质谱分析导向的稳定同位素标记技术进展
张倩，宋玮，王昊阳*
（中国科学院 上海有机化学研究所，上海 200032）
摘要：介绍了近年来发展的一系列具有代表性的质谱分析导向的低残留稳定同位素标记技术：二甲氧基甲砜基嘧啶衍生化、低残留稳定同位素标记季铵化衍生化、新型胍剂化合物的衍生化等技术与方法。一些在常规电喷雾或基质辅助激光解吸电离条件下无法有效离子化的目标分子，在衍生化后产生新的正电荷中心或成为容易被电离物种而被质谱检测，从而提高了这类化合物的质谱学检测灵敏度。该类研究显著优势在于所开发的衍生化试剂本身不是离子型化合物，新产生的电荷中心或易于离子化的基团由衍生化反应引入。过量的衍生化试剂易于除去，不会对随后的质谱分析产生明显干扰。这一系列研究成果在代谢组学、食品安全分析，质谱成像以及单细胞分析领域等方面具有广泛的应用价值。
关键词：质谱学；衍生化；同位素标记；生物活性小分子分析；电荷标签
中图分类号：O657.6 文献标识码：A 文章编号：0258-3283（2022）
Recent Progress on Mass Spectrometry Analysis--oriented Stable Isotopic Labeling Technologies ZHANG Qian, SONG Wei, WANG Hao-yang* (Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China)
Abstract: This article introduced a series of representative mass spectrometry-oriented low-residual stable isotope labeling techniques developed in recent years: dimethoxy-methylsulfoxide pyrimidine-based derivatization,low residual stable isotopic labeling quaternary ammonium derivatization, and new guanidino compoundsderivatization and other technologies and methods. Derivatization reactions introduced isotope labeling charge tags or easily-ionized groups into the target molecules for detected by mass spectrometry, which could not be effectively ionized under conventional ESI or MALDI conditions. Thus, the sensitivity of mass spectrometry detectionwas improvedof these compounds.The most significant advantage of these researchesis that thedeveloped derivatization reagent were not ionic compounds, and the newly isotope labeling charge tags or easily-ionized group is introduced by the derivation biochemical reaction. Excessive derivatization reagents were easy to remove and will not significantly interfere with subsequent mass spectrometry analysis.Therefore, these derivatization reagents and methods would have wide range of potential applications in metabolomics, food safety analysis, mass spectrometry imaging and single cell analysis.
Key words: mass spectrometry; derivatization; isotope labeling; bioactive small molecule analysis; charge tags
引用本文：张倩，宋玮，王昊阳.质谱分析导向的稳定同位素标记技术进展[J].化学试剂，2022, 44（1）：1-9.
低共熔溶剂在天然产物萃取中的应用进展
黄一波* a,b，蒋磊a
（常州工程职业技术学院 a. 检验检测认证学院，b. 江苏省生物酶工程技术研究开发中心，江苏 常州 213164）
摘要：为了取代传统有毒有害有机溶剂，实现对天然产物的绿色高效萃取，低共熔溶剂（DES）已得到广泛应用和普遍关注。DES是一种新型绿色溶剂，具有易于合成、低毒或无毒及环境友好等优点。通过对近10年各类数据库中相关研究论文的梳理分析，简介了DES的分类、合成及性质，重点阐述低共熔溶剂DES在萃取天然产物中生物活性物质（如黄酮类化合物、酚类、酚酸、生物碱、多糖、萜类和皂苷类）的应用，尤其是在多糖和黄酮类物质的提取工艺中的广泛使用。分析了影响DES萃取效率的主要因素。最后，进一步展望了DES未来的发展趋势和应用前景。
关键词：低共熔溶剂；天然产物；萃取；应用进展
中图分类号：O69 文献标识码：A 文章编号：0258-3283（2022）--
Application Progress of Deep Eutectic Solvent (DES) in Natural Products Extraction HUANG Yi-bo* a, b, JIANG Lei a(a. School of Testing, Inspection and Certification, b. Jiangsu Provincial Biological Enzymatic Engineering Technology Research Development Center, Changzhou Vocational Institute of Engineering College, Changzhou 213164, China), Huaxue Shiji, 2022, 44(1), ～
Abstract: In order to replace the traditional toxic and harmful organic solvents and realize the green and efficient extraction of natural products, deep eutectic solvent (DES) has been widely used and concerned. DES is a new type of green solvents, which has the advantages of easy synthesis, low toxicity or non-toxicity and environmental friendliness. This review aimed to make the researchers engaged in the study of natural products to better understand the advantages of DES and promote the wide application of DES in the field of natural products extraction. The relevant research papers in the database have been collected and analyzed in recent 10 years. The classification, synthesis and properties of DES were introduced, and focuses on the application of extracting biological active compounds (such as flavonoids, phenolic components, phenolic acid, alkaloids,polysaccharides, terpenoids and saponins) from natural products, especially in the extraction process of polysaccharides and flavonoids. The main factors were analyzed influencing extract efficiency of EDC. Finally, the development trends and application perspective were forwarded.
Key words: deep eutectic solvent; natural products; extraction; application progress
引用本文：黄一波，蒋磊. 低共熔溶剂在天然产物萃取中的应用进展[J]. 化学试剂，2022, 44(1): 10-20.
作用于γ-氨基丁酸受体的杀虫剂研究进展
刘东东1,2，朱晨1,2，王峰1,2，高一星1，张静1,2，张立新*1,2
（1.辽宁科技大学 化学工程学院，辽宁 鞍山 114051；
2.沈阳化工大学 功能分子研究所 辽宁省绿色功能分子设计与开发重点实验室 沈阳市靶向农药重点实验室，辽宁 沈阳 110142）
摘要：随着杀虫剂的不断使用，昆虫会对所使用的化学物质产生抗药性。γ-氨基丁酸（γ -Aminobutyric acid，GABA）受体是重要的杀虫剂靶标之一，农药学家和昆虫毒理学家对其进行了广泛的研究。作用于该类受体的杀虫剂杀虫活性高、安全性好，使其成为新农药创制的热点。概述了GABA受体的结构与分类、作用于GABA受体的杀虫剂的化学结构、杀虫活性、致毒机理、分类、抗性研究及其在农业病虫害防治的应用，其中新型异噁唑啉类和间二酰胺类因其独特的作用位点、对哺乳动物低毒以及优异的选择性，具有良好的发展前景。
关键词：γ-氨基丁酸；γ-氨基丁酸受体；拮抗剂；杀虫剂；抗性
中图分类号：TQ460 文献标志码：A 文章编号：0258-3283（2022）
Research Progress of Insecticide Acting on γ-aminobutyric Acid Receptors LIU Dong-dong1,2, ZHU Chen1,2, WANG Feng1,2, GAO Yi-xing1，ZHANG Jing1,2, ZHANG Li- xin1,2*(1. School of Chemical Engineering, University of Science and Technology Liaoning, Anshan 114051, China; 2. Institute of Functional Molecules, Liaoning Province Key Laboratory of Green Functional Molecular Design and Development, Shenyang Key Laboratory of Targeted Pesticides, Shenyang University of Chemical Technology, Shenyang 110142, China), Huaxue Shiji, 2022, 44(1),
Abstract: With the continuous use of insecticides, insects will become resistant to the chemicals substances. Gamma aminobutyric acid （GABA） receptor is an important target of insecticides, and extensive study have been done on it by pesticide scientists and insect toxicologists. The insecticides acting on these receptors has becomeresearch focus of new pesticides discovery by the effective insecticidal activity and excellent safety. This paper reviews the structure and classification of GABA receptors, chemical structures, insecticidal activities, toxic mechanism and classification of pesticides that acted on GABA receptors, resistance research and the application prospects in the prevention and management of agricultural pests and diseases. Among them, the new isoxazolines and meta-diamides have wonderful prospects because of their unique sites of action, low toxicity to mammals and better selectivity.
Key words: gamma-aminobutyric acid; gamma-aminobutyric acid receptor; antagonist; insecticide; resistance
引用本文：刘东东，朱晨，王峰，等.作用于γ氨基丁酸受体的杀虫剂研究进展[J].化学试剂，2022，44（1）：21-31.
酒糟总氨基酸、总多酚、多糖含量测定及抗氧化活性研究
许世浩，刘宏炳，何晨露，黎玲玲，燕雪花*
（新疆医科大学 中医学院，新疆 乌鲁木齐 830011）
摘要：酿酒行业每年都会产生大量酒糟，为减少酒糟的丢弃浪费与环境污染，研究酒糟内总成分含量，总抗氧化能力，可为后期开发利用提供理论支持。研究采用茚三酮法、福林酚法、苯酚-硫酸法测定酒糟内总氨基酸、总多酚、多糖含量，同时采用1,1-二苯基-2-三硝基苯肼（1,1-Diphenyl-2-trinitrophenylhydrazyl，DPPH）法、2,2'-联氮双-（3-乙基苯并噻唑林-6-磺酸）二胺盐[2,2'-Azinobis（3-ethylbenzothi azoline-6-sulfonic acid）ammonium salt，ABTS]法、超氧阴离子（Superoxide anion，O2-）法测定酒糟液不同稀释倍数抗氧化能力。谷物酿酒后的副产物中总氨基酸、总多酚、多糖平均含量分别达到9.7998、0.6289、2.8203 mg/mL，对DPPH、ABTS、O2-的自由基清除率均达到90%以上。酒糟液富含大量氨基酸、多酚、多糖，有较强抗氧化能力，可可开发为新型产品，为企业带来下游效益的同时，减轻环境污染，为后续高效利用酒糟液奠定基础。
关键词：酒糟；茚三酮法；福林酚法；苯酚-硫酸法；抗氧化能力
中图分类号：R284.1 文章标识码：A 文章编号：0258-3283（2022）
Determination of Total Amino Acids, Total Polyphenols, Polysaccharide Content and Antioxidant Activity of Distiller's Grains XU Shi-hao, LIU Hong-bing, HE Chen-lu, LI Ling-ling, YAN Xue-hua* (College of TCM, Xinjiang Medical University, Urumqi 830011, China), Huaxue Shiji, 2022, 44(1)
Abstract: :Liquor-making industry produces a large amount of distiller's grains every year. In order to reduce the waste and environmental pollution of distiller's grains, the total composition content and total antioxidant capacity of distiller's grains were studied to provide theoretical support for later development and utilization. In this study, the contents of total amino acids, total polyphenols and polysaccharides in distiller's grains were determined by ninhydrin method, folin-phenol method and phenol-sulfuric acid method. At the same time, 1, 1-diphenyl-2-trinitrophenylhydrazyl (DPPH) method, 2, 2' -azinobis-(3-ethylbenzothiazoline-6-sulfonic acid) ammonium salt (ABTS) method, superoxide anion (O2-) method were used todetermine the antioxidant capacity of different dilution multiples of distiller's grains. The average contents of total amino acids, total polyphenols and polysaccharides in the by-products after liquor-making reached 9.7998 mg/ mL, 0.6289 mg/ mL and 2.8203 mg/ mL, respectively. The free radical scavenging rates of DPPH, ABTS and O2- reached more than 90%. Distillers' grains liquid is rich in a large number of amino acids, polyphenols and polysaccharides, and has strong antioxidant capacity. It can be developed as a new product, which will not only bring downstream benefits to enterprises,but also reduce environmental pollution and lay a foundation for the efficient utilization of distillers' grains in the future.
Key words: distillers' grains; ninhydrin method; folinol method; phenol-sulfuric acid method; antioxidant capacity
引用本文：许世浩，刘宏炳，何晨露，等. 酒糟总氨基酸、总多酚、多糖含量测定及抗氧化活性研究[J]. 化学试剂, 2022, 44(1): 32-38。
EGFR(T790M)抑制剂的设计、合成及活性评价
黄怀征，姚华良，张洁，曾宪霞，覃廷胜，梁倩，曹思思，何林洪*
（广西医科大学 药学院，广西 南宁 530021）
摘要：表皮生长因子受体（EGFR）的T790M突变最为频发，也是肺癌临床治疗失败的主要原因之一。鉴于先导化合物B6优良的抗H1975细胞系和异植瘤活性，对其进行了EGFR（T790M）激酶抑制活性的确认，并使用Autodock软件确认了两者的相互作用。以EGFR（T790M）为靶点对B6进行定向结构修饰，所得目标化合物经NMR和MS表征后，联合体外激酶、细胞生物活性与Autodock软件解释它们的构效关系。结果表明，3-（苯并[d] [1,3]二氧杂-5-基）-1-（1-（乙烯基磺酰基）哌啶-4-基）-1H-吡唑并[3,4-d]嘧啶-4-胺的抗H1975细胞增殖活性（IC50 =（1.16±0.24）µmol/L）与B6（IC50 = （0.91±0.36）µmol/L）相似，尽管其对EGFR（T790M）的抑制活性（IC50 = （148.2±7.2）nmol/L）不如B6（IC50 = （22.0±2.6）nmol/L）；以7H-吡咯并[2,3-d]嘧啶-4-胺为母核、取代基分别为胡椒环基和4-取代哌啶基者可开发活性更优的EGFR（T790M）抑制剂，指导后期研究。
关键字：EGFR（T790M）；抑制剂；合成；耐药肺癌
中图分类号：R9 文献标识码：A 文章编号：0258-3283（2022）--
Study of Design, Synthesis and Bioactivity Evaluationfor EGFR(T790M) Inhibitors Huang Huai-zheng, YAO Hua-liang, ZHANG Jie, ZENG Xian-xia, QIN Ting-sheng, LIANG Qian,CAO Si-si, HE Lin-hong*( Pharmaceutical Colleg,Guangxi Medical University，Nanning 530021, China),HuaxueShiji, 2021, 44(1), ～
Abstract: The mutation of T790M in Epidermal growth factor receptor (EGFR) is the most frequent, which also is the main reason for the failure oflung cancer’s clinical treatments.In view of the previous study, lead compound B6displayed the good anti-proliferation against H1975 cell line and inhibited the growth of H1975 xenograft tumor, this article confirmed its inhibitory activity against EGFR(T790M), as well as confirmed their interaction by Autodock. Then we carried out the structural modifications for B6 aiming at the target of EGFR(T790M). All the obtained targete compounds were characterized by NMR and MS. The structure-activity relationship was analyzed by Autodock based on the bioactivity evaluation on in vitrokinase level and cell. The results showed that only compound II1 exhibited similar anti-proliferation activity against H1975 cell line (IC50 = (1.16±0.24) µmol/L) to B6 (IC50 = (0.91±0.36) µmol/L), although its inhibition against EGFR(T790M) (IC50 = (148.2±7.2) nmol/L) was weaker than B6 (IC50 = (22.0±2.6) nmol/L). Comprehensive analysis indicated that that compounds with 7H-pyrrolo[2,3-d]pyrimidin-4-amine as the core, and substituted with piperonyl and 4-substituted piperidinyl may get EGFR(T790M) inhibitors with good bioactivity, which could guide later research.
Key words: EGFR(T790M); inhibitors; synthesis; lung cancer with drug resistant
引用本文：黄怀征，姚华良，张洁，等.EGFR(T790M)抑制剂的设计、合成及活性评价[J]. 化学试剂，2021，44(1): 39-45。
芦丁与弹性蛋白酶相互作用的研究
姚红柳，付金凤，尹广婷，周雪健，苏丽红*
（长春师范大学 化学学院，吉林 长春 130032）
摘要：天然产物芦丁（Rutin）可以抑制弹性蛋白酶的活性，采用多光谱法与分子对接技术研究芦丁与弹性蛋白酶（PPE）的相互作用。研究结果表明，Rutin对PPE存在荧光猝灭效应，且为静态猝灭。Rutin与PPE能形成1∶1复合物，在298 K下其结合常数为4.90×104 L/mol，主要结合力为氢键和范德华力。根据Förster's非辐射能量转移理论，计算得到Rutin与PPE的结合距离r为4.55 nm。紫外光谱与同步荧光光谱结果表明，Rutin可使PPE周围微环境发生改变，极性增加、亲水性增加和疏水性减弱。傅里叶变换红外光谱与圆二色光谱分析表明，Rutin使PPE的α-螺旋、β-折叠含量降低，酶结构变得松散，改变了PPE的二级结构。分子对接模拟表明，Rutin与PPE距离在0.4 nm之内的氨基酸残基共有11个，共形成5条氢键，同时还有强大的范德华力与π-阳离子相互作用，多种作用力使Rutin与PPE形成稳定的复合物，抑制了弹性蛋白酶的活性。
关键词：芦丁；弹性蛋白酶；光谱法；分子对接；相互作用
中图分类号：O629 文献标识码：A 文章编号：0258-3283（2022）
Study on the Interaction between Rutin and Elastase YAO Hong-liu, FU Jin-feng, YIN Guang-ting, ZHOU Xue-jian, SU Li-hong* (College of Chemistry, Changchun Normal University, Changchun 130032, China), Huaxue Shiji, 2022, 44(1)
Abstract: The natural product Rutin can inhibit the activity of elastase. The interaction between Rutin and Elastase (PPE) was studied by multispectral method and molecular docking techniques. The results showed that Rutin quenched the fluorescence of elastase and it was static quenching. Rutin and Elastase could form a 1:1 complex with a binding constant of 4.90×104L/mol at 298 K, the main binding force washydrogen bonds and van der Waals force between Rutin and Elastase. The binding distance between Rutin and Elastase was calculated to be 4.55 nm according to Förster's non-radiative energy transfer theory. The results of ultravioletspectrum(UV) and synchronous fluorescence spectrum (SFS) showed that Rutin could change the microenvironment around PPE, increasing polarity, increasing hydrophilicity and decreasing hydrophobicity. Fourier transform infrared (FT-IR) and circular dichroism spectra (CD) showed that Rutin reduced the content of α -helix and β-foldof PPE, made the elastase structure more loose, and changed the secondary structure of PPE. The molecular docking simulation showed that there were 11 amino acid residues within 0.4 nm distance between Rutin and PPE, and six hydrogen bonds were formed. At the same time, there were strong van der Waals forces interacting with π -cation, thus multiple forces exist between Rutin and elastase system to form a stable compound, which inhibitedthe activity of elastase.
Key words: rutin; elastase; spectroscopy; molecular docking; interaction
引用本文：姚红柳，付金凤，尹广婷，等. 芦丁与弹性蛋白酶相互作用的研究[J]. 化学试剂, 2022, 44(1): 46-51。
含亚胺结构片段的喹唑啉酮衍生物的合成与抗肿瘤活性研究
鄢龙家，王琴，刘力，乐意*
(贵州大学 药学院，贵州 贵阳 550025)
摘要：设计并合成了一系列含亚胺结构片段的新型喹唑啉酮衍生物，最终的15个化合物结构经1HNMR、13CNMR和HR-MS确证，并评价了它们对野生型表皮生长因子受体酪氨酸激酶(EGFRwt-TK)和两种人癌细胞株(A549、HepG2)的体外抗肿瘤活性。结果表明，部分化合物具有良好的活性，特别是化合物（E）-2-（（4-（（3,4-二氟亚苄基）氨基）苯氧基）甲基）-3-甲基喹唑啉-4（3H）-酮对EGFR激酶的IC50达到0.037 µmol/L，对A549和HepG2两种肿瘤细胞的IC50值优于吉非替尼。
关键词：喹唑啉酮；亚胺；合成；抗肿瘤；活性
中图分类号：O622.31文献标识码：A 文章编号：0258-3283(2022)
Synthesis and Studies of Anti-tumor Activities of Quinazolone Derivatives Containing Imine Fragments YAN Long-jia, WANG Qin, LIU Li, LE Yi* (School of Pharmaceutical Sciences, Guizhou University, Guiyang 550025, China), HuaxueShiji, 2022,
Abstract: A series of novel quinazoline derivatives containing enamine moiety were designed and synthesized. The structures of the final 15 compounds were confirmed by 1HNMR, 13CNMR and HRMS, and their antitumor activities against wild-type epidermal growth factor receptor tyrosine kinase (EGFRwt-TK) and two human cancer cell lines (including A549 and HepG2) in vitro were evaluated. The results showed that some compounds have good activity, especially the IC50 value of (E)-2-((4-((3,4-difluorobenzylidene)amino)phenoxy)methyl)-3-methylquinazolin-4(3H)-one against EGFR reached 0.037μmol/L, and itsIC50 values against A549 and HepG2 tumor cells were better than Gefitinib.
Key words: quinazolone; enamine; synthesis; anti-tumor; activity
引用本文：鄢龙家，王琴，刘力，等. 含亚胺结构片段的喹唑啉酮衍生物的合成与抗肿瘤活性研究[J]. 化学试剂，2022，44（1）：52-58.
新型花菁近红外荧光探针CySeN的合成及其识别性能
赵鹏宇b，冯书晓*a，曹泽林b，王开开b
（河南科技大学 a.化工与制药学院，b.农学院/牡丹学院，河南 洛阳 471023）
摘要：硒-氮共价键（Se-N）具有活泼易断裂的化学性质，一定条件下具备化学开关式的调控性能。以IR-780碘化物作为荧光染料，与依布硒啉衍生物缩合合成了含有Se-N化学开关的新型花菁近红外荧光探针CySeN，结构得到核磁共振氢谱和碳谱以及高分辨质谱（HR-MS）确认。该探针对丙酮具有非线性响应识别能力，可用于激光共聚焦细胞成像，但对丙酮的荧光增强不明显，高分辨质谱对识别机理的分析认为， Se-N键的断裂以及丙酮-硒共价化合物CySeA的形成是Se-N化学开关识别丙酮的分子机制。
关键词：硒-氮化学开关；IR-780碘化物；有机硒化合物；近红外荧光探针；性能识别
中图分类号：O627.6 文献标识码：A 文章编号：0258-3283（2022）
Synthesis and Recognition Performance of a Novel Near Cyanine Infrared Fluorescent Probe CySeN ZHAO Peng-yub, FENG Shu-xiao*a, CAO Ze-linb, WANG Kai-kaib (a. College of Chemical Engineering & Pharmaceutical; b. Agricultural College/Peony College，Henan University of Science and Technology, Luoyang 471023, China), Huaxue Shiji, 2022, 44(1),
Abstract: Selenium-nitrogen covalent bond (Se-N) has the chemical properties of being active and easy to break, and has the regulation and control performance as a chemical switch under certain conditions. In this paper, a new cyanine near infrared fluorescence probe CySeN with Se-N chemical switch was synthesized by condensation of the fluorochrome IR-780 iodide and the Ebselen derivative. The structure was confirmed by nuclear magnetic resonance (1H and 13C) and high resolution mass spectrum (HR-MS). The probe has the ability of nonlinear response recognition for acetone and could be used for laser confocal cell imaging, but it was not obvious for the fluorescence enhancement of acetone. Through the analysis of the recognition mechanism by HR-MS suggested that the breaking of Se-N bond and the formation of acetone-selenium covalent compound CySeA were the molecular mechanism of Se-N chemical switch to recognize acetone.
Key words: selenium-nitrogen chemical switch; IR-780 iodide; organo selenium compounds; near-infrared fluorescence probe; performance to identify
引用本文：赵鹏宇，冯书晓，曹泽林，等.新型花菁近红外荧光探针CySeN的合成及其识别性能[J].化学试剂，2022，44（1）：59-64.
改性水滑石/聚乙烯醇复合膜的制备及性能
郑秀君*，江欣悦，李木子，赵冬梅，初小宇
（黑龙江东方学院 食品与环境工程学部，黑龙江 哈尔滨 150066）
摘要：采用焙烧复原法将山梨酸（SA）插入水滑石（LDH）层间合成了纳米插层材料SA-LDH，将其与聚乙烯醇（PVA）共混，通过溶液流延法制备得到复合薄膜SA-LDH/PVA。采用傅里叶变换红外光谱（FTIR）、X射线衍射（XRD）、热重-差热分析（TG-DSC）和扫描电镜（SEM）对其结构、热稳定性以及形貌进行表征，并测试了复合薄膜的力学性能、溶胀率、溶解率和抑菌性能。结果表明：SA-LDH含量为5 wt%得到的LDH晶型最为完整；SA-LDH片层在PVA薄膜中分散比较均匀；3 wt%添加SA-LDH可提高PVA膜的热稳定性；SA-LDH添加量为5 wt%和7 wt%时提高了复合膜的抗拉性能和断裂伸长率；SA-LDH的添加提高了PVA膜的耐水性能；SA-LDH的添加量分别为5 wt%和6 wt%时，SA-LDH/PVA复合薄膜对金黄色葡萄球菌和大肠杆菌的抑菌效果最佳。制备的水滑石/聚乙烯醇复合抑菌膜，为食品包装领域提供一种广谱的抑菌材料。
关键词：水滑石；山梨酸；聚乙烯醇复合薄膜；抑菌性能
中图分类号：O614.2； 文献标识码：A 文章编号：0258-3283(2022)
Preparation and Properties of Modified Hydrotalcite/Polyvinyl Alcohol Composite Membrane ZHENG Xiu-jun*, JIANG Xin-yue, LI Mu-zi, ZHAO Dong-mei, CHU Xiao-yu (Department of Food and Environmental Engineering, Heilongjiang East University, Harbin 150066, China), Huaxue Shiji, 2022, 44(1),
Abstract：The nanointercalated material SA-LDH was synthesized by inserting sorbic acid (SA) intothe layers of hydrotalcite (LDH) by calcination-regeneration method，then it was blended with polyvinyl alcohol (PVA) and the composite membrane SA-LDH/PVA was prepared by the solution casting method. The structure,thermal stability and morphology were characterized with Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric-differential thermal analysis (TG-DSC) and scanning electron microscope (SEM). And the mechanical properties, swelling rate, dissolution rate and antibacterial properties of the composite membrane were tested. The results showed that the LDH crystal form obtained with SA-LDH content of 5wt% was the most complete; the SA-LDH layers were uniformly dispersed in the PVA membrane; 3wt% addition of SA-LDH could improve the thermal stability of PVA membrane; the tensile propertiesand elongation at break of the composite membrane were improved when the addition of SA-LDH was 5 and 7wt%; the addition of SA-LDH improved the water resistance of the PVA membrane; the SA-LDH/PVA composite membrane had the best antibacterial effect on Staphylococcus aureus and Escherichia coli when the addition amount of SA-LDH was 5 and 6wt% respectively. The hydrotalcite/polyvinyl alcohol composite antibacterial membrane provides an inclusive antibacterial material for the food packaging field.
Key words：hydrotalcites; sorbic acid; polyvinyl alcohol composite membrane; antibacterial performance
引用本文：郑秀君，江欣悦，李木子，等. 改性水滑石/聚乙烯醇复合膜的制备及性能[J]. 化学试剂, 2022, 44(1): 65-72。
一种制备唾液酸磁性表面分子印迹聚合物的新方法
刘浩1，欧阳敬禹1，刘恋1，樊世萌1，尤祥宇*1，李玲玲2，苏江涛1
（1. 湖北工业大学 生物工程与食品学院，湖北 武汉 430068；2.武汉文理学院 医学院，湖北 武汉 430345）
摘要：一锅法合成的氨基化磁性纳米颗粒Fe3O4@NH2，与对甲酰基苯硼酸（FPBA）反应嫁接上硼酸官能团，通过硼酸基与模板唾液酸Neu5Ac分子上的顺式二醇共价反应，将Neu5Ac定向固定于磁性纳米颗粒。以多巴胺（DA）及3-氨基苯硼酸（3-APBA）为功能单体，自聚合反应形成共聚壳层包覆在磁性纳米颗粒的表面，制备得Neu5Ac磁性分子印迹聚合物（MMIPs）。通过透射电镜、红外光谱对其形态及结构进行表征，并评价其吸附性能。结果表明，Neu5Ac磁性分子印迹聚合物对Neu5Ac具有较好的吸附量、较好的印迹效率、较好的特异性等优点；通过对Neu5Ac至少5轮吸附-洗脱的循环实验表明，MMIP具有较好的重复再利用能力。
关键词：唾液酸Neu5Ac；多巴胺；分子印迹；磁性纳米颗粒；吸附
中图分类号：TB34 文献标识码：A文章编号：0258-3283（2022）
A Novel Method for Preparing of Sialic Acid Magnetic Surface Molecularly Imprinted Polymer LIU Hao1, Ouyang Jing-yu1,Liu Lian1, Fan Shi-meng1, You Xiang-yu*1, Li Ling-ling2, Su Jiang-tao1(1. School of Food and Biological Engineering, Hubei Universityof Technology, Wuhan 430068, China; 2. Medical School, Wuhan University of Arts and Science, Wuhan 430345, China), Huaxue Shiji, 2022, 44(1)
Abstract: Amino-functionalized magnetic nanoparticles Fe3O4@NH2 were synthesized by one-pot method, then grafted with boric acid group on their surface by reaction withp-formyl phenylboric acid (FPBA). Templatesialic acid Neu5Ac was directionally fixed to magnetic nanoparticles by covalent reaction between its cis-diol group and boric acid group. Neu5Ac magnetic molecularly imprinted polymers (MMIPs) was prepared by self-polymerization of functional monomers dopamine (DA) and 3-aminophenylboric acid (3-APBA), forming a polymer shell coated on the surface of magnetic nanoparticles. Their morphology and structure wwere characterized by transmission electron microscopy, infrared spectroscopy, and their adsorption properties were evaluated. The results showed that Neu5Ac-MMIPshadgood adsorption capacity, imprinting efficiency and specificity for Neu5Ac. After at least five rounds of adsorption-elution cycling experimentson Neu5Ac, MMIPsstill had good reusability.
Keywords: sialic acid Neu5Ac; dopamine; molecular imprinting; magnetic nanoparticles; absorption
引用本文：刘浩，欧阳敬禹，刘恋，等. 一种制备唾液酸磁性表面分子印迹聚合物的新方法[J]. 化学试剂, 2022, 44(1):73-79。
4-[(1H-苯并咪唑-2-亚氨基)-甲基]-1,3-苯二醇的合成及金属离子识别研究
侯学清a,刘恩弟a,王军刚a,宝冬梅a,陶敏a,何淑花*b
(贵州民族大学 a.化学工程学院，b.材料科学与工程学院，贵州 贵阳 550025)
摘要：以苯并咪唑胺为原料，通过与2,4-二羟基苯甲醛反应合成了标题化合物，并利用IR和NMR对其结构进行表征。通过紫外吸收光谱和荧光光谱研究其对不同金属离子的识别作用。结果表明，金属离子的加入，使目标化合物的紫外吸收光谱和荧光光谱发生了不同程度的变化，尤其是对Zn2+的识别能力最佳，具有较强的专一识别能力和抗干扰性，其荧光检出限为3.5×10-7 mol/L。同时，通过核磁滴定法对目标化合物和Zn2+的配位方式进行了探讨。
关键词：苯并咪唑；席夫碱；锌离子；离子识别；荧光探针
中图分类号：O626.2 文献标识码：A 文章编号：
Synthesis and Metal Ion Recognition of 4-[(1H-Benzimidazol-2-imino)methyl]-1,3-benzene –diol HOU Xue-qinga, LIU En-dia, WANG Jun-ganga, BAO Dong-meia, TAO Mina, HE Shu-hua*b (a. College of Chemistry and Chemical Engineering, b. College of Materials Science and Engineering, Guizhou Nationalities University, Guiyang 550025, China)
Abstract：4-[(1H-Benzimidazol-2-imino)methyl]-1,3-benzenediolwas synthesized from benzimidazole amine and 2,4-dihydroxybenzaldehyde, and its structure was characterized by IR and NMR. The recognition of different metal ions was studied by UV absorption spectrumand fluorescence spectrum. The results showed that the addition of metal ions changes the absorption spectrumand fluorescence spectrum of the target compound in different degrees, especially the best recognition of Zn2+, with strong specific recognition ability and anti-interference, and the fluorescence detection limit was 3.5×10-7 mol/L. At the same time, the coordination mode between the target compound and Zn2+ was discussed by NMR titration.
Key words：benzimidazole; schiff base; zinc ion; ion recognition; fluorescent probe
引用本文：侯学清,刘恩弟,王军刚,等.4-[(1H-苯并咪唑-2-亚氨基)-甲基]-1,3-苯二醇的合成及金属离子识别研究[J]. 化学试剂，44(1):80-83.
草果不同极性萃取物总黄酮、总多酚含量与其抗氧化活性的相关性
师聪，宫号，李茹，李璐璐，陈学红*
（徐州工程学院 食品与生物工程学院，江苏 徐州 221018）
摘要：以草果为原料，通过50%乙醇、水、乙酸乙酯、丙酮、正丁醇、甲醇和石油醚不同极性溶剂萃取活性物质，探讨萃取物中总黄酮和总多酚含量与总还原能力及对DPPH·、ABTS+·、OH-、NO2-清除能力的相关性。结果表明：50%乙醇萃取物总黄酮和总多酚含量均最高，各萃取物均有抗氧化能力，且呈明显的量效关系，其中50%乙醇萃取物总还原能力、清除ABTS+·和DPPH·能力最强，石油醚萃取物清除OH-和NO2-能力最强。相关性分析表明草果萃取物中总黄酮含量与ABTS+·清除能力呈极显著相关，与DPPH·
清除能力呈显著相关，总多酚含量与对ABTS+·和DPPH·的清除能力呈极显著相关，可为草果作为天然抗氧化剂提供理论依据。
关键词：草果萃取物；总黄酮；总多酚；抗氧化能力；相关性
中图分类号：R284 文献标识码：A 文章编号：0258-3283（2022）--
Correlation between the Content Total Flavonoids and Total Polyphenols Inamomum Tsaoko with Different Polar Extracts and Their Antioxidant Activities SHI Cong, GONG Hao, LI Ru, LI Lu-lu, CHEN Xue-hong* (School of Food and Biological Engineering, Xuzhou University of Technology, Xuzhou 221018, China), Huaxue Shiji, 2022, 44(1), ～
Abstract：The active materials were extracted with 50% ethanol, water, ethyl acetate, acetone,n-butanol, methanol and petroleum ether from Amomum tsaoko.The correlation of the contents of total flavonoids, total polyphenols with the total reducing ability and the scavenging ability of DPPH·,ABTS+·,OH- and NO2- were explored. The results showed that the highest total flavonoids and total polyphenols contents were obtained in 50% ethanol extract.All extracts from Amomum tsaoko had antioxidant activity and showed a dose effect relationship. The 50% ethanol extract from Amomum tsaoko had the strongest scavenging ability of DPPH· and ABTS+· and the best reducing power. The petroleum ether extract had the strongest scavenging ability of OH- and NO2-. Correlation analysis showed that the total flavonoids contents were significantly correlated with the scavenging ability of DPPH· and extremely significant correlation with the scavenging ability of ABTS+·. The total polyphenols contents were extremely significant correlation with the scavenging ability of ABTS+· and DPPH·. The results could provide a theoretical basis for the development of Amomum tsaoko as a natural antioxidant．
Key words：Amomum tsaoko extracts; total flavonoids; total polyphenols; antioxidant activity; correlation
引用本文：师聪，宫号，李茹，等. 草果不同极性萃取物总黄酮、总多酚含量与其抗氧化活性的相关性[J]. 化学试剂，2022，44(1): 84-89。
黑果腺花楸不同极性物质抗氧化及抗炎镇痛研究
苟鼎*，张腊梅，黄红琴，李敏
（达州中医药职业学院 药学院，四川 达州 635000）
摘要：为了高效的提取及分离黑果腺花楸活性物质，以黑果腺花楸为原料，不同极性溶剂作为溶媒（石油醚、乙酸乙酯、正丁醇和水），采用超声波辅助提取法，分别提取到不同极性物质（石油醚相、乙酸乙酯相、正丁醇相和水相）。利用不同的抗氧化模型（铁还原力、清除羟自由基（OH) ·）能力、清除ABTS自由基能力、抗肝组织自发性脂质过氧化和花生油氧化能力）、炎症模型（小鼠耳廓肿胀和小鼠肉芽肿胀）和镇痛模型（小鼠热板痛阈值和冰醋酸致小鼠扭体次数）来评价黑果腺花楸不同极性物质的活性。结果表明：正丁醇相具有较强的抗氧化能力和消炎镇痛能力。正丁醇可以作为提取黑果腺花楸活性物质及分离抗氧化活性及抗炎镇痛成分的溶剂。
关键词： 黑果腺花楸；不同极性；抗氧化；抗炎；镇痛
中图分类号：R284 文献标志码：A 文章编号：0258-3283（2022）- -
Study on Antioxidant, Anti-inflammatory and Analgesic Activity of Different Polar Parts from Aronia Melanocarpa GOU Ding*, ZHANG La-mei, HUANG Hong-qin, LI Min (Department of Pharmacy in Dazhou Vocational College of Chinese Medicine, Dazhou 635000, China), Huaxue shiji, 2022, 44(1), ～
Abstract: In order to efficiently extract and separate the active components from Aronia melanocarpa, taking Aronia melanocarpa as raw material, different polar components (petroleum ether phase, ethyl acetate phase, n-butanol phase and water phase) were extracted with different polar solvents (petroleum ether, ethyl acetate, n-butanol and water) by using ultrasonic wave assisted extraction method. Different antioxidant models(icon-reducing ability, hydroxyl radical scavanging capacity, ABTS radical scavenging activity, inhibitory effects on lipid peroxidation), inflammatory models mouse ear swelling andmouse granuloma) and analgesic models( heat sensitivity in mice and the number of writhing responsesinduced by acetic acid in mice) were used to evaluate biological acitivity of different polar parts. The results showed that n-butanol phase has better antioxidant capacity, anti-inflammatory and analgesic capacity. Butanol could be used as a solvent for extracting active substances and separating antioxidant, anti-inflammatory and analgesic components from Aronia melanocarpa.
Key words: Aronia melanocarpa; different polar parts; antioxidant activity; anti-inflammatory; analgesia
引用本文：苟鼎，张腊梅，黄红琴，等.黑果腺花楸不同极性物质抗氧化及抗炎镇痛研究[J]. 化学试剂，2022，44(1):90-96。
基于鲁米诺-白藜芦醇荧光体系检测花生衣中的白藜芦醇和苷
宋吉英，汪琪琦，王艳丽*
（青岛农业大学 化学与药学院，山东 青岛 266109）
摘要：探讨了鲁米诺-白藜芦醇体系的荧光性质，提取了3种颜色花生衣中的白藜芦醇和苷并进行测定。实验采用超声-微波协同萃取技术进行提取，正交实验确定最佳提取条件，白藜芦醇和苷的含量用荧光法进行测定。结果表明，花生衣中白藜芦醇和苷提取的最佳实验条件是乙醇作萃取剂、料液比1:25 (g/mL)，微波功率50 W，萃取时间15 min；在pH 9的弱碱性环境下反应20 min，白藜芦醇对鲁米诺的荧光增敏作用最强，在0.5～50 µg/mL浓度范围内，白藜芦醇对鲁米诺的荧光增敏作用呈线性关系，由此测定3种颜色（粉、红、黑）的花生衣中白藜芦醇和苷的含量分别为0.261、0.370、0.257 mg/g。该方法可成功用于花生衣中白藜芦醇和苷的分析检测。
关键词：白藜芦醇；鲁米诺；荧光；花生衣
中图分类号:O657 文献标识码: A 文章编号：0258-3283（2022）- -
Detection of Resveratrol and Glycosides in Peanut Coat based on Fluorescence System of Luminol-Resveratrol SONG Ji-ying, WANG Qi-qi, WANG Yan-li* (College of Chemistry & Pharmacy, Qingdao Agricultural University, Qingdao 266109, China）, Huaxue shiji, 2022, 44(1), ～
Abstract：In this work, the resveratrol and glycosides in three colors peanut coat were extracted and determined. Meanwhile, the fluorescence properties of luminol-resveratrol system were investigated. The ultrasonic-microwave synergistic extraction strategy was successfully used in resveratrol and glycosides extraction from peanut coat. The extraction conditions were optimized by orthogonal tests, the contents of resveratrol and glycosides were detected by fluorescence method. The results indicated that the optimal experimental conditions for extraction of resveratrol and glycosides from peanut coat were obtained when extractant wasethyl alcohol, solid–liquid ratio was 1:25 (g/mL), microwave power was 50 W and extraction time was 15 min. Fluorescence sensitizing effect was enhanced strongest when pH 9 and reaction time was 20 min. The fluorescence sensitizing effect of resveratrol towards luminol exhibited excellent linearly increased trend with the increased concentration of resveratrol ranging from 0.5 to 50 µg/mL. The contents of resveratrol and glycosides in three colors (pink, red and black) peanut coat were 0.261, 0.370 and 0.257 mg/g, respectively. The strategy can be successfully employed in the determination of resveratrol and glycosides in peanut coat.
Key words: resveratrol; luminol; fluorescence; peanut coat
引用本文：宋吉英，汪琪琦，王艳丽. 基于鲁米诺-白藜芦醇荧光体系检测花生衣中的白藜芦醇和苷[J]. 化学试剂，2022，44(1):97-101。
甲醛吸附与催化氧化技术基础原理及研究进展
魏家锋1，沈王庆*2
(安徽理工大学 材料科学与工程学院，安徽 淮南 232001；2.内江师范学院 化学化工学院，四川 内江 641100）
摘要：为了给筛选新居室内甲醛污染治理方案提供参考，通过综合列表法概述了不同甲醛背景浓度下物理化学吸附、贵金属-过渡金属氧化物催化氧化、新型TiO2复合型光催化氧化等理论除醛技术进展及应用，简略阐述了理论除醛技术相关原理，基于各类除醛技术进展及原理提出在未来应用于新居室内环境治醛中的改进措施，这些技术进展、原理以及改进措施为未来室内环境治醛提供了新方案，综合对比得出新型TiO2复合型光催化剂催化氧化因具有高降醛率、耗时短等特点，有望成为未来替代空气净化器成为新居室内治醛新技术。
关键词：甲醛；污染治理；原理；吸附；催化氧化
中图分类号：TB33；X701 文献标志码：A 文章编号：0258-3283（2022）
Basic Principles and Research Progress of Formaldehyde Adsorption and Catalytic Oxidation Technology WEI Jia-feng1, SHEN Wang-qing*2(1.College of Materials Science and Engineering, Anhui University of Science and Technology, Huainan 232001; 2.College of Chemistry and Chemical Engineering, Neijiang Normal University, Sichuan, Neijiang 641100), Huaxue Shiji, 2022, 44(1),
Abstract: In order to provide reference and help for screening indoor formaldehyde pollution control schemes in new houses in the future, the progress and application of theoretical formaldehyde removal technologies such as physicochemical adsorption under different formaldehyde background concentrations, catalytic oxidation of noble metal transition metal oxides and new TiO2 composite photocatalytic oxidation weresummarized by comprehensive tabulation method, and the relevant principles of theoretical formaldehyde removal technologieswerebriefly described.Based on the progress and principles of various formaldehyde removal technologies, this paper puts forward the improvement measures applied to the formaldehyde control in the indoor environment of new houses in the future. These technical progress, principles and improvement measures provide a new scheme for the formaldehyde control in the indoor environment in the future. Through comprehensive comparison, it was concluded that the catalytic oxidation of the new TiO2 composite photocatalyst has the characteristics of high formaldehyde reduction rate and short time-consuming, it was expected to become an alternative air purifier and a new technology for indoor formaldehyde control in new houses in the future.
Key words:formaldehyde; pollution control; theory; adsorption;catalytic oxidation
引用本文：魏家锋，沈王庆.甲醛吸附与催化氧化技术基础原理及研究进展[J].化学试剂，2022，44（1）：102-109.
酸碱净化-改进的衍生化气相色谱/质谱法测定土壤中11种酚类化合物
侯博*1，范艳2，韩永辉1，张国龙1，安国荣1
（1. 青海省地质矿产测试应用中心，青海 西宁 810000；2. 青海师范大学 化学化工学院，青海 西宁 810000）
摘要：实现了土壤用溶剂快速提取，提取液经酸碱净化后，改进的五氟苄基溴衍生，建立了气相色谱-质谱法同时测定土壤中11种酚类化合物的新方法，目标化合物通过SIM方式扫描，对保留时间和特征离子定性，通过内标法定量。土壤采用二氯甲烷/正己烷共同提取后，在酸碱净化过程中优化了不同萃取溶剂比例和不同体系下五氟苄基溴衍生效果的影响，以及考查了不同衍生温度和时间的作用。当取样量10 g时，11种酚类化合物方法检出限为1.06 ～4.21 μg/kg，低、中、高基质加标回收率为77.3%～93.9%，相对标准偏差（RSDs）为4.6 %～8.2 %。
关键字：改进的五氟苄基溴；酚类化合物；气相色谱-质谱法
中图分类号：O652.1 文献标识码：A 文章编号：0258-3283（2022）--
Determination of 11 Phenolic Compounds in Soil by Acid-base Purification-modified Derivatization Gas Chromatography/mass Spectrometry HOU Bo*1, FAN Yan2, HAN Yong-hui1, ZHANG Guo-long1, AN Guo-rong1 (1.Geological and Mineral Testing and Application Center, Xining 810000, Qinghai; 2.Qinhai Normal University College of chemistry and chemical engineering, Xining 810000, Qinghai）, Huaxue Shiji, 2022, 44(1), ～
Abstact: A new method was developed for the simultaneous determination of 11 phenolic compounds in soil by gas chromatography-mass spectrometry (GC-MS) after rapid extraction with solvent, purification with acid and alkali, derivatization with improved pentafluorobenzyl bromide. The target compounds were scanned by SIM method, the retention time and characteristic ions were characterized, and quantitative by internal standard method. After the extraction of dichloromethane/hexane, the effects of different extraction solvent ratio and different system on the derivatization of pentafluorobenzyl bromide were optimized in the process of acid-base purification, and the effects of different derivatization temperature and time were investigated. When the sample size was 10 g, the detection limits of 11 phenolic compounds were 1.06 ～4.21 μg/kg, the recoveries of low, medium and high matrix were 77.3%～93.9%, and the relative standard deviations (RSDS) were 4.6%～8.2%.
Key words：modified pentafluoro-benzyl bromide; phenolic compounds; gas chromatography-mass spectrometry
引用本文：侯博，范艳，韩永辉，等. 酸碱净化-改进的衍生化气相色谱/质谱法测定土壤中11种酚类化合物[J]. 化学试剂，2021，44(1):110-115。
液相色谱串联质谱法检测油菜籽中27种除草剂残留
汪雪芳1,3,4，戚欣1,3,4，马飞1,3,4，王秀嫔*1,3,4，张良晓*1,3,4,5，李培武1,2,3,4,5
（1. 中国农业科学院油料作物研究所，湖北 武汉 430062；2. 农业部油料作物生物学与遗传育种重点实验室，湖北 武汉 430062；3. 农业部油料产品质量安全风险评估实验室（武汉），湖北 武汉 430062；4. 农业部油料及制品质量监督检验测试中心，湖北 武汉 430062；5. 湖北洪山实验室，湖北 武汉 430070）
摘要：基于液相色谱-串联质谱仪（LC-MS/MS），建立了油菜籽中27种除草剂残留的分析方法。样本采用改进的QuEChERS方法提取净化，用乙腈-乙酸溶液提取30 min，添加缓冲盐，振荡，冷冻离心去除脂肪和蛋白，将上清液转移至净化管中，加入PSA（N-丙基乙二胺）/C18（BONDESIL-C18）/GCB（石墨炭黑）混合粉末净化包，去除基质干扰，过0.22 μm有机相滤膜。利用LC-MS/MS外标法定量分析。方法学考察结果表明，检出限为0.009～0.454 μg/L，油菜籽基质中27种除草剂在2.0～200 μg/L浓度范围内线性关系良好，相关系数r≥0.992；在0.50～25.0 μg/kg添加水平下，27种除草剂的平均加标回收率为75.3%～102.0%，相对标准偏差在1.3%～11.2%之间。将该方法用于实际油菜籽样品的检测，结果显示，所有样品均符合农药残留限量标准。该方法具有简便、灵敏度高、精密度和准确度好的优势，适合油菜籽中27种除草剂残留检测。
关键词：油菜籽；液相色谱串联质谱；除草剂；QuEChERS；残留
中图分类号：O657.63 文献标识码：A 文章编号：0258-3283（2022）
Simultaneous Determination of 27 Herbicides Residues in Rapeseed by LC-MS/MS WANG Xue-fang1,3,4, QI Xin1,3,4, MA Fei1,3,4, WANG Xiu-pin*1,3,4, ZHANG Liang-xiao*1,3,4,5, LI Pei-wu1,2,3,4,5 (1. Oil Crops Research Institute, Chinese Academy of Agricultural Sciences, Wuhan 430062, China; 2. Key Laboratory of Biology and Genetic Improvement of Oil Crops, Ministry of Agriculture, Wuhan 430062, China; 3. Laboratory of Risk Assessment for Oilseeds Products (Wuhan), Ministry of Agriculture, Wuhan 430062, China; 4. Quality Inspection and Test Center for Oilseeds Products, Ministry of Agriculture, Wuhan 430062, China; 5. Hubei Hongshan Laboratory, Wuhan 430070, China), Huaxue Shiji, 2022, 44(1)
Abstract：A liquid chromatography-tandem mass spectrometric method (LC-MS/MS) was developed for the simultaneous determination of 27 herbicides residues in rapeseed. Samples were extracted and purified by improved QuEChERS method. The samples were extracted with acetonitrile-acetic acid solution for 30 min, buffer salt was added and oscillation, the fat and protein were removed by freezing centrifugation. The supernatant was transferred to the purification tube. PSA/C18/GCB was added to remove matrix interence, 0.22 μm organic phase filtration membrane was used for filtration, and then quantitativelyanalyzed by LC-MS/MS external standard method. The results of methodological investigation indicated that the limits of detection were 0.009～0.454 μg/L. All of herbicides showed good linear with R2≥0.996 from 2.0 to 200 μg/L and the average recoveries of the 27 herbicides at 0.50～25.0 μg/kg were 75.3%～102.0% with the relative standard deviations(RSDs)ranging from 1.3%～11.2%. This method was used to detect these herbicide residues in rapeseeds. The detection results indicated the contents of 27 herbicides in all of rapeseeds were below the maximum residue limits. This method showed simple, highly sensitive and accurate, which could be used to detect 27 herbicides residues in rapeseed.
Key words: rapeseed; LC-MS/MS; herbicide; QuEChERS; residue
引用本文：汪雪芳，戚欣，马飞，等. 液相色谱串联质谱法检测油菜籽中27种除草剂残留[J]. 化学试剂, 2022, 44(1):116-122。
ICP-MS检测三氟化硼-苯甲醚配合物中11B同位素的丰度
任倩倩，李瑜哲，艾波，吴高胜，高慧敏，宗睿，雷雯，陆铭捷，许保云*
(上海化工研究院有限公司，上海 200062)
摘要：建立了基于ICP-MS技术测定三氟化硼-苯甲醚配合物样品中11B同位素丰度的分析检测方法。采用酸碱交替洗涤方法减少记忆效应对11B同位素丰度测定的影响，采用标准品-样品溶液交叉测量方法降低质量歧视效应的影响。实验结果表明，当样品溶液的硼浓度在2.62～17.49 mg/L时，采用3.50 mg/L的标准品进行交叉测量，测量后采用8次酸碱交替洗涤，可大大减小同位素记忆效应和质量歧视效应。分析多次测量标准品溶液的结果表明，该方法的精密度低于0.1%，绝对偏差低于0.8%，平均回收率为101.0%。按照所建立的方法测定3份不同硼浓度的三氟化硼-苯甲醚配合物样品溶液，11B同位素丰度的相对标准偏差(RSDs)均低于0.05%。与目前现有的其他ICP-MS检测方法相比，该方法具有前处理简单快捷、测量精密度高的优势，可为富集11B同位素的实验研究提供基础。
关键词：ICP-MS；三氟化硼-苯甲醚配合物；11B同位素丰度；记忆效应；质量歧视效应
中图分类号：O657 文献标识码：A 文章编号：0258-3283（2022）
Detection of 11B Isotope Abundance in Boron Trifluoride-Anisole Complex by ICP-MS REN Qian-qian, LI Yu-zhe, AI Bo, WU Gao-sheng, GAO Hui-min, ZONG Rui, LEI Wen, LU Ming-jie, XU Bao-yun* (Shanghai Research Institute of Chemical Industry Co., Ltd., Shanghai 200062, China), Huaxue Shiji, 2022, 44(1)
Abstract: An analytical method for the determination of 11B isotope abundance in boron trifluoride-anisole complex samples based on ICP-MS technology has been established. The acid-base alternate washing method was used to reduce the influence of the isotope memory effecton the determination of 11B isotope abundance, and the standard-sample solution cross-measurement method was used to reduce the mass discrimination effect. The results showed that when the boron concentration of the sample solution was in the range of 2.62～17.49 mg/L, using 3.5 mg/L standard solution and 8 times alternating acid-base washings couldgreatly reduce the isotope memory effect and mass discrimination effect. The analysis results indicatedthat the precision of the method wasless than 0.1%, the absolute deviation wasless than 0.8%, and the average recovery rate was101.0%. The 11B abundance in three BF3-anisole complex samples with different concentrationsare determined according to the established method, and the relative standard deviations (RSDs) were all less than 0.05%. Compared with other existing ICP-MS detection methods, the method in this research showedgood precision with simplified operation, which can provide a basis for experimental research on enrichment of 11B isotope.
Key words: ICP-MS; boron trifluoride-anisole complex; 11B isotope abundance; memory effect; mass discrimination effect
引用本文：任倩倩，李瑜哲，艾波，等. ICP-MS检测三氟化硼-苯甲醚络合物中11B同位素的丰度[J]. 化学试剂, 2022, 44(1):123-127。
QuEChERS-HPLC-MS/MS法快速筛查与确证人参花中14种农药残留
胡婷婷1,2b，韩颖2a，赵巍巍1，葛丽蕊2a，赵韫慧1，杨璐1，宋清莲1，李燕鹭1，张勋*1
（1.长春海关技术中心，吉林 长春 130062；2.吉林大学a. 公共卫生学院，b.化学学院超分子结构与材料国家重点实验室，吉林 长春 130000）
摘要：建立了QuEChERS-高效液相色谱-三重四极杆质谱法测定人参花中14种农药残留的分析方法。样品使用1%醋酸乙腈进行初步提取，再用乙二胺-N-丙基硅烷(PSA)、C18和石墨化炭黑(GCB)这3种吸附剂进行净化，采用多反应监测模式(MRM)进行检测，基质外标法定量。结果表明，在1～100 μg/L范围内呈良好线性(R2＞0.999)，在3个添加水平下测得回收率在70.8%～108.7%之间，测定结果的相对标准偏差在2.06%～10.35%范围内(n=6)。该方法灵敏度高、净化效果好，可同时快速检测人参花中多种农药残留，具有良好的定性和定量检测性能。
关键词：QuEChERS；高效液相色谱三重四极杆质谱；农药残留；人参花
中图分类号：S482.99 文献标识码：A 文章编号：0258-3283（2022）
QuEChERS-HPLC-MS/MS Method for Rapid Screening and Confirmation of 14 Pesticide Residues in Ginseng FlowersHU Ting-ting1,2b, HAN Ying2a, ZHAO Wei-wei1, GE Li-rui2a, ZHAO Yun-hui1, YANG Lu1, SONG Qing-lian1, LI Yan-lu1, ZHANG Xun*1(1.Changchun Customs Technology Center, Changchun 130062, China; 2a.School of Public Health, 2b.State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130000, China), HuaxueShiji, 2022, 44(1)
Abstract: A method based on QuEChERS-High-performance liquid chromatography triple quadrupole mass spectrometry (HPLC-MS/MS) was established for the determination of 14 pesticide residues in ginseng flower．The samples were initiallyextracted with 1% acetonitrile acetate．The extract was purified with ethylenediamine-N-propyl silane (PSA)， C18 andgraphitized carbon black (GCB). After that, the samples were detected by multiple reaction monitoring mode (MRM) and quantified by matrix external standard method.The analytical results showed that the calibration curves for the 14 pesticides obtained by HPLC-MS/MS were linear in the range of 1~100 μg/L，with the correlation coefficients higher than 0.999．The recoveries ranged from 70.8% to 108.7% with relative standard deviations (RSDs) ranging from 2.06% to 10.35%at the three supplemental levels (n=6). This method has the advantages of high sensitivity and good purification effect. The proposed method can simultaneously detect multi-pesticides residues with a good performance in terms of qualitative and quantitative detection．
Key words: QuEChERS; high-performance liquid chromatography triple quadrupole mass spectrometry; pesticide residues; ginseng flowers
引用本文：胡婷婷，韩颖，赵巍巍，等.QuEChERS-HPLC-MS/MS法快速筛查与确证人参花中14种农药残留[J]. 化学试剂，2022, 44（1）：136-141。
以苦参碱类生物碱为前体的D环抗肿瘤活性结构改造
赵俊，蔡小华*
(贵州民族大学 化学工程学院，贵州 贵阳550025)
摘要：苦参碱是从苦参、苦豆子等植物中分离得到的一类喹诺里西啶类生物碱，具有抗肿瘤、抗病毒、神经保护、杀虫等多种生物活性。苦参碱系列生物碱是一种极好的结构改造的前体，引起广大学者的浓厚兴趣。近年来，许多基于苦参碱为原料的衍生物被设计并合成出来，取得了较好的研究结果。对研究苦参碱及其衍生物抗肿瘤作用的文献进行分析和整理，从苦参碱的C-13、C-14、C-15羰基、D环的开环、形成离子配合物和拼合物的结构改造方面综述了其相关的研究进展。
关键词：苦参碱；生物碱；前体；结构改造；抗肿瘤
中图分类号：R914.5 文献标识码:A 文章编号：0258-3283（2022）--
Structural Modification of D-ring Antitumor Activity Employing Matrine Alkaloids as Precusors ZHAO Jun, CAI Xiao-hua*(School of Chemical Engineering, Guizhou Minzu University, Guiyang 550025, China), HuaxueShiji, 2022, 44(1), ～
Abstract：Matrine is a kind of quinolizidine alkaloids isolated from Sophoraflavescens and Sophoraalopecuroides, andshows many biological activities such as antitumor, antiviral, neuroprotective, insecticidal and so on. Matrine-type alkaloids are excellent precursors for the synthesis and modification, which have aroused great interest of scholars. In recent years, many derivatives based on matrine-type alkaloids have been designed and synthesized, and good results have been achieved. In this paper, the anti-tumor effects of matrine and its derivatives were analyzed and sorted out, and the related research progress was summarized from the structural modification of C-13, C-14, C-15 carbonyl, ring opening of D-ring, formation of ionic complexes and complexes of matrine.
Key words：matrine; alkaloids; precursor; structural modification; antitumor
引用本文：赵俊，蔡小华. 以苦参碱类生物碱为前体的D环抗肿瘤活性结构改造[J]. 化学试剂,2022, 44(1):128-135。
系列三联吡啶衍生物的合成及在催化氧化中的应用
范伟伟，刘建奇，李攀攀，詹红菊，熊航行*
（荆楚理工学院 化工与药学院，湖北 荆门 448000）
摘要：采用一步法合成了5例三联吡啶的衍生物：4'-(吡啶-4-基)-2,2':6',2''-三联吡啶（L1）、4'-苯基-2,2':6',2''-三联吡啶（L2）、4'-(3,5-二氯吡啶-4-基)-2,2':6',2''-三联吡啶（L3）、4'-(3,5-二溴吡啶-4-基)-2,2':6',2''-三联吡啶（L4）、4'-(4-(吡啶-4-基)苯基)-2,2':6',2''-三联吡啶（L5），其中L3和L4为尚未见诸报道的新颖化合物。以制备的多吡啶化合物为配体，和MnCl2共同催化苄基醇的氧化反应，研究发现5种多吡啶配体均具备良好的性能，配体分子结构中的4'-吡啶取代基对提高催化活性有重要作用；最后选用性能最优的4'-(4-(吡啶-4-基)苯基)-2,2':6',2''-三联吡啶为配体，与MnCl2共同催化叔丁基过氧化氢氧化苄基醇和苄基烷烃，5种典型底物的转化率均在95%以上，产率在90%以上。该催化氧化方法有望应用于芳香酮类化合物及相关药物中间体的绿色、高效合成。
关键词：多吡啶化合物；催化；氧化反应；叔丁基过氧化氢；芳香酮
中图分类号：TQ032 文献标志码：A 文章编号：0258-3283（2022）- -
Synthesis of a Series of Terpyridine Derivatives and Their Application in Catalytic Oxidation Reactions FAN Wei-wei, LIU Jian-qi, LI Pan-pan, ZHAN Hong-ju, XIONG Hang-xing*(College of Chemical Engineering and Pharmacy, Jingchu University of Technology, Jingmen 448000, China),Huaxue shiji, 2022, 44(1), ～
Abstract: Five terpyridinederivatives, 4'-(pyridin-4-yl)-2,2':6',2''-terpyridine (L1), 4'-phenyl-2,2':6',2''-terpyridine (L2), 4'-(3,5-dichloropyridin-4-yl)-2,2':6',2''-terpyridine (L3), 4'-(3,5-dibromopyridin-4-yl)-2,2':6',2''-terpyridine (L4) and 4'-(4-(pyridin-4-yl)phenyl)-2,2':6',2''-terpyridine (L5), were synthesized by one-step method. Among them, the novel compounds L3 and L4 have not yet been reported. Then these polypyridine compounds were used as the ligand to catalyze the oxidation of benzyl alcohol with MnCl2. It was found that all the five polypyridine ligands had good properties. The 4' -pyridine substituent in the molecular structure of the ligands played an important role in improving the catalytic activity. Finally, 4'-(4-(pyridine-4-yl) phenyl)-2,2':6',2 "-tribipyridine was selected as the best ligand to catalyze the oxidation of benzyl alcohols and benzyl alkanes with MnCl2. The conversion rates of five typical substrates were all above 95% and the yields were all above 90%. This catalytic oxidation method is expected to be applied to the green and efficient synthesis of aromatic ketones and related drug intermediates.
Key words: polypyridine compound; catalysis; oxidation; tert-butyl hydroperoxide; aromatic ketone
引用本文：范伟伟，刘建奇，李攀攀，等. 系列三联吡啶衍生物的合成及在催化氧化中的应用[J]. 化学试剂，2022，44(1):142-146。
不饱和腙类化合物的三氟甲基化反应
李志刚*
（沂水县第四中学，山东 沂水 276400)
摘要：氟具有强的吸电子性、亲脂性，将含氟的取代基引入药物中能显著改变药物的药代动力学性质，包括极性、亲脂性、代谢稳定性等，因此向化合物中引入三氟甲基是近期有机合成及医药领域的热点，开发利用经济、高效、绿色的三氟甲基试剂具有重要的意义。以三氟甲烷亚磺酸钠为三氟甲基源，在温和的条件下实现不饱和腙类化合物的三氟甲基化。结果表明，三氟甲烷亚磺酸钠作为三氟甲基源具有良好的反应活性，反应条件温和，符合绿色化学要求，并提供了向不饱和腙类化合物引入三氟甲基的新方法。
关键词：三氟甲烷亚磺酸钠；不饱和腙类化合物；三氟甲基；绿色合成；有机氟化物
中图分类号：O621 文献标识码：A 文章编号：0258-3283（2022）
Study on Trifluoromethylation of Unsaturated Hydrazone Compounds LI Zhi-gang*(Yishui County No. 4 Middle School, Yishui 276400, China), HuaxueShiji, 2022, 44(1),
Abstract：Fluorine has strong electron absorption and lipophilicity. The introduction of fluorine-containing substituents into drugs can significantly change the pharmacokinetic properties of drugs, including polarity, lipophilicity, metabolic stability and so on. Therefore, the introduction of trifluoromethyl into compounds is a hot spot in the field of organic synthesis and medical field, and the development and utilization of economical and efficient trifluoromethyl reagents is of great significance. We used sodium trifluoromethanesulfinate as the source of trifluoromethyl to achieve trifluoromethylation of unsaturated hydrazone compounds under mild conditions. The results showed that sodium trifluoromethanesulfinate had the good reactivity as a source of trifluoromethyl, and the reaction conditions were mild, which met the requirements of green chemistry. The research also provided a new method for introducing trifluoromethyl group into unsaturated hydrazone compounds.
Key words：sodiumtrifluoromethanesulfinate; unsaturated hydrazone compound; trifluoromethyl; green synthesis; organic fluoride
引用本文：李志刚. 不饱和腙类化合物的三氟甲基化反应[J]. 化学试剂, 2022, 44(1): 147-152。
三组分串联反应合成苯并硫氮杂卓衍生物
张杰1，吴庆国，贾纪萍，吴卓航，唐盈盈，耿梦囡，汤伟
(江苏农牧科技职业学院 动物药学院，江苏 泰州 225300)
摘要：以原位生成的芳基重氮盐为自由基源，在无过渡金属条件下，以单质硫作为硫源，利用碘化钾促进的2-(1H-吡咯-1-基)苯胺/单质硫/炔三组分自由基串联反应，经过自由基型的单质硫插入/加成/环化等过程，成功构建了20个苯并硫氮杂卓衍生物，通过1HNMR、13CNMR和HR-MS对产物的结构进行确证。反应产率为45% ~ 73%，底物适用范围较广并具有良好的官能团兼容性。通过自由基捕获实验结合液质分析，推测了反应过程可能产生的中间体。
关键词：单质硫；无过渡金属；三组分反应；自由基；苯并硫氮杂卓
中图分类号：O621.25 文献标识码：A 文章编号：0258-3283（2022）
Three-component Cascade Reactionto Synthesize Benzothiazepinones Derivatives ZHANG Jie*, WU Qing-guo, JIA Ji-ping, WU Zhuo-hang, TANG Ying-ying, GENG Meng-nan, TANG Wei (College of Animal Pharmacetical Sciences, Jiangsu Agri-animal Husbandry Vocational College, Taizhou Jiangsu, 225300, China), Huaxue Shiji, 2022,
Abstract: Using aryldiazonium salt in-situ generated as radical source, an efficient KI promoted three-component radical seriesreaction of 1-(2-aminoaryl) pyrroles, elemental sulfur and alkyne for constructing of benzothiazepinones through radical insertion of sulfur, addition and cyclization under transition-metal-free conditions has been developed. Elemental sulfur acted as sulfur source. The structures of thecorresponding products were characterized by 1HNMR, 13CNMR and HR-MS.Twenty kinds of benzothiazepinones derivatives were obtained in 45%~73% yields with good functional group compatibility and the method had advantages of wide raw material sources. Through free radical capture experiment and LC-MS, thepossible intermediate specie was speculated.
Key words: elemental sulfur; transition-metal-free; three-component reaction; radical; benzothiazepinones
引用本文：张杰，吴庆国，贾纪萍，等. 三组分串联反应合成苯并硫氮杂卓衍生物[J]. 化学试剂，2021，44（1）：153-159.
