BiOI/g-C₃N₄修饰电极伏安法检测磺胺甲噁唑

武天恒，刘蕊^*，韩雪，刘日嘉，孙源

（哈尔滨商业大学药学院药物工程技术研究中心，哈尔滨 150076）

摘要：通过热聚合法高温煅烧尿素得到g-C₃N₄纳米片，再以溶剂热法得到BiOI/g-C₃N₄复合材料，采用X射线衍射（XRD）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）、红外光谱（FT-IR）等手段对BiOI/g-C₃N₄纳米复合材料的微观结构和形貌进行了表征。通过滴涂法将BiOI/g-C₃N₄复合材料修饰在玻碳电极（GCE）表面，构建了用于快速检测磺胺甲噁唑（SMX）的电化学传感平台，通过循环伏安（CV）和差分脉冲伏安（DPV）技术对SMX进行电化学分析，峰值电流随SMX浓度呈线性增加，线性范围为5~1000 μmol/L，检出限为0.025 μmol/L。采用加标回收法测定自来水样品中的SMX，加标回收率为90.0%~103.4%。

关键词：g-C₃N₄纳米片；电化学传感器；磺胺甲噁唑

中图分类号：O657.1；X703    文献标识码：A    文章编号：1000-0720（2024）01-0001-08

Detection of sulfamethoxazole by cyclic voltammetric method based on BiOI/g-C₃N₄ modified electrode

WU Tianheng，LIU Rui^*，HAN Xue，LIU Rijia，SUN Yuan

Center of Pharmaceutical Engineering and Technology，School of Pharmacy，Harbin University of Commerce，Harbin 150076，China）

Abstract：The g-C₃N₄ nanosheet was obtained by high-temperature calcination of urea with thermal polymerization，and the BiOI/g-C₃N₄ composites were obtained by a solvothermal method. The microstructure and morphology of the BiOI/g-C₃N₄ nanocomposites were verified by different techniques including X-ray diffraction （XRD），scanning electron microscopy （SEM），transmission electron microscopy （TEM） and infrared （FT-IR） spectroscopy. The electrochemical sensing platform for the rapid detection of sulfamethoxazole （SMX） was constructed by drop-coating the BiOI/g-C₃N₄ composites on the surface of a glassy carbon electrode （GCE）. SMX was detected by cyclic voltammetry （CV） and differential pulsed voltammetry （DPV），and the peak current increased linearly with SMX concentration in the linear range of 5-1000 μmol/L，with a limit of detection of 0.025 μmol/L. The spiked recoveries of SMX in tap water samples ranged from 90.0% to 103.4%.

Keywords：g-C₃N₄ nanosheet；electrochemical sensor；sulfamethoxazole

基于拉曼频移的SERS分析平台在胃癌早期诊断中的应用研究

韦伟¹，朱群山³，黄永¹，石立新⁶，吴正³，杨永国⁴，刘佳²，袁梦轩⁵，王震光¹，蒋丰娟^*2

（1. 扬州大学附属江都人民医院胃肠外科，扬州 225200；2. 扬州大学附属江都人民医院消化内科，扬州 225200；3. 扬州大学附属江都人民医院普通外科，扬州 225200；4. 扬州大学附属江都人民医院病理科，扬州 225200；5. 扬州大学附属江都人民医院放射科，扬州225200；6. 扬州大学附属江都人民医院检验科，扬州 225200）

摘要：利用界面自组装方法制备了具有优良均一性、稳定性和SERS活性的金银纳米梭（Au-AgNSs）基底。通过将4-巯基苯甲酸（4-MBA）修饰在Au-AgNSs基底表面，并结合癌胚抗原（CEA）的单克隆抗体，实现了Au-AgNSs基底的功能化。血清样本中CEA可被其抗体捕获并使4-MBA发生形变，导致特征峰发生偏移。经验证，该基于拉曼频移的SERS分析平台具有优异的特异性、重复性和灵敏度，对血清中CEA的检测限（LOD）低至1.22 pg/mL。利用其对胃癌（GC）患者和健康受试者血清中CEA的表达水平进行测定，并与酶联免疫吸附测定法（ELISA）结果比较。结果表明，GC患者血清CEA表达水平高于健康受试者，且2种方法结果无明显差异。因此基于拉曼频移的SERS分析平台在GC诊断中具有应用价值。

关键词：拉曼频移；表面增强拉曼散射；胃癌；早期诊断；生物标志物

中图分类号：O657.37    文献标识码：A    文章编号：1000-0720（2024）01-0009-09

Raman frequency shift-based SERS analysis platform for early diagnosis of gastric cancer

WEI Wei¹，ZHU Qunshan³，HUANG Yong¹，SHI Lixin⁶，WU Zheng³，YANG Yongguo⁴，LIU Jia²，YUAN Mengxuan⁵，WANG Zhenguang¹，JIANG Fengjuan^*2

1. Department of Gastrointestinal Surgery，Jiangdu People’s Hospital Affiliated to Yangzhou University，Yangzhou 225200，China；2. Department of Gastroenterology，Jiangdu People’s Hospital Affiliated to Yangzhou University，Yangzhou 225200，China；3. Department of General Surgery，Jiangdu People’s Hospital Affiliated to Yangzhou University，Yangzhou 225200，China；4. Department of Pathology，Jiangdu People’s Hospital Affiliated to Yangzhou University，Yangzhou 225200，China；5. Department of Radiology，Jiangdu People’s Hospital Affiliated to Yangzhou University，Yangzhou 225200，China；6. Department of Clinical Laboratory，Jiangdu People’s Hospital Affiliated to Yangzhou University，Yangzhou 225200，China）

Abstract：Au-AgNSs substrates with excellent uniformity，stability and SERS activity were prepared using an interface self-assembly strategy. The functionalization of Au-AgNSs substrates was achieved by modifying 4-mercaptobenzoic acid （4-MBA） onto the surface of Au-AgNSs substrates and binding the anti-CEA. CEA in serum samples can be captured by anti-CEA and deforms 4-MBA，resulting in a shift of the characteristic peak. The Raman frequency shift-based SERS platform was validated to have excellent specificity，reproducibility，and sensitivity，with the limit of detection （LOD） as low as 1.22 pg/mL for CEA in serum. The SERS analysis platform was applied for the determination of CEA expression levels in gastric cancer （GC） patients and healthy human，and compared with ELISA method. The results showed that the expression levels of CEA in GC patients were higher than those of healthy human，and there was no significant difference between the two methods. Therefore，the SERS platform based on Raman frequency shift is valuable in the diagnosis of GC.

Keywords：Raman frequency shift；surface-enhanced Raman scattering；gastric cancer （GC）；early diagnosis；biomarker

构建电化学适配体传感器快速检测中药材中的赭曲霉毒素A

范申，黄榕芬，毛伟伟，张红艳^*

（福建中医药大学药学院，福州 350122）

摘要：利用壳聚糖（CS）、还原氧化石墨烯（rGO）与氮掺杂多壁碳纳米管（N-MWCNTs）合成N-MWCNTs-rGO-CS复合材料，制备修饰电极，结合赭曲霉毒素A（OTA）的特异性适配体，构建高灵敏度电化学生物传感器，并用于中药中OTA的含量测定。在最优条件下，峰电流变化值与OTA浓度对数值的线性响应范围为2.3 pmol/L~2.3 nmol/L，检测限为0.53 pmol/L。应用该方法对中药饮片中OTA的含量进行加标回收实验，回收率在97.6%~103.2%之间。该方法有望用于中药材中OTA污染的快速检测。

关键词：赭曲霉毒素A；电化学适配体传感；快速检测；中药材

中图分类号：O657.1    文献标识码：A    文章编号：1000-0720（2024）01-0018-06

Construction of electrochemical aptamer sensor for rapid detection of OTA in Chinese herbal medicine

FAN Shen，HUANG Rongfen，MAO Weiwei，ZHANG Hongyan^*

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

Abstract：An electrochemical biosensor was constructed based on specific aptamer for the rapid detection of ochratoxin A （OTA） in Chinese herbal medicine. The modified electrode was prepared by N-MWCNTs-rGO-CS composites consisting of chitosan （CS），reduced graphene oxide （rGO） and nitrogen-doped multi-walled carbon nanotubes （N-MWCNTs）. Under the optimal conditions，a linear response range between the logarithm of OTA concentration and peak current change was 2.3 pmol/L-2.3 nmol/L，and the detection limit was 0.53 pmol/L. This method was used to detect the content of OTA in Chinese herbal decoction pieces，and the recoveries of the standard addition were 97.6%-103.2%. This method is expected to be used for the rapid detection of OTA in Chinese herbal medicine.

Keywords：ochratoxin A；electrochemical biosensor；rapid detection；Chinese herbal medicine

基于羧基化单壁碳纳米角的荧光传感体系检测胰蛋白酶

冯婷婷¹，闫姝竹¹，马洪志¹，杨丽霞¹，王晓华^*2

（1. 山西中医药大学中药与食品工程学院，晋中 030619；2. 桂林医学院药学院，桂林 541004）

摘要：构建了一种基于羧基化单壁碳纳米角 （oxSWCNHs）的简单、灵敏的荧光传感体系用于胰蛋白酶的检测。实验中合成了水溶性的oxSWCNHs，并设计了一段羧基荧光素（FAM）标记肽段作为胰蛋白酶的底物，该底物能与胰蛋白酶进行特异性反应。当体系中没有胰蛋白酶存在时，FAM标记的肽段可以被oxSWCNHs强烈吸附，致使体系具有较低的荧光背景；当体系中有胰蛋白酶存在时，胰蛋白酶可以与其底物肽段发生特异性水解反应，导致FAM标记的肽段水解为单个氨基酸，致使FAM远离oxSWCNHs表面，FAM荧光不能被oxSWCNHs淬灭，体系具有较强的荧光强度，从而实现荧光传感体系对胰蛋白酶的检测。该传感体系线性范围为0~2.5 μg/mL，可用于尿液中胰蛋白酶的测定。

关键词：单壁碳纳米角；荧光传感体系；胰蛋白酶

中图分类号：O657.39    文献标识码：A    文章编号：1000-0720（2024）01-0024-06

A fluorescence sensing system for the detection of trypsin based on carboxylic group-functionalized single-walled carbon nanohorns

FENG Tingting¹，YAN Shuzhu¹，MA Hongzhi¹，YANG Lixia¹，WANG Xiaohua^*2

1. College of Traditional Chinese Medicine and Food Engineering，Shanxi University of Chinese Medicine，Jinzhong 030619，China；2. Pharmacy School of Guilin Medical University，Guilin 541004，China）

Abstract：A simple fluorescent sensing system for the detection of trypsin by assembling a dye-labeled peptide with carboxylic group-functionalized single-walled carbon nanohorns （oxSWCNHs） was constructed. oxSWCNHs was prepared by nitric acid oxidation of single-walled carbon nanohorn，and the carboxyfluorescein （FAM） labeled peptide （FAM-RRRRRR） was chosen as a trypsin-sensitive core substrate，which can react specific with trypsin. Without the trypsin in the system，FAM-labeled peptide could be strongly adsorbed by oxSWCNHs，resulting in a low fluorescence background of the system. The system reacted with trypsin to cleave the peptide，resulting in the release of the dye moiety and a substantial increase in fluorescence intensity，and trypsin could be quantified accordingly. The linear range of the system was 0-2.5 μg/mL，and the method can be applied to detect trypsin in urine samples.

Keywords：single-walled carbon nanohorns；fluorescence sensing system；trypsin

基于量子点微球免疫层析法快速灵敏检测鸡肉中甲氧苄啶

谢敏¹，费丹¹，徐俊¹，赖科洋²，陈媛³，罗凯³，彭娟⁴，周瑶敏^*1

（1. 农业农村部禽类产品质量安全控制重点实验室，江西省农业科学院农产品质量安全与标准研究所，南昌 330200；2. 荷兰瓦赫宁根大学及研究中心，瓦赫宁根 6700AA；3. 江西维邦生物科技有限公司，南昌 330029；4. 南昌大学食品科学与技术国家重点实验室，南昌 330047）

摘要：建立了一种快速灵敏检测甲氧苄啶的量子点微球免疫层析法，对pH、标记抗体浓度、试纸条检测线上的抗原浓度以及试纸条结合垫上的探针体积进行了优化。通过量子点微球试纸条检测仪读取试纸条上检测线和质控线的荧光信号强度，以甲氧苄啶的浓度为横坐标，检测线和质控线荧光信号强度的比值为纵坐标，建立标准曲线。结果表明，方法定量检测范围为1~32 μg/L，半抑制率为3.3 μg/L，回收率在99.8%~117.4%之间，与12种磺胺类药物均只有不到2%的交叉反应率。该方法适合大批量样品的现场筛查。

关键词：量子点微球；甲氧苄啶；检测；免疫层析法

中图分类号：O657.6    文献标识码：A    文章编号：1000-0720（2024）01-0030-06

Quantum dots-based lateral flow assay for the rapid and sensitive detection of trimethoprim in chicken muscle

XIE Min¹，FEI Dan¹，XU jun¹，LAI Keyang²，CHEN Yuan³，LUO Kai³，PENG Juan⁴，ZHOU Yaomin^*1

1. Key Laboratory for Quality and Safety Control of Poultry Products，Ministry of Agriculture and Rural Affairs of the People's Republic of China，Institute for Quality & Safety and Standards of Agricultural Products Research，Jiangxi Academy of Agricultural Sciences，Nanchang 330200，China；2. Wageningen University and Research Centre，Wageningen 6700AA，Netherlands；3. Jiangxi Weibang Biotechnology Co.，Ltd.，Nanchang 330029，China；4. State Key Laboratory of Food Science and Technology，Nanchang University，Nanchang 330047，China）

Abstract：A method for rapid and sensitive detection of trimethoprim by the quantum dot nanobeads （QBs）-based lateral flow assay was developed. Four parameters were optimized，including pH，the concentration of antibody used for labeling，the concentration of the antigen sprayed on the test line，and the volume of antibody-QB probe on the conjugated pad. With a quantum dot strip reader，the fluorescence signal intensities of the test line （T） and control line （C） on the lateral flow strip were recorded. The standard curve was established by plotting the T/C ratio against the concentration of trimethoprim. This assay showed a good linear range from 1 to 32 μg/L and a half inhibition rate of 3.3 μg/L. The recoveries of this assay ranged from 99.8% to 117.4%，the cross-reactivity of this assay with twelve sulfonamides was less than 2%. This method could be used for screening a large batch of samples on site.

Keywords：quantum dot nanobeads；trimethoprim；detection；immunochromatography

Toehold链置换辅助智能手机比色法特异性检测废水中新冠病毒靶标RNA

张琳，张颖，宋九华，韩耀霞，杨孝容，雷欣梦，黄莉翔，徐君茹，何思仪，邱小凤，史铠^*

（乐山师范学院新能源材料与化学学院，乐山 614000）

摘要：基于Toehold介导的链置换反应（TSDR）与DNA酶，构建了一个强特异性及低成本检测废水中SARS-CoV-2靶标RNA单碱基突变的比色生物传感器。SARS-CoV-2靶标RNA与双链DNA（dsDNA）引发TSDR，释放出完整的G-四链体序列并与氯化血红素（Hemin）结合，形成G-四链体/Hemin DNA酶，进而催化双氧水氧化3，3’，5，5’-四甲基联苯胺，使溶液呈蓝色。当SARS-CoV-2靶标RNA存在单碱基突变时，TSDR被抑制，导致裸眼观察到的溶液颜色与未突变异的靶标相比更浅。同时采用智能手机摄像头捕捉溶液的RGB值变化（ΔRGB），对裸眼观察结果的准确性进行验证。在最优条件下，构建的比色生物传感器能够特异性识别单个碱基突变的SARS-CoV-2靶标RNA，具有用于废水中SARS-CoV-2变异毒株检测的潜力。

关键词：新冠病毒靶标RNA；Toehold链置换；智能手机；废水

中图分类号：O654.2    文献标识码：A    文章编号：1000-0720（2024）01-0036-06

Toehold-mediated strand displacement reaction assisted smart phone colorimetry for specific detection of SARS-CoV-2 RNA in wastewater

ZHANG Lin，ZHANG Ying，SONG Jiuhua，HAN Yaoxia，YANG Xiaorong，LEI Xinmeng，HUANG Lixiang，XU Junru，HE Siyi，QIU Xiaofeng，SHI Kai^*

College of New Energy Materials and Chemistry，Leshan Normal University，Leshan 614000，China）

Abstract：A colorimetric biosensor based on toehold-mediated strand displacement reaction （TSDR） and DNAzyme with high specificity and low cost was constructed to detect single base mutation of SARS-CoV-2 target RNA in wastewater. The SARS-CoV-2 target RNA could bind to the toehold region of the DNA1/DNA2 duplex，and displace the DNA1 through TSDR，followed by liberating the pre-blocked G-quadruplex sequence，which could associate with Hemin to form G-quadruplex/Hemin DNAzyme. Subsequently，the G-quadruplex/Hemin DNAzyme could catalyze H₂O₂ to oxide the TMB efficiently，and change the colorless solution to be blue. However，the TSDR procedure could be inhibited when a single base was mutational in the target RNA. This resulted in a lighter color of the solution. Meanwhile，a smartphone was employed to capture the change of RGB value of the solution to verify the accuracy of the measurement results. Under the optimal conditions，the developed biosensor could specifically identify SARS-CoV-2 target RNA with a single base mutation，and has an application prospect for the detection of SARS-CoV-2 variants in wastewater.

Keywords：SARS-CoV-2 target RNA；toehold-mediated strand displacement；smart phone；wastewater

己烯雌酚分子印迹聚合物的合成及吸附性

才旭红¹，刘俊渤^*1，唐珊珊²，梁大栋¹，靳瑞发³

（1. 吉林农业大学资源与环境学院，长春 130118；2. 秸秆综合利用与黑土保护教育部重点实验室，吉林农业大学生命科学学院，长春 130118；3. 赤峰学院化学化工学院，赤峰 024000）

摘要：以己烯雌酚（DES）为印迹分子，甲基丙烯酸（MAA）为功能单体，采用沉淀聚合法制备了DES分子印迹聚合物（DES-MIPs）。采用密度泛函理论LC-ωPBE/6-31G（d，p）方法，模拟优化DES 和MAA作用的摩尔比例，并考察了DES印迹作用的机理。通过静态吸附、动态吸附、选择吸附、竞争吸附方法考察了DES-MIPs的亲和性与选择性。结果表明：DES与MAA之间通过氢键相互作用，当DES与MAA摩尔比为1∶5时，形成DES-MAA有序排列的复合物氢键数目最多（9），结合能最低（-146.62 kJ/mol）。该条件下制备的DES-MIPs对DES的最大吸附量为60.17 mg/g，且其动力学吸附符合准二级动力学模型。在一元及二元吸附体系中，DES-MIPs对DES都具有优异的选择吸附性。

关键词：己烯雌酚；甲基丙烯酸；分子印迹聚合物；模拟；吸附性

中图分类号：O641.3    文献标识码：A    文章编号：1000-0720（2024）01-0042-09

Study on synthesis and adsorbability of diethylstilbestrol molecularly imprinted polymers

CAI Xuhong¹，LIU Junbo^*1，TANG Shanshan²，LIANG Dadong¹，JIN Ruifa³

1. College of Resource and Environment，Jilin Agricultural University，Changchun 130118，China；2. Key Laboratory of Straw Comprehensive Utilization and Black Soil Conservation，The Ministry of Education，College of Life，Jilin Agricultural University，Changchun 130118，China；3. College of Chemistry and Chemical Engineering，Chifeng University，Chifeng 024000，China）

Abstract：Diethylstilbestrol （DES） and methacrylic acid （MAA） were respectively empolyed as the imprinting molecule and functional monomer to prepare the DES molecularly imprinted polymers （DES-MIPs）using precipitation polymerization method. The molar ratio of DES to MAA was simulated and optimized using LC-ωPBE/6-31G（d，p） methodm and the imprinting action was explored. The affinity and selectivity of DES-MIPs were analyzed by static adsorption，dynamic adsorption，selective adsorption，and competitive adsorption. The results showed that DES interacts with MAA through hydrogen bonds. When the molar ratio of DES to MAA was 1∶5，the formed DES-MAA ordered complex possessed the largest amount of hydrogen bonds （9） and the lowest binding energy （-146.62 kJ/mol）. The maximum adsorption capacity of DES-MIPs to DES was about 60.17 mg/g under the present condition. The adsorption of DES-MIPs to DES is consistent with the quasi-secondary kinetic model. The selective adsorption of DES-MIPs to DES are excellent both in single and binary adsorption systems.

Keywords：diethylstilbestrol；methacrylic acid；molecularly imprinted polymers；simulation；adsorption property

超高效液相色谱-串联质谱法测定化妆品中5种免疫抑制剂

吴姣娇¹，刘玉玲¹，涂晓琴¹，殷帅¹，李启艳²，黄海萍^*1

（1. 湖南省药品检验检测研究院，湖南省药品质量评价工程技术研究中心，长沙 410001；2. 山东省食品药品检验研究院，济南 250101）

摘要：建立并验证了超高效液相色谱-串联质谱法（UHPLC-MS）同时测定化妆品中他克莫司、吡美莫司、依维莫司、西罗莫司、环孢菌素A这5种免疫抑制剂的方法。样品采用甲醇超声提取，Atlantis dC18 （100 mm× 2.1 mm，2 μm）色谱柱分离，0.1%乙酸-5 mmol/L乙酸铵水溶液和0.1%乙酸-5 mmol/L乙酸铵甲醇溶液为流动相，多反应监测模式下测定，外标法定量。结果表明，这5种免疫抑制剂在0.5~100 ng/mL浓度范围内线性关系良好，方法检出限均低于10 ng/g，在不同化妆品基质中低、中、高3个浓度水平的加标回收率为93.3%~117.4%，相对标准偏差（RSD）为0.4%~7.5%。日内RSD为2.4%~8.4%，日间RSD为3.9%~26%。该方法弥补了化妆品中非法添加违禁物质检测方法的缺失，为化妆品日常监管提供技术支撑。

关键词：免疫抑制剂；化妆品；超高效液相色谱-串联质谱

中图分类号：TQ658.2    文献标识码：A    文章编号：1000-0720（2024）01-0051-06

Quantitative determination of five immunosuppressants in cosmetics by ultra high-performance liquid chromatography-tandem mass spectrometry

WU Jiaojiao¹，LIU Yuling¹，TU Xiaoqin¹，YIN Shuai¹，LI Qiyan²，HUANG Haiping^*1

1. Hunan Institute for Drug Control，Hunan Engineering & Technology Research Center for Pharmaceutical Quality Evaluation，Changsha 410001，China；2. Shandong Institute for Food and Drug Control，Jinan 250101，China）

Abstract：An ultra high-performance liquid chromatography-tandem mass spectrometry （UHPLC-MS/MS） method for simultaneous determination of five immunosuppressants in cosmetics，including tacrolimus，pimeclimus，everolimus，sirolimus and cyclosporine A，was established and verified. The samples were ultrasound extracted by methanol and separated by an Atlantis dC18 column （100 mm×2.1 mm，2 μm）. The mobile phases were 0.1% acetic acid-5 mmol/L ammonium acetate solution and 0.1% acetic acid-5 mmol/L ammonium acetate methanol solution. The target components were quantified by external standard method under positive ion electrospray ionization and multiple reaction monitoring （MRM） mode. The results showed that the five immunosuppressants had good linear relationships in the concentration ranges of 0.5-100 ng/mL，and the detection limits were all lower than 10 ng/g. The recoveries of the five immunosuppressants at three levels of low，medium and high concentrations in different cosmetic substrates were 93.3%-117.4% and the relative standard deviations （RSDs） were 0.4%-7.5%. The intra-day RSDs were 2.4%-8.4%，and the inter-day RSDs were 3.9%-26%. The method makes up for the lack of detection methods for illegal additives in cosmetics，and provides technical support for the daily supervision of cosmetics.

Keywords：immunosuppressant；cosmetics；ultra high-performance liquid chromatography-tandem mass spectrometry

新型靛红腙类合成大麻素质谱裂解规律研究

范一雷¹，陈显鑫²，薛锦锋³，吴昊⁴，柯星¹，徐雨^*2

（1. 浙江省毒品防控技术研究重点实验室，浙江警察学院，杭州 310053；2. 浙江省禁毒和毒情监测关键技术研究重点实验室，国家毒品实验室浙江分中心，杭州 310053；3. 嘉兴市公安局，嘉兴 314015；4. 浙江迪安司法鉴定中心，杭州 310007）

摘要：研究了新型靛红腙类合成大麻素在电子轰击（EI）和电喷雾（ESI）电离模式下的质谱裂解规律，并建立了可疑物中该类合成大麻素的鉴定方法。采用气相色谱-质谱联用（GC-MS）和液相色谱-高分辨质谱联用（LC-Q-Orbitrap/MS）技术，对5种新型靛红腙类合成大麻素（MDA-19 （BZO-HEXOXIZID），5C-MDA-19 （Pentyl MDA-19，BZO-POXIZID），CHM-MDA-19 （BZO-CHMOXIZID），4en-pentyl MDA-19 （BZO-4en-POXIZID），5F-MDA-19 （5F-BZO-POXIZID））的主要碎片离子和碎裂过程进行分析，并对获得的质谱图进行解析，推测该类合成大麻素的EI-MS及ESI-MSⁿ碎裂规律。EI-MS可获得比ESI-MSⁿ更多的碎片离子用于该类合成大麻素的结构推断。碎片离子6，7和8对应的质荷比（m/z）118 （C₈H₈N⁺），132 （C₈H₆NO⁺）和146 （C₈H₆N₂O^?+）为2-氧代吲哚母核的特征碎片离子。经酰胺键断裂（碎裂途径i）生成碎片离子1（m/z 105，C₇H₅O⁺），以及通过腙键及N1与侧链之间发生断裂（碎裂途径iv）生成碎片离子8（m/z 146，C₈H₆N₂O^?+），可用于确定该类合成大麻素N8'位上取代基和N1末端取代侧链。本研究阐述了5种新型靛红腙类合成大麻素的质谱裂解规律，并根据获得的质谱裂解规律建立了可疑物中该类合成大麻素的鉴定方法，为其快速结构鉴定提供依据。

关键词：靛红腙类合成大麻素；质谱裂解规律；快速筛查；电子轰击质谱；电喷雾质谱

中图分类号：O657.31；X832    文献标识码：A    文章编号：1000-0720（2024）01-0057-07

Investigation of mass spectrometry-based fragmentation patterns of new “OXIZID” synthetic cannabinoids

FAN Yilei¹，CHEN Xianxin²，XUE Jinfeng³，WU Hao⁴，KE Xing¹，XU Yu^*2

1. Key Laboratory of Drug Prevention and Control Technology of Zhejiang Province，Zhejiang Police College，Hangzhou 310053，China；2. Key Laboratory of Drug Monitoring and Control of Zhejiang Province，National anti-Drug Laboratory Zhejiang Regional Center，Hangzhou 310053，China；3. Jiaxing Public Security Bureau，Jiaxing 314015，China；4. Zhejiang Dian Regional Forenic Science Institute，Hangzhou 310007，China）

Abstract：The mass spectrometry-based fragmentation patterns of new “OXIZIDs” （N-alkylisatin-acylhydrazones） synthetic cannabinoids under electron ionization （EI） and electrospray ionization （ESI） modes were investigated，and the identification method for this kind of synthetic cannabinoids in the suspicious material was developed. Gas chromatography-mass spectrometry （GC-MS） and liquid chromatography high-resolution mass spectrometry （LC-Q-Orbitrap/MS） were used to analyze five new “OXIZID”synthetic cannabinoids，including MDA-19 （BZO-HEXOXIZID），5C-MDA-19 （Pentyl MDA-19，BZO-POXIZID），CHM-MDA-19 （BZO- CHMOXIZID），4en-pentyl MDA-19 （BZO-4en-POXIZID） and 5F-MDA-19 （5F-BZO-POXIZID. The obtained mass spectra of EI-MS and ESI-MSⁿ were analyzed and the fragmentation patterns of “OXIZID” synthetic cannabinoids were speculated. The results showed that the EI-MS could obtain more fragment ions than that of the ESI-MSⁿ for structural identification of “OXIZID”synthetic cannabinoids. The fragment ions 6，7 and 8 correspond to mass-to-charge ratios of 118 （C₈H₈N⁺），132 （C₈H₆NO⁺） and 146 （C₈H₆N₂O^?+），respectively，which are characteristic fragment ions of the 2-oxoindole parent nucleus. Fragment ions 1 （m/z 105，C₇H₅O⁺） and 8 （m/z 146，C₈H₆N₂O^?+），generated through the cleavage of amide bond （fragmentation pathway i），hydrazone bonds and the bond between N1 and side chains （fragmentation pathway iv），respectively，can be applied to infer the N8' position substituent and the N1 terminal substitution side chain of “OXIZID” synthetic cannabinoids. The results elucidated the mass spectrometry fragmentation patterns of new “OXIZID” synthetic cannabinoids. And the identification method for this kind of synthetic cannabinoids in the suspicious material was developed based on the obtained EI-MS and ESI-MSⁿ fragmentation patterns of “OXIZID”synthetic cannabinoids，which could provide a basis for their rapid structural identification their.

Keywords：“OXIZID”synthetic cannabinoids；fragmentation patterns；rapid screen；EI-MS；ESI-MSⁿ

聚β-环糊精修饰电极零流电位法检测氯吡脲

马明明^*1，何成毅²，史帅¹，崔淑慧¹，刘佳¹

（1. 西安工程大学环境与化学工程学院，西安 710048；2. 西安市农产品质量安全检验监测中心，西安 710077）

摘要：采用电聚合方法，在多壁碳纳米管修饰的铅笔芯电极（MWCNT-PEC）表面制备聚β-环糊精-氯吡脲（CPPU）复合材料（P-β-CD-CPPU），并对其结构和形貌进行表征。结果表明，含有CPPU分子残留活性点的P-β-CD-CPPU拥有较大筒腔结构，能重新包合识别CPPU分子，据此建立了P-β-CD-CPPU修饰电极零流电位法检测CPPU的新方法。考察了影响P-β-CD-CPPU重新包合CPPU前后零流电位差值变化的条件。在优化条件下，修饰电极的零流电位与CPPU浓度在0.5~50 μmol/L范围内成正比，CPPU的检出限为21.4 nmol/L。CPPU体系可能共存的有机物及金属离子均不干扰测定；同一根修饰电极对同一浓度CPPU零流电位测定值在14 d内的相对标准偏差（RSD）为2.0%；5根不同批次修饰电极的零流电位测定值的RSD为1.7%。应用本方法检测实际猕猴桃样品中CPPU残留浓度，平均回收率为102.7%~109.1%，与液相色谱-质谱联用法检测结果基本一致。

关键词：氯吡脲；零流电位法；β-环糊精；电聚合；超分子识别

中图分类号：O657.1；O625.63    文献标识码：A    文章编号：1000-0720（2024）01-0064-06

Determination of forchlorfenuron by zero current potentiometry using poly-β-cyclodextrin modified electrode

MA Mingming^*1，HE Chengyi²，SHI Shuai¹，CUI Shuhui¹，LIU Jia¹

1. School of Environmental and Chemical Engineering，Xi’an Polytechnic University，Xi’an 710048，China；2. Center for Quality and Safety Inspection and Testing of Agricultural Products of Xi’an City，Xi’an 710077，China）

Abstract：Poly β-cyclodextrin-forchlorfenuron composite （P-β-CD-CPPU） was prepared using electropolymerization on the surface of a pencil core electrode modified by multiwalled carbon nanotubes （MWCNT-PEC）. The structure and surface morphology were characterized. The results showed that P-β-CD-CPPU has a much larger tube structure with active sites of forchlorfenuron residue，which could recognize and include forchlorfenuron again. A new method for the determination of forchlorfenuron was established based on this mechanism. All conditions for the detection of forchlorfenuron with the P-β-CD-CPPU modified electrode were investigated. Under the optimal conditions，the zero potential of the modified electrode had a linear relationship with forchlorfenuron concentrations in the range of 0.5-50 μmol/L. The detection limit was 21.4 nmol/L. The possible coexisting organic compounds and metal ions in the CPPU system did not interfere with the determination. The relative standard deviation （RSD） of the zero current potential of the same CPPU concentration was 2.0% during 14 d for the same modified electrode，indicating that the stability of the modified electrode was good. The RSD of five different batches electrodes was 1.7%，suggesting that the reproducibility of this electrode was excellent. This method was used to detect the remaining concentration of forchlorfenuron in real kiwifruit samples with average recoveries ranging from 102.7% to 109.1%，which was basically in agreement with that of liquid chromatography mass spectrometry methods.

Keywords：forchlorfenuron；zero current potentiometry；β-cyclodextin；electropolymerization；supramolecular recognition

气相色谱-串联质谱法测定花椒中106种农药残留及膳食暴露风险评估

陈敏，尹全，邓强，刘茜，张义蓉，杨晓凤^*

（四川省农业科学院农业质量标准与检测技术研究所，成都 610066）

摘要：建立了固相萃取结合气相色谱-串联质谱（GC-MS/MS）测定花椒中106种农药残留量的方法。采用多反应监测（MRM）模式检测，基质匹配标准曲线法定量。结果表明：106种农药的定量限（LOQ）范围为0.010~0.10 mg/kg，且在定量限~1.0 mg/L范围内线性关系良好，线性相关系数R²≥0.99。106种农药的平均加标回收率在60.8%~118.6%之间，相对标准偏差（RSD）在0.79%~19%之间。将该方法用于53批次市售花椒样品的筛查，结果检出21种农药残留，其中有最大残留限量值（MRL）的农药有9种，无MRL值的农药有12种。无MRL值的农药慢性膳食摄入风险值（ADI）为0.002%~0.343%，12种农药ADI总计为1.03%，花椒中农药残留的膳食摄入风险较低。

关键词：气相色谱-串联质谱；花椒；固相萃取；农药多残留；膳食风险评估

中图分类号：TS207.5；O657.63    文献标识码：A    文章编号：1000-0720（2024）01-0070-09

Determination of 106 pesticide residues by gas chromatography-tandem mass spectrometry and dietary exposure risk assessment in Chinese prickly ash

CHEN Min，YIN Quan，DENG Qiang，LIU Qian，ZHANG Yirong，YANG Xiaofeng^*

Institute of Quality and Testing Technology for Agro-products of Sichuan Academy of Agricultural Sciences，Chengdu 610066，China）

Abstract：A method for the determination of 106 pesticide residues in Chinese prickly ash by solid phase extraction （SPE） combined with gas chromatography-tandem mass spectrometry （GC-MS/MS）was developed. The samples were detected by multiple-reaction monitoring scanning and quantified using the matrix-matched standard calibration method. The results showed that the limits of quantification（LOQs） of 106 pesticides ranged from 0.010 to 0.10 mg/kg. There were good linear relationships in the range of LODs-1.0 mg/L，with the correlation coefficients R²≥0.99. The average recoveries for the 106 pesticides at three spiked levels were 60.8%- 118.6%，and the relative standard deviations （RSDs） were between 0.79% and 19%. The method was applied to the screening of 53 sample batches，the results showed that 21 pesticide residues were detected，including 9 kinds with maximum residue limits （MRLs） for pesticides and 12 kinds without MRLs. The chronic dietary intake risk （ADI） was 0.002%-0.343%，and the total ADI of 12 pesticides was 1.03%，so the dietary intake risk of pesticide residues in Chinese prickly ash was low.

Keywords：gas chromatography-tandem mass spectrometry；Chinese prickly ash；solid phase extraction；pesticide multi-residue；dietary intake risk assessment

银纳米粒子修饰半导体薄膜SERS基底的仿真研究

鲍士仟，李东明，马成举^*，张跃斌，李咪，金嘉升，张垚，张贻歆，刘洺，刘芊震

（西安石油大学理学院，西安 710065）

摘要：设计了一种银纳米粒子（Ag NPs）修饰的半导体薄膜锗（Ge）表面增强拉曼散射（SERS）基底。利用时域有限差分（FDTD）方法仿真分析了该SERS基底的消光光谱、局域电场和SERS特性，考察了Ag NPs半径和Ge薄膜厚度对SERS基底拉曼散射信号增强的影响。对比分析了硅（Si）、砷化镓（GaAs）、砷化铟（InAs）和Ge薄膜对SERS基底拉曼散射信号增强的影响。研究发现：Ag NPs半径和半导体介电常数都会影响SERS基底拉曼散射信号的增强。通过计算发现，在半导体薄膜厚度为10 nm时，Ag NPs/Ge薄膜SERS基底在633 nm入射光激发下产生的增强因子（EF）高达7.02×10⁷，对拉曼散射信号的增强作用最佳。

关键词：银纳米粒子；半导体；时域有限差分法；局域电场；增强因子

中图分类号：O433.4    文献标识码：A    文章编号：1000-0720（2024）01-0079-07

Simulation study on semiconductor film SERS substrate modified by silver nanoparticles

BAO Shiqian，LI Dongming，MA Chengju^*，ZHANG Yuebin，LI Mi，JIN Jiasheng，ZHANG Yao，ZHANG Yixin，LIU Ming，LIU Qianzhen

School of Science，Xi'an Shiyou University，Xi’an 710065，China）

Abstract：A kind of silver nanoparticles （Ag NPs） modified semiconductor germanium （Ge） film was designed as the surface-enhanced Raman scattering （SERS） substrates. The extinction spectra，local electric fields and SERS properties of the SERS substrates were simulated and analyzed by the finite difference time domain （FDTD） method. The influence of the radius of Ag NPs and the thickness of Ge film on the enhancement of Raman scattering signal of the SERS substrate was discussed. The influence of different film materials including silicon （Si），gallium arsenide （GaAs），indium arsenide （InAs），and Ge film on the enhancement of Raman scattering signal of the SERS substrate was further analyzed. It was found that both the radius of Ag NPs and the dielectric constant of semiconductor had effects on the enhancement of Raman scattering signal of the SERS substrate. It was found that when the semiconductor Ge film thickness was 10 nm，the SERS substrate of Ag NPs/Ge film under the excitation of 633 nm incident light had the high enhancement factor （EF） of 7.02×10⁷，which provided the best enhancement effect on Raman scattering signal.

Keywords：silver nanoparticles；semiconductor；finite difference time domain method；local electric field；enhancement factor

基于金纳米粒子探针比色法检测乙基谷硫磷

张亚莉¹，田璐肖²，徐鑫林¹，王未肖¹，哈婧^*2

（1. 河北科技大学理学院，石家庄 050018；2. 河北科技大学化学与制药工程学院，石家庄 050018）

摘要：基于乙基谷硫磷在酸性条件下可以诱导金纳米粒子（AuNPs）发生聚集，建立了以AuNPs为探针、结合比色和分光光度法检测乙基谷硫磷的方法。通过改变氯金酸和还原剂柠檬酸钠的比例，制备了不同粒径的AuNPs。酸性溶液中乙基谷硫磷分子中-P=S键发生质子化，形成的-SH与Au形成S-Au键，使AuNPs发生聚集，溶液颜色由红色转变为蓝色。考察了乙酸-乙酸钠缓冲溶液的pH和浓度以及乙基谷硫磷与AuNPs的作用时间对AuNPs聚集程度的影响。在优化条件下，吸光度比值（A_{694 nm}/A_{524 nm}）与乙基谷硫磷浓度在0.392~0.603 μmol/L范围内具有良好的线性关系，检出限为0.0782 μmol/L。

关键词：金纳米粒子；乙基谷硫磷；比色法；分光光度法；聚集

中图分类号：TQ131；G642    文献标识码：A    文章编号：1000-0720（2024）01-0086-05

Colorimetric detection of ethyazinphos-methyl based on gold nanoparticle probes

ZHANG Yali¹，TIAN Luxiao²，XU Xinlin¹，WANG Weixiao¹，HA Jing^*2

1. College of Sciences，Hebei University of Science and Technology，Shijiazhuang 050018，China；2. College of Chemical & Pharmacetical Engineering，Hebei University of Science and Technology，Shijiazhuang 050018，China）

Abstract：Based on the aggregation of gold nanoparticles （AuNPs） induced by ethyazinphos-methyl under acidic conditions，a new method for the detection of ethyazinphos-methyl using AuNPs as a probe combined with colorimetric and Uv-visible spectrophotometry was developed. AuNPs of different sizes were prepared by varying the ratio of sodium citrate to chloroauric acid. The -P=S bond was protonated in ethyl azinphos-methyl in acidic solution，the produced -SH formed an S-Au bond with Au，causing AuNPs aggregation and the color of the solution changed from red to blue. The effects of pH and concentration of acetic acid-sodium acetate buffer solution，and the interaction time between ethyazinphos-methyl and AuNPs were investigated. There was a good linear relationship between the absorbance ratio （A_{694 nm}/A_{524 nm}） and the concentration of ethyl azinphos-methyl in the range of 0.392-0.603 μmol/L，and the detection limit was 0.0782 μmol/L.

Keywords：gold nanoparticles；azinphos-ethyl；colorimetry；spectrophotometry；aggregate

基于ZIF-8电化学传感器构建及用于检测饮料中新橙皮苷二氢查耳酮

张亮¹，徐俊晖¹，王亚珍^*1，2

（1. 江汉大学光电材料与技术学院，武汉 430056；2. 湖北省健康代糖产品企校联合创新中心，武汉 430056）

摘要：采用电泳沉积法，成功在玻碳电极（GCE）表面制备了一层ZIF-8材料薄膜，再在其表面滴涂一层全氟化树脂溶液（Nafion），形成ZIF-8/Nafion复合膜，用于构建检测高倍甜味剂新橙皮苷二氢查耳酮（NHDC）的电化学传感器。利用电化学交流阻抗（EIS）技术对该传感器进行表征，采用循环伏安法（CV）研究NHDC在ZIF-8/Nafion电极表面的电化学行为，并优化实验条件。NHDC在ZIF-8/Nafion膜上有灵敏的响应。采用差分脉冲伏安法（DPV）建立了定量检测NHDC的方法，方法线性范围为0.16~160 μmol/L，检出限为56 nmol/L。该方法检测饮料中NHDC的加标回收率范围为99.0%~101.3%。

关键词：ZIF-8；电泳沉积法；新橙皮苷二氢查耳酮（NHDC）；电化学传感器

中图分类号：TS207.3；O657.1    文献标识码：A    文章编号：1000-0720（2024）01-0091-07

Construction of ZIF-8 based electrochemical sensor for the detection of neohesperidin dihydrochalcone in beverage

ZHANG Liang¹，XU Junhui¹，WANG Yazhen^*1，2

1. School of Optoelectronic Materials and Technology，Jianghan University，Wuhan 430056，China；2. Hubei Enterprise-College Joint Innovation Center of Healthy Sugar Substitute Product，Wuhan 430056，China）

Abstract：The electrophoretic deposition method was used to prepare ZIF-8 film on the surface of glassy carbon electrode （GCE），then an amount of perfluorinated resin solution （Nafion） was dropped on the surface of ZIF-8 modified GCE，and thus a ZIF-8/Nafion composite film modified electrode（ZIF-8/Nafion GCE） was obtained and an electrochemical sensor for the high concentration of sweetener neohesperidin dihydrochalcone （NHDC） was constructed. The sensor was electrochemically characterized by electrochemical impedance spectroscopy （EIS），the electrochemical behavior of NHDC on the surface of the ZIF-8/Nafion GCE electrode was investigated，and the experimental conditions were optimized by using the cyclic voltammetry （CV） method. The sensor evinced a sensitive response to NHDC on the ZIF-8/Nafion GCE electrode. Differential pulse voltammetry （DPV） method was used to establish a quantitative detection method for NHDC with a linear range of 0.16-160 μmol/L and a detection limit of 56 nmol/L. The spiked recoveries of this method for the detection of NHDC in beverages were 99.0%-101.3%.

Keywords：ZIF-8；electrophoretic deposition；neohesperidin dihydrochalcone （NHDC）；electrochemical sensor

八面体二氧化铈负载金纳米粒子的电化学传感器检测邻氨基苯酚

黄青¹，诸葛文凤¹，凌晨东²，张翠忠¹，向刚¹，彭金云^*1，黄海冰¹

（1. 广西民族师范学院化学与生物工程学院，光电化学传感与区域环境分析实验室，崇左 532200；2. 中国-泰国崇左产业园管理委员会，崇左 532200）

摘要：采用原位生长法制备了八面体二氧化铈（CeO₂）负载金纳米粒子（Au NPs）复合材料Au NPs@ CeO₂，用扫描电镜及能量色散X射线光谱仪对复合材料进行形貌表征与元素分析。利用此复合材料修饰玻碳电极，构筑了一种邻氨基苯酚电化学传感器。CeO₂性质稳定，其八面体结构提供了较大的比表面积，Au NPs具备极佳的导电性，二者复合协同发挥良好的电催化能力。研究发现，Au NPs@CeO₂复合材料修饰电极对邻氨基苯酚表现出较高的检测灵敏度，在优化实验条件下，邻氨基苯酚浓度与氧化峰电流成正比，在1.00×10^-7~3.38×10^-5 mol/L浓度范围内呈现2段较好的线性关系，线性回归方程分别为I₁（A）=3.29×10^-2c（mol/L）+1.08×10^-8 （R=0.9967）和I₂（A）=1.32×10^-2c（mol/L）+1.22×10^-7 （R=0.9956），检出限（LOD）为1.16×10^-8 mol/L。该电化学传感器用于实际样品中邻氨基苯酚的测定，回收率为98.0%~105.3%，相对标准偏差为0.9%~3.1%。

关键词：二氧化铈；金纳米粒子；电化学传感器；邻氨基苯酚

中图分类号：O657.1    文献标识码：A    文章编号：1000-0720（2024）01-0098-06

An electrochemical sensor based on the octahedral cerium dioxide-loaded gold nanoparticles for the detection of o-aminophenol

HUANG Qing¹，ZHUGE Wenfeng¹，LING Chendong²，ZHANG Cuizhong¹，XIANG Gang¹，PENG Jinyun^*1，HUANG Haibing¹

1. Photochemical Sensing and Regional Environmental Analysis Laboratory，Chemical and Biological Engineering College，Guangxi Normal University for Nationalities，Chongzuo 532200，China；2. China- Thailand Chongzuo Industrial Park Management Committee，Chongzuo 532200，China）

Abstract：The composite of octahedral cerium dioxide-loaded gold nanoparticles （Au NPs@CeO₂） was prepared by the in-situ growth method. The morphology and elemental analysis of the composite were characterized by scanning electron microscope and energy dispersion X-ray spectrometer. An o-amino phenol electrochemical sensor was constructed by using the composite modified glass carbon electrode. The octahedral cerium dioxide （CeO₂） has the advantages of stable chemical property and a large specific surface area. It has excellent electrocatalytic performance in combination with gold nanoparticles （Au NPs）. It was found that Au NPs@CeO₂ modified electrode showed high detection sensitivity to o-aminophenol. Under the optimal experimental conditions，the concentration of o-aminophenol was proportional to the oxidation peak current，and there were two good linear relationships between the concentration of o-aminophenol and the oxidation peak current in the range of 1.00×10^-7-3.38×10^-5 mol/L. The linear regression equations were I₁（A）=3.29×10^-2c（mol/L）+1.08×10^-8 （R=0.9967） and I₂（A）=1.32×10^-2c（mol/L）+1.22×10^-7 （R=0.9956），respectively. The detection limit （LOD） was 1.16×10^-8 mol/L. The electrochemical sensor could be used for rapid detection of o-aminophenol in real samples，the recoveries of o-aminophenol were 98.0%-105.3%，and the relative standard deviations were 0.9%-3.1%.

Keywords：cerium dioxide；gold nanoparticles；electrochemical sensor；o-aminophenol

基于低共熔溶剂的分散液液微萃取-高效液相色谱法测定环境水样和饮料中的柯依定、金胺O和罗丹明B

于洋，曹天荟，罗安梦，高树林^*，葛丹丹

（昆明学院化学化工学院，昆明 650214）

摘要：建立了基于低共熔溶剂的涡旋辅助分散液液微萃取-高效液相色谱联用检测柯衣定、金胺O和罗丹明B的方法。以香芹酚为氢键给体，薄荷醇、正癸酸或正辛酸为氢键受体，制备疏水性低共熔溶剂（DESs）并作为萃取溶剂。采用红外光谱（FT-IR）和量子化学计算研究DESs的形成机理。对DESs组成、萃取溶剂体积、萃取时间、溶液pH和盐浓度等实验条件进行了优化。在最优化条件下，柯衣定、金胺O和罗丹明B在5~1000 ng/mL范围内线性关系良好，相关系数均大于0.9950，检出限和定量限分别为1.0~1.5 ng/mL和3.5~4.7 ng/mL。模拟计算研究表明，DESs萃取3种合成色素的主要作用力是氢键和静电相互作用力。将所建立的方法用于检测环境水样和饮料样品中的金胺O、罗丹明B和柯衣定，加标回收率为85.7%~106.8%，相对标准偏差为0.2%~7.7%。

关键词：疏水性低共熔溶剂；模拟计算；合成色素；分散液-液微萃取；高效液相色谱法

中图分类号：O661.1    文献标识码：A    文章编号：1000-0720（2024）01-0104-07

Determination of chrysoidin，auramine O and rhodamine B in environmental water and beverage by deep eutectic solvents based dispersive liquid-liquid microextraction combined with high performance liquid chromatography

YU Yang，CAO Tianhui，LUO Anmeng，GAO Shulin^*，GE Dandan

School of Chemistry and Chemical Engineering，Kunming University，Kunming 650214，China）

Abstract：A vortex-assisted liquid-liquid microextraction method combined with high performance liquid chromatography-diode array detector was established for the determination of chrysoidin，auramine O and rhodamine B in environmental water and beverage. The water-immiscible deep eutectic solvents （DESs） were prepared using carvacrol as hydrogen-bonding donor and menthol，n-decanoic acid or n-octanoic acid as hydrogen-bonding acceptor at different molar ratios，and the DESs were used as extraction solvents. The formation mechanism of DESs was investigated using Fourier transform infrared spectroscopy （FT-IR） and quantum chemical calculations. Several parameters influencing the extraction efficiencies of synthetic dyes including types of DESs，volume of extraction solvent，extraction time，pH of solution and salt concentration were optimized. Under the optimum conditions，synthetic dyes can be determined in the range of 5.0-1000 ng/mL with the coefficient higher than 0.9950. Limits of detection of the method ranged from 1 to 1.5 ng/mL and limits of quantification were in a range of 3.5-4.7 ng/mL. The possible interactions of DESs with synthetic dyes were investigated by computational modeling. The results revealed that hydrogen bonds and electrostatic interactions were the main driving forces for the extraction of synthetic dyes. The proposed method was applied to determine the synthetic dyes in environmental water and beverage with the recoveries in the range of 85.7%-106.8% and the relative standard deviations （RSDs） between 0.2%-7.7%.

Keywords：hydrophobic deep eutectic solvents；computational modeling；synthetic dyes；dispersive liquid-liquid microextraction；high performance liquid chromatography

用于磁珠法核酸提取的微流控芯片及自动化平台

刘晨曦，姚延禄，周新丽^*

（上海理工大学健康科学与工程学院，上海 200093）

摘要：基于磁珠法核酸提取原理，设计并制作出旋转驱动式核酸提取微流控芯片及自动化平台。微流控芯片包括裂解腔、清洗腔以及洗脱腔等结构，步进电机带动微流控芯片旋转，通过电磁铁吸附微流控芯片内的磁珠，实现磁珠在各腔室转移，完成核酸提取和纯化。对芯片表面疏水性、磁力大小、磁珠分散程度以及核酸洗脱时间进行优化。结果表明，当磁力大小为250 N时，可实现磁珠转移；磁铁放置于芯片上方1 mm时，腔室内磁珠分散程度最好。洗脱时间为20 min时，芯片上提取大肠杆菌的核酸浓度较高。微流控芯片与磁珠核酸提取技术相结合提取的核酸样本，可直接应用于后续聚合酶链式反应扩增环节，有利于实现核酸自动提取及扩增的一体化。

关键词：微流控技术；核酸提取；磁珠法；自动化提取

中图分类号：R331    文献标识码：A    文章编号：1000-0720（2024）01-0111-07

Microfluidic chip and automation platform for nucleic acid extraction by magnetic bead method

LIU Chenxi，YAO Yanlu，ZHOU Xinli^*

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

Abstract：Based on the principle of magnetic bead method for nucleic acid extraction，a rotary-driven  microfluidic chip and an automation platform were designed and manufactured. The microfluidic chip includes a lysis chamber，a cleaning chamber and an elution chamber. The stepping motor drives the microfluidic chip to rotate. The magnetic beads in the microfluidic chip are adsorbed by the electromagnet to realize the transfer of the magnetic beads between each chamber. In this way，nucleic acid extraction and purification are completed. The hydrophobicity of the chip surface，the magnitude of the magnetic force，the degree of magnetic beads dispersion，and the elution time of nucleic acid were optimized，respectively. The results showed that when the magnetic force was 250 N，the transfer of magnetic beads were capable of realizing. When the magnet was placed 1 mm above the chip，the magnetic beads in the chamber was well dispersed. When the elution time was 20 min，the nucleic acid concentration of E. coli extracted on the chip was higher. The nucleic acid samples extracted by the microfluidic chip cooperating with magnetic bead nucleic acid extraction technology can be directly applied to the subsequent polymerase chain reaction amplification. This is beneficial to realize the integration of nucleic acid automatic extraction and amplification.

Keywords：microfluidics；nucleic acid extraction；magnetic bead method；automated extraction

分子印迹聚合物在核苷类药物分离分析中的应用

薛俊萍，魏国，柴佩君，吴文璞，张异梦，李桂生^*，宋志花^*

（新型制剂与生物技术药物研究山东省高校协同创新中心，分子药理和药物评价教育部重点实验室，烟台大学药学院，烟台 264005）

摘要：核苷类药物在新型冠状病毒肺炎（COVID-19）、艾滋病及肝炎等病毒性疾病治疗方面效果显著，应用广泛，其准确定量具有重要意义。近年来，基于分子印迹技术合成的分子印迹聚合物（MIPs）备受关注。MIPs可模拟酶与底物或抗体与抗原之间的相互作用，对目标物进行高选择性识别。将MIPs应用于核苷类药物分离分析过程，可显著提高选择性和检测灵敏度。本文对近5年MIPs在核苷类药物样品前处理（固相萃取、固相微萃取等）、色谱分离及传感分析等检测中的应用进行综述，总结了检测过程中面临的挑战，并对其应用前景进行了展望。

关键词：分子印迹聚合物；核苷类药物；样品前处理；色谱分析；传感分析

中图分类号：O657.31；X832    文献标识码：A    文章编号：1000-0720（2024）01-0118-10

Applications of molecularly imprinted polymers in separation and analysis of nucleoside drugs

XUE Junping，WEI Guo，CHAI Peijun，WU Wenpu，ZHANG Yimeng，LI Guisheng^*，SONG Zhihua^*

Ministry of Education，Collaborative Innovation Center of Advanced Drug Delivery System and Biotech Drugs in Universities of Shandong，Key Laboratory of Molecular Pharmacology and Drug Evaluation，School of Pharmacy，Yantai University，Yantai 264005，China）

Abstract：Nucleoside drugs are effective in the treatment of novel coronavirus pneumonia （COVID-19），HIV，hepatitis and other viral diseases in recent years. Therefore，the accurate quantitative analysis of them is of great significance. For the past few years，molecularly imprinted polymers （MIPs） synthesized by molecular imprinting technology have attractedmuch attention. The MIPs can stimulate the interactions between enzymes with substrates or antibodies and antigens，and support a recognition of the target with high selectivity. The selectivity and sensitivity can be greatly improved using MIPs in the separation and analysis of nucleoside drugs. In this review，the applications of MIPs in three fields including sample pretreatment （solid phase extraction，solid phase microextraction，etc.），chromatographic separation and sensor analysis of nucleoside drugs in the last five years are summarized. The advantages of MIPs in detection of nucleoside drugs are discussed. Meanwhile，the challenges and prospects are expected.

Keywords：molecularly imprinted polymers （MIPs）；nucleoside drugs；sample pretreatment；chromatographic analysis；sensor analysis

基于智能手机现场快速检测技术研究进展

唐博¹，陈佳敏¹，韩永辉^*1，2，崔建升^*1，刘大喜¹

（1. 河北科技大学环境科学与工程学院，石家庄 050018；2. 河北省固体废弃物资源化技术创新中心，石家庄 050018）

摘要：作为一种便携式的功能性移动电子设备，智能手机的广泛应用为便携式检测提供了发展平台，并在临床诊断、食品安全分析和环境监测等领域表现出巨大的应用潜力。本文综述了2018~2022年，基于智能手机与比色法、荧光法、化学发光法、电化学分析、免疫分析及微流控分析等技术联用的即时检测应用研究进展，并对其发展趋势和应用前景进行了展望。

关键词：智能手机；即时检测；综述

中图分类号：O657    文献标识码：A    文章编号：1000-0720（2024）01-0128-11

Advances in portable detection technology based on smartphone

TANG Bo¹，CHEN Jiamin¹，HAN Yonghui^*1，2，CUI Jiansheng^*1，LIU Daxi¹

1. College of Environmental Science and Engineering，Hebei University of Science and Technology，Shijiazhuang 050018，China；2. Hebei Technology Innovation Centre of Solid Wastes Utilization，Shijiazhuang 050018，China）

Abstract：As a portable functional mobile electronic device，the wide application of smartphones provides a tremendous platform for the development of portable detection，which shows great potential for application in the fields of clinical diagnosis，food safety analysis，and environmental monitoring. In this review，the advances in real-time detection application based on smart phone combined with colorimetry，fluorescence，chemiluminescence，electrochemical analysis，immunoassay and microfluidic analysis from 2018 to 2022 were summaried，and provides a prospect of the development trend of this technology in analytical testing.

Keywords：smartphone；point-of-care testing；review

药食同源中药材鉴定技术研究进展

谢以清^1，2，符鸽³，闰凌君¹，闫萌萌^1，2，雷海民²，马强^*1

（1. 中国检验检疫科学研究院，北京 100176；2. 北京中医药大学中药学院，北京102488；3. 中国消费品质量安全促进会，北京 100125）

摘要：药食同源中药材具有营养和药用的双重价值，因此被广泛应用于食品、医药等领域。药食同源中药材鉴定是药食同源中药材应用的基础。近年来，随着各学科内容和方法的丰富和创新，药食同源中药材鉴定技术也得到了发展，涌现出一些新的技术和方法。同时，多元化的现代鉴定技术和传统鉴定技术形成了相互补充、相互促进的关系，有利于研究制定规范化的药食同源中药材质量标准，并推动中医药的现代化、科学化、国际化创新发展。本文介绍了药食同源中药材的历史背景和发展现状，总结了传统经验鉴定、分子生物学鉴定、光谱鉴定、色谱-质谱联用鉴定等各种鉴定技术的特点和优势，对国内外新技术、新方法的应用进行了重点阐述，并对药食同源中药材鉴定技术的发展趋势进行了展望，以期为相关领域技术人员提供参考。

关键词：药食同源中药材；鉴定技术；研究进展

中图分类号：R282.5    文献标识码：A    文章编号：1000-0720（2024）01-0139-10

Research progress of identification techniques on medicinal and edible traditional Chinese medicine

XIE Yiqing^1，2，FU Ge³，RUN Lingjun¹，YAN Mengmeng^1，2，LEI Haimin²，MA Qiang^*1

1. Chinese Academy of Inspection and Quarantine，Beijing 100176，China；2. School of Chinese Materia Medica，Beijing University of Chinese Medicine，Beijing 102488，China；3. China Association for Consumer Products Quality and Safety Promotion，Beijing 100125，China）

Abstract：Medicinal and edible traditional Chinese medicine has both nutritional and medicinal values，and therefore is widely used in the fields of food and medicine. The identification techniques of medicinal and edible traditional Chinese medicine are the basis of its applications. In recent years，with the enrichment and innovation of the contents and methods of various subjects，the identification technologies of Chinese herbal medicines with homology of medicine and food have also been developed，and some new technologies and methods have emerged. Moreover，diversified modern and traditional identification techniques are mutually complementing and promoting，which are beneficial for the formulation of quality standards as well as the modernization，scientification，and internationalization of medicinal and edible traditional Chinese medicine. In this paper，the historical background and current development of medicinal and edible traditional Chinese medicine were introduced. The characteristics and advantages of various identification techniques，such as identification based on traditional experience，molecular biology，spectroscopy，and hyphenation of chromatography and mass spectrometry were summarized. The applications of novel techniques and methods were highlighted. The future prospect of the identification techniques of medicinal and edible traditional Chinese medicine was discussed. This paper may provide a useful guidance for relevant researchers in this field.

Keywords：medicinal and edible traditional Chinese medicine；identification techniques；research progress