6个、苯丙素类5个、其它类14个。该方法可为半夏质量控制和药效物质研究提供参考。

关键词：半夏；UHPLC-Q-Orbitrap四极杆-静电场轨道阱高分辨质谱；化学成分；生物碱；氨基酸

中图分类号：R284.1    文献标识码：A    文章编号：1000-0720（2024）05-0711-08

Rapid identification of chemical components in Pinelliae Rhizoma by UHPLC-Q-Orbitrap high resolution mass spectrometry

WANG Jing，CUI Jie，LIU Ziyi，YANG Yang，LI Zhan，LIU Huiling^*

Institute of Medicinal Plant Development，Chinese Academy of Medical Sciences，Beijing 100193，China）

Abstract：An UHPLC-Quadrupole-Orbitrap high resolution mass spectrometry method was developed to rapidly identify the chemical components from Pinelliae Rhizoma by using 80% （V/V） methanol as the extraction solution. For UHPLC separation，Acquity UPLC BEH C18 column （2.1 mm×100 mm，1.7 μm） was used，and gradient elution was performed with 0.1% formic acid water （A）-0.1% formic acid acetonitrile （B） solution as mobile phase. The chemical components in Pinelliae Rhizoma were quickly identified by the mass spectrometry adopting positive and negative ion monitoring modes，full scanning and automatic triggering of secondary mass spectrometry. As a result，a total of 111 compounds have been identified from Pinelliae Rhizoma，including 37 kinds of alkaloids，20 kinds of amino acids and derivants，17 kinds of flavonoids，12 kinds of terpenoids，6 kinds of organic acids and derivants，5 kinds of phenylpropanoids，and 14 other kinds of compounds. The method provides a reference for quality control and pharmacodynamic material basics.

Keywords：Pinelliae Rhizoma；UHPLC-Q-Orbitrap high resolution mass spectrometry；chemical components；alkaloid；amino acid

基于小区域地表感知横纵波时差的页岩压裂定位方法研究

田新琦¹，魏冰^*2，郝晓敏^*2，胡照乾²

（1. 中石化石油工程地球物理有限公司，北京 100024；2. 中石化石油工程地球物理有限公司科技研发中心，南京 211100）

摘要：针对页岩油勘探中传统的压裂定位方法存在定位模型复杂、精度低以及技术成本高等不足，提出了基于小区域地表感知横纵波时差的页岩压裂定位模型及其算法。首先，采用变分模态分解的信号处理技术分解微地震波低频响应，可提高原始压裂响应的信噪比。其次，将长短时窗算法（STA/LTA）与赤池信息准则（AIC）算法相结合，有效地识别分解信号的起跳点，从而完成横纵波之间的时差拾取。最后，建立了横纵波时差与压裂源坐标、小区域地表检波器坐标之间定位数学模型，通过最小二乘法，实现基于多个定位数学模型的压裂源坐标计算，其坐标值均值可有效提高定位计算精度。

关键词：页岩压裂；定位；信号分解；时差拾取；小区域地表

中图分类号：TE377    文献标识码：A    文章编号：1000-0720（2024）05-0719-07

Research on shale fracturing localization method based on transverse and longitudinal wave time difference of small-region surface perception

TIAN Xinqi¹，WEI Bing^*2，HAO Xiaomin^*2，HU Zhaoqian²

1. Sinopec Geophysical Corp.，Beijing 100024，China；2. Research and Development Center，Sinopec Geophysical Corp.，Nanjing 211100，China）

Abstract：Aiming at the shortcomings of the traditional shale fracturing localization methods for shale oil exploration，such as the complexity of localization model，low accuracy and high technical cost，both a shale fracturing localization model and its algorithm are proposed based on the time difference of transverse and longitudinal waves of small-area surface sensing. Firstly，the signal processing technology of variational mode decomposition is used to decompose the low frequency response of microseism wave，which can improve the signal-to-noise ratio of the original fracturing response. Secondly，the long and short time window algorithm （STA/LTA） is combined with the Akaike information criterion （AIC） algorithm to effectively identify the take-off point of the decomposed signal，so as to complete the time difference picking between the transverse and longitudinal waves. At last，the localization mathematical model is established among the time difference of transverse and longitudinal waves and the coordinates of fracturing source and the coordinates of small area surface geophones，the calculation of fracturing source coordinates based on various localization mathematical models can be realized by means of the least square method，and the average value of coordinate value can effectively improve the accuracy of localization calculation.

Keywords：shale fracturing；localization；signal decomposition；time difference picking；small-region surface

基于不同背景选取方式四极质谱仪数据库匹配分析

于佳佳^*1，2，沈辉^1，2，王玉涵¹，罗勇¹，唐朝阳¹

（1. 上海裕达实业有限公司，上海 200240；2. 上海卫星装备研究所，上海 200240）

摘要：电解液测试属于锂电池研究的重点方向之一。质谱法在线测试电解液时，背景信号对搜库结果匹配度有明显的影响。研究了在不同背景选取方式下四极质谱仪识别电解液谱峰的匹配度，结果表明，基于进样阶段选取背景的扣除方法，可更有效地去除环境空气对搜库的干扰，获得更高的搜库匹配度。实验结果为锂电池电解液溶剂原位测试与谱库匹配数据处理提供了科学依据，为复杂环境现场测试的数据处理方法提供了思路。

关键词：锂电池；背景扣除；谱图检索；质谱仪

中图分类号：O657.63    文献标识码：A    文章编号：1000-0720（2024）05-0726-05

Quadrupole mass spectrometer database identification analysis based on different background selection methods

YU Jiajia^*1，2，SHEN Hui^1，2，WANG Yuhan¹，LUO Yong¹，TANG Chaoyang¹

1. Shanghai Yuda Industrial Co.，Ltd.，Shanghai 200240，China；2. Shanghai Institute of Spacecraft Equipment，Shanghai 200240，China）

Abstract：Electrolyte analysis is one of the key directions of lithium ion battery research. When testing the electrolyte online by mass spectrometry，the background signal has a significant effect on the matching degree of the sprectrum identification. The matching degree of electrolyte sprectrum identified by quadrupole mass spectrometer upon different background selection methods was studied. The results showed that the deduction method based on the background selection in the injection stage can more effectively remove the interference of ambient air on the spectrum identification and obtain a higher matching degree. The experimental results provide a scientific basis for the in-situ test and spectrum identification of electrolyte，and ideas for the data processing method of complex environments testing.

Keywords：lithium-ion batteries；background deduction；spectrum identification；mass spectrometry

复杂基质中有机磷酸酯化合物的2D NMR快速分析

张盈盈¹，吕家乐²，刘石磊³，黄桂兰³，夏俊美³，夏明珠^*1，袁铃^*3

（1. 南京理工大学化学与化工学院，南京 210094；2. 四川轻化工大学化学工程学院，自贡 643002；3. 国民核生化灾害防护国家重点实验室，北京 102205）

摘要：以有机磷酸酯为目标物，编译包含¹H-³¹P异核多键相关谱（HMBC）和¹H-¹H DQF-同核位移相关谱（COSY）的NOAH2_BD脉冲序列，并与非均匀采样技术相结合，通过优化远程耦合演化延迟时间和非均匀采样比例等采集参数，得到¹H-³¹P HMBC和¹H-¹H DQF-COSY谱图，实现了复杂有机废液中有机磷酸酯的快速鉴定。方法检出限可达到10 μg/mL；与传统的二维核磁方法相比，在保持相近的谱图质量下，NOAH2_BD能将检测时间缩短44%，NOAH2_BD结合NUS=30%可将检测时间缩短82%。

关键词：有机磷酸酯；二维核磁；氢核检测有序采样核磁共振；非均匀采样

中图分类号：O657    文献标识码：A    文章编号：1000-0720（2024）05-0731-06

Rapid 2D NMR analysis for organophosphate compounds in complex matrixes

ZHANG Yingying¹，LYU Jiale²，LIU Shilei³，HUANG Guilan³，XIA Junmei³，XIA Mingzhu^*1，YUAN Ling^*3

1.School of Chemistry and Chemical Engineering，Nanjing University of Science and Technology，Nanjing 210094，China；2.School of Chemical Engineering，Sichuan University of Science & Engineering，Zigong 643002，China；3. State Key Laboratory of NBC Protection for Civilian，AMS，Beijing 102205，China）

Abstract：A new NMR by ordered acquisition using ¹H-detection （NOAH）2_BD pulse program with non-uniform sampling containing ¹H-³¹P heteronuclear multiple-bond correlation （HMBC） and ¹H-¹H DQF-correlation spectroscopy （COSY） was compiled. The ¹H-³¹P HMBC and ¹H-¹H DQF-COSY spectra were obtained by optimizing the acquisition parameters such as the delay for evolution of long range couplings time and non-uniform sampling ratio to achieve rapid identification of organophosphates in complex matrixes. The results showed that the detection limit of the method for organophosphates can reach 10 μg/mL. Compared with the traditional 2D NMR methods，the detection time of NOAH2_BD can be reduced by 44% and the detection time of NOAH2_BD with NUS ratio of 30% can be reduced by 82% while maintaining the similar spectral quality.

Keywords：organophosphates；2D NMR；NMR by ordered acquisition using ¹H-detection （NOAH）；non-uniform sampling

纳米材料在漆酶电化学传感器中的应用和研究进展

张钰涓^1，2，陶文强¹，张志衡^1，2，宋志华^1，2，钱立生^*1，张越^*1

（1. 安徽科技学院生命与健康科学学院，滁州 233100；2. 安徽科技学院食品工程学院，滁州 233100）

摘要：高性能纳米材料通过负载漆酶制备生物传感电极，可以实现漆酶电化学传感器的高灵敏度、宽线性检测范围、较好的稳定性和较强的固定化强度，能够应用于食品、环境、医药等领域目标物浓度的精准检测。近年来，随着许多新型纳米材料不断开发以及与漆酶分子之间固定化方式研究的不断深入，证明了纳米材料在漆酶电化学传感电极构建中的巨大潜力。开发新型纳米材料和建立与酶分子之间搭配和固定化策略，能够实现高性能传感电极的制备，进而指导组建面向性能需求的高应用性传感器，最终推动生物传感、酶工程与蛋白质工程和材料学之间的交叉应用。本文对固定漆酶制备传感电极的高性能纳米材料种类进行了分析与讨论，主要从金属纳米材料、碳纳米材料和高分子纳米材料固定化漆酶在生物电化学传感方面的研究进展进行综述，并对纳米材料在漆酶电化学中的应用前景与未来进行了讨论，为今后在漆酶电化学传感器中开发新型纳米材料和选择固定化方式提供参考。

关键词：漆酶；纳米材料；电化学

中图分类号：O657.1    文献标识码：A    文章编号：1000-0720（2024）05-0737-12

Application and research progress of nanomaterials in laccase biosensors

ZHANG Yujuan^1，2，TAO Wenqiang¹，ZHANG Zhiheng^1，2，SONG Zhihua^1，2，QIAN Lisheng^*1，ZHANG Yue^*1

1. College of Life and Health Sciences，Anhui Science and Technology University，Chuzhou 233100，China；2. College of Food Science and Engineering，Anhui Science and Technology University，Chuzhou 233100，China）

Abstract：Nanomaterials with high performance are used to produce biosensing electrodes through loading laccase，which contributes to the high sensitivity，wide linear range，better stability and strong immobilization strength for laccase electrochemical sensors，and can also be applied to the precise determination of target components in food，environmental and medical fields. In recent years，with the continuous development of advanced nanomaterials and the deeper studies on the immobilization modes between laccase molecules，the great potential of nanomaterials in the construction of laccase electrochemical sensing electrodes has been demonstrated. Attempts to develop novel nanomaterials and establish collocation and immobilization strategies with enzyme molecules can enable the preparation of high-performance sensing electrodes，thereby guide the formation of highly applicable sensors meeting the high performance needs，which ultimately promote cross-applications between biosensing，enzyme engineering and protein engineering and materials science. In this paper，the types of high performance nanomaterials for sensing electrodes prepared by immobilized laccase were discussed，mainly including the research progress of metal nanomaterials，carbon nanomaterials and polymer nanomaterials used in immobilized laccase in bioelectrochemical sensing fields. The prospect and future application of nanomaterials in laccase electrochemistry were also discussed to provide references for the development of advanced nanomaterials and methods selection for laccase in electrochemical fields.

Keywords：laccase；nanomaterials；electrochemistry

树枝状介孔纳米粒子检测有害物质研究进展

王艳妮¹，何花²，王亚斌^*1，2，丁秀萍³

（1. 延安大学化学与化工学院，延安 716000；2. 三嗪化合物与多级孔材料研究所，延安 716000；3. 中国科学院青海盐湖研究所，西宁 810008）

摘要：有机和无机有害物质严重危害着环境安全和人类健康，因此，加强对这些有害物质的检测具有实际意义。本文总结了树枝状介孔纳米粒子（DMNs）在有害物质检测领域的最新研究进展。涉及的有害物质主要包括酚类化合物、医药及农药、食品添加剂、挥发性有机化合物（VOCs）、苯甲酮类紫外线吸收剂、重金属离子及有毒非金属元素。重点分析了以树枝状介孔纳米粒子为基础，构建有害物质检测传感器的设计思路和制备过程，为发展其它新型检测系统提供参考。对树枝状介孔纳米粒子型传感器的未来研究方向进行了讨论与展望。

关键词：有害物质；树枝状介孔纳米粒子；检测传感器

中图分类号：O611.4    文献标识码：A    文章编号：1000-0720（2024）05-0749-08

Recent progress on the detection of hazardous substances by dendritic mesoporous nanoparticles

WANG Yanni¹，HE Hua²，WANG Yabin^*1，2，DING Xiuping³

1. College of Chemistry and Chemical Engineering，Yan’an University，Yan’an 716000，China；2. Institute for Triazine Compounds & Hierarchical Porous Materials，Yan’an 716000，China；3. Qinghai Institute of Salt Lakes，Chinese Academy of Sciences，Xining 810008，China）

Abstract：Organic and inorganic hazardous substances can badly destroy environmental safety and human health，which makes the detection of these compounds practically significant. This article summarizes the latest progress on the detection of hazardous substances by dendritic mesoporous nanoparticles （DMNs）. The hazardous substances mainly cover phenolic compounds，pharmaceutical and agricultural chemicals，food additives，volatile organic compounds （VOCs），benzophenone-type UV filters，heavy metal ions，and nonmetallic toxic elements. The design strategies and preparation processes of detection sensors based on DMNs have been emphatically reviewed to provide references for the development of other new detection systems. In addition，the future research direction and prospect have been discussed.

Keywords：hazardous substances；dendritic mesoporous nanoparticles；detection sensors

人体呼气中挥发性有机化合物检测方法在肺癌无创诊断中的应用

陈京¹，宗成华²，徐永红¹，李荣鹏^*1，3

（1. 江苏师范大学生命科学学院，徐州 221000；2. 江苏师范大学化学与材料科学学院，徐州 221000；3. 江苏氙能生命科学研究院，徐州 221000）

摘要：肺癌是最常见最难治疗的恶性肿瘤之一。由于在早期阶段几乎是无症状的，绝大多数肺癌被发现时即为晚期。而早发现可以提高肺癌患者的生存率，因此，肺癌的早期诊断至关重要。呼气分析具有快速、无创、采样方便以及对人体友好等优点，具有应用于肺癌早筛的巨大潜力。本文综述了人体呼气中挥发性有机化合物的采样与富集方法以及不同检测技术在肺癌中的应用，并对其存在的局限性及未来发展趋势进行了讨论。

关键词：肺癌；挥发性有机化合物；呼气检测

中图分类号：R734.2    文献标识码：A    文章编号：1000-0720（2024）05-0757-10

Application of volatile organic compound detection method for human breath in non-invasive diagnosis of lung cancer

CHEN Jing¹，ZONG Chenghua²，XU Yonghong¹，LI Rongpeng^*1，3

1. College of Life Science，Jiangsu Normal University，Xuzhou 221000，China；2. College of Chemistry and Materials Science，Jiangsu Normal University，Xuzhou 221000，China；3. Jiangsu Xenon Life Science Research Institute，Xuzhou 221000，China）

Abstract：Lung cancer is one of the most common and the most lethal malignant tumors. Since lung cancer is almost asymptomatic in its early stage，most of them are advanced when diagnosed. Early detection can improve the survival rate of lung cancer，therefore，early diagnosis of lung cancer is essential. Breath analysis method has the advantages of rapid，non-invasive，convenient sampling and human friendly，leading to its great potential for early screening of lung cancer. In this paper，the methods of sampling and enrichment of volatile organic compounds （VOCs） in human breath and the applications of different detection techniques in lung cancer were reviewed，and their limitations and future development trends were discussed.

Keywords：lung cancer；volatile organic compounds；breath testing