【特约专题】
近红外光谱结合化学计量学的掺伪杜仲判别
胡子康1，刘庭恺1，饶艳敏1，龙婉君1，佘远斌2，付海燕*1
（1.中南民族大学 药学院，湖北 武汉 430074；2.浙江工业大学 化学工程学院，浙江 杭州 310014）
摘要：中药杜仲具有多种医疗功能，常被不法分子选作掺假目标以牟取暴利，对掺假杜仲进行快速判别能够更好的保障杜仲质量安全以及维护消费者的利益。使用近红外光谱结合化学计量学，构建了一种用于快速检测杜仲中的几类常见掺假物的方法，可以实现杜仲的真伪鉴别。从结果上看，偏最小二乘判别分析(PLS-DA)获得的训练集和测试集的识别率分别为99%、96%，随机森林（RF）获得的训练集和测试集的识别率分别为99%、92%。此外，采用PLS回归模型对杜仲中不同类型掺假物的掺假程度进行定量，良好的线性相关性和准确度证明了PLS回归模型对于杜仲掺假比例的预测结果是可靠的。该方法可以快速、准确地进行杜仲的真伪鉴别和掺假样品的掺假程度预测。
关键词：中药；杜仲；掺假；近红外；化学计量学
中图分类号：R284.1 文献标识码：A 文章编号：0258-3283（2023）-
DOI:10.13822/j.cnki.hxsj.2023.0155
Near Infrared Spectroscopy Combined with Chemometric for Identification of Adulterated Eucommiae Cortex HU Zi-kang1, LIU Ting-kai1, RAO Yan-min1, LONG Wan-jun1, SHE Yuan-bin2, FU Hai-yan*1 (1．School of Pharmaceutical Sciences，South-central Min Zu University，Wuhan 430074，China; 2．College of Chemical Engineering，Zhejiang University of Technology，Hangzhou 310014， China)
Abstract: Eucommiae Cortex has a variety of medical functions, and is often chosen as the adulterated target by criminals to seek huge profits. Rapid identification and quantification of potential adulteration in Eucommiae Cortex can better protect the quality and safety of Eucommiae Cortex and safeguard the interest of consumers. A method for rapid detection of several common adulterants in Eucommiae Cortex was constructed by combining near infrared spectroscopy with chemometric, and the authenticity of Eucommiae Cortex was realized. From the modeling results, the recognition rates of training set and test set obtained by the PLS-DA analysis were 99% and 96%, respectively. The recognition rates of the training set and the test set obtained by random forest reached 99% and 92%, respectively. Besides, the PLS regression model was used to quantify the adulteration degree of different types of adulterants in Eucommiae Cortex. The good linear correlation and accuracy proved that the PLS regression model was reliable in predicting the adulteration ratio of Eucommiae Cortex. This method could identify the authenticity of Eucommiae Cortex and predict the adulteration degree of adulterated samples quickly and accurately.
Key words: traditional Chinese medicine; Eucommiae Cortex; adulteration; near infrared.; chemometric
引用本文：胡子康，刘庭凯，饶艳敏，等. 近红外光谱结合化学计量学的掺伪杜仲判别[J]. 化学试剂, 2023, 45(10): 1-7。
紫外-可见光谱传感对高温大曲白酒真实性的准确鉴别
苏媛媛1，姜雪1*，仓义鹏1，朱艳美2，向福双2，陈亨业2，付海燕2
(1.江苏省宿迁市产品质量监督检验所，江苏 宿迁，223800；
2.中南民族大学 药学院，湖北省民族药物现代化工程技术研究中心，湖北 武汉, 430074)
摘要：由于高温大曲白酒品质优良价格高昂，不法商贩常以高档酒瓶罐装同香型低档白酒以次充好。基于4种有机染料与风味化合物竞争配位锌离子的紫外-可见光谱结合偏最小二乘判别分析（PLS-DA)对高温大曲白酒的香型和品牌进行识别和分类。结果表明，风味化合物与锌离子的配位能力大于有机染料与锌离子的配合能力，使得光谱信号变化显著，同香型白酒鉴别的PLS-DA训练集和预测集准确率从原始光谱的98.63%和100%均提高到100%，且传感阵列的鉴别结果总体上是优于单传感点和原始光谱的。因此，基于有机染料与风味化合物竞争配位锌离子的紫外-可见传感方法可用于高温大曲白酒真实性的鉴别分析。
关键词：风味化合物；有机染料；紫外-可见传感；高温大曲白酒；PLS-DA
中图分类号：TS261.4 文献标识码：A 文章编号：0258-3283（2023）
DOI:10.13822/j.cnki.hxsj.2023.0450
Accurate Identification of High-temperature Daqu Liquor by UV-VIS Sensing SU Yuan-yuan1,, JIANG Xue1*, CANG Yi-peng1 ZHU Yan-mei2, XIANG Fushuang2, CHEN Heng-ye2, FU Hai-yan2 （1.Suqian Product Quality Supervision and Testing Institute of Jiangsu Province. Suqian 223800, China; 2. The Modernization Engineering Technology Research Center of Ethnic Minority Medicine of Hubei Province, School of Pharmaceutical Sciences, South-Central Minzu University, Wuhan 430074, China）
Abstract: Due to the excellent quality and high price of high-temperature Daqu liquor, unscrupulous traders often adulterate low-grade liquor of the same aroma with high-quality bottles. In this article, the UV-Vis spectral changes caused by the competition coordination of Zn2+ between the flavor compounds in liquor and four organic dyes were used in combination with the partial least squares discriminant analysis (PLS-DA). This method was used to identify and classify the aroma and brand of high temperature Daqu liquor. The results showed that the coordination ability of flavor compounds with Zn2+ was greater than that of organic dyes, resulting in significant changes in spectral signals. The accuracy of the training set and prediction set of PLS-DA for the same aroma type liquor increased from 98.63% and 100% of the original spectrum to 100%. The identification results of the sensor array were generally better than that of the single sensing point and the original spectrum. Therefore, the UV-Vis sensing method based on the competitive coordination of Zn2+ between organic dyes and flavor compounds could be used for the identification and analysis of high-temperature Daqu liquor.
Key words: flavor compounds; organic dyes; UV-vis sensor; high-temperature Daqu liquor; PLS-DA
引用本文：苏媛媛，姜雪，仓义鹏，等. 紫外-可见光谱传感对高温大曲白酒真实性的准确鉴别[J].化学试剂，2023，45（10）：8-13.
4种干扰物对中红外光谱血糖检测影响研究
吕亚玲1,2,3，张朱珊莹*1,2,3，冉康1,2,3，岳岩松1,2,3，张献文*4，曹汇敏*1,2,3
(1.中南民族大学 生物医学工程学院，湖北 武汉 430074；2. 认知科学国家民委重点实验室，湖北 武汉 430074；3. 医学信息分析及肿瘤诊疗湖北省重点实验室，湖北 武汉 430074；4. 临沂格莱普园林机械有限公司，山东 临沂 276700)
摘 要：选取150份干扰物和浓度不同的葡萄糖样本数据，按照全干扰、缺失胆固醇、缺失乳酸、缺失白蛋白和缺失尿素将数据划分5个子集。每个子集进行卷积平滑滤波法（Savitzky-Golay smoothing, SG）处理后，建立偏最小二乘回归（Partial Least Squares Regression, PLSR）模型。利用克拉克误差网格（Clarke Error Grid, CEG）及t检验分析4种干扰物对葡萄糖预测影响。结果表明，子集1~5对应模型预测集相关系数(Correlation Coefficient of Prediction, Rp)分别为0.9131、0.7115、0.7624、0.8578和0.8658，预测集均方根误差（Root Mean Square Error of Prediction, RMSEP）分别为54.8993、239.5512、162.3715、133.9682和106.0521 mg/dL。5个子集位于CEG的A+B区分别为100%、71.43%、66.67%、85.71%和88.89%。t检验中每1 mg/dL的胆固醇、乳酸和白蛋白分别使葡萄糖预测值降低5.288 mg/dL、增高2.214 mg/dL和增高0.031 mg/dL。故胆固醇和乳酸的影响相当显著，其次是白蛋白，而尿素的影响则相对较弱。因此，在中红外血糖定量分析中必须考虑胆固醇、乳酸和白蛋白对血糖检测的影响。
中图分类号：O433.4 文献标识码：A 文章编号：0258-3283（2023）
DOI: 10.13822/j.cnki.hxsj.2023.0517
Study on the Influence of Four Interferents on Blood Glucose Detection by Mid-Infrared Spectrum LV Ya-ling1,2,3, ZHANG Zhu-shan-ying*1,2,3, RAN Kang1,2,3, YUE Yan-song1,2,3, ZHANG Xian-wen*4, CAO Hui-min*1,2,3 (1.College of Biomedical Engineering, South-Central MinZu University, Wuhan 430074, China ; 2.Key Laboratory of Cognitive Science, State Ethnic Affairs Commission, Wuhan 430074, China ; 3.Hubei Key Laboratory of Medical Information Analysis and Tumor Diagnosis & Treatment, Wuhan 430074, China; 4. Linyi Grepo Garden Machinery CO LTD, Linyi 276700, China)
Abstract：Taking 150 parts of glucose sample data containing different interferences and different concentrations, the infrared spectral data were divided into 5 subsets according to full interference, missing cholesterol, missing lactate, missing albumin and missing urea. Each subset was smoothed by Savitzky-Golay smoothing (SG) to construct a partial least squares regression (PLSR) model. The Clarke Error Grid (CEG) and t-test were used to analyze the influence of four interferents on glucose prediction. The results showed that the corresponding model correlation coefficient of prediction (Rp) for subsets 1 to 5 were 0.9131, 0.7115, 0.7624, 0.8578 and 0.8658, respectively, and the root mean square error of prediction (RMSEP) were 54.8993, 239.5512, 162.3715, 133.9682 and 106.0521 mg/dL. The five subsets fell in the A+B zone of CEG, which were 100%, 71.43%, 66.67%, 85.71% and 88.89%, respectively. Cholesterol (decreased by 5.288 mg/dL), lactate (increased by 2.214 mg/dL) and albumin (increased by 0.031 mg/dL) per 1 mg/dL in t-test decreased and increased the predictive value of glucose, respectively. So, cholesterol and lactate have significant effects, followed by albumin, urea has relatively weak effects. Therefore, the effects of cholesterol, lactate and albumin on blood glucose detection must be considered in the quantitative analysis of mid-infrared blood glucose.
Key words：mid-infrared spectrum; spectral analysis; blood glucose detection; interferents; quantitative models
引用本文：吕亚玲，张朱珊莹，冉康，等. 4种干扰物对中红外光谱血糖检测影响研究[J].化学试剂，2023，45（10）：14-20.
【综述与专论】
酶/功能性框架材料光催化转化CO2的研究进展
仇逸楠1，王宜峰2,3，王燕飞4，胡嘉欢2，罗希2，尹丰伟2，付永前*2
(1.浙江理工大学 生命科学与医药学院，浙江 杭州 310018；2.台州学院 台州市生物质功能材料开发与应用重点实验室，浙江 台州 318000；3.南京师范大学 食品与制药工程学院，江苏 南京 210023；4.台州市产品质量安全检测研究院，浙江 台州 31800)
摘要：功能性框架材料包括金属有机框架（Metal organic frameworks，MOFs）和共价有机框架（Covalent organic frameworks，COFs），前者是一类金属离子与有机配体配位连接的聚合物，后者是一类无金属共价连接的有机聚合物，具有比表面积大、结构可调性等特点，是近年来功能性材料研究热点。功能性框架材料自身的结构优势决定其在载酶光催化转化CO2方面具有的良好应用潜力，简要总结了近年来酶/功能性框架材料光催化转化CO2的研究进展，介绍了MOFs材料与COFs材料在酶光催化转化CO2中的应用、优势、存在问题及未来发展机遇进行了总结和展望。
关键词：金属有机框架；共价有机框架；酶；催化；二氧化碳
中图分类号：Q819 文献标识码：A 文章编号：
DOI:10.13822/j.cnki.hxsj.2023.0384
Recent Advances in Photocatalytic Conversion of Carbon Dioxide by Enzyme/Functional Framework Materials QIU Yi-nan1, WANG Yi-feng2,3, WANG Yan-fei4, HU Jia-huan2, LUO Xi2, YIN Feng-wei2, FU Yong-qian*2 (1. College of Life and Medicine, Zhejiang Sci-Tech University, Hangzhou 310018, China; 2. Taizhou Key Laboratory of Biomass Functional Materials Development and Application, Taizhou University, Taizhou 318000, China; 3. College of Food and Pharmaceutical Engineering, Nanjing Normal University, Nanjing 210023, China; 4 Taizhou Institute of Product Quality and Safety Inspection, Taizhou 318000, China)
Abstract: Functional framework materials include metal-organic frameworks (MOFs) and covalent organic frameworks (COFs). The former is a kind of polymer coordinated by metal ions and organic ligands, and the latter is a kind of organic polymer without a metal covalent connection. With large specific surface areas, adjustable structures, and other characteristics, these functional materials have been a research hotspot in recent years. The structural advantages of functional framework materials determined their good application potential in the field of photocatalytic conversion of CO2 with enzymes. The research progress of enzyme/functional framework materials for photocatalytic conversion of CO2 in recent years was briefly summarized. The application, advantages, existing problems, and future development opportunities of MOFs and COFs in enzymatic photocatalytic conversion of CO2 were reviewed.
Key words：metal organic frameworks; covalent organic frameworks; enzyme; catalysis; carbon dioxide
引用本文：仇逸楠, 王宜峰, 胡嘉欢, 等. 酶/功能性框架材料光催化转化CO2的研究进展[J]. 化学试剂, 2023, 45（10）：21 -30 .
有机小分子谷胱甘肽荧光探针研究进展
李娜娜1，王振1，邢志勇2,*
(1. 忻州师范学院 化学系，山西 忻州 034000； 2. 右江民族医学院 医学检验学院，广西 百色 533000)
摘要：荧光探针是一种会对pH、温度、特定的物质产生荧光响应的分子。荧光探针由3个基本单元：荧光基团、连接体和识别基团组成。荧光基团具有讯号传递功能，能直接影响到探针对检测对象的敏感性。识别基因作为一种具有特定或识别作用的结构，其特征在于其高度的选择性和特异性。连接体就是在荧光基团和识别基团之间起到衔接的作用。谷胱甘肽（GSH）是由谷氨酸、半胱氨酸和甘氨酸构成的三肽类物质。它在抗HIV、抗过敏、保护巯基酶的活性以及抗氧化和维持体内血红球蛋白表面细胞膜的结构稳定性等方面有着重要作用，并且它还可以用作食品添加剂，广泛应用于环境监测。基于此，开发以谷胱甘肽为被测物质的多功能或多通道的荧光探针分子就成了一项具有挑战性的新任务。主要叙述了基于谷胱甘肽的荧光探针的设计合成和使用方面的最新进展。
关键词：谷胱甘肽；荧光探针；识别位点；特异性
中图分类号：O656.3 文献标识码：A 文章编号：0258-3283（2023）
DOI:10.13822/j.cnki.hxsj.2023.0891
Recent Progress of Organic Small Molecule Fluorescent Probes for Detection of Glutathione LI Na-na1，WANG Zhen1，XING Zhi-yong2，* (1. Xinzhou Teachers University，Department of Chemistry, Xinzhou 034000；2. School of Laboratory Medicine, Youjiang Medical University for Nationalities, Baise 533000, China）
Abstract: Fluorescent probe is a kind of molecule that can produce fluorescent responses to pH, temperature, and specific substances. The fluorescent probe consists of three basic units: fluorescent group, linker, and recognition group. Fluorescent groups have the function of signal transmission, which can directly affect the sensitivity of the probe to the detection object. A recognition gene, as a structure with a specific or recognition function, is characterized by its high selectivity and specificity. Linker is the link between the fluorescent group and recognition group. Glutathione is a tripeptide composed of glutamic acid, cysteine, and glycine. It plays an important role in anti-HIV, anti-allergy, protecting the activity of sulfhydrylase, resisting oxidation, and maintaining the structural stability of hemoglobin surface cell membrane in vivo. It can also be used as a food additive and is widely used in environmental monitoring. Therefore, it is a challenging new task to develop multifunctional or multi-channel fluorescent probe molecules with glutathione as the measured substance. This paper mainly describes the latest progress in the design, synthesis, and application of fluorescent probes for GSH.
Key words: glutathione; fluorescent probe; recognition site; specificity
引用本文：李娜娜，王振，邢志勇. 有机小分子谷胱甘肽荧光探针研究进展[J]. 化学试剂，2023，45（10）：31-39.
【生化与药用试剂】
基于银纳米颗粒免疫比色法检测甲胎蛋白
张建花*，章志翔，李蓄涵，曹惟嘉，耿佳琦，于成云，阎新宇
（临沂大学 化学化工学院，山东 临沂 276000）
摘要：甲胎蛋白（AFP）是临床诊断肝细胞癌（HCC）最广泛使用的血清标志物，可用于HCC的诊断、治疗评估、预后预测和复发监测。基于银纳米颗粒（AgNPs）比色法是癌蛋白检测的一种崭新技术方案，具有操作简便、响应速度快、成本低的优点。实验中，将AgNPs标记抗体作为AFP检测的探针，当AFP存在时，AgNPs-抗体探针与目标蛋白发生免疫识别，形成纳米颗粒二聚体或多聚体等，导致AgNPs的颜色发生变化，可用肉眼或紫外光谱观察到。结果表明，随着AFP浓度的增大，AgNPs的颜色逐渐从黄色变为无色，且其最大紫外吸收峰值降低；在5 ~ 1000 ng/mL范围内，吸光度和AFP浓度的对数之间存在较好的线性关系，检出限为7.4 ng/mL，并对AFP的检测表现出较强的选择性。
关键词：甲胎蛋白；免疫反应；比色法；银纳米颗粒；分析；检测
中图分类号：O652.3 文献标识码：A 文章编号：0258-3283（2023）
DOI：10.13822/j.cnki.hxsj.2023.0391
Alpha Fetoprotein Detection Based on Colorimetric Method of Silver Nanoparticles Immunoassay ZHANG Jian-hua*, ZHANG Zhi-xiang, LI Xu-han, CAO Wei-jia, GENG Jia-qi, YU Cheng-yun, YAN Xin-yu (School of Chemistry and Chemical Engineering, Linyi University, Linyi 276000, China)
Abstract: Alpha fetoprotein (AFP) is the most widely used serum marker for the clinical diagnosis of hepatocellular carcinoma (HCC), which can be used for the diagnosis, treatment evaluation, prognosis prediction, and recurrence monitoring of HCC. The colorimetric method based on silver nanoparticles (AgNPs) can provide a new approach to cancer protein detection, which has the advantages of simple operation, fast response, and low cost. In the experiments, the AgNPs-labeled antibodies served as the detection probes, which were bound to AFP by specific molecular biorecognition, forming AgNP dimers or multimers. The AFP-induced aggregation would change the color of AgNPs, which can be observed or detected by UV-vis spectroscopy. The results show that the color of AgNPs gradually changed from dark yellow to colorless as the concentration of AFP increased and the maximum UV absorption peak decreased. The absorbance exhibited a linear relationship with the logarithm of AFP concentration from 5 to 1000 ng/mL and a limit of detection as low as 7.4 ng/mL, and it showed good selectivity for AFP detection.
Key words：Alpha fetoprotein; immune reaction; colorimetric method; AgNPs; analysis; detection
引用本文：张建花, 章志翔, 李蓄涵, 等. 基于银纳米颗粒免疫比色法检测甲胎蛋白[J]. 化学试剂, 2023, 45(10):40-45.
简单BODIPY光动力化合物的合成及其抗胶质瘤活性
常婧a，杨田田a，王淑云a，付腊腊a，唐婉毓a，王小波*a，胡美纯*b
（湖北科技学院医学部 a.药学院，b.基础医学院，湖北 咸宁 437100）
摘要：设计合成了基于BODIPY母核的简单化合物I2-BODIPY,通过核磁共振波谱法、高分辨质谱法(HRMS)对其进行了表征。1,3-二苯基异苯并呋喃（DPBF）检测单线态氧实验表明I2-BODIPY在溶液中有良好的活性氧（ROS）释放能力。以不同浓度的BODIPY、I2-BODIPY (0、0.625、1.25、2.5、5、10 μmol/L)处理胶质瘤U87、U251细胞。MTT法验证BODIPY、I2-BODIPY能剂量依赖性地抑制胶质瘤细胞的增殖。在绿光（520 nm）照射下I2-BODIPY对U87 (IC50=1.21 μmol/L)、U251 (IC50=0.54 μmol/L)细胞具有优异的光动力活性。JC-1法证明BODIPY、I2-BODIPY能诱导细胞线粒体膜电位丧失进而触发U87和U251细胞早期凋亡，其机制可能是光照产生的大量ROS氧化破坏了线粒体膜，进而诱导细胞凋亡，发挥其抗胶质瘤活性。
关键词：光动力治疗；BODIPY；胶质瘤；活性氧；细胞凋亡
中图分类号：R917 文献标识码：A 文章编号：0258-3283（2023）--
DOI：10.13822/j.cnki.hxsj.2023.0389
Synthesis and Anti-glioma Activity of Simple BODIPY Photodynamic Compounds CHANG Jinga, YANG Tian-tiana, WANG Shu-yuna, FU La-laa, TANG Wan-yua, WANG Xiao-bo*a, HU Mei-chun*b (a. School of Pharmaceutical Sciences, b. School of Basic Medical Sciences, Hubei University of Science and Technology, Xianning 437100, China)
Abstract: A simple compound I2-BODIPY based on BODIPY core was designed and synthesized, and characterized by NMR and high-resolution mass spectrometry (HRMS). The singlet oxygen detection experiments using 1,3-diphenylisobenzofuran (DPBF) showed that I2-BODIPY had good release ability of reactive oxygen species (ROS) in solution. Glioma U87 and U251 cells were treated with different concentrations of BODIPY and I2-BODIPY (0, 0.625, 1.25, 2.5, 5, 10 μmol/L). MTT assay showed that BODIPY and I2-BODIPY could inhibit the proliferation of glioma cells in a dose-dependent manner. I2-BODIPY had excellent photodynamic activity against glioma U87 and U251 under green light irradiation (wavelength=520 nm), with the IC50 = 1.21 μmol/L for U87, and the IC50 = 0.54 μmol/L for U251. JC-1 method demonstrated that BODIPY and I2-BODIPY could induce the loss of mitochondrial membrane potential in cells and further trigger early apoptosis of U87 and U251 cells. The mechanism may be that a large amount of light-produced ROS induced oxidative damage on the mitochondrial membrane, thereby inducing cellular apoptosis and exerting its anti-glioma activity.
Key words: photodynamic therapy; BODIPY; glioma; reactive oxygen species; cell apoptosis
引用本文：常婧，杨田田，王淑云，等. 简单BODIPY光动力化合物的合成及其抗胶质瘤活性[J]. 化学试剂, 2023, 45(10): 46-52.
杨俊1，梁玉清1，尹彩霞1，梁光平*1，刘雄伟2，刘雄利2
（1. 遵义医药高等专科学校，贵州 遵义 563006；
2. 贵州大学 西南药食两用资源开发利用技术国家地方联合工程研究中心，贵州 贵阳 550025）
摘要：研究新型鬼臼毒素拼接抗肿瘤活性分子衍生物的抗肺癌活性及其机制。以鬼臼毒素为原料，丁二酰基为linker，分别与奎宁、喜树碱、1-Boc-3-羟甲基-2-甲基吲哚反应得到化合物2a ~ 2c，采用MTT法评价其对人肺腺癌耐顺铂细胞株（A549/DDP）、人非小细胞肺癌细胞株（A549）的抗增殖活性；不同浓度的化合物2a作用于A549/DDP细胞后，PI染色法检测细胞周期，DAPI染色法检测细胞核状态，Annexin V-FITC/PI双染法检测细胞凋亡，细胞划痕实验检测细胞的迁移能力。化合物2a ~ 2c对A549细胞、A549/DDP细胞具有非常好的细胞毒性，均明显优于阳性对照药（依托泊苷、顺铂），其中化合物2a对A549/DDP细胞的细胞毒性是依托泊苷的80多倍，具有很好的抗耐药作用，化合物2a显著的阻滞A549/DDP细胞周期的G0/G1期，诱导A549/DDP细胞发生凋亡，抑制A549/DDP细胞的迁移能力，且与化合物2a剂量呈正相关。化合物2a对耐药细胞株A549/DDP具有很好的细胞毒活性，其作用机制为通过阻滞A549/DDP细胞周期G0/G1期，诱导A549/DDP细胞发生凋亡，同时抑制A549/DDP细胞的迁移能力。
关键词：鬼臼毒素；奎宁；衍生物；人肺癌耐顺铂株A549/DDP
中图分类号：R914.4 文献标识码：A 文章编号：0258-3283（2023）
DOI:10.13822/j.cnki.hxsj.2023.0411
Synthesis and Antiproliferation Activities of New Podophyllotoxin Spliced Antitumor Active Molecule Derivatives on Lung Cancer YANG Jun1, LIANG Yu-qing1, YIN Cai-xia1, LIANG Guang-ping*1, LIU Xiong-wei2, LIU Xiong-li2（1. Zunyi Medical And Pharmaceutical College, Zunyi 563006, China; 2. National ＆ Local Joint Engineering Research Center for the Exploition of Homology Resources of Medicine and Food, Guizhou University, Guiyang 550025, China)
Abstract: This study was performed to investigate the inhibitory effects of new podophyllotoxin spliced antitumor active molecule derivatives on lung cancer cells and its mechanisms. Using podophyllotoxin as raw material and succinic acyl group as linker, compounds 2a ~ 2c were obtained by reacting with quinine, camptothecin, and 1-Boc-3-hydroxymethyl-2-methylindole, respectively. Its antiproliferative activity in vitro against cisplatin-resistant human lung adenocarcinoma cells (A549/DDP) and human non-small cell lung cancer cells (A549) was evaluated using the MTT method. After A549/DDP cells were treated with compound 2a at different concentrations, the cell cycle, nuclear state, apoptosis, and migration ability of cells were individually detected by PI staining, DAPI staining, Annexin V-FITC/PI double staining, and cell scratch assays. Compounds 2a to 2c showed very high cytotoxicity against A549 cells and A549/DDP cells, which were significantly better than the positive control drugs (etoposide and cisplatin). Among them, the cytotoxicity of compound 2a against A549/DDP cells was more than 80 times that of etoposide, with superior anti-drug resistance. Compound 2a significantly blocked the G0/G1 phase of A549/DDP cells, induced their apoptosis, and inhibited their migration abilities. These influences were positively correlated with the doses of compound 2a.
Key words: podophyllotoxin; quinine; derivatives; cisplatin-resistant human lung cancer cells
引用本文：杨俊, 梁玉清, 尹彩霞, 等. 新型鬼臼毒素拼接抗肿瘤活性分子衍生物的合成及抗肺癌活性研究[J]. 化学试剂, 2023, 45（10）：53-60.
【功能材料】
李江*，王溪梦，李晨，张文燕
(中国石油大学（北京） 新能源与材料学院，北京 102249)
摘要：化石能源的过度开发利用造成的能源危机和环境问题促使研究人员尝试利用可再生能源来生产增值化学品。生物质作为一种来源丰富的可再生有机碳源，可用于转化制备许多有价值的化工产品。其中可通过乳酸氧化制备的丙酮酸备受关注，可用于制备各种工业产品，如香水、食品添加剂、药品等。金属有机框架材料(MOF)由于其高度多样化的结构、高比表面积和可调节的孔径而成为近10年来备受关注的材料，可用于制备活性催化剂或载体。在本工作中，MOF衍生的钒基碳材料被用于催化乳酸乙酯有氧氧化为丙酮酸乙酯。在最佳条件下，MOF-5衍生的钒催化剂的乳酸乙酯转化率为95.72%，丙酮酸乙酯选择性为67.10%。经过多次循环，该催化剂具有良好的稳定性。实验及表征结果表明：V5+/V4+物种的比例，而非孔道结构，是决定催化性能的关键。
关键词：生物质；钒基碳材料；金属有机骨架；乳酸乙酯；丙酮酸乙酯；有氧氧化
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2023）--
DOI: 10.13822/j.cnki.hxsj.2023.0107
Catalytic Aerobic Oxidation of Ethyl Lactate to Ethyl Pyruvate over Metal-organic Framework-derived Carbon-supported Vanadium Catalysts LI Jiang*, WANG Xi-meng, LI Chen, ZHANG Wen-yan ( College of New Energy and Materials, China University of Petroleum, Beijing 102249)
Abstract: The energy crisis and environmental problems caused by over-exploitation and utilization of fossil energy have made the researchers to attempt the utilization of renewable energy to produce value-added chemicals. As an abundant renewable organic carbon source on earth, biomass can be converted into many value-added chemicals. Among them, pyruvate, which can be prepared by oxidation of lactic acid, has attracted much attention and can be used to prepare various industrial products, such as perfumes, food additives, pharmaceuticals, etc. Metal-organic frameworks (MOF) are highly appealing materials in last decade due to the highly diversified structure, high specific surface area, and adjustable pore size. They can also be used to prepare active catalysts or supports. In this work, MOF-derived vanadium-based carbonaceous materials were used to catalyze aerobic oxidation of ethyl lactate to yield ethyl pyruvate. Under optimal conditions, the conversion of ethyl lactate reached 95.72% using MOF-5-derived vanadium catalyst, while the selectivity of ethyl pyruvate was 67.10%. The catalytic performance of the catalyst remained unchanged after multiple cycles, demonstrating the good stability. The experimental and characterization results suggested that the ratio of V5+/V4+ species, instead of pore structure, played a critical role in determining the catalytic performance of the V catalyst.
Key words: biomass; vanadium-based carbon material; metal-organic frameworks; ethyl lactate; ethyl pyruvate; aerobic oxidation
引用本文：李江，王溪梦，李晨，等. 金属有机骨架衍生的钒碳催化剂催化氧化乳酸乙酯制备丙酮酸乙酯[J]. 化学试剂, 2023, 45(10): 61-69。
三苯基膦功能化聚酰胺/铑催化烯烃氢甲酰化
张志超，李璐，韩双*
(沈阳化工大学 理学院，辽宁 沈阳 110142)
摘要：以三(3-氨基苯基)膦与联苯-4,4'-二甲酸为原料合成了一种三苯基膦功能化的聚酰胺有机载体，并通过红外光谱、固体核磁对其结构进行表征。聚酰胺载体与Rh(acac)(CO)2组成的多相催化体系可以有效地催化1-己烯的氢甲酰化反应。研究表明，该多相催化剂具有较好的化学稳定性和催化效果。在90 ⁰C下，在甲苯溶剂中，催化剂在15 h内完全催化转化1-己烯生成庚醛和2-己烯，产物中醛的选择性为37.4%。通过离心的方法可以实现催化剂与产物的快速分离及多次利用。催化剂的循环使用研究表明，在使用5次后，对1-己烯的催化活性仍高达100%，醛的选择性在34.9%以上，产物醛的正异构比约为2.5。
关键词：多相催化；膦-铑催化剂；聚合物载体；氢甲酰化反应；1-己烯
中图分类号：O62 文献标识码：A 文章编号：0258-3283（2023）
DOI:10.13822/j.cnki.hxsj.2023.0475
Hydroformylation of Olefins Catalyzed by Triphenylphosphine Functionalized Polyamide/Rhodium Catalyst ZHANG Zhi-chao, LI Lu, HAN Shuang* (School of Science, Shenyang University of Chemical Technology, Shenyang 110142, China)
Abstract: A triphenylphosphine functionalized porous organic polyamide was synthesized using tri(3-aminophenyl) phosphine and biphenyl-4,4'-dicarboxylic acid as starting materials. The structure of the isolated polyamide was identified by Fourier transform infrared spectroscopy and solid-state nuclear magnetic resonance. A heterogeneous catalyst was prepared by combination of the porous polyamide and Rh(acac)(CO)2 for catalytic hydroformylation of 1-hexene. It was shown that the heterogeneous catalyst displayed good chemical stability and catalytic performance. The conversion of 1-hexene to heptal and 2-hexene was 100% at 90 oC for 15 h with toluene as the reaction solvent, and the selectivity of aldehyde products was 37.4%. Furthermore, the heterogeneous catalyst can be rapidly separated from the reaction mixtures by centrifugation and recycled for multiple uses. The heterogeneous catalyst showed excellent catalytic activity after 5 runs. The conversion of 1-hexene was still as high as 100%, with the selectivity for aldehyde products higher than 34.9%. Meanwhile, the ratio of the linear aldehyde to the branched product was approximately 2.5.
Key words：heterogeneous catalysis; phosphine-rhodium catalyst; polymer carriers; hydroformylation reaction; 1-hexene
引用本文：张志超，李璐，韩双. 三苯基膦功能化聚酰胺/铑催化烯烃氢甲酰化[J]. 化学试剂，2023，45（10）：70-76 .
羧甲基纤维素钠凝胶的吸水性能研究
马艳梅*，苗书颜
(信阳学院 工学院，河南 信阳464000)
摘要：以滤纸、氢氧化钠、一氯乙酸为原料，制备羧甲基纤维素钠，再加入含有Al3+的交联试剂，即获得羧甲基纤维素钠凝胶。并探究最合适的交联试剂浓度，进而探究羧甲基纤维素钠凝胶的吸水及保水性能。利用单因素分析法探究pH和温度对羧甲基纤维素钠凝胶吸水性能的影响。结果表明：羧甲基纤维素钠凝胶在去离子水中的吸水性能及吸满水后的保水性能较好，交联试剂中Al3+浓度为0.1 mol/L，温度为20 ℃，pH 5.0时，质量吸水倍率最大，为12.48。表明羧甲基纤维素钠凝胶具有一定的吸水性和保水性。
关键词：羧甲基纤维素钠凝胶；吸水性能；保水率；质量吸水倍率
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2023）
DOI:10.13822/j.cnki.hxsj.2023.0406
Water Absorption Performance of Sodium Carboxymethylcellulose Gel MA Yan-mei*, MIAO Shu-yan (School of Science and Technology, Xinyang University, Xinyang 464000, China)
Abstract: In this experiment, sodium carboxymethyl cellulose was prepared with filter paper, sodium hydroxide, and chloroacetic acid. Further introduction of Al3+-contained crosslinking reagent produced sodium carboxymethyl cellulose gel. The optimum concentration of cross-linking reagent was determined to study the water absorption and water retention properties of carboxymethyl cellulose sodium gel. The effects of pH and temperature on water absorption of sodium carboxymethyl cellulose gel were investigated by single-factor analysis. The results showed that sodium carboxymethyl cellulose gel had good water absorption in deionized water and water retention after full water absorption. The maximum water absorption ratio was 12.48 under the conditions of 0.1 mol/L Al3+ in the crosslinking reagent, 20°C, and pH 5.0. The results showed that the sodium carboxymethyl cellulose gel had certain water absorption and water retention properties.
Key words：sodium carboxymethylcellulose; water absorption properties; water retention; mass water absorption rate
引用本文：马艳梅，苗书颜. 羧甲基纤维素钠凝胶的吸水性能研究[J]. 化学试剂，2023，45（10）：77 -82 .
【分离提取技术】
高纯试剂环己烷的提纯方法
田洪旭，曲健，倪余文*，陈吉平
(中国科学院 分离分析化学重点实验室，大连化学物理研究所，辽宁 大连116023)
摘要：环己烷作为一种重要的有机试剂，在工业生产、实验室分析等领域有着广泛的应用。利用环己烷的熔点与其杂质差异较大的特点，通过重结晶-过滤提纯-萃取除醇-干燥脱水等步骤，获得了纯度为99.998%的高纯环己烷，各项指标优于T/CRIAC 0072-2022 《化学试剂高效液相色谱用试剂环己烷》中相关指标要求。解决了环己烷试剂痕量杂质除去难度大、成本高等问题。降低了环己烷的提纯成本，减少了环境污染。所获得的高纯试剂环己烷在光谱分析、痕量污染物分析、化工合成等领域有着广泛的应用前景。
关键词：高纯试剂；环己烷；重结晶；提纯；乙醇
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2023）
DOI:10.13822/j.cnki.hxsj.2023.0423
Purification Methods of High-purity Reagent Cyclohexane TIAN Hong-xu, QU Jian, NI Yu-wen*, CHEN Ji-ping (CAS Key Laboratory of Separation Science for Analytical Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China)
Abstract: As an important organic reagent, cyclohexane has been widely used in industrial production and laboratory analysis. In this work, a recrystallization-filtration purification-extraction alcohol removal-drying and dehydration method was adopted to obtain 99.998% cyclohexane based on the distinct melting points between cyclohexane and other impurities. The indicators are better than the relevant requirements in T/CRIAC 0072-2022 “Chemical reagent cyclohexane for high-performance liquid chromatography”. It solves the problems of difficulty and high cost of removing trace impurities of cyclohexane reagent. It reduces the purification cost of cyclohexane and reduces environmental pollution. The obtained high-purity cyclohexane has broad application prospects in spectral analysis, trace contaminant analysis, chemical synthesis, and other fields.
Key words：high purity solvent; cyclohexane; recrystallization; purification;alcohol
引用本文：田洪旭，曲健. 高纯试剂环己烷的提纯方法[J].化学试剂，2023，45（10）：83-87.
大青叶黄酮化合物的分离纯化及对小鼠运动耐力的影响
翟兆峰1,2*，王延宝2
(1. 曲阜师范大学，曲阜，273165；2. 济宁学院，曲阜，273155)
摘要：通过大孔树脂纯化大青叶黄酮提取物后，比较提取物与纯化物对小鼠运动耐力的影响。以吸附率、解吸率及产物中总黄酮含量为评价指标，优化大青叶黄酮提取物的纯化工艺条件，并测定小鼠的力竭游泳时间和相关抗疲劳生化指标，考察纯化前后大青叶黄酮的抗运动疲劳活性。结果表明，采取AB-8大孔树脂纯化大青叶总黄酮提取物的最佳工艺条件为：上样浓度1.0 mg/mL、上样液pH 3.5、上样体积50 mL、上样流速1.5 mL/min、乙醇溶液体积分数70%、洗脱液用量 80 mL、洗脱流速1.0 mL/min。该条件下所得产物的总黄酮含量为65.0%，约为纯化前3.3倍。与空白对照组相较，大青叶黄酮有助于增长小鼠的运动时间，减少乳酸、尿素氮在体内的累积，并提高肝组织中抗氧化酶 (谷胱甘肽过氧化物酶)活力，表明其具有良好的抗运动疲劳活性。另外灌胃相同剂量大青叶黄酮提取物与纯化物的小鼠之间抗运动疲劳作用有显著性差异 (P < 0.05, P < 0.01)，显示大青叶黄酮纯化物可进一步提高小鼠的运动耐力。
关键词：大青叶；总黄酮；分离纯化；运动耐力；大孔树脂
中图分类号：TS201.2 文献标识码：A 文章编号：0258-3283（2023）
DOI: 10.13822/j.cnki.hxsj.2023.0420
Isolation and Purification of Total Flavonoids from Isatidis Folium and Effect on Exercise Endurance of Mice ZHAI Zhao-feng1,2*，WANG Yan-bao2 (1. Qufu Normal University，Qufu 273165, China；2. Jining University，Qufu 273155, China)
Abstract: After purifying the flavonoid extracts from Isatidis Folium by macroporous resin, the effects of the extracts and the purified substances on exercise endurance in mice were compared. The adsorption rate, desorption rate, and the total flavonoids in products were selected as the evaluation indicators, and the purified conditions of total flavonoids extract from Isatidis Folium were optimized. The exhaustion swimming time and related anti-fatigue biochemical indices of mice were measured, and the anti-exercise fatigue activity of Isatidis Folium flavonoids before and after purification was investigated. The results showed that the optimum purified conditions of total flavonoids from Isatidis Folium with AB-8 macroporous resin were as follows: loading sample concentration, 1.0 mg/mL; pH value of loading solution, 3.5; loading sample volume, 50 mL; loading flow rate, 1.5 mL/min; ethanol, 70% (v/v); eluent volume, 80 mL, and elution flow rate, 1.0 mL/min. After purification by these conditions, the contents of total flavonoids in the purified product increased to 65.0%, which was about 3.3 times higher than that before being purified. Compared with the blank control group, Isatidis Folium flavonoids helped to increase the exercise time of mice, reduce the accumulation of lactic acid and urea nitrogen in the body, and increase the activity of the antioxidant enzyme (glutathione peroxidase) in liver tissue, indicating that it has good anti-exercise fatigue activity. Moreover, there was a significant difference in the activity of resisting movement fatigue between different groups of mice that were treated with intragastric administration of extract and purified product of flavonoids from Isatidis Folium, respectively (P < 0.05, P < 0.01). This result presented that purified product could further improve the exercise endurance of mice.
Key words：isatidis folium; total flavonoids; isolation and purification; exercise endurance; macroporous resin
引用本文：翟兆峰，王华伟，王延宝. 大青叶黄酮化合物的分离纯化及对运动耐力的影响[J]. 化学试剂，2023，45（10）：88-94 .
【电化学和新能源】
碱金属和稀土金属对CuFe8-LDO催化剂的CO2加氢反应性能的影响
黄菊1，张志远1，孟影子2，李淳2，郭立升1，张成华1，魏宇学*1，孙松1
（1. 安徽大学 化学化工学院，安徽 合肥 230601；2. 安徽碳鑫科技有限公司，安徽 淮北 235141）
摘要：研究了碱金属元素Na、K和稀土金属元素La、Ce、Y对铜铁层状双金属氧化物催化剂（CuFe8-LDO）的CO2加氢反应性能影响，采用XRD、SEM-EDS、低温N2吸附-脱附、H2-TPR、CO2-TPD等方法表征了催化剂的结构和物化性质，在此基础上结合其CO2加氢反应性能，研究了构效关系。实验结果表明，碱金属元素Na、K改性能够促进催化剂的还原，改变其对CO2的吸附强度，从而提高了CO2加氢反应活性。其中，Na/CuFe8-LDO催化剂更有利于C5+烃类的生成，K/CuFe8-LDO催化剂更有利于C2-C4烃类的生成。稀土金属元素La、Ce、Y的加入不利于提高催化剂的C2+烃类选择性，Y/CuFe8-LDO催化剂的CO2加氢反应活性略有增加。
关键词：二氧化碳；加氢；助剂；铜铁基催化剂；层状双金属氢氧化物
中图分类号： O64 文献标志码：A 文章编号：0258-3283（2023）
DOI： 10.13822/j.cnki.hxsj.2023.0368
Effects of Alkali and Rare Earth Metals on The Performance of CuFe8-LDO Catalysts for CO2 Hydrogenation Reaction HUANG Ju1, ZHANG Zhi-yuan1, Meng Ying-zi2, Li Chun2, GUO Li-sheng1, ZHANG Cheng-hua1, WEI Yu-xue*1, SUN Song1 (1. School of Chemistry and Chemical Engineering, Anhui University, Hefei 230601, China; 2. Anhui Tanxin Technology Co., Ltd., Huaibei 235141, China)
Abstract: The effect of modifications of copper-iron layered bimetallic oxide catalysts (CuFe8-LDO) by alkali metal elements (Na and K) and rare earth metal elements (La, Ce, and Y) on their CO2 hydrogenation performance were investigated. The structures and physicochemical properties of the catalysts were characterized by XRD, SEM-EDS, low temperature N2 adsorption-desorption, H2-TPR, and CO2-TPD. On this basis, the structure-activity relationships were studied in conjunction with their CO2 hydrogenation reaction performance. The results showed that the modification with alkali metal elements (Na and K) promoted the reduction of the catalyst and changed its adsorption strength of CO2, thus improving its CO2 hydrogenation reaction activity. Among them, the Na/CuFe8-LDO catalyst was more favorable to the formation of C5+ hydrocarbons, and the K/CuFe8-LDO catalyst was more favorable to the formation of C2-C4 hydrocarbons. The addition of rare earth metal elements (La, Ce, and Y) was not favorable to improve the C2+ hydrocarbon selectivity of the catalysts, while only the CO2 hydrogenation reaction activity of the Y/CuFe8-LDO catalyst was slightly increased.
Key words：carbon dioxide; hydrogenation; promoter; CuFe-based catalyst; layered double hydroxide
引用本文：黄菊, 张志远, 孟影子, 等. 碱金属和稀土金属对CuFe8-LDO催化剂的CO2加氢反应性能的影响[J]. 化学试剂, 2023,45（10）：95-100.
MOF基电化学传感器及其重金属离子检测应用研究进展
任书芳*，吕蕊，王仲来，曹莉，郭童，刘晓航，冯静
（甘肃政法大学a.甘肃省证据科学技术研究与应用重点实验室，b.司法警察学院（公安分院）兰州730070）
摘要：现代工业化快速发展，重金属等环境污染严重影响生态系统和公众健康。基于MOFs及其复合材料的电化学传感系统是重金属污染物分析检测领域的研究热点。综述了基于MOFs及其复合材料的电化学传感器的构建及其在重金属离子检测中的应用研究进展，简要概述了MOFs材料的组成、结构、分类命名、制备技术、电化学传感优势性能等；探讨了MOF/碳纳米材料、MOF/金属纳米材料和MOF/导电聚合物复合材料应用于电化学传感器的优势特性；详细讨论了MOF基电化学传感器在Pb2+、Hg2+和Gd2+等重金属离子检测方面的应用研究进展；对MOFs基电化学传感器在重金属离子检测应用中的优势及存在的问题进行了分析，并对未来研究发展进行了展望。
关键词：重金属离子；金属有机框架（MOFs）；电化学传感器；MOF基复合材料；污染物
DOI:10.13822/j.cnki.hxsj.2023.0365
Research Progress of MOF-based Electrochemical Sensors and Their Detection Application in the Field of Heavy-metal Ion REN Shu-fang*, LV Rui, WANG Zhong-lai, CAO Li, GUO Tong, LIU Xiao-hang, FENG Jing （a. Gansu Provincial Key Laboratory of Evidence Science and Technology Research and Application, b. Judicial Police College (Public Security Branch)，Gansu University of Political Science and Law, Lanzhou 730070, China）
Abstract: With the rapid development of modern industrialization, environmental pollution such as heavy metals has seriously affected ecosystems and public health. Electrochemical sensing systems based on MOFs and their composites have become a research hotspot in the field of analysis and detection of heavy metal contaminants. The research progress on the construction of such electrochemical sensors and their application in heavy metal detection was reviewed. The compositions, structures, classification and naming, preparation technology, and superior performance of electrochemical sensing materials were briefly summarized. The advantages and characteristics of MOF/carbon nanomaterials, MOF/metal nanomaterials and MOF/conductive polymer composites applied to electrochemical sensors were discussed. The application progress of such electrochemical sensors in the detection of heavy metal ions such as Pb2+, Hg2+, and Gd2+ was discussed in detail. The advantages and existing problems of MOFs-based electrochemical sensors in heavy metal detection were analyzed, and the future research and technical development were prospected.
Keywords: heavy metal ions; metal-organic frameworks (MOFs); electrochemical sensors; MOF-based composites；contaminant
引用本文：任书芳，吕蕊，王仲来，等. MOF基电化学传感器及其重金属离子检测应用研究进展[J]. 化学试剂，2023，45（10）： 101-109.
【化学品与环境】
虚拟模板表面分子印迹聚合物固相萃取噻虫嗪
杜雪1，孙梦圆1，翁娇静1，田园1，陈静1，何娟*1，李华雨*2
（1.河南工业大学 化学化工学院，河南 郑州 450001；2.河南卷烟工业烟草薄片有限公司技术中心，河南 许昌 461100）
摘要：本研究采用共价有机骨架MCTP-1为载体材料，6-苄氨基嘌呤为虚拟模板，采用沉淀聚合的方法合成噻虫嗪表面分子印迹聚合物（MCTP-1@MIPs）。利用红外光谱、扫描电镜和X-射线衍射对所合成的聚合物进行表征。吸附测试表明，在0.5~30 μg/mL测定范围内最大吸附量可达8.81 μg/mg，且10 min即可达吸附-解析平衡，聚合物对噻虫嗪的印迹因子为2.04，对于噻虫嗪具有高选择性。将聚合物作为柱填料，制备成固相萃取柱，优化固相萃取柱使用条件，使用高效液相色谱-二极管阵列检测器进行检测，建立一种灵敏可靠的检测噻虫嗪的方法。该研究为水中噻虫嗪残留的分离富集检测提供了新思路。
关键词：表面分子印迹聚合物；噻虫嗪；共价有机骨架；固相萃取；分离介质
中图分类号：0652.62 文献标识码：A 文章编号：0258-3283（2023）
DOI:10.13822/j.cnki.hxsj.2023.0387
Virtual Template-based Surface Molecularly Imprinted Polymers for Solid-phase Extraction of Thiamethoxam Du Xue1, Sun Meng-yuan1, Weng Jiao-jing1, Tian Yuan1, Chen Jing1, He Juan*1, Li Hua-yu*2 (1. School of Chemistry and Chemical Engineering, Henan University of Technology, Zhengzhou 450001, China; 2. Technology Center, Henan Cigarette Industrial Reconstituted Tobacco Sheet, Xuchang 461100, China)
Abstract: A novel surface molecularly imprinted polymers (MCTP-1@MIPs) was synthesized through precipitation polymerization using a covalent organic framework MCTP-1 as the carrier material and 6-benzylaminopurine as a virtual template. The synthesized polymers were characterized using Fourier-transform infrared spectroscopy, scanning electron microscopy, and X-ray diffraction. Adsorption tests revealed a maximum adsorption capacity of 8.81 μg/mg within the concentration range of 0.5~30 μg/mL. Furthermore, adsorption-desorption equilibrium was achieved within 10 min. The polymers exhibited high selectivity for thiamethoxam, with an imprinting factor of 2.04. The polymers were further employed as column packing materials to prepare solid-phase extraction columns. Conditions for the solid-phase extraction columns were optimized, and a sensitive and reliable method for detecting new neonicotinoid pesticides was established using high-performance liquid chromatography coupled with a diode array detector. This research offers a novel perspective for the separation, enrichment, and detection of neonicotinoid pesticides in water, presenting innovative ideas for the analysis and monitoring of these compounds.
Key Words: surface molecularly imprinted polymers; thiamethoxam; covalent organic frameworks; solid phase extraction; separation media
引用本文：杜雪，孙梦圆，翁娇静，等.印迹材料对新烟碱类农药的吸附性能测定及样品前处理中的应用[J].化学试剂，2023，45（10）：110-116.
ZnMnCo-LDHs的制备及其对磷酸根废水吸附性能研究
崔宝玉1，李阳1，王家花1，崔节虎*1,2
（1.郑州航空工业管理学院 材料学院，河南 郑州 450000；2.郑州市环境功能材料重点实验室，河南 郑州 450000)
摘要：采用水热法合成三元过渡金属ZnMnCo-LDHs纳米材料，探究Co元素的含量对磷酸根废水吸附性能的影响。在温度100℃、2 h、1 mL三乙醇胺的条件下，制备不同比例ZnMnCo-LDHs纳米材料，以浓度为100 mg/L的KH2PO4 溶液模拟含磷废水测试材料的吸附性能。利用SEM、XRD和FT-IR等技术表征。结果表明：3种ZnMnCo-LDHs纳米材料均为片层状结构，层间插层离子为NO3-。随着Co含量的增加，ZnMnCo-LDHs片状的厚度逐渐变薄，证明Co含量的增加对片状结构具有调控作用。3种ZnMnCo-LDHs纳米材料对磷酸根废水的最大吸附量分别为738.14、732.69、709.6 mg/g。吸附等温线符合Freundlich模型；吸附动力学符合准二级动力学；吸附热力学得出为自发进行的吸热反应。ZnMnCo-LDHs纳米材料经过6次循环性能的测试，去除率仍保持在80%以上，具有良好的循环性能。
关键词：ZnMnCo-LDHs；水热法；磷酸根废水；吸附性能；循环实验
中图分类号：X703 文献标识码：A 文章编号：0258-3283（2023）--
DOI:10.13822/j.cnki.hxsj.2023.0429
Preparation of ZnMnCo-LDHs and its adsorption properties to phosphate wastewater Cui Bao-yu1, Li Yang1, Wang Jia-hua1, Cui Jie-hu*1,2（1.Department of Civil and Architecture, Zhengzhou University of Aeronautical, Zhengzhou 450000,China; 2. Key Laboratory of Environment Functional Materials, Zhengzhou University of Aeronautical, Zhengzhou 450000, China)
Abstract: The ternary transition metal-based ZnMnCo-LDHs nanomaterials were synthesized by hydrothermal method to investigate the effect of the Co contents on the adsorption performance of phosphate wastewater. ZnMnCo-LDHs nanomaterials were prepared at different ratios under the conditions of 100 °C, 2 h, and 1 mL triethanolamine. The adsorption performance of the materials was tested with KH2PO4 solution at a concentration of 100 mg/L as simulating phosphate-containing wastewater. The materials were characterized by SEM, XRD and FTIR techniques. The results showed that the three ZnMnCo-LDHs nanomaterials were all lamellar structures with 
as the intercalating ion between the layers. The thickness of ZnMnCo-LDHs lamellae gradually became thinner with the increase of Co content, which proves that the increase of Co content has a modulating effect on the lamellae structure. The maximum adsorption capacities of the three ZnMnCo-LDHs nanomaterials on phosphate wastewater were 738.14, 732.69, and 709.6 mg/g, respectively. The adsorption isotherms were in accordance with the Freundlich model; the adsorption kinetics followed quasi-secondary kinetics; and the adsorption thermodynamics indicated that the process was a spontaneous endothermic reaction. The ZnMnCo-LDHs nanomaterials were tested for six cycles, and the removal rate remained above 80% with good cycling performance.
Key words：ZnMnCo-LDHs; hydrothermal method; phosphoric acid wastewater; adsorption property; cyclic experiment
引用本文：崔宝玉，李阳，王家花，等. ZnMnCo-LDHs的制备及其对磷酸根废水吸附性能研究[J].化学试剂，2023，45（10）：117-123.
【分析与测试】
娄婷婷*[1]，王淞1，闫枫蕾2，温华蔚1，章骅1，张宏宇2，马兴1
（1.天津海关动植物与食品检测中心，天津，300461; 2.天津商业大学 生物技术与食品科学学院 天津市食品生物技术重点实验室，天津 300134）
摘要：作为天然污染物之一，真菌毒素是全球食品安全的重要威胁。但是，真菌在食品生产中的污染是不可避免的，真菌毒素含量的快速检测及其污染程度的确定可以为真菌毒素的风险防控提供有效的手段。作为一种快速、简单、低成本的分析方法，表面等离子共振(Surface Plasmon Resonance, SPR)传感器已广泛用于多种污染物的实时定性和定量检测，而基于不同分析方法的SPR传感器极大地扩大了其检测目标物的范围，提高了其灵敏度。综述了基于竞争性抑制免疫分析法、分子印迹法、核酸适配体法的SPR传感器在食品真菌毒素检测中的最新研究进展，并对其未来发展前景进行了展望，旨在为其进一步的开发和应用提供研究思路和理论参考。
关键词：真菌毒素；表面等离子共振；食品安全；检测技术；传感器
中图分类号:TS207.3 文献标识码: A 文章编号:
DOI:10.13822/j.cnki.hxsj.2023.0426
Application of Surface Plasmon Resonance Sensor in the Detection of Mycotoxins in Food LOU Ting-ting*1, WANG Song1, YAN Feng-lei2, WEN Hua-wei1, ZHANG Hua1, ZHANG Hong-yu2, MA Xing1
(1. Animal, Plant and Foodstuffs Inspection Center of Tianjin Customs, Tianjin 300461, China; 2. Tianjin Key Laboratory of Food Biotechnology, College of Biotechnology and Food Science, Tianjin University of Commerce, Tianjin 300134, China)
Abstract: As one of the natural pollutants, mycotoxins constitute an important threat to global food safety. However, the contamination of fungi in food production is inevitable. Hence, the rapid detection of mycotoxin content and the determination of the contamination degree can provide an effective means for the risk control of mycotoxins. As a fast, simple, and low-cost analytical method, surface plasmon resonance (SPR) sensors have been widely used for real-time qualitative and quantitative detection of a variety of pollutants. SPR sensors based on different analytical methods greatly expand the object’s detection range and improve its sensitivity. In this paper, the latest research progress of SPR sensors based on competitive immunosuppression assay, molecular imprinted method, and aptamer method for the detection of mycotoxins in food was reviewed, and their future developments were prospected. This study aimed to provide research ideas and theoretical references for their further development and application.
Key words: mycotoxin; surface plasmon resonance; food safety; detection technology; sensor
引用本文：娄婷婷，王淞，闫枫蕾，等. 表面等离子共振传感器在食品真菌毒素检测中的应用[J].化学试剂，2023，45（10）：124-131.
高压密闭消解-ICP-AES法在农产品分析8种元素中的应用
袁润蕾*1,2, 于亚辉1,2, 胡家祯1,2, 刘春霞1,2
（1.河南省岩石矿物测试中心河南，郑州 450012；2.自然资源部贵金属分析与勘查技术重点实验室，河南 郑州 450012)
摘要：为了达到快速、准确的测定大批量农业产品中多种元素含量的目的，建立了基于密闭消解前处理方式结合电感耦合等离子体发射光谱法同时测定农产品中K、Na、Ca、Mg、Fe、Al、S、P元素的方法。通过谱线干扰试验，确定了S、P的最佳分析谱线，极大地提高了分析的准确性。并对消解酸试剂、消解温度、消解时间等实验条件进行探讨，建立了最优密闭消解条件。考察了方法的标准曲线线性关系、检出限、准确度和精密度，结果表明：在最优的实验条件下，在一定的浓度范围内所分析的8种元素具有良好的线性关系，线性相关系数R2达到0.999以上。选择农产品国家标准物质GBW10010（大米）、GBW10011（小麦）、GBW10014（圆白菜）、GBW10015（菠菜）进行方法验证，方法检出限范围为0.007～0.11 µg/g，相对误差RE%为-2.91%～1.87%，相对标准偏差RSD%为0.15%～4.40%。采用本实验方法进行实际农产品的加标回收实验，回收率在91%～109%。本实验方法能够实现同时大批量、快速、准确的测定农产品中8元素的含量。
关键词：密闭消解；ICP-AES；农产品
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2023）--
DOI：10.13822/j.cnki.hxsj.2023.0372
Application of High Pressure Closed Digestion-ICP-AES in the Analysis of 8 Elements in Agricultural Products YUAN Run-lei*1,2, YU Ya-hui1,2, HU Jia-Zhen1,2, LIU Chun-xia1,2 (1. Henan Province Rock and Mineral Testing Center, Zhengzhou 450012, China; 2. Key Laboratory of Precious Metals Analysis and Exploration Technology, Ministry of Natural Resources, Zhengzhou 450012, China)
Abstract: To quickly and accurately determine the contents of various elements in bulk agricultural products, the closed digestion pretreatment method was used for the simultaneous determination of K, Na, Ca, Mg, Fe, Al, S, and P in agricultural products by inductively coupled plasma emission spectrometry. Through the spectral line interference test, the best analysis spectral lines of S and P were determined, and the accuracy of the analysis was greatly improved. The optimum airtight digestion conditions were determined through the discussion of the digestion acid reagent, digestion temperature, and digestion time. The linear relation of the standard curve, detection limit, accuracy, and precision was also investigated. The linear correlation coefficient R2 of the 8 elements in a certain concentration range was higher than 0.999. The national standards for agricultural products GBW10010 (Rice), GBW10011 (wheat), GBW10014 (cabbage), and GBW10015 (spinach) were selected to validate the method. The detection limit was 0.007~0.11 μg/g, the relative error RE% was -2.91%~1.87%, and the relative standard deviation RSD% was 0.15%~4.40%. The experimental method was used to conduct the actual recovery of agricultural products, and the recovery rate was 91%~109%. This method achieves simultaneous large-scale, rapid, and accurate determination of the contents of 8 elements in agricultural products.
Key words：closed digestion；ICP-AES；agricultural products
引用本文：袁润蕾，于亚辉，胡家祯，等. 高压密闭消解-ICP-AES法在农产品分析8种元素中的应用[J]. 化学试剂, 2023, 45(10):132-137.
【合成与工艺技术】
吡咯烷-2-酮化合物的合成
李金辉1，赵敏*1，陈建中*2
（1. 华东理工大学 化学与分子工程学院 上海 200237；
2. 上海交通大学 化学化工学院 上海 200240）
摘要：以常见的苯乙酮为起始原料，通过盐酸羟胺的加成形成肟，部分肟在钯碳/氢气的条件下直接还原以较好产率得到相应伯胺；另一部分难以直接还原的肟，通过二苯基氯化膦的修饰，随后用硼氢化钠还原、氯化氢脱保护可得到一系列相应的伯胺。最后伯胺在碱性条件下与4-氯丁酰氯进行环化反应，以良好产率得到广泛用于生物活性物质的N-(1'-芳基烷基)-2-吡咯烷酮化合物。目标产物结构通过1HNMR、13CNMR、HRMS-ESI等方式表征。
关键词：吡咯烷-2-酮；芳基烷基酮；芳基烷基酮肟；N-(二苯基膦酰基)-亚胺；伯胺
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2023）
DOI: 10.13822/j.cnki.hxsj.2023.0327
Synthesis of Pyrrolidine-2-ones LI Jin-hui1, ZHAO Min*1, CHEN Jian-zhong*2 (1. School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, China; 2. School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China)
Abstract: N-(diphenylphosphinyl)-imines were prepared via the reaction of aryl acetophenone with hydroxylamine hydrochloride. Among them, some primary amines were obtained by directly reducing the corresponding oximes under Pd/C/H2 conditions. Regarding the oximes that are difficult to be directly reduced, they were modified with diphenyl phosphorus chloride, reduced with sodium borohydride, and deprotected with hydrogen chloride to obtain primary amines. The desired products, which can be used in the synthesis of many bioactive compounds, were obtained by cyclization of a primary amine with 4-chlorobutyryl chloride under basic conditions. The structures of the target products were characterized by 1HNMR, 13CNMR, and HRMS-ESI.
Key words：pyrrolidin-2-one; aryl alkyl ketone; aryl alkyl ketone oxime; N-(diphenylphosphine)-imine; primary amines
引用本文：李金辉, 赵敏, 陈建中. 吡咯烷-2-酮化合物的合成[J]. 化学试剂, 2023, 45（10）：138-148.
简单高效合成缩丙酮保护的N-保护的左旋多巴衍生物
徐鹏舒，李如雯，谢树英，高磊，刘中强*
（海南大学 药学院，海南 海口 570100）
摘要：通过采用先保护羧基再保护氨基的策略，优化了美国专利中Boc-DOPA (Acetonide)-OH的合成方法，以左旋多巴为原料，采用SOCl2/MeOH甲基化代替原路线的CH3I/KHCO3/DMF酯化反应，然后通过与三氟乙酸甲酯的酯酰胺交换反应，实现了一锅合成法，简单高效地保护了羧基和氨基。接着利用2,2-二甲氧基丙烷的高反应活性和CaCl2对甲醇与水的强吸附性质，成功制备了缩丙酮保护的L-DOPA中间体。最后，完全脱去氨基与羧基保护再偶联上N-保护基或者仅选择性脱去甲酯，制得了Boc-DOPA (Acetonide)-OH，Fmoc-DOPA (Acetonide)-OH和另外两种新的缩丙酮保护的L-DOPA试剂。此合成策略避免了使用高沸点溶剂，不产生含碘废物，并且具有产物易分离纯化、产率高、低成本的优点。
关键词：左旋多巴；缩丙酮；叔丁氧基羰基；9-芴基甲氧基羰基；邻苯二甲酰基；三氟乙酰基；寡肽
中图分类号：O625.63 文献标识码：A 文章编号：0258-3283（2023）
DOI:10.13822/j.cnki.hxsj.2023.0263
Simple and Efficient Synthesis of Acetonide-Protected and N-Protected L-DOPA Derivatives XU Peng-shu, LI Ru-wen, XIE Shu-ying, GAO Lei, LIU Zhong-qiang* (School of pharmacy, Hainan University, Haikou 570100, China)
Key words：L-DOPA; acetonide; Boc; Fmoc; Phth; trifluoroacetyl; oligopeptide
引用本文：徐鹏舒, 李如雯, 谢树英, 等. 简单高效合成缩丙酮保护的N-保护的左旋多巴衍生物[J]. 化学试剂, 2023, 45（10）： 149-154.
