CRISPR-Cas12a信号放大策略与便携式血糖仪耦合定量检测黄曲霉毒素B1

尹会，刘素君，李杨，贺范祥，周媛媛，李娜，舒琴，乔文艳，史铠^*

（乐山师范学院新能源材料与化学学院，乐山 614000）

摘要：建立了CRISPR-Cas12a与便携式血糖仪耦合定量检测黄曲霉毒素B1（AFB1）的方法。体系中AFB1能够激活Cas12a的反式切割活性，激活后的Cas12a切割电极上蔗糖酶修饰的发夹探针，使得蔗糖酶游离到电极表面的溶液中。蔗糖酶催化蔗糖产生可以被血糖仪监测的响应信号，进而实现对AFB1的检测。在浓度0.001~0.1 ng/mL范围内，AFB1浓度与血糖信号呈良好的线性关系，线性方程为S=3.5+229.1c，检出限为0.3 pg/mL。该方法特异性强，适用于实际样品中AFB1的检测。

关键词：CRISPR-Cas12a；血糖仪；黄曲霉毒素B1；便携式定量检测

中图分类号：TS201.6    文献标识码：A    文章编号：1000-0720（2024）03-0301-06

Quantitative detection of aflatoxin B1 by CRISPR-Cas12a signal amplification strategy coupled with portable glucose meter

YIN Hui，LIU Sujun，LI Yang，HE Fanxiang，ZHOU Yuanyuan，LI Na，SHU Qin，QIAO Wenyan，SHI Kai^*

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

Abstract：A method for the quantitative detection of aflatoxin B1 （AFB1） by coupling CRISPR-Cas12a with a portable glucose meter was established. The presence of AFB1 in the system will activate the trans-cleavage activity of CRISPR-Cas12a to cleave the sucrase modified hairpin DNA on the electrode and release sucrase from the electrode surface into the solution. The released sucrase could catalyze sucrose to produce a response signal that can be monitored by the personal glucose meter to realize the detection of AFB1. The developed biosensor exhibited a good linear relationship in AFB1 concentration range of 0.001-0.1 ng/mL，along with the linear equation of S=3.5+229.1c，with the detection limit of 0.3 pg/mL. This method has highly specificity and can be used for the detection of AFB1 in actual samples.

Keywords：CRISPR-Cas12a；personal glucose meter；aflatoxin B1；portable quantitative detection

荧光偏振免疫法测定水产品中的丁香酚 

王强，王旭峰，张英侠，黄珂^*

（中国水产科学研究院南海水产研究所，农业农村部水产品加工重点实验室，广州 510300）

摘要：将丁香酚（Eul）与丙烯酸甲酯进行衍生化反应，合成了一种新型的丁香酚半抗原4-（4羟基-3-甲氨基苯基）-丁-2-烯酸（Eul-Aca）。采用活性酯法将丁香酚半抗原与乙二胺异硫氰酸荧光素（EDF）偶联，分别制备了同源和异源荧光示踪物。通过比较不同示踪物的抗体稀释度和灵敏度，优化反应时间等检测条件，建立了一种检测水产品中丁香酚的荧光偏振免疫分析法（FPIA）。结果表明：异源示踪物（Eul-Aca-EDF）具有更优的检测灵敏度，抗体稀释度为1/200，反应时间仅需5 min。该方法的半抑制浓度（IC₅₀）为11.2 μg/L，检测线性范围为1.1~111.5 μg/L，检出限（LOD）为0.24 μg/L。实际样品中丁香酚的加标回收率为80.6%~107.4%，相对标准偏差（RSD）<15%。FPIA检测结果与气相色谱-质谱（GC-MS）法结果具有良好的一致性（r=0.993），适用于水产品中丁香酚的残留检测。

关键词：荧光偏振免疫分析法；示踪物；丁香酚；水产品

中图分类号：O657.6    文献标识码：A    文章编号：1000-0720（2024）03-0307-07

A fluorescence polarization immunoassay for the detection of eugenol residues in aquatic products

WANG Qiang，WANG Xufeng，ZHANG Yingxia，HUANG Ke^*

South China Sea Fisheries Research Institute，Chinese Academy of Fishery Sciences，Key Laboratory of Aquatic Product Processing，Ministry of Agriculture and Rural Affairs，Guangzhou 510300，China）

Abstract：Eugenol was derivatized with methyl acrylate to obtain 4-（4-hydroxy-3-methamphenyl）-butyl-2-acrylic acid. The hapten was coupled to fluoresceinthiocarbamyl ethylenediamine （EDF） using the active ester method to produce homologous and heterologous tracers. The influence of tracer structures on assay parameters such as antibody dilution and incubation time were investigated. Furthermore，a fluorescence polarization immunoassay （FPIA） was developed to detect eugenol residues in aquatic products. The results showed that the heterologous tracer （Eul-Aca-EDF） exhibited higher sensitivity with an antibody titer of 1/200. The reaction time of FPIA was only 5 min. The detection limit of eugenol，the IC₅₀ value，and the working range were 0.24，11.2 and 1.1-111.5 μg/L，respectively. The recoveries of spiked aquatic products were in the range of 80.6%-107.4%，with the relative standard deviations （RSDs） less than 15%. The FPIA also showed a good correlation to the GC-MS method （r=0.993）. Therefore，the developed FPIA exhibited potential practicality in the detection of eugenol residues in aquatic products.

Keywords：fluorescence polarization immunoassay；tracer；eugenol；aquatic product

一步法制备铁氮掺杂碳点荧光探针用于测定丙酮酸

石晓冉¹，赵慧¹，张涵¹，李群芳^1，3，娄方明^*1，2，3

（1. 湖北民族大学化学与环境工程学院，恩施 445000；2. 遵义医科大学药学院，遵义 563000；3. 风湿性疾病发生与干预湖北省重点实验室，恩施 445000）

摘要：以邻苯二甲酸为前体，三乙烯二胺为氮源，氯化血红素为铁源，采用一步微波法制备了荧光量子产率约20.8%的新型铁氮掺杂碳点（Fe，N@CDs），并对其形貌、组成及发光性能进行了研究。Fe，N@CDs在425 nm激发波长下能够发射出500 nm的绿色荧光。基于Fe，N@CDs的荧光猝灭作用，建立了对丙酮酸定量测定的方法。在50~350 μmol/L范围内，Fe，N@CDs的荧光猝灭程度与丙酮酸浓度呈良好的线性关系，相关系数R²=0.998，检出限（LOD）为16.7 μmol/L。该方法成功应用于胎牛血清蛋白中丙酮酸含量的检测，回收率范围为99.3%~103.4%。

关键词：铁氮掺杂量子点；荧光；丙酮酸；一步微波法

中图分类号：O657.3    文献标识码：A    文章编号：1000-0720（2024）03-0314-08

One-step preparation of iron-nitrogen doped carbon dot fluorescent probe for the detection of pyruvic acid

SHI Xiaoran¹，ZHAO Hui¹，ZHANG Han¹，LI Qunfang^1，3，LOU Fangming^*1，2，3

1. School of Chemistry and Environmental Engineering，Hubei University for Nationalities，Enshi 445000，China；2. School of Pharmacy，Zunyi Medical University，Zunyi 563000，China；3. Hubei Provincial Key Laboratory of Rheumatic Disease Occurrence and Intervention，Enshi 445000，China）

Abstract：The new iron-nitrogen doped carbon dots （Fe，N@CDs） with a fluorescence quantum yield of about 20.8% were prepared by a one-step microwave method using phthalic acid as the precursor，triethylenediamine as the nitrogen source，and heme chloride as the iron source. The morphology，composition，and luminescence properties of the prepared Fe，N@CDs were investigated. Fe，N@CDs are capable of emitting green fluorescence of 500 nm at an excitation wavelength of 425 nm. A method for the quantitative determination of pyruvate was developed based on the quenching effect of Fe，N@CDs. The quenching of Fe，N@CDs showed a good linear relationship with pyruvate concentration in the range of 50-350 μmol/L，with a correlation coefficient of R²=0.998. The limit of detection （LOD） was 16.7 μmol/L. This method was successfully applied to the determination of pyruvate in fetal bovine serum proteins with recoveries ranging from 99.3%to 103.4%.

Keywords：iron and nitrogen doped quantum dots；fluorescent；pyruvic acid；one-step microwave method

玉米苞衣热解法制备碳点及荧光猝灭法测定Hg²⁺

王越，刘根起^*，刘建勋，王刚，赵伶俐，刘莉莎，孙辰昕，马晓燕

（西北工业大学化学与化工学院，西安 710129）

摘要：以农业废弃物玉米苞衣为碳源，采用一步热解法制备荧光碳点（CDs），利用透射电子显微镜、红外光谱、X射线光电子能谱、紫外-可见光谱和荧光光谱等对CDs的结构和光学性能进行了表征。结果表明，制备得到的CDs呈球形，粒径约为5.5 nm，其表面富含羟基和羧基。CDs在紫外光照射下可以发出明亮的蓝色荧光。Hg²⁺对CDs溶液的荧光具有显著的猝灭作用，据此建立了检测Hg²⁺的新体系。在0~4.0 μmol/L范围内，CDs溶液的荧光猝灭程度与Hg²⁺浓度呈良好的线性关系，检出限为0.011 μmol/L。本方法适用于自来水和湖水水样中Hg²⁺的测定。

关键词：玉米苞衣；碳点；热解法；汞离子；荧光猝灭法

中图分类号：O657.3    文献标识码：A    文章编号：1000-0720（2024）03-0322-06

Preparation of carbon dots by pyrolysis of maize bract and determination of Hg²⁺ by fluorescence quenching method

WANG Yue，LIU Genqi^*，LIU Jianxun，WANG Gang，ZHAO Lingli，LIU Lisha，SUN Chenxin，MA Xiaoyan

School of Chemistry and Chemical Engineering，Northwestern Polytechnical University，Xi'an 710129，China）

Abstract：The fluorescent carbon dots （CDs） were prepared by one-step pyrolysis from agricultural waste maize bract. The structure and optical properties of the CDs were characterized by transmission electron microscopy，Fourier transform infrared，X-ray photoelectron spectroscopy，ultraviolet-visible spectrscopy and fluorescence spectroscopy. The results showed that the prepared CDs were spherical in shape with a particle size of about 5.5 nm，and their surface were rich in hydroxyl and carboxyl groups. CDs can emit bright blue fluorescence when exposed to ultraviolet light，and Hg²⁺ had a significant quenching effect on the fluorescence of CDs solution. Thus，a new method for detecting Hg²⁺ was established. In the range of 0-4.0 μmol/L，the fluorescence quenching degree of CDs solution showed a good linear relationship with the concentration of Hg²⁺，and the detection limit was 0.011 μmol/L. The proposed method can be used for the determination of Hg²⁺ in tap water and lake water samples.

Keywords：corn bract；carbon dots（CDs）；pyrolysis；mercury ions；fluorescence quenching method

基于三线态一三线态湮灭上转换发光的比率型pH纳米探针

许宗意¹，陈硕然^*1，2，王董煊¹，李琳^1，2，王筱梅^1，2，叶常青^*1，2

（1. 绿色印刷纳米光子工程技术研究中心，苏州科技大学材料科学与工程学院，苏州 215009；2. 苏州市新能源材料与低碳技术重点实验室，苏州 215009）

摘要：通过将pH荧光探针分子异硫氰酸荧光素（FITC）引入三线态―三线态湮灭上转换（TTA-UC）体系中，使TTA-UC的发射与FITC的吸收重叠，从而实现从TTA-UC到FITC的能量传递过程。TTA-UC由光敏剂四苯基四苯骈铂（PtTPBP）和湮灭剂9，10-双苯乙炔基蒽（BPEA）组成，可以实现“红转青”上转换发光。将上述有机染料负载于两亲性嵌段共聚物Pluronic P123形成的纳米胶束内，能够形成比率型上转换纳米探针，并应用于水溶液中的pH检测。光敏剂PtTPBP的磷光发射由于不受pH影响，可以作为构建比率探针的内参比信号。上转换发射强度与光敏剂磷光发射强度之间的比率信号（I₅₀₇/I₇₇₀）在pH 5~8范围内呈良好线性。这种新型的比率型上转换pH纳米探针为制备基于TTA-UC的比率型检测传感体系提供了新的思路和视角。

关键词：上转换；三线态-三线态湮灭；比率型探针；pH检测；纳米胶束

中图分类号：O657.3    文献标识码：A    文章编号：1000-0720（2024）03-0328-07

Ratiometric pH nanoprobe based on triplet-triplet annihilation upconversion

XU Zongyi¹，CHEN Shuoran^*1，2，WANG Dongxuan¹，LI Lin^1，2，WANG Xiaomei^1，2，YE Changqing^*1，2

1. Research Center for Green Printing Nanophotonic Materials，School of Materials Science and Engineering，Suzhou University of Science and Technology，Suzhou 215009，China；2. Suzhou Key Laboratory for New Energy Materials and Low Carbon Technologies，Suzhou 215009，China）

Abstract：By introducing the pH fluorescent probe fluorescein isothiocyanate （FITC） into the triplet-triplet annihilation upconversion （TTA-UC） system，an energy transfer process from TTA-UC to FITC could be achieved when UC emission overlapped with FITC absorption. The TTA-UC system consisting of the sensitizer Pt-tetraphenyltetrabenzoporphyrin （PtTPBP） and the annihilator 9，10-bis（phenylethynyl）anthracene （BPEA） could achieve red-to-cyan upconversion luminescence. By encapsulating the above organic dyes in nanomicelles assembled by the amphiphilic block copolymer Pluronic P123，a ratiometric upconversion nanoprobe could be constructed and applied for pH detection in aqueous solution. Since the phosphorescence emission of the sensitizer PtTPBP was not affected by pH，it could be used as an internal reference signal for the ratiometric probe. The ratio signal （I₅₀₇/I₇₇₀） between UC emission intensity and phosphorescence emission intensity of the sensitizer showed a good linear relationship with pH in the range from 5 to 8. This novel ratiometric upconversion pH nanoprobe provides a new perspective for the construction of ratiometric sensing platforms based on TTA-UC.

Keywords：upconversion；triplet-triplet annihilation；ratiometric probe；pH detection；nanomicelle

Cu⁰-Fe₃O₄@壳聚糖微球的制备及其对染料污染物的催化氧化

李豪，赵凤，沈忱思^*

（东华大学环境科学与工程学院，上海201620）

摘要：采用Fe²⁺以及Cu²⁺与壳聚糖形成的双金属络合物作为前驱体溶液，一步成球后通过水热法制得Cu⁰-Fe₃O₄@壳聚糖微球。表征结果证明，Cu⁰以及Fe₃O₄均以纳米尺寸均匀镶嵌在壳聚糖微球中。当此壳聚糖微球投加量为0.5 g/L，H₂O₂投加量为40 mmol/L时，对初始浓度为20 mg/L的活性红73在60 min中内的脱色效率可达99%，且在pH 3.0~9.0范围内均能维持较高的效率。纳米Cu⁰在有氧条件下表面易形成Cu₂O层，不仅能够活化H₂O₂产生?OH，还可提供电子加快Fe（III）/Fe（II）之间的循环，使类芬顿反应高效进行。

关键词：零价铜；四氧化三铁；类芬顿催化剂；染料废水

中图分类号：X832    文献标识码：A    文章编号：1000-0720（2024）03-0335-05

Preparation of Cu⁰-Fe₃O₄@chitosan microspheres and its catalytic oxidation of dye contaminants

LI Hao，ZHAO Feng，SHEN Chensi^*

College of Environmental Science and Engineering，Donghua University，Shanghai 201620，China）

Abstract：Fe²⁺，Cu²⁺ and chitosan were used to form a bimetallic complex as precursor to prepare Cu⁰-Fe₃O₄@chitosan microspheres catalyst in one step by hydrothermal method. The characterization results showed that both Cu⁰ and Fe₃O₄ were uniformly embedded in chitosan microspheres. When the dosages of the catalysts  and H₂O₂ were 0.5 g/L and 40 mmol/L，respectively，99% of C. I. Acid Red 73 at the initial concentration of 20 mg/L could be removed in 60 min. The catalyst could maintain high efficiency in the pH range of 3.0-9.0. Cu₂O sphere can generate on the surface of Cu⁰ under aerobic condition，which not only activated H₂O₂ to produce ?OH，but also provided electrons to accelerate the cycle of Fe（III）/Fe（II），promoting the Fenton-like reactions.

Keywords：zero-valent copper；Fe₃O₄；Fenton-like catalyst；dye wastewater

多光谱法和分子对接模拟研究对羟基苯甲酸甲酯与乳铁蛋白的相互作用

史梦洁，李泽萌，陆勇睿，徐敏华，何进锋，林晓莲，刘红艳^*，姜铁民

（桂林理工大学化学与生物工程学院，桂林541006）

摘要：利用多光谱法和分子模拟法研究了天然人乳铁蛋白（HLF）、重组人乳铁蛋白（rHLF）和对羟基苯甲酸甲酯（MP）之间相互作用的机制。稳态荧光光谱和时间分辨荧光光谱法发现MP与乳铁蛋白的猝灭机理为静态猝灭。热力学分析计算得范德华力和氢键是乳铁蛋白和MP之间的主要作用力。同步荧光光谱分析表明酪氨酸残基和色氨酸残基均参与了MP与乳铁蛋白的作用过程；三维荧光光谱分析表明MP的加入引起peak 1和peak 2的峰强度降低。紫外-可见吸收光谱、傅里叶红外光谱和圆二色谱则表明乳铁蛋白的二级结构发生变化。分子对接表明乳铁蛋白与MP间主要通过氢键和疏水作用力相互作用，分子动力学表明MP改变了HLF的二级结构。研究还表明，rHLF与MP的反应效果更加明显。本研究为揭示MP在生物体内的分布、代谢及毒理作用机制等提供参考，同时也可以为MP的生产应用提供理论参考。

关键词：乳铁蛋白；对羟基苯甲酸甲酯；多光谱法；分子对接

中图分类号：O657.3    文献标识码：A    文章编号：1000-0720（2024）03-0340-09

Interaction between methyl paraben and lactoferrin studied by multispectral method and molecular docking simulation

SHI Mengjie，LI Zemeng，LU Yongrui，XU Minhua，HE Jinfeng，LIN Xiaolian，LIU Hongyan^*，JIANG Tiemin

College of Chemistry and Bioengineering，Guilin University of Technology，Guilin 541006，China）

Abstract：The mechanism of interaction between natural human lactoferrin，recombinant human lactoferrin and methyl paraben （MP） was investigated using multispectral and molecular simulation methods. The quenching mechanism of MP with lactoferrin was found to be a static quenching by steady-state fluorescence spectroscopy and time-resolved fluorescence spectroscopy. Thermodynamic analysis calculated that van der Waals forces and hydrogen bonds were the main forces between lactoferrin and MP. Simultaneous fluorescence spectroscopy showed that both Tyrosine residues and Tryptophan residues involved in the interaction between MP and lactoferrin；three-dimensional fluorescence spectroscopy showed that the addition of MP caused a decrease in the peak intensities of peak 1 and peak 2. UV-vis absorption spectroscopy，Fourier infrared spectroscopy and circular dichroism indicated that the secondary structure of lactoferrin had changed. Molecular docking showed that lactoferrin interacted with MP mainly through hydrogen bonds and hydrophobic forces，and molecular dynamics indicated that MP changed the secondary structure of HLF. It was also shown that the reaction of rHLF with MP was more effective. The results of this study can provide a reference for revealing the distribution，metabolism and toxicological mechanism of MP in living organisms，as well as a theoretical reference for the production and application of MP.

Keywords：lactoferrin；methyl paraben；multispectral method；molecular docking

基于3，3'，5，5'-四甲基联苯胺光热法检测维生素C

刘晓霞^*，侯文雅，郭晓迪，张建刚，赵晋忠

（山西农业大学基础部，晋中 030801）

摘要：构建了一种基于3，3'，5，5'-四甲基联苯胺（TMB）的光热效应检测饮料中维生素C含量的方法。TMB在木瓜蛋白酶催化作用下可与过氧化氢反应，生成蓝色的氧化态产物（ox-TMB）。由于ox-TMB具有强烈的光热效应，吸收808 nm近红外光后可将其转换为热能，从而导致溶液温度升高；维生素C存在时可以将一部分ox-TMB还原，导致温度增量下降，且下降的温度增量与维生素C的浓度在5.0~125 μmol/L范围内存在线性关系，检出限为2.3 μmol/L。该方法仅用笔式数字温度计作为信号读取器，已成功用于市售饮料中维生素C的定量检测。本文所提出的策略为开发低成本的生物和临床诊断方法提供了一种新的思路。

关键词：3，3'，5，5'-四甲基联苯胺；光热效应；数字温度计；维生素C

中图分类号：O655    文献标识码：A    文章编号：1000-0720（2024）03-0349-06

Determination of vitamin C based on the photothermal effect of 3，3'，5，5'-tetramethylbenzidine

LIU Xiaoxia^*，HOU Wenya，GUO Xiaodi，ZHANG Jiangang，ZHAO Jinzhong

Department of Basic Teaching，Shanxi Agricultural University，Jinzhong 030801，China）

Abstract：A new method for the determination of vitamin C in beverages was developed based on the photothermal effect of 3，3'，5，5'-tetramethylbenzidine （TMB）. TMB can react with hydrogen peroxide in the presence of papain to form the blue oxidized product （ox-TMB），which exhibits a strong photothermal effect. The ox-TMB can adsorb 808 nm near-infrared light and transform the analysis signal into heat，leading to a rise in solution temperature. In the presence of vitamin C，a part of ox-TMB can be reduced to TMB，resulting in the decrease of temperature increment. There was a linear relationship between the concentration of vitamin C and the temperature increment in the concentration range of 5.0-125 μmol/L，with a limit of detection of 2.3 μmol/L. This method only uses an easily operated pen-style digital thermometer as the signal reader，and was successfully applied to the quantitative detection of vitamin C in commercial beverages. The proposed strategy may provide a new way for the development of low-cost biological and clinical diagnostic methods.

Keywords：3，3'，5，5'-tetramethylbenzidine；photothermal effect；digital thermometer；vitamin C

基于金属有机骨架的分散固相萃取-高效液相色谱法测定麦冬等样品中6种新烟碱类农药残留

李娜，黄海智，俞晓平，叶子弘^*

（中国计量大学生命科学学院，浙江省生物计量及检验检疫技术重点实验室，杭州 310018）

摘要：通过热溶剂法合成了金属有机骨架（MOF）材料NH₂-MIL-101（Fe），并建立了基于NH₂-MIL-101（Fe）的分散固相萃取-高效液相色谱（DSPE-HPLC）法，用于检测麦冬等药食同源样品中6种新烟碱类农药（噻虫嗪、噻虫胺、吡虫啉、氯噻啉、啶虫脒、噻虫啉）残留。与MIL-53（Al）、多壁碳纳米管（MWCNTs）、ZIF-8及MIL-53（Fe）等吸附剂相比，NH₂-MIL-101（Fe）的吸附能力更好，回收率更高；与液相色谱-质谱联用（LC-MS）相比，HPLC在达到检测要求的同时能降低检测成本。利用场发射扫描电子显微镜（FESEM）和傅里叶变换红外光谱（FT-IR）表征制备的NH₂-MIL-101（Fe），对吸附剂的种类和用量、萃取溶剂体积、萃取时间、洗脱溶剂体积和萃取洗脱方式进行优化。结果表明，NH₂-MIL-101（Fe）稳定性高、选择性好、能在水中快速分散。据此构建的方法检测6种新烟碱类农药，在0.01~2.5 mg/L浓度范围内线性关系良好（R²>0.9993），加标样品检出限（LOD）为0.50~1.0 μg/L，平均回收率为93.8%~104.2%，相对标准偏差小于6.5%。本文建立的基于MOF的DSPE-HPLC方法可极大减少实际样品中复杂基质的干扰。

关键词：新烟碱类农药；NH₂-MIL-101（Fe）；分散固相萃取；高效液相色谱；吸附

中图分类号：TS207.3    文献标识码：A    文章编号：1000-0720（2024）03-0355-09

Determination of six neonicotinoid pesticide residues in Ophiopogonis samples by dispersed solid-phase extraction coupled with high-performance liquid chromatography based on metal-organic frameworks

LI Na，HUANG Haizhi，YU Xiaoping，YE Zihong^*

Zhejiang Provincial Key Laboratory of Biometrology and Inspection & Quarantine，College of Life Science，China Jiliang University，Hangzhou 310018，China）

Abstract：Metal-organic framework （MOF） material NH₂-MIL-101（Fe） was synthesized by thermal solvent method，and a dispersive solid-phase extraction coupled with high-performance liquid chromatography （DSPE-HPLC） method based on NH₂-MIL-101（Fe） was established. It was used to detect the residues of six neonicotinoid pesticides （thiamethoxam，clothiandin，imidacloprid，imidaclothiz，acetamiprid，thiacloprid） in medicine and food homologous products of Ophiopogon. NH₂-MIL-101（Fe） had better adsorption capacity and higher recoveries than the adsorbents MIL-53（Al），multi-walled carbon nanotubes（MWCNTs），ZIF-8，and MIL-53（Fe）. Compared with the liquid chromatography-mass spectrometry （LC-MS） method，HPLC method can not only meet the detection requirements，but also reduce the detection cost. NH₂-MIL-101（Fe） was characterized by field emission scanning electron microscopy （FESEM） and Fourier transform infrared （FT-IR） spectroscopy. The conditions such as the amount and type of adsorbent，volume of extraction solvent，extraction time，volume of elution solvent，and extraction elution methods were optimized. The results showed that NH₂-MIL-101（Fe） had high stability，good selectivity，and rapid dispersion in water. For the constructed method based on NH₂-MIL-101（Fe），the six neonicotinoids had good linear relationships in the range of 0.01-2.5 mg/L（R²>0.9993），the limits of detection （LODs） of the spiked samples were 0.25-0.5 μg/kg，the average recoveries were 93.8%-104.2%，and the relative standard deviations were less than 6.5%. The proposed DSPE-HPLC method based on MOFs can greatly reduce the interference of complex matrix in real samples.

Keywords：neonicotinoid pesticides；NH₂-MIL-101（Fe）；dispersed solid phase extraction；high performance liquid chromatography；adsorption

手持式拉曼光谱仪结合双金属Au@AgNPs聚集体检测环境水中结晶紫

董锦汝¹，冯紫临¹，沈雪怡¹，王文璇¹，王凯强^*2

（1. 中国海洋大学海德学院，青岛 266100；2. 中国海洋大学食品科学与工程学院，青岛 266404）

摘要：构建了一种基于手持式拉曼光谱仪，结合双金属银包金粒子（Au@AgNPs）聚集体的现场快速检测结晶紫的表面增强拉曼光谱（SERS）方法。首先制备了“核-壳”粒径分别约为30 nm和6 nm的双金属银包金粒子（Au@AgNPs），并以NaCl作为聚集剂，获得了具有SERS活性的Au@AgNPs聚集体。结合激发光源785 nm的手持式拉曼光谱仪，实现了结晶紫的快速检测。以结晶紫位于1621 cm^-1处的特征峰进行定量分析，方法检出限为8.20 μg/L，对河水和湖水中结晶紫的加标回收率为71.0%~128.4%。本文所构建的方法可用于监测结晶紫的非法使用。

关键词：结晶紫；表面增强拉曼光谱；Au@AgNPs；环境水；手持拉曼光谱仪

中图分类号：O657.31；X832    文献标识码：A    文章编号：1000-0720（2024）03-0364-07

Detection of crystal violet in environmental water by a handheld Raman spectrometer combined with bimetallic Au@AgNPs aggregates

DONG Jinru¹，FENG Zilin¹，SHEN Xueyi¹，WANG Wenxuan¹，WANG Kaiqiang^*2

1. College of Haide，Ocean University of China，Qingdao 266100，China；2. College of Food Science and Engineering，Ocean University of China，Qingdao 266404，China）

Abstract：A surface-enhanced Raman spectroscopy （SERS） method for the rapid and in situ detection of crystal violet was developed based on a handheld Raman spectrometer combined with bimetallic silver coated gold particles （Au@AgNPs）. Firstly，the Au@AgNPs with core and shell sizes of about 30 nm and 6 nm respectively were prepared. Sodium chloride was used as an inducer to prepare Au@AgNPs aggregate substrates with SERS activity. In combination with a handheld Raman spectrometer with an excitation source of 785 nm，the rapid detection of crystal violet was achieved. Quantitative analysis was conducted through the characteristic peak of crystal violet at 1621 cm^-1 accompanied by the detection limit of 8.20 μg/L and the recoveries of 71.0%-128.4%. The constructed SERS method can be applied to monitor the illegal use of crystal violet.

Keywords：crystal violet；surface-enhanced Raman spectroscopy；Au@AgNPs；environmental water；handheld Raman spectrometer

磁性核壳型Ni（II）印迹聚合物的制备及其吸附性能

邓秀君¹，李悦¹，胡兴亮²，陆茜¹，孙婷¹，张炜业¹，何红星^*1

（1. 云南省金属有机分子材料与器件重点实验室，昆明学院化学化工学院，昆明 650214；2. 昆明绿岛环境科技有限公司，昆明 650228）

摘要：以2-丙烯酰胺-2-甲基-1-丙磺酸（AMPS）为功能单体，2-膦酸丁烷-1，2，4-三羧酸为配体，绿色溶剂水为致孔剂，利用表面印迹技术制备了一种新型磁性核壳型Ni（II）印迹聚合物。考察了溶液pH、吸附时间、Ni（II）初始浓度和温度对印迹材料吸附性能的影响。利用傅立叶红外光谱仪（FTIR）、X射线粉末衍射仪（XRD）、扫描电镜（SEM）、热重分析仪（TGA）和振动样品磁强计（VSM）对印迹聚合物的结构、表面形貌、热稳定性和磁性能进行了表征，并探究了印迹聚合物对Ni（II）的吸附机理。结果表明：磁性核壳型Ni（II）印迹聚合物在25 ℃，pH 6时吸附平衡时间为30 min，最大吸附量可达38.09 mg/g，吸附过程符合准二级动力学模型和Langmuir吸附等温模型。吸附热力学研究表明，印迹聚合物对Ni（II）的吸附是一个自发、吸热、熵增的过程。印迹聚合物相较于非印迹聚合物展现出较好的选择性，在Ni（II），Co（II），Cu（II）和Zn（II）的混合溶液中，对Ni（II）的分配系数达319.01 mL/g，证明该印迹聚合物具有选择性吸附Ni（II）的能力。

关键词：Ni（II）；表面印迹技术；磁性核壳；选择性

中图分类号：O657.31；X832    文献标识码：A    文章编号：1000-0720（2024）03-0371-08

Preparation and adsorption properties of magnetic core-shell Ni（II） imprinted polymer

DENG Xiujun¹，LI Yue¹，HU Xingliang²，LU Xi¹，SUN Ting¹，ZHANG Weiye¹，HE Hongxing^*1

1. Yunnan Key Laboratory of Metal-Organic Molecular Materials and Device，School of Chemistry and Chemical Engineering，Kunming University，Kunming 650214，China；2. Kunming Lvdao Environmental Technology Co.，Ltd.，Kunming 650228，China）

Abstract：A novel magnetic core-shell Ni（II） imprinted polymer was prepared by surface imprinting technique using 2-acrylamide-2-methyl-1-propanesulfonate （AMPS） as functional monomer，2-phosphonobutane-1，2，4-tricarboxylic acid as ligand and green solvent water as porogen. Different conditions such as the solution pH，adsorption time，initial concentration of Ni（II），and temperature on the adsorption properties of the imprinted material were studied. The structure，stability，surface morphology，thermal stability and magnetic properties of imprinted polymers were characterized by Fourier transform infrared （FTIR） spectroscopy，X-ray diffraction （XRD），scanning electron microscopy （SEM），thermal analysis （TGA） and vibrating sample magnetometry （VSM），and the adsorption mechanism of imprinted polymers for Ni（II） was investigated. The results showed that the adsorption equilibrium time of the magnetic core-shellimprinted polymer was 30 min at 25 ℃ and pH 6，and the maximum adsorption capacity could reach 38.09 mg/g. The adsorption process could be well fitted bypseudo-second-order kinetic model and Langmuir adsorption isotherm model. The adsorption thermodynamic results showed that the adsorption of Ni（II） on the imprinted polymer was a spontaneous，endothermic and entropy-increasing process. Moreover，the imprinted polymer showed better selectivity compared with the non-imprinted polymer. In the mixed solution of Ni（II），Co（II），Cu（II） and Zn（II），the distribution coefficient of Ni（II） reached 319.01 mL/g，which proved that the imprinted polymer could selectively adsorb Ni（II）.

Keywords：Ni（II）；surface imprinting technology；magnetic core-shell；selectivity

一种三苯胺酰腙荧光探针的合成及其对Al³⁺的选择性识别

王欣，薛蕾，曾姿涵，徐阳，张杨，王海滨^*

（宁夏师范学院化学化工学院，固原 756000）

摘要：将4-二苯基氨基苯甲酰肼和2，4-二羟基苯甲醛结合，合成了一种新的三苯胺酰腙类荧光探针（N18），并利用核磁共振氢谱（¹H NMR）、碳谱（¹³C NMR）和质谱（MS）技术对其结构进行了表征。在二甲基亚砜（DMSO）/H₂O溶液中对N18的光学性能进行了测定。紫外-可见（UV-vis）吸收光谱和荧光发射光谱结果表明，N18对Al³⁺识别表现出高选择性和高灵敏度，并且对其他金属离子有较强的抗干扰能力。利用Job曲线和¹H NMR测得N18与Al³⁺的结合比为1∶1，通过荧光滴定得到N18对Al³⁺的检出限为4.9×10^-8 mol/L，结合常数（K_a）为5.95×10⁵ L/mol。探针N18可以检测实际水样中的Al³⁺，并且可以制备成试纸用于检测Al³⁺，具有一定的应用前景。

关键词：荧光探针；三苯胺；酰腙；识别；Al³⁺

中图分类号：O657.31    文献标识码：A    文章编号：1000-0720（2024）03-0379-07

Synthesis of a triphenylamine acylhydrazone based fluorescent probe and its selective recognition for Al³⁺

WANG Xin，XUE Lei，ZENG Zihan，XU Yang，ZHANG Yang，WANG Haibin^*

College of Chemistry and Chemical Engineering，Ningxia Normal University，Guyuan 756000，China）

Abstract：A novel triphenylamine acylhydrazone based fluorescent probe （N18） was synthesized from

4-（diphenylamino）benzohydrazide and 2，4-dihydroxybenzaldehyde，and the structure of N18 was characterized by ¹H NMR，¹³C NMR and mass spectrometry （MS）. The optical performance of N18 was measured in dimethyl sulfoxide （DMSO）/H₂O solution. According to the UV-vis absorption and fluorescence spectra results，N18 exhibited high selectivity and sensitivity towards Al³⁺，and had strong anti-interference ability to other metal ions. The binding ratio between N18 and Al³⁺ was obtained as 1∶1 by Job’ plot and ¹H NMR. The detection limit was 4.9×10^-8 mol/L and the binding constant （K_a） was 5.95×10⁵ L/mol based on the fluorescence titration data. In addition，the probe N18can detect Al³⁺ in actual water sample and can be prepared into test papers for Al³⁺ detection，which has a good application prospect.

Keywords：fluorescent probe；triphenylamine；acylhydrazone；recognition；Al³⁺

气相色谱-四极杆飞行时间质谱快速筛查和确证农药制剂中51种非法添加化合物

黄培鑫，杨红菊，李玲，黄宝勇^*，于寒冰^*

（北京市农产品质量安全中心，北京 100029）

摘要：建立了气相色谱-四极杆飞行时间质谱（GC-Q-TOF/MS）筛查农药制剂中51种非法添加化合物的方法。乳油等15种农药剂型被分为3组，经丙酮溶解提取，GC-Q-TOF/MS测定，建立了51种化合物的一级精确质量数据库和二级碎片质谱库。结果表明，51种化合物在各自线性范围内线性关系良好，相关系数（R²）均大于0.99，检出限（LODs）为0.04~0.2 mg/kg，0.5，1.0，5.0 mg/kg 3个浓度的加标回收率为93.0%~105.2%，相对标准偏差（RSDs）为2.5%~7.8%。该方法适用于农药制剂中非法添加化合物的分析。

关键词：气相色谱-四极杆-飞行时间质谱；农药制剂，快速筛查；非法添加

中图分类号：O657.63；X839.2    文献标识码：A    文章编号：1000-0720（2024）03-0386-08

Rapid screening and quantitative analysis of 51 illegally added compounds in pesticide preparations by gas chromatography-quadrupole time-of-flight mass spectrometry

HUANG Peixin，YANG Hongju，LI Ling，HUANG Baoyong^*，YU Hanbing^*

Beijing Center of Agricultural Products Quality and Safety，Beijing 100029，China）

Abstract：A method based on gas chromatography-quadrupole time-of-flight mass spectrometry （GC-Q-TOF/MS） was established to determine 51 illegally added compounds in pesticide preparations. Emulsifiable concentrate and other 14 pesticide formulations were divided into three groups，which were extracted by acetone and determined by GC-Q-TOF/MS. Thus，an accurate primary mass database and fragment ion database of 51 compounds were established. The experiment results revealed that all compounds showed good linear relationships in their corresponding concentration ranges，with the correlation coefficients （R²） above 0.99. The limits of detection （LODs） were 0.04-0.2 mg/kg. The recoveries at the three spiked levels of 0.5，1.0 and 5.0 mg/kg were 93.0%-105.2%，and the relative standard deviations （RSDs） ranged from 2.5% to 7.8%. This method is suitable for the determination of illegally added compounds in pesticide preparations.

Keywords：Gas chromatography-quadrupole time-of-flight mass spectrometry （GC-Q-TOF/MS）；pesticide preparations；rapid screening；illegal addition

磁性表面分子印迹聚合物的制备及对梓醇的选择性吸附

秦兵¹，张伟东²，李淑贤^*1

（1. 佳木斯大学药学院，佳木斯 154000；2. 吉林大学药学院，长春 130000）

摘要：以Fe₃O₄@SiO₂磁性复合材料为载体，梓醇为模板分子，采用沉淀聚合法合成了新型磁性表面分子印迹聚合物。优化了吸附条件，通过静态与动态吸附实验，考察了新型复合材料的吸附性能。结果表明，该材料对梓醇的最大吸附量为69.07 μg/mg，印迹因子为1.97，对梓醇有优良的特异性识别能力。重复使用6次后，回收率仍在85%以上，重复利用性良好。基于此，结合磁固相萃取法，建立了应用于地黄中梓醇富集和检测的高效液相色谱法，梓醇回收率为89.5%~96.8%，相对标准偏差（RSD）≤2.0%，线性范围为0.1~1.15 mg/mL，线性相关系数R²>0.9998，检出限（LOD）为5.4 ng/mL。该新型磁性复合材料为天然产物中活性成分的富集和分析提供了一种新的预处理策略。

关键词：磁性表面分子印迹聚合物；梓醇；HPLC；磁性材料

中图分类号：O657.31；X832    文献标识码：A    文章编号：1000-0720（2024）03-0394-08

Preparation of magnetic surface molecular imprinted polymer and its selective adsorption for catalpol

QIN Bing¹，ZHANG Weidong²，LI Shuxian^*1

1. College of Pharmacy，Jiamusi University，Jiamusi 154000，China；2. College of Pharmacy，Jilin University，Changchun 130000，China）

Abstract：A novel magnetic surface molecularly imprinted polymer was synthesized by precipitation polymerization using Fe₃O₄ and SiO₂ magnetic composites as carriers and catalpol as template molecules. The adsorption conditions were optimized and the adsorption performance of the new composite material was investigated by static and dynamic adsorption experiments. The results showed that the maximum adsorption capacity of the material for catalpol was 69.07 μg/mg with the imprinted factor （IF） of 1.97，showing excellent specific recognition ability for catalpol. After 6 times of reuse，the recovery was still above 85%，showing good reuse performance. Combined with magnetic solid phase extraction，the high performance liquid chromatography method was established and successfully applied to enrich and determine catalpol in rehmannia glutinosa. The recoveries of catalpol were 89.5%-96.8%，with the relative standard deviations （RSDs） lower than 2%. The linear range was 0.1-1.15 mg/mL，with the correlation coefficient （R²） above 0.9998，and the limit of detection （LOD） of 5.4 ng/mL. The new composite magnetic material can provide a promising pretreatment strategy for the enrichment and analysis of active components in natural products.

Keywords：magnetic surface molecularly imprinted polymer；catalpol；HPLC；magnetic material

超高效合相色谱-质谱法对甲卡西酮对映异构体的手性分离和定量检测

胡爽¹，武磊¹，黄钰²，杜宇²，花镇东^*3

（1. 北京警察学院刑事科学技术系，北京 102202；2. 中国药科大学药学院，南京 210009；3. 公安部禁毒情报技术中心，北京 100193）

摘要：建立了超高效合相色谱-质谱法（UPC²-MS）对甲卡西酮（MC）对映异构体进行手性分离和定量检测。使用Acquity UPC² Trefoil CEL2 （2.5 μm，3.0 mm×150 mm）手性色谱柱，以超临界流体CO₂为主要流动相，含10 mmol/L甲酸铵和0.1%甲酸的异丙醇为改性剂进行梯度洗脱，可以在13 min内实现2个对映异构体的基线分离。在三重四极杆质谱多反应监测（MRM）模式下，2个对映异构体的检出限为0.5 ng/mL，定量限为1.0 ng/mL，在1~100 ng/mL质量浓度范围内线性关系良好，线性相关系数（R²）≥0.999，10种常见毒品和药品对检测均无干扰。对实际缴获毒品的检测结果表明：直接作为毒品销售的MC主要为外消旋体，而非法制造麻黄碱的地下窝点缴获的MC以S构型为主。

关键词：超高效合相色谱-质谱；甲卡西酮；对映异构体；手性分离

中图分类号：O656.2    文献标识码：A    文章编号：1000-0720（2024）03-0402-07

Chiral separation and quantitative determination of methcathinone enantiomers by ultra-performance convergence chromatography-mass spectrometry

HU Shuang¹，WU Lei¹，HUANG Yu²，DU Yu²，HUA Zhendong^*3

1. Department of Criminal Science and Technology，Beijing Police College，Beijing 102202，China；2. School of Pharmacy，China Pharmaceutical University，Nanjing 210009，China；3. Anti-drug Information Technology Center of the Ministry of Public Security，Beijing 100193，China）

Abstract：A chiral separation and quantification method for methcathinone （MC） enantiomers based on ultra-performance convergence chromatography-mass spectrometry （UPC²-MS） was developed. The baseline separation of two enantiomers could be achieved within 13 min under the conditions of acquity UPC² Trefoil CEL2 （2.5 μm，3.0 mm×150 mm） as chiral column，supercritical fluid CO₂ as primary mobile phase，isopropanol containing 10 mmol/L ammonium formate and 0.1% formic acid as the modifier for gradient elution. Under the multi reaction monitoring （MRM） mode of triple quadrupole mass spectrometry，the limits of detection were 0.5 ng/mL and the limits of quantification were 1.0 ng/mL for both enantiomers. There were great linear relationships in the concentration range of 1.0-100 ng/mL，and the correlation coefficients （R²） were not less than 0.999. 10 common drugs did not interfere with the determination of target substances. The seized drug samples were analyzed using this method，and the results showed that the methcathinone products seized in the market as drugs were mainly in racemic form，while that seized from illegal ephedrine manufacturing dens were mainly in S-configuration.

Keywords：ultra performance convergence chromatography-mass spectrometry；methcathinone；enantiomers；chiral separation

磁性功能介孔材料固相萃取-气相色谱法测定水中的多氯联苯

张利¹，李莉²，张登耀²，张盛贵^*1，陈自弟¹

（1. 甘肃农业大学食品科学与工程学院，兰州 730070；2. 甘肃农业大学理学院，兰州 730070）

摘要：采用一锅法合成Fe₃O₄纳米粒子，并利用溶胶-凝胶法制备了SBA-15@Fe₃O₄磁性介孔复合材料。以介孔二氧化硅材料（SBA-15）的表面硅羟基为靶位，借助苯基三氯硅烷与硅羟基的硅烷化反应将苯基基团接枝到材料表面，得到苯基功能化磁性介孔材料Ph-SBA-15@Fe₃O₄，该材料有良好的疏水性，并保留了SBA-15的有序二维六方孔道结构。将其用于磁性固相萃取（MSPE）吸附水样中的多氯联苯（PCBs），建立了气相色谱-电子捕获检测法（GC-ECD）检测PCBs。在优化条件下，7种PCBs在0.025~50 μg/L范围内呈良好线性关系，线性相关系数（R²）均大于0.9999，方法回收率为89.8%~108%。该方法可用于实际水样中痕量PCBs的高效快速检测。

关键词：磁性固相萃取（MSPE）；多氯联苯（PCBs）；气相色谱-电子捕获检测法（GC-ECD）

中图分类号：O657.7    文献标识码：A    文章编号：1000-0720（2024）03-0409-06

Determination of polychlorinated biphenyls in water by magnetic functional mesoporous materials solid phase extraction-gas chromatography

ZHANG Li¹，LI Li²，ZHANG Dengyao²，ZHANG Shenggui^*1，CHEN Zidi¹

1. College of Food Science and Engineering，Gansu Agricultural University，Lanzhou 730070，China；2. College of Science，Gansu Agricultural University，Lanzhou 730070，China）

Abstract：Fe₃O₄ nanoparticles were synthesized by one pot method，and SBA-15@Fe₃O₄ magnetic mesoporous composites were synthesized by sol-gel method. Surface silicon hydroxyl groups of mesoporous silica material （SBA-15） served as target，Ph-SBA-15@Fe₃O₄ functional magnetic mesoporous material were obtained by grafting phenyl groups onto SBA-15@Fe₃O₄ surface via silylation reaction between phenyl trichlorosilane and silanol group. The material not only possessed good hydrophobicity，but also retained the ordered two-dimensional hexagonal pore-like structure of SBA-15. The material was used in magnetic solid-phase extraction （MSPE） pretreatment to adsorb polychlorinated biphenyls （PCBs） in water samples，and a gas chromatography method for the determination of PCBs was established. Under the optimized conditions，the seven PCBs exhibited good linear relationships in the range of 0.025-50 μg/L，the correlation coefficients （R²） were greater than 0.9999，and the recoveries were 89.8%-108%. The MSPE method could be applied to the determination of trace PCBs in real water samples.

Keywords：magnetic solid-phase extraction （MSPE）；polychlorinated biphenyls （PCBs）；gas chromatography-electron capture detection （GC-ECD）

高效液相色谱-串联质谱法测定稻谷和糙米中的溴硝醇

王飞^*，俞子萱，张静

（天津海关动植物与食品检测中心，天津 300457）

摘要：建立了稻谷和糙米中溴硝醇的高效液相色谱-串联质谱检测方法。样品采用酸性乙腈提取，经HLB固相萃取柱净化，以Hypersil GOLD-C₁₈柱分离，在负离子模式下采集数据，基质外标法定量。溴硝醇在电喷雾负离子模式下的母离子m/z 167.8，实际为溴硝醇发生反应后的产物2-溴-2-硝基乙醇的分子离子峰。溴硝醇在0~5.0 μg/mL浓度范围内呈良好线性，线性相关系数大于0.99，平均回收率为86.2%~94.6%，相对标准偏差不超过13%。该方法适用于大批量粮谷样品中溴硝醇的快速检测。

关键词：高效液相色谱-串联质谱；溴硝醇；稻谷；糙米

中图分类号：O657.63    文献标识码：A    文章编号：1000-0720（2024）03-0415-05

Determination of 2-bromo-2-nitropropane-1，3-diol residues in grain and unpolished rice by high performance liquid chromatography-tandem mass spectrometry

WANG Fei^*，YU Zixuan，ZHANG Jing

Tianjin Customs Plants Animals and Foods Inspection Center，Tianjin 300457，China）

Abstract：A high performance liquid chromatography-tandem mass spectrometry （HPLC-MS/MS） method was established for the determination of 2-bromo-2-nitropropane-1，3-diol residues in grain and unpolished rice products. The acetonitrile solution containing formic acid and HLB solid phase extraction column were used for the extraction and purification of 2-bromo-2-nitropropane-1，3-diol，respectively，following separation via Hypersil GOLD-C₁₈ column. The target analyte was detected in the negative ion mode using an electrospray ionization （ESI） source with external standard method. The parent ion m/z 167.8 of 2-bromo-2-nitropropane-1，3-diol was actually the molecular ion peak of 2-bromo-2-nitroethanol，which was the degraded product of reversible aldehyde alcohol reaction of 2-bromo-2-nitropropane-1，3-diol. The results showed that there was a good relationship with correlation coefficient above 0.99 in the concentration range of 0-5.0 μg/mL. Average recoveries for the residues were in the range of 86.2% to 94.6%，and the relative standard deviations （RSDs） was no more than 13% in grain and unpolished rice products. The developed method was suitable to determinate 2-bromo-2-nitropropane-1，3-diol residues in grain and unpolished rice.

Keywords：HPLC-MS/MS；2-bromo-2-nitropropane-1，3-diol；grain；unpolished rice

KED-ICP-MS法测定电子级丙二醇甲醚中的银、镉和铅

万曦¹，刘涌²，郑玉婷²，陈辰¹，郭登峰^*1

（1. 常州大学石油化工学院，常州 213164；2. 江苏怡达化学股份有限公司，无锡 214441）

摘要：建立了电感耦合等离子体质谱法（ICP-MS）测定电子级丙二醇甲醚中银（Ag）、镉（Cd）和铅（Pb）含量的方法。样品经超纯水稀释后直接进样，采用标准加入法作为定量方法，选择待测同位素为¹⁰⁷Ag，¹¹¹Cd，²⁰⁸Pb，并通过选择检测模式和碰撞/反应池气体流量有效消除质谱干扰。结果表明，在碰撞模式下利用动能歧视技术（KED），He流量为4 mL/min时，质谱干扰消除效果最佳。该方法的线性范围为0.2~5 μg/L，线性相关系数大于0.9995，各元素检出限（LODs）为0.002~0.009 μg/L，加标回收率为93.8%~104.2%，相对标准偏差（RSDs）小于9.5%。使用KED-ICP-MS法可以准确测定电子级丙二醇甲醚中Ag，Cd和Pb的含量。

关键词：电感耦合等离子体质谱法（ICP-MS）；动能歧视（KED）；标准加入法；电子级丙二醇甲醚；金属元素银、镉和铅

中图分类号：TQ413.2    文献标识码：A    文章编号：1000-0720（2024）03-0420-05

Determination of silver，cadmium and lead in electronic grade propylene glycol methyl ether by inductively coupled plasma mass spectrometry with kinetic energy discrimination

WAN Xi¹，LIU Yong²，ZHENG Yuting²，CHEN Chen ¹，GUO Dengfeng^*1

1. Collage of Petrochemical Technology，Changzhou University，Changzhou 213164，China；2. Jiangsu Yida Chemical Co.，Ltd.，Wuxi 214441，China）

Abstract：A method for the determination of silver （Ag），cadmium （Cd） and lead （Pb） in electronicgrade propylene glycol methyl ether by inductively coupled plasma mass spectrometry with kinetic energy discrimination （KED-ICP-MS） was established. The sample was diluted with ultra-pure water and then injected directly. The quantitative method is the standard addition method. The isotopes to be measured were ¹⁰⁷Ag，¹¹¹Cd，²⁰⁸Pb，and the interference of the mass spectrum was effectively eliminated by selecting the detection mode and the gas flow rate in the collision/reaction cell. When the collision mode was used as the best detection mode，and the He flow of the collision gas was 4 mL/min，the best effect of mass spectrometry interference elimination could be obtained. The linear range of the method was 0.2-5 μg/L，the linear correlation coefficients were not less than 0.9995，and the limits of detection （LODs） were in the range of 0.002-0.009 μg/L. The spiked recoveries for each element ranged from 93.8% to 104.2%，and the relative standard deviations （RSDs） were less than 9.5%. The contents of Ag，Cd，and Pb in electronic grade propylene glycol methyl ether can be accurately determined by KED-ICP-MS.

Keywords：inductively coupled plasma mass spectrometry （ICP-MS）；kinetic energy discrimination （KED）；standard addition method；electronic grade propylene glycol methyl ether；metal elements of Ag，Cd，and Pb

基于5-氨基水杨酸的碳量子点用于测定高锰酸根

朱建涛^*，温翯，韩伟，车春霞，张峰，刘超伟

（中国石油天然气股份有限公司兰州化工研究中心，兰州 730060）

摘要：采用简单的水热法制备了以5-氨基水杨酸为前驱体的氮掺杂碳量子点 （N-CQDs）。合成的N-CQDs呈球形，平均粒径3.45 nm，表面含有丰富的功能基团。在紫外灯照射下，N-CQDs发出绿色荧光，荧光量子产率为10.4%，最大激发和发射波长分别为340 nm和502 nm。加入MnO₄^-后，N-CQDs的荧光强度呈浓度依赖性猝灭，基于此，构建了灵敏的“开-关”型纳米探针。通过考察紫外-可见吸收光谱、荧光寿命和Stern-Volmer常数，MnO₄^-猝灭N-CQDs荧光归因于内滤效应和静态猝灭。在优化条件下，N-CQDs检测MnO₄^-的线性范围为0~14 μmol/L，检出限（LOD）为0.14 μmol/L。N-CQDs对水中常见的其他阳离子和阴离子表现出优良的选择性和抗干扰能力。该方法已成功应用于湖水中MnO₄^-的测定。

关键词：氮掺杂碳量子点；高锰酸根；纳米探针

中图分类号：O657.31； X832    文献标识码：A    文章编号：1000-0720（2024）03-0425-08

Carbon quantum dots based on 5-aminosalicylic acid for the determination of permanganate

ZHU Jiantao^*，WEN He，HAN Wei，CHE Chunxia，ZHANG Feng，LIU Chaowei

Lanzhou Petrochemical Research Center，Petro China Company Limited，Lanzhou 730060，China）

Abstract：A simple hydrothermal method was used to prepare the nitrogen doped carbon quantum dots （N-CQDs） with 5-aminosalicylic acid as precursor. The synthesized N-CQDs were spherical with an average particle size of 3.45 nm and had abundant functional groups on the surface. N-CQDs emitted green fluorescence under ultraviolet irradiation with quantum yield of 10.4%，and the maximum excitation and emission wavelengths were 340 and 502 nm，respectively. Upon the addition of MnO₄^-，the fluorescence intensity of N-CQDs was quenched with a concentration-dependent manner. Based on this result，a sensitive “on-off” probe was constructed. Through examining UV-visible absorption spectrum，fluorescence lifetime and Stern-Volmer constant，the fluorescence quenching triggered by MnO₄^- was attributed to inner filter effect and static quenching. Under the optimized conditions，the linear detection range of MnO₄^- was 0-14 μmol/L，with the detection limit （LOD） of 0.14 μmol/L. N-CQDs showed excellent selectivity and anti-interference ability to other common cations and anions in water. The method has been successfully applied to the determination of MnO₄^- in lake water.

Keywords：nitrogen doped carbon quantum dots；permanganate；nanoprobe

基于核酸适配体的比色生物传感器研究进展

黄丽珊，胡奕津，范申，张红艳^*

（福建中医药大学药学院，福州 350122）

摘要：核酸适配体因能与目标物特异性结合而被用作生物识别元件，广泛用于生物传感器的研究。基于适配体的比色生物传感器，因简便、经济且直观可视等特点，在环境保护、医疗诊断和食品安全等领域备受青睐。随着生物技术和纳米技术的迅速发展，结合不同显色途径和信号放大方法，已建立了多种操作简便、特异性强、灵敏度高的基于适配体的比色传感方法，为现场快速检测技术的发展提供了新思路和新选择。识别元件、信号探针及信号放大策略都是影响比色生物传感器准确性和灵敏度的重要因素，纳米材料和放大策略的选择及设计非常重要。本文主要基于酶催化和等离子体共振比色原理，介绍了近年来比色适配体传感器的研究进展，为高灵敏比色生物传感器的研究和应用提供参考。

关键词：核酸适配体；比色生物传感器；传感模式；综述

中图分类号：Q503；TP212.3    文献标识码：A    文章编号：1000-0720（2024）03-0433-10

Advance of aptamer-based colorimetric biosensor

HUANG Lishan，HU Yijin，FAN Shen，ZHANG Hongyan^*

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

Abstract：Aptamers have been widely used as biological recognition elements of biosensor because of their specific binding to the targets. The colorimetric biosensors based on aptamers are popular in the fields of environmental protection，medical diagnosis and food safety due to their advantages of simplicity，economy and visualization. With the rapid development of biological technology and nano science technology，many colorimetric methods based on aptamers with easy operation，strong specificity and high sensitivity have been established by combining different color rendering pathways and signal amplification methods，providing new ideas and choices for the development of on-site rapid detection. Definitely，recognition elements，signal probes and signal amplification strategies are key factors that affect the accuracy and sensitivity of colorimetric biosensors. Therefore，it is very important to select and design them ingeniously. Accordingly，this paper will mainly introduce the advance of colorimetric sensors in recent years based on the two most common colorimetric principles of enzymatic catalysis and plasma resonance，providing a reference for the research and application of highly sensitive colorimetric biosensors.

Keywords：aptamer；colorimetric biosensor；sensing mode；review

全细胞生物传感器用于检测农药的研究进展

杨瑞¹，张纪媛¹，唐博¹，刘大喜^1，2，马小龙^*1，2，崔建升^*1，2

（1. 河北科技大学环境科学与工程学院，石家庄 050018；2. 河北省污染防治生物技术实验室，石家庄 050018）

摘要：农药残留以多种形式存在于自然环境中，并通过迁移、生物积累等方式对各种环境基质和人类健康造成不利影响。全细胞生物传感器（WCBs）是一种新型的污染物分析装置，因其操作简便、低成本、高灵敏度和选择性好被广泛应用于环境监测领域。本文综述了近年来基于藻类、细菌和真菌的全细胞生物传感器在检测环境中各类农药的应用进展，并展望了全细胞生物传感器未来的研究重点和发展趋势。

关键词：农药残留；全细胞生物传感器；光学测量；电信号测量；综述

中图分类号：TP212.3；O657    文献标识码：A    文章编号：1000-0720（2024）03-0443-12

Advances in pesticide detection using whole cell biosensors

YANG Rui¹，ZHANG Jiyuan¹，TANG Bo¹，LIU Daxi^1，2，MA Xiaolong^*1，2，CUI Jiansheng^1，2

1. College of Environmental Science and Engineering，Hebei University of Science and Technology，Shijiazhuang 050018，China；2. Pollution Prevention Biotechnology Laboratory of Hebei Province，Shijiazhuang 050018，China）

Abstract：Pesticide residues exist in natural environment in many forms，which have adverse effects on various environmental substrates and human health through migration and bioaccumulation. Whole-cell biosensors （WCBs） are a new type of pollutant analysis device that is widely applied in the field of environmental monitoring due to its ease of operation，low cost，high sensitivity，and good selectivity. Hence，this review summarized the recent progress in the application of WCBs based on algae，bacteria and fungi for the detection of various pesticides in the environment. The future research focus and development trend of WCBs were also prospected.

Keywords：pesticide residues；whole cell biosensors；optical measurement；electrical signal measurement；review