壳聚糖纳米粒子的制备方法及其作为药物递送载体的应用
贤凤a，程婉婷a，高静*b
（广东药科大学 a. 公共卫生学院，b. 食品科学学院，广东 中山 528458）
摘要：以片剂、胶囊、溶液等为代表的传统药物剂型，具有生物利用率低、控制释放能力弱、依从性低等缺点。因此，寻找新型的递送载体来改善药物的有效性、稳定性及安全性尤为重要。壳聚糖纳米粒子具有生物相容性、生物可降解性、无毒，可以延长药物在吸收时的保留时间，提高药物稳定性及利用率。综述了壳聚糖纳米粒子的制备方法，如沉淀法、复凝聚法、离子交联法、微乳液法、自组装法等，并且总结了这几种方法及其各自优缺点。此外，还综述了壳聚糖纳米粒子在口服给药、皮肤给药、吸入给药、注射给药中的应用。最后对壳聚糖纳米粒子应用于药物递送系统进行了展望，为壳聚糖纳米粒子在药物递送系统中的未来研究和应用提供参考。
关键词：壳聚糖；纳米粒子；制备方法；药物载体；应用；研究进展
中图分类号：R943.41；TQ469 文献标识码：A 文章编号：
A Review on the Preparation Methods of Chitosan Nanoparticles and Their Applications as Drug Delivery Carriers XIAN Fenga，CHENG Wan-tinga，GAO Jing*b (a. School of Public Health，b.School of Food Science, Guangdong Pharmaceutical University，Zhongshan 510220, China), Huaxue Shiji, 2021, 43(12)
Abstract: Tablets, capsules, and solutions et al. are traditional dosage forms with low bioavailability, weak controlled release ability, and low compliance. Therefore, it is particularly important to find novel delivery carriers to improve the efficacy, stability, and safety of drugs. Chitosan nanoparticles have useful features, such as biocompatible, biodegradable, and non-toxic. It can prolong the retention time of drugs during absorption and improve drug stability and utilization. The preparation methods of chitosan nanoparticles and their advantages and disadvantages were introduced in this review, such as precipitation, complex coalescence, ionic cross-linking, microemulsion, and self-assembly. Furthermore, the applications of chitosan nanoparticles in oral drug delivery, skin drug delivery, inhalation drug delivery, and injection drug delivery were reviewed. Finally, the application of chitosan nanoparticles in drug delivery systems was proposed. The review provides a useful information for future research and application of chitosan nanoparticles in drug delivery systems.
Key words: chitosan; nanoparticles; preparation methods; drug carriers; applications; research progress
引用本文：贤凤, 程婉婷, 高静. 壳聚糖纳米粒子的制备方法及其作为药物递送载体的应用[J]. 化学试剂，43(12):1615-1622.
核黄素衍生物的合成及其光交联明胶的应用研究
林娜，余万韬，李丹，饶萌，张汉桥，苏江涛*
（湖北工业大学 生物工程与食品学院，湖北 武汉 430068）
摘要：通过化学合成的方法获得了具有不同化学基团修饰的核黄素衍生物，化合物的结构中均保留了与核黄素相同的光激发响应基团，并且分别作为光敏剂实现了光诱导明胶交联，验证了核黄素光诱导交联明胶的作用机理。考察了所得交联明胶膜的机械性能，优选水溶性核黄素为光敏剂，使得明胶在载药蒙脱石微粒表面光诱导原位交联，从而实现对微粒的包覆制粒。包覆后的蒙脱石微粒流动性更好，堆密度大，更适合作为制剂粉体进行加工，而且对模型药物（阿奇霉素）的具有一定的掩味效果，体现了用交联明胶包覆载药蒙脱石微粒的优势。
关键词：核黄素；光交联；明胶；蒙脱石；结构改性；粉体制剂
中国分类号：O621 文献标识码：A 文章编号：0258-3283（2021）--
Synthesis of Riboflavin T Derivatives and Their Application in Photo-Cross-Linked Gelatin LIN Na, YU Wan-tao, LI Dan, RAO Meng, ZHANG Han-qiao, SU Jiang-tao*（Department of Biological and Food Engineering College, Hubei University of Technology, Wuhan 430068,China), Huaxue Shiji, 2021, 43(12), ～
Abstract: Riboflavin derivatives with different group modifications were obtained by chemical synthesis method，in which the structures of the synthesized compounds have the same photo-excitation response group as riboflavin. These compounds acted as photosensitizers, respectively, to carry out the photocross-linked procedure of gelatin, which verified the same mechanism as riboflavin. The mechanical properties of the cross-linked gelatin film were investigated, and hydrophilic riboflavin derivatives were selected as the photosensitizers to make the gelatin in situ photocross-linked on the surface of drug-loaded montmorillonite particles, so as to realize the encapsulation and granulation of the particles. The coated montmorillonite particles have better fluidity, higher bulk density, which are more suitable for processing as preparation powder. Moreover, the coated montmorillonite particles have certain flavor masking effect on the model drug azithromycin, which reflecting the advantages of using cross-linked gelatin to coat the drug-loaded montmorillonite particles.
Key words: riboflavin; photo-cross-linked; gelatin; montmorillonite; structural modification; powder preparation
引用本文：林娜，余万韬，李丹，等. 核黄素衍生物的合成及其光交联明胶的应用研究[J]. 化学试剂，2021，43（12）：1623-1630.
磁性分子印迹麦秆炭吸附环丙沙星性能研究
毛艳丽1,2，李朝阳1,2，刘超朋1，田丽1，康海彦1，宋忠贤1，延旭1，王召东*1
（1. 河南城建学院 河南省水体污染控制与修复重点实验室，河南 平顶山 467036；2. 江西理工大学 土木与测绘工程学院，江西 赣州 341000）
摘要：通过原子转移自由基聚合法在乙烯基改性的磁性麦秆颗粒表面形成聚合层得到磁性分子印迹材料(MMIPs)。傅里叶红外光谱（FT-IR）、热重分析仪（TGA）表征吸附剂表面印迹聚合层具有识别功能；pH变化、热力学和动力学的吸附实验表明25℃、pH 6时MMIPs在40 min内对环丙沙星呈Langmuir（R2=0.999）单层吸附82.26 mg/L及拟二级动力学（R2=0.999）化学主导的86.46 mg/g最大吸附容量，可循环吸附5次。MMIPs对四环素（TC）、磺胺二甲基嘧啶(SMC)、恩诺沙星（ENR）竞争吸附表明MMIPs具有选择性吸附能力。
关键词：生物碳质材料；环丙沙星；分子印迹；特异识别性吸附；聚合军；离子空穴
中图分类号：X703.1 文献标识码：A 文章编号：0258-3283（2021）--
Study on Adsorptive Performance of Ciprofloxacin by Molecularly Imprinted Polymers Based on Magnetic Wheat Straw Biochar MAO Yan-li1,2, LI Zhao-yang1,2, LIU Chao-peng1, TIAN Li1, KANG Hai-yan1, SONG Zhong-xian1, YAN Xu1, WANG Zhao-dong*1 (1. Henan Key Laboratory of Water Pollution Control and Rehabilitation Technology, Henan University of Urban Construction, Pingdingshan 467036, China; 2. School of Civil and Surveying Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, China), Huaxue Shiji, 2021, 43(12), ～
Abstract: Magnetic molecularly imprinted materials (MMIPS) were prepared by atom transfer radical polymerization on the surface of vinyl modified magnetic wheat straw particles. The recognition function on the surface of the polymeric layer of adsorbent was characterized by FT-IR and TGA. The adsorption experiments on pH, thermodynamics and kinetics showed that Ciprofloxacin (CIP) was adsorbed by MMIPS at pH 6 at 25 °C for 40 min. with a maximum adsorption capacity of 82.26 mg/L by the Langmuir (R2 = 0.999) monolayer adsorption while that of 86.46 mg/L by the pseudo second-order kinetics (R2 = 0.999). MMIPS could be reused for five times. The competitive adsorption of Tetracycline (TC), Sulfamethazine (SMC), and Enrofloxacin (ENR) indicated that MMIPS exhibited selective adsorption capacity.
Key words: carbonaceous material; ciprofloxacin; molecular imprinting; specific discriminant adsorption
引用本文：毛艳丽，李朝阳，刘超朋，等.磁性分子印迹麦秆炭吸附环丙沙星性能研究[J]. 化学试剂，2021，43(12): 1631-1637。
一锅煮法由芦丁合成槲皮素五芳基甲酸酯及生物活性研究
冯亚莉，李浩，白现祥，刘双强，裴媛媛，翟广玉*
（郑州工业应用技术学院 药学与化学工程学院，河南 郑州 451100）
摘要：使用易得的芦丁和芳酰氯为原料，利用“一锅煮法”策略，在吡啶的促进下首次实现了槲皮素五芳基甲酸酯类化合物的高效制备。该策略避免了直接使用槲皮素作为原料容易发生氧化或聚合等副反应，且后处理仅需重结晶的简单操作，即可以44%～68% 收率得到10个尚未见文献报道的新颖五芳基甲酸酯类化合物（3b～3k），目标产物的结构经核磁、质谱、红外确证。采用溴化噻唑蓝四氮唑（MTT）法，初步评价了化合物3b～3k对人食管癌细胞EC-109、人食管鳞癌细胞EC-9706、人胃癌细胞SGC-7901及小鼠黑色素瘤细胞B16-F10等4株肿瘤细胞的体外增殖抑制作用。生物活性测试结果表明所合成的10个槲皮素五芳基甲酸酯类衍生物对于这4种癌细胞均有不同程度的抑制作用，其中槲皮素五对氯苯甲酸酯3i对EC-9706 的半数抑制浓度IC50为26.6 ± 1.3 µmol/L，活性分别比母药槲皮素、槲皮素五乙酸酯3a和对照药5-氟尿嘧啶提高了1～3倍，是一个很有潜力的新型抗癌候选化合物。这也证明通过对槲皮素的五芳基酯衍生化策略是克服母体分子槲皮素的生物利用率低、并开发具有高效生物活性分子的一种有效手段。
关键词：一锅煮法；槲皮素五芳基甲酸酯；酯化反应；合成；生物活性评价
中图分类号：O629.9 文献标识码：A 文章编号：0258-3283（2021）- -
Synthesis and Bioactive Evaluation of Quercetin Pentabenzoates from Rutin in One-pot Procedure FENG Ya-li, LI Hao, BAI Xian-xiang, LIU Shuang-qiang, PEI Yuan-yuan, ZHAI Guang-yu* (School of Pharmacy and Chemical Engineering, Zhengzhou University of Industrial Technology, XinZheng 451100, China), Huaxue shiji, 2021, 43(12), ～
Abstract: A highly efficient one-pot procedure for the preparation of quercetin pentabenzoates by the utilization of easily accessible rutin and aroyl chlorides in the presence of pyridine was developed. By overcoming the plausible oxidation or polymerization side reactions by direct employing quercetin as the starting material, ten unknown quercetin pentabenzoates (3b～3k) were synthesized in 44%～68% yields after simple recrystallization. The structures of these newly synthesized molecules were identified by their NMR, MS and IR spectra, respectively. In order to investigate the effects of inhibitory proliferation in vitro of the obtained ten target compounds on four types of cancer cells, including human esophageal carcinoma cell line EC-109, human esophageal carcinoma cell line EC-9706, human gastric cancer cell line SGC-7901, and mouse melanoma cell line B16-F10, MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetraazolium bromide) assay were carried out and the results indicated that all 10 quercetin pentabenzoates showed different degrees of inhibitory effects on the four types of cancer cells. Among them, quercetin penta(4-chlorobenzoate) 3i has been identified as a very promising anti-tumor candidate because of its better inhibition effect on EC-9706 growth with the half maximal inhibitory concentration (IC50) value of (26.6 ± 1.3) µmol/L, higher one to three folds than that of the parent quercetin, quercetin pentacetate 3a, and control medicine 5-fluoropyrimidine. The study demonstrated that the pentabenzoation of quercetin was a reliable strategy to develop new effective bioactive molecules by overcoming the low bioavailability of quercetin.
Key words: one-pot procedure; quercetin pentabenzoates; esterification reaction; synthesis; bioactivity evaluation
引用本文：冯亚莉，李浩，白现祥，等. 一锅煮法由芦丁合成槲皮素五芳基甲酸酯及生物活性研究[J]. 化学试剂，2021，43(12):1638-1643。
含4-氟苯乙烯基取代钌配合物的合成及其抗菌活性研究
廖向文* 1，姜桂娟1，蒋光彬2，王金涛1
(1. 江西科技师范大学 药学院，江西 南昌 330013；2. 桂林理工大学 化学与生物工程学院，广西 桂林 541004)
摘要：以含氟原子取代邻菲啰啉衍生物为主配体合成了两个多吡啶类钌配合物Ru(bpy)2(CFPIP)](ClO4)2 、 [Ru(dmb)2(CFPIP)](ClO4)2，并研究了两个钌配合物对金黄色葡萄球菌的抑制活性。通过最低抑菌浓度测定、生物被膜形成实验、兔红细胞溶血与棋盘联用实验研究了两个配合物的体外抑菌活性。结果显示，两个钌配合物在体外均具有较强的抗菌活性(0.012～0.030 mg/mL)，[Ru(dmb)2(CFPIP)](ClO4)2在亚抑菌浓度下导致细菌生物被膜的形成量降低了19.8%，溶血霉素的分泌量减少了29.6%。更为重要的是，该配合物与卡那霉素以及庆大霉素等氨基糖苷类抗生素合用时显示出较强的联用活性(FICI＜0.5)。最后采用小鼠皮肤感染实验进一步研究了[Ru(dmb)2(CFPIP)](ClO4)2配合物的体内抗菌活性，结果显示含该配合物乳膏能有效抑制小鼠皮肤感染部位细菌的生长。研究结果表明含氟取代的钌配合物对金黄色葡萄球具有显著的抑菌活性。
关键词：钌配合物；抗菌活性；金黄色葡萄球菌；氟取代；联用活性
中图分类号：R916 文献标识码：A 文章编号：0258-3283（2021）
Synthesis and Antibacterial Activity of Ruthenium Complexes with 4-Fluorostyryl Substituted Ligands LIAO Xiang-wen* 1, JIANG Gui-juan1, JIANG Guang-bin2, WANG Jin-tao1 (1.School of Pharmacy, Jiangxi Science and Technology Normal University, Nanchang 330013, China; 2.College of Chemistry and Bioengineering, Guilin University of Technology, Guilin 541004, China) , Huaxue Shiji, 2021
Abstract: Two novel ruthenium complexes with ligand fluorides: [Ru(bpy)2(CFPIP)](ClO4)2 (Ru(Ⅱ)-1), [Ru(dmb)2(CFPIP)](ClO4)2 (Ru(II)-2), (CFPIP=2-(4-fluorostyryl)-1H-imidazo[4,5-f][1,10]phenanthroline), have been synthesized and their antimicrobial activities were examined. Minimal inhibitory concentration assay, biofilms formation, and rabbit erythrocyte hemolysis assays, checker board assay were performed. The results indicated that two complexes Ru(II)-1 and Ru(II)-2 displayed significantly antimicrobial activity against Staphylococcus aureus (MIC: 0.012～0.030 mg/mL), Ru(II)-2 could efficiently inhibited the biofilms formation and toxin secretion of Staphylococcus aureus (19.8% and 29.6%, respectively). More importantly, Ru(II)-2 could increase the susceptibility of S. aureus to some aminoglycoside antibiotics (kanamycin and gentamicin) (FICI＜0.5). At last, in vivo bacterial infection treatment studies with mouse also showed that ointments contained Ru(II)-2 were highly effective against mouse skin infection. In summary, ruthenium complexes with ligand fluorides have markedly antimicrobial activity against Staphylococcus aureus in vitro and in vivo.
Key words: ruthenium complexes; antimicrobial activity; staphylococcus aureus; fluorides; synergism
引用本文：廖向文，姜桂娟，蒋光彬，等. 含4-氟苯乙烯基取代钌配合物的合成及其抗菌活性研究[J]. 化学试剂，2021，43(12):1644-1650。
FeOCl-COF的制备及其在非均相芬顿反应中的应用
范德锴，吴志园，吴怀欣，陈文凯，赵焕新*
(沈阳化工大学 环境与安全工程学院，辽宁 沈阳 110142)
摘要：采用熔融浸渍-焙烧工艺制备FeOCl-COF复合催化剂，并应用于类芬顿高级氧化技术。以苯酚为目标污染物，在类芬顿体系下，探究了催化剂组分、剂量、pH、H2O2浓度、温度等因素对降解效率的影响。在复合催化剂FeOCl掺杂量为15%，投加量为0.7 g/L，H2O2浓度为5 mmol/L、pH 6.5和室温（25 ℃）的条件下，苯酚的去除率可达99%，反应活化能为53.91 kJ/mol。自由基捕获实验证明·OH是起主要降解作用的活性物种。紫外全波段扫描实验证实了污染物苯酚得到了有效的去除。本研究为FeOCl-COF在水处理中的实际应用提供了实验基础。
关键词：FeOCl-COF；非均相Fenton；苯酚；共价有机骨架；高级氧化
中图分类号：X703 文献标识码：A 文章编号：0258-3283（2021）
Preparation of FeOCl-COF and Its Application in Heterogeneous Fenton Reaction FAN De-kai, WU Zhi-yuan, WU Huai-xin, CHEN Wen-kai, ZHAO Huan-xin* (College of Environmental and Safety Engineering, Shenyang University of Chemical Technology, Shenyang 110142, China), Huaxue Shiji, 2021, 43(12)
Abstract: FeOCl-COF composite catalyst was prepared by melt impregnation roasting process and applied to Fenton-like advanced oxidation technology. The effects of catalyst components, dosage, pH, H2O2 concentration and temperature on degradation efficiency were studied in the Fenton-like system. The removal rate of phenol can reach 99% with the activation energy of 53.91 kJ/mol under the conditions of 15% doping, 0.7 g/L of the catalyst, 5 mmol/L H2O2, pH 6.5, and 25 °C room temperature. The free radical capture experiment proved that •OH was the main degradation active species. The UV full band scanning experiment confirmed that phenol was effectively removed. This study provides the experimental basis for the practical application of FeOCl-COF in water treatment.
Key words: FeOCl-COF; heterogeneous Fenton; phenol; covalent organic framework; advanced oxidation
引用本文：范德锴，吴志园，吴怀欣，等. FeOCl-COF的制备及其在非均相芬顿反应中的应用[J]. 化学试剂, 2021, 43(12): 1651-1656。
国内外分析检测标准品市场现状与趋势
徐银1,2，佟庆龙1，黄海娟1，张磊*1,2
（1. 天津阿尔塔科技有限公司，天津 300457；2. 阿尔塔（天津）标准物质研究院有限公司，天津 300457）
摘要：标准品是分析检测的“标尺” “砝码”，近几十年来标准品的需求随着分析检测行业的发展而急剧增加，我国标准品行业形成了进口标准品品牌、国家标准物质/标准样品和民营标准品品牌共存的格局。总结了国内外标准品行业发展的历史和现状，对国内外标准品生产者尤其是具有CNAS-CL04/ISO 17034标准物质/标准样品生产者资质认可的企业进行了总结，对我国标准品行业目前存在的问题进行了归纳，并对标准品市场的趋势做出了展望。
关键词：标准品；标准物质；标准样品；有证标准物质；国家标准样品；标准物质/标准样品生产者
中图分类号：O622.4 文献标识码：A 文章编号：0258-3283（2021）
Status and Trends of Domestic and Oversea Markets of Reference Materials XU Yin1,2, TONG Qing-long1, HUANG Hai-juan1, ZHANG Lei*1,2 (1. Alta Scientific Co., Ltd., Tianjin 300457, China; 2. Alta Institute for Reference Materials Co., Ltd., Tianjin 300457, China), Huaxue Shiji, 2021, 43(12)
Abstract: Reference materials are the “ruler” and “weight” of analysis and testing. In recent decades, the demand for reference materials is increasing tremendously with the development of analytical testing industry, the domestic analytical reference material industry has formed a coexistence pattern of imported reference material brands, national certified reference materials, and private reference material brands. This paper summarized the development history and current situation of the domestic and foreign reference material industry, the domestic and foreign reference material producers, especially those with CNAS-CL04/ISO 17034 accreditation. The problems in China's reference material industry are pointed out, the trends of the market is forecasted.
Key words: reference material (RM); certified reference material (CRM); GBW; GSB; standard reference material; reference material producer (RMP)
引用本文：徐银，佟庆龙，黄海娟，等. 国内外分析检测标准品市场现状与趋势[J]. 化学试剂，2021,43（12）：1657-1667。
二氧化硫残留量检测新方法研究进展
陈晓磊，邓高琼，王硕，韦柳娜，陈亨业，付海燕，兰薇*
（中南民族大学 药学院，湖北 武汉 430074）
摘要：二氧化硫类化合物是国内外允许使用的一种食品/药品添加剂，可发挥防腐、抗氧化、漂白和护色等作用，主要以亚硫酸盐的形式存在。但超过最大允许残留量的二氧化硫类化合物不仅会影响食药的质量，更会损害人体健康。因此准确、高效的二氧化硫类化合物检测方法是食品/药品质量安全的重要保障之一。本论文综述了近五年来食品/药品中二氧化硫残留量的检测新方法，分析了各种技术的优点及不足，并对其发展方向进行了展望。
关键词：二氧化硫；色谱-质谱法；荧光传感法；表面增强拉曼光谱法；电化学分析法；免仪器检测法
中图分类号：TS219；R284.1 文献标识码：A 文章编号：0258-3283（2021）
Advances in New Methods for Detection of Sulfur Dioxide Residues CHEN Xiao-lei, DENG Gao-qiong, WANG Shuo, WEI Liu-na, FU Hai-yan, LAN Wei * (School of Pharmaceutical Science, South-Central University for Nationalities, Wuhan 430074, China), Huaxue Shiji, 2021, 43(12)
Abstract: Sulfur dioxide compounds are a class of permitted food/medicine additives, which can play anticorrosive, antioxidant, bleaching, and color protection functions. They mainly exist in the form of sulfites. However, sulfur dioxide residues more than the maximum allowable amount will not only affect the quality of food and medicine, but also harm human health. Therefore, an accurate and efficient method for detecting sulfur dioxide compounds is one of the important guarantees for the quality and safety of food/medicine. In this paper, the new methods for the determination of sulfur dioxide residues in the last five years are reviewed. The advantages and disadvantages of these methods are analyzed, and the development direction of the detection methods is prospected.
Key words: sulfur dioxide; chromatography-mass spectrometry; fluorescence sensing method; surface enhanced raman spectroscopy; electrochemical analysis; instrument-free testing
引用本文：陈晓磊，邓高琼，王硕，等. 二氧化硫残留量检测新方法研究进展[J]. 化学试剂，2021，43（12）：1668-1676。
柴胡皂苷提取工艺及其含量测定研究
彭依晴1a，刘爽1a，康泽鹏1a，杜晨阳1b，梁宗锁*1a,2
(1. 西北农林科技大学 a. 生命科学学院，b. 化学与药学院，陕西 杨凌 712100；2. 浙江理工大学 生命科学与医药学院，浙江 杭州 310000)
摘要：柴胡为我国大宗药材之一，其含有的主要活性成分柴胡皂苷具有抗氧化、抗炎、抗癌等药理作用，被广泛应用于中药方剂配伍和中成药生产中。传统柴胡皂苷提取方法存在时间长、效率低、损失大等问题，大大降低了柴胡原药利用率与生产效率。近年来，基于各种新兴技术与新型仪器的高效提取检测方法具有很大的开发和研究价值。综述了中药材柴胡活性成分柴胡皂苷提取纯化工艺及其成分检测手段的研究进展，为柴胡皂苷的开发应用和进一步研究提供理论依据。
关键词：柴胡；活性成分；柴胡皂苷；提取工艺；检测方法
中图分类号：TQ460 文献标识码：A 文章编号：0258-3283（2021）
Study on Extraction Technology and Content Determination of Saikosaponin PENG Yi-qing1a, LIU Shuang1a, KANG Ze-peng1a, DU Chen-yang1b, LIANG Zong-suo*1a,2 (1 a. College of Life Sciences, 1b. College of Chemistry and Pharmacy, Northwest A&F University, Yangling 712100, China; 2. College of Life Science and Medicine, Zhejiang Sci-Tech University, Hangzhou 310000, China), Huaxue Shiji, 2021, 43(12),
Abstract: Radix bupleuri is one of the bulk medicinal materials in China. The main active component saikosaponin contained in radix bupleuri has the pharmacological effects of anti-oxidation, anti-inflammation and anti-cancer, which is widely used in the compatibility of traditional Chinese medicine prescriptions and the production of Chinese patent medicines. The traditional saikosaponin extraction method has the problems of long time, low efficiency and large loss, which greatly reduces the utilization rate and production efficiency of radix bupleuri. In recent years, efficient extraction and detection methods based on various emerging technologies and new instruments have great development and research value. This paper reviews the research progress of extraction and purification technology and component detection methods of saikosaponin, the active ingredient of radix bupleuri, and provides a theoretical basis for the development and application of saikosaponin and further research.
Key words: radix bupleuri; active ingredient; saikosaponin; extraction process; detection method
引用本文：彭依晴，刘爽，康泽鹏，等.柴胡皂苷提取工艺及其含量测定研究[J].化学试剂，2021，43（12）：1677-1682.
花色苷提取及其纯化工艺研究进展
黄金a，刘志国*a，穆立蔷b，付玉杰a
（东北林业大学 a. 化学化工与资源利用学院，森林植物生态学教育部重点实验室, b. 林学院，黑龙江 哈尔滨 150040）
摘要：花色苷是广泛存在于天然果蔬中的黄酮类有机化合物，它具备良好的抗氧化、抗炎、抗肿瘤等功效，已广泛应用于食品、保健品、化妆品、医药、化工等领域；花色苷提取、纯化工艺是花色苷及其衍生品广泛应用的核心环节。花色苷提取法中传统溶剂提取法由于效能较低已很少单独使用，新兴方法中超声和微波法较常见；花色苷纯化常用大孔树脂法，色谱法通常用于制备纯度在90%以上的花色苷。综述了花色苷提取和纯化方法的原理、工艺参数、优缺点以及在实际生产实践中的应用，为我国花色苷产业近一步开发利用提供更多依据。
关键词：花色苷；提取；纯化；超声提取法；微波提取法
中图分类号：O652.2 文献标识码：A 文章编号：0258-3283（2021）
Research Progress on Extraction and Purification of Anthocyanins HUANG Jina, LIU Zhi-guo*a, MU Li-qiangb, FU Yu-jiea (a. Chemical Engineering and Resource Utilization, Key Laboratory of Forest Plant Ecology, Ministry of Education, b. School of Forestry, Northeast Forestry University, Harbin 150040 , China), Huaxue Shiji, 2021, 43(12)
Abstract: Anthocyanins are flavonoid organic compounds widely existing in natural fruits and vegetables. They have good antioxidant, anti-inflammatory and anti-tumor effects, and have been widely used in food, health products, cosmetics, medicine, chemical industry and other fields. The extraction and purification of anthocyanins are the core of the wide application of anthocyanins and their derivatives. Among the anthocyanin extraction methods, the traditional solvent extraction method is rarely used alone due to its low efficiency, and the ultrasonic and microwave-assisted methods are more common. The purification of anthocyanins is usually carried out by macroporous resin, and chromatography is usually used to prepare anthocyanins with purity above 90%. The principles, process parameters, advantages, and disadvantages of the extraction and purification methods of anthocyanins and their application in practical production were introduced in this review, providing more basis for the further development and utilization of anthocyanin industry in China.
Key words: anthocyanins; extraction; purification; ultrasonic extraction; microwave extraction
引用本文：黄金，刘志国，穆立蔷，等. 花色苷提取及其纯化工艺研究进展[J]. 化学试剂，2021,43（12）：1683-1690。
大麻二酚及其类似物合成研究进展
崔雪莲1，高兴文*2
（1.贵州警察学院 法律系 ，贵州 贵阳 550002；2.贵州城市职业学院 ，贵州 贵阳 550025）
摘要：大麻二酚（CBD）是一种从大麻中发现的非精神活性物质，由于其潜在的治疗作用，包括神经保护、抗癫痫、抗炎、抗焦虑和抗癌等，近年来受到越来越多的关注。大麻二酚及其类似物主要是从大麻植物提取，但传统的提取方法存在质量控制差、纯化困难等缺点。合成手段是一个有效的途径。此外，围绕大麻二酚的结构，通过分子设计还可以合成具有更高生物活性的新型大麻二酚类似物。简要综述了大麻二酚及其类似物合成的研究进展。
关键词：大麻二酚；大麻二酚类似物；合成；生物活性；研究进展
中图分类号：R914 文献标志码：A 文章编号：0258-3283（2021）
Progress in Synthesis of Cannabidiol and Its Analogues CUI Xue-lian1, GAO Xing-wen*2 (1. Department of Law, Guizhou Police College, Guiyang 550005, China; 2. Guizhou City Vocational College, Guiyang 550025, China), Huaxue Shiji, 2021, 43(12)
Abstract: Cannabinoid (CBD) is a nonpsychoactive substance found in cannabis plants. Due to its potential therapeutic effects, including neuroprotection, antiepileptic, anti-inflammatory, antianxiety, and anti-cancer, more and more attention has been attracted by CBD in recent years. CBD and its analogues are mainly extracted from hemp plants, but the traditional extraction methods have some disadvantages, such as poor quality control and difficult purification. Synthesis is an effective method. In addition, based on the structure of CBD, neotype CBD analogues with higher bioactivity can be synthesized through molecular design. The synthesis and research progress of CBD and its analogues are summarized in this review.
Key words: cannabidiol（CBD）; analogs; synthesis; bioactivity; research progress
引用本文：崔雪莲，高兴文. 大麻二酚及其类似物合成研究进展[J]. 化学试剂，2021，43（12）：1691-1698.
UPLC-MS/MS同时测定“壮根灵”类农肥中18种植物生长调节剂的含量
朱仁愿1, 2，刘兴国1, 2，丁辉1, 2，李岩1, 2，李成明3，续艳丽*1, 2
(1. 兰州市食品药品检验检测研究院，甘肃 兰州 730050；2. 甘肃省种植中药材外源性污染物监测工程研究中心，甘肃 兰州 730050；3. 甘肃省中医院 药学部，甘肃 兰州 730050)
摘要：建立超高效液相色谱-串联质谱法（UPLC-MS/MS）同时测定“壮根灵”类农肥中18种植物生长调节剂的含量。样品经1%醋酸乙腈提取后，采用UPLC-MS/MS进行测定。色谱柱：Waters Acquity UPLC BEH C18（2.1 mm×100 mm，1.7 μm）；流动相：0.1%甲酸水溶液(A)-乙腈(B)，梯度洗脱；流速：0.3 mL/min；柱温：20 ℃；多反应监测（MRM）检测模式。结果表明，18种植物生长调节剂线性关系良好，线性范围为2～300 μg/L（r≥0.997），检出限为0.09～2.51 μg/g，定量限为0.22～7.69 μg/g，精密度RSD均小于9%，平均加样回收率为85.4%～95.3%，RSD为2.6%～8.1%（n = 9）。采用该法对10批次“壮根灵”类农肥中植物生长调节剂含量进行了检测，含量为0.19～122.60 mg/g。本方法前处理简单、灵敏度高、准确快速，可用于“壮根灵”类农肥中植物生长调节剂的定性和定量分析。
关键词：“壮根灵”类农肥；植物生长调节剂；超高液相色谱-串联质谱法
中图分类号： O657.63 文献标识码：A 文章编号：0258-3283（2021）
Simultaneous Determination of Contents of 18 Plant Growth Regulators in Agricultural Fertilizer of “Zhuanggenling” by Ultra Performance Liquid Chromatography-Tandem Mass Spectrometry ZHU Ren-yuan1,2, LIU Xing-guo1,2, DING Hui1,2, LI Yan1,2, LI Cheng-ming3, XU Yan-li *1,2 (1. Lanzhou Institute for Food and Drug Control, Lanzhou 730050, China; 2. Gansu Engineering Research Center for Monitoring Exogenous Harmful Residues in Traditional Chinese Medicines, Lanzhou 730050, China; 3. Department of Pharmacy, Gansu Hospital of Traditional Chinese Medicine, Lanzhou 730050, China), Huaxue Shiji, 2021, 43(12)
Abstract: To establish an ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) method for the simultaneous determination of contents of 18 plant growth regulators (PGRs) in agricultural fertilizer of “Zhuanggenling”. Samples were extracted with 1% acetonitrile acetic acid, and then determined by UPLC-MS/MS with a Waters Acquity UPLC BEH C18 (2.1 mm×100 mm, 1.7 μm) chromatographic column, the mobile phase consisted of 0.1% formic acid solution (A) and acetonitrile (B) for gradient elution at a flow rate of 0.3 mL/min at the column temperature of 20 ℃ using multiple reaction monitoring (MRM) mode. The result shows that the linear range of 18 PGRs were 2～300 μg/L with r no less than 0.997. The detection and quantitative limits were 0.09～2.51 μg/g and 0.22～7.69 μg/g, respectively with the RSDs of precision less than 9%. Average recovery was 85.4%～95.3% with RSD 2.6%～8.1% (n = 9). The contents of 18 PGRs in 10 batches of agricultural fertilizer of “Zhuanggenling” were 0.19～122.60 mg/g. The method proved a simple pre-treatment, rapid, sensitive, accurate, and suitable way for the simultaneous qualitative and quantitative determination of 18 PGR contents in agricultural fertilizer of “Zhuanggenling”.
Key words: agricultural fertilizer; “Zhuanggenling”; plant growth regulator; UPLC-MS/MS
引用本文：朱仁愿，刘兴国，丁辉，等. UPLC-MS/MS同时测定 “壮根灵”类农肥中18种植物生长调节剂的含量[J]. 化学试剂，2021，43（12）：1699-1706.
高压密闭消解-电感耦合等离子体质谱法测定煤中锂
宋兴1,2，解锡超*1,2，屠文涛1，胡春莲1
(1. 山西省地质矿产研究院，山西 太原 030001；2. 煤与煤系气地质山西省重点实验室，山西 太原 030001)
摘要：为准确测定煤中锂元素含量，采用高压密闭消解法直接消解煤样，电感耦合等离子体质谱仪进行上机检测。制备11份样品空白溶液进行检测，计算方法的检出限。选用锂含量有差异的3个煤样进行精密度试验。选用国家一级标准物质GBW07103、GBW07108和GBW07408进行准确度试验。分析结果表明，该方法检出限为0.0129 μg/g；3个煤样锂元素测试的精密度分别为1.1%、0.86%、1.4%；GBW07103、GBW07108和GBW07408这3个标准样品检测值与标准值之间的差值均在标准值不确定度范围内，准确度可靠。
关键词：高压密闭消解；电感耦合等离子体质谱；煤；锂；测定
中图分类号：P599 文献标识码：A 文章编号：0258-3283（2021）--
Determination of Lithium in Coal by High-Pressure Closed Digestion-Inductively Coupled Plasma Mass Spectrometry SONG Xing1,2, XIE Xi-chao*1,2, TU Wen-tao1, HU Chun-lian1 (1. Shanxi Institute of Geology and Mineral Resources, Taiyuan 030001, China；2. Shanxi Provincial Key Laboratory of Coal and Coal Measures Gas Geology, Taiyuan 030001, China), Huaxue Shiji, 2021, 43(12), ～
Abstract：In order to determine lithium content in coal accurately, the coal samples were digested by high-pressure closed digestion method immediately and tested directly by inductively coupled plasma mass spectrometry. The detection limit was calculated by the detected values of eleven blank samples. The precision experiments were conducted with three coal samples with different lithium contents. The determination accuracy was verified with national first grade standard materials of GBW07103, GBW07108, and GBW07408. The results showed that the detection limit of the established method was 0.0129 μg/g. The relative standard deviations of the three selected coal samples were 1.1%, 0.86%, and 1.4%, respectively. The detected values of the lithium contents of GBW07103, GBW07108, and GBW07408 were within the uncertainties of the standard values, showing high accuracy of the method.
Key words：high-pressure closed digestion; inductively coupled plasma mass spectrometry; coal; lithium; determination
引用本文：宋兴，解锡超，屠文涛，等. 高压密闭消解-电感耦合等离子体质谱法测定煤中锂[J]. 化学试剂,2021, 43(12): 1707-1710。
LLE-GC-MS法测定地表水中23种痕量含氯有机污染物
巩文静，张厚磊，王诗雨，韩晓梦，孔维珠，张永昊，崔文*
（济宁医学院 法医学与医学检验学院 山东 济宁 272067)
摘要：建立了以液液萃取（LLE）-气相色谱-质谱-SIM扫描（GC-MS-SIM）技术同时检测城区河道表层水样中16种有机氯农药和7种多氯联苯残留的分析方法。样本量为200 mL时，方法检出限（S/N≥3）为0.5～12.5 ng/L，空白水样平均加标回收率在77.8%～110.1%之间，线性范围内方法准确度和精密度范围分别为89.4%～103.5% (n = 6)和0.7%～9.9% (n = 18)，满足方法学要求。采用该方法对流经济宁市境内3条河流表层水样进行检测，结果显示17个站位表层水样中普遍检出艾氏剂、ɑ-氯丹、γ-氯丹、o,p’-DDT和PCB 52，部分站点污染程度超出GB 3838-2002标准限值。该方法结果准确可靠，具有较高的灵敏度和准确度，且操作简便、成本较低，能够满足地表水水质监测的需要。
关键词：液液萃取；气相色谱-质谱；有机氯农药；多氯联苯；地表水
中图分类号：O657.63 文献标识码：A 文章编号：0258-3283（2021）--
Simultaneous Determination of 23 Trace Chlorinated Organic Pollutants in Surface Water with LLE-GC-MS Method GONG Wen-jing1,2, ZHANG Hou-lei1, WANG Shi-yu1, HAN Xiao-meng1, KONG Wei-zhu1, ZHANG Yong-hao1, CUI Wen*1,2 ( Institute of Forensic Medicine and Laboratory Medicine, Jining 272067, China), Huaxue shiji, 2021, 43(12), ～
Abstract: A method for detecting 16 organochlorine pesticides (OCPs) and 7 polychlorinated biphenyl (PCB) residues in surface water in urban rivers simultaneously using the liquid-liquid extraction (LLE) method, combined with gas chromatography-mass spectrometry-SIM scanning (GC-MS-SIM), was established. For 200 mL of detecting samples, the detection limits of the method (S/N≥3) were 0.5～12.5 ng/L, and the average recoveries ranged from 77.8% to 110.1%. The accuracy and precision of the method were in the range of 89.4～103.5% (n =6) and 0.7%～9.9% (n = 18), respectively, which met the methodological requirements, among the range of the linear relationship. The method was then used to detect the surface water samples of three rivers in Jining City, Shandong Province. The results showed that aldrin, ɑ-chlordane, γ-chlordane, o,p’-DDT, and PCB 52 were generally detected in the surface water samples of 17 stations, and the pollution degree of some stations exceeded the standard limit of GB 3838-2002. The pollution degrees of DDTs (Dichlorodiphenyltrichloroethane) and PCBs exceed the corresponding environmental thresholds and are urgently paid social attention and treated. It can be concluded that the method developed has high sensitivity and accuracy as well as simple operation and low cost, that could meet the needs of quality monitoring in surface water.
Key words: liquid-liquid extraction; gas chromatographic mass spectrometry; organochlorine pesticides; polychlorinated biphenyls; surface water
引用本文：巩文静，张厚磊，王诗雨，等.LLE-GC-MS法测定地表水中23种痕量含氯有机污染物[J]. 化学试剂，2021，43(12):1711-1716。
卡尔费休-气相色谱联用测定液态有机体系中的水分含量
王桂华*，郑虓，姚春海
(北京水木滨华科技有限公司,北京 100192)
摘要：水分含量是评价有机体系的重要指标之一。有机体系中水分含量测定方法多种多样，不同有机体系需采用不同方法检测，无通用方法。本论文采用卡尔费休法标定的甲醇水体系作外标物，建立了卡尔费休-气相色谱外标法测定含有醛、酮、醇、酸、酯、氧化剂、还原剂等有机体系产品中水分的普适性方法。该方法检出限(N/S=3)为0.0077%，定量限(N/S=10)为0.0232%。加标回收率为91.7%～100.8%，测定的相对偏差(n =9)均小于2%。该方法操作简单、快速、准确、环保；稳定可靠，重现性好，适用范围和检测范围广泛，检测范围可达0.03%～8%。
关键词：卡尔费休；气相色谱；有机体系；水分含量；外标法
中图分类号：O661 文献标识码：A 文章编号：0258-3283（2021）--
Determination of Water Content in Liquid Organic System by Karl Fischer-Gas Chromatography Method WANG Gui-hua*, ZHENG Xiao, YAO Chun-hai (Behigh China Technology Co., Ltd., Beijing 100192, China), Huaxue Shiji, 2021, 43(12)～
Abstract: Moisture content is one of the important indicators for evaluating organic systems. There are various methods for measuring moisture content in organic systems. Different organic system needs to be detected by the corresponding methods, and there is no universal method. The Karl Fischer method has high measurement speed and high accuracy, but it has the significant disadvantages because it cannot be used to detect substances, such as aldehydes, ketones, oxidants, and reducants that can react with the KF reagent, and the KF reagent is expensive and toxic. The advantages of high separation efficiency of gas chromatography are used to overcome the shortcomings of the Karl Fischer method that cannot separate water from background compounds. Meanwhile, internal standard methods for gas chromatographic need stable and anhydrous internal standard substances. With the benzene-water mixed system as a standard, the external standard method for gas chromatography could be used to determine the moisture in the organic system, but its application is limited due to toxic benzene, which is harmful to health, and environmental-unfriendly. Based on the above statement, combining these two methods organically would expand the range of moisture measurement. A universal method for the determination of moisture in organic compounds has been established by the external standard method for gas chromatography with the methanol-water system calibrated by the Karl Fischer method as the external standard, which can be applied to determine the water content of organic compounds containing aldehydes, ketones, alcohols, acids, esters, oxidants, and reducing agents. The effects of chromatographic column type, inlet temperature, detector temperature, and chromatographic column heating program on the separation effect and detection sensitivity were studied. With the present method, the limits of detection (3N/S) and quantification (10N/S) are 0.0077% and 0.0232%, respectively. In the three systems of alcohol, ketone, and reaction mixture, the recovery tests of the added standard were carried out at three concentration levels of 80%, 100%, and 120%, respectively. The recovery rate varied 91.7%-100.8%, and the relative deviation of the determination (n = 9) was less than 2%. The method is simple, fast, accurate, and environmentally friendly with wide scope of application and detection. The detection results are stable and reproducible with the detection range of 0.03%～8%.
Key words: Karl Fischer method; gas chromatography; organic compound; moisture; external standard
引用本文：王桂华，郑虓，姚春海.卡尔费休-气相色谱联用测定液态有机体系中的水分含量[J]. 化学试剂，2021，43(12): 1717-1721。
改进QuEChERS-气相色谱-串联质谱法测定韭菜中24种农药的残留含量
张放1，杨金川2，杨霏* 3
(1. 贵阳职业技术学院，贵州 贵阳 550081；2. 贵州省产品质量检验检测院，贵州 贵阳 550016；3. 贵州省计量测试院，贵州 贵阳 550003)
摘要：建立了一种改良QuEChERS前处理结合气相色谱-串联质谱(GC-MS/MS)检测韭菜中24种农药残留的方法。样品经乙腈提取，N-丙基乙二胺 (PSA)、十八烷基键合硅胶 (C18)和石墨化炭黑 (GCB)粉末分散固相萃取净化浓缩后，采用GC-MS/MS选择反应监测 (SRM)模式测定，内标法定量。结果表明：24种农药在10 ～ 400 μg/L的浓度范围内，各农药峰面积与进样质量浓度间线性关系良好，相关系数 R > 0.999 1，定量限(LOQ)低于0.007 9 mg/kg；在添加水平分别为0.01、0.04、0.2 mg/kg时，24种农药的平均回收率在73% ～ 109%之间，相对标准偏差(RSDs)在0.9% ～ 8.9%之间，符合农药残留分析的要求。基质效应测定结果发现，甲胺磷等11种农药存在强基质效应，敌敌畏等6种农药显示中等基质效应，嘧霉胺等7种农药表现弱基质效。研究表明，通过基质匹配标准曲线定量，可以很好的消除基质效应的影响，能够对韭菜中24种农药的残留进行快速、准确的测定。
关键词：QuEChERS；气相色谱-串联质谱；韭菜；多残留；基质效应
中图分类号：O657.7 文献标识码：A 文章编号：0258-3283（2021）
Determination of 24 Pesticide Residues in Chinese Chives Using Improved QuEChERS-Gas Chromatography-Tandem Mass Spectrometry ZHANG Fang1, YANG Jin-chuan2, YANG Fei*3 (1. Guiyang Vocational and technical College, Guiyang 550081, China; 2. Guizhou Institute of Products Quality Inspection & Testing, Guiyang 550016, China; 3. Guizhou Institute of Metrology, Guiyang 550003, China), Huaxue Shiji, 2021, 43(12), ～
Abstract: A method was developed for the determination of 24 pesticide residues in Chinese chives by using modified QuEChERS combined with gas chromatography-tandem mass spectrometry (GC-MS/MS). The samples were extracted with acetonitrile, cleaned-up with a mixture of sorbents (PSA, C18 and GCB), concentrated, and detected by GC-SRM-MS/MS using the internal standard method. The results showed that the linear relationship of 24 pesticides in the linear range from 10 to 400 μg/L was good, and the linear correlation coefficients (R) was higher than 0.9991, with the limit of quantitation (LOQs) lower than 0.0079 mg/kg. The average recoveries at three spiking levels (0.01, 0.04, 0.1 mg/kg) in Chinese chives ranged from 73% to 109%, and the relative standard deviations (RSDs) were from 0.9% to 8.9%, which were good enough for the routine analysis of the pesticide residues. The measurement results of matrix effect showed that 11 pesticides (methamidophos etc.), had strong matrix effect, 6 pesticides (dichlorvos etc.) had medium matrix effect, and 7 pesticides (pyrimethanil etc.) exhibited weak matrix effect. Matrix effect could be eliminated by using matrix-matched standards, and 24 pesticide residues in Chinese chives could be determined quickly and accurately.
Key words: QuEChERS; GC-MS/MS; chinese chives; multi-residue; matrix effect
引用本文：张放，杨金川，杨霏. 改进QuEChERS-气相色谱-串联质谱法测定韭菜中24种农药的残留含量[J]. 化学试剂，2021，43（12）：1722-1728.
玉米MON863质粒DNA标准物质的研制
马丽侠1，周李华*1，叶德萍1，蒋子敬1，姜展樾1,2，蒲春如2，杜娟兰2，韩国全2
(1.中国测试技术研究院 生物研究所，四川 成都 610021；2.四川农业大学 食品学院，四川 雅安 625000)
摘要：转基因成分检测是转基因生物安全应用和管理的重要技术支撑，转基因标准物质种类的不足可影响转基因生物检测方法的建立和标准化。选取玉米MON863中外源基因MON863与内标基因Adh1构建质粒标准物质，通过测序验证；以双重数字PCR技术对获得的质粒DNA进行均匀性及不同温度下（-20、4、25、37 oC）短期（7 d）和-20 oC长期（6个月）稳定性检验，联合8家实验室进行定值分析。结果显示，玉米MON863质粒 DNA 标准物质具备良好的均匀性，可以在-20 oC稳定存放6个月；外源与内标基因的拷贝数比值为1.01，扩展不确定度为 0.04；拷贝数为 5.78×1010 copies/μL，扩展不确定度为0.29×1010 copies /μL。本文获得的标准物质适用于玉米MON863的方法学建立、定性定量检测和实验室质控等应用。
关键词：质粒DNA；标准物质；数字PCR；双重数字PCR；转基因玉米
中图分类号：Q819 文献标识码：A 文章编号：0258-3283（2021）
Development of Plasmid DNA Reference Material of Genetically Modified Maize (Zea mays) MON863 MA Li-xia1, ZHOU Li-hua*1, YE De-ping1, JIANG Zi-jing1, JIANG Zhan-yue1,2, PU Chun-ru2, DU Juan-lan2, HAN Guo-quan2(1. Institute of Biology,National Institute of Measurement and Testing Technology, Chengdu 610021, China; 2. College of Food, Sichuan Agriculture University, Ya´an 625000, China), HuaxueShiji, 2021, 43(12),
Abstract：The detection of genetically modified components is an important part of the safety application and management of genetically modified organisms. Due to the insufficient types of reference materials, the establishment and standardization of testing methods for genetically modified organisms are affected. The alcohol dehydrogenase 1 (Adh1) gene of maize and MON863 event-specific gene were selected as target to construct plasmid standards. It was verified by sequencing. In this study, the homogeneity and short-term (seven days, -20, 4, 25, 37 °C) and long-term(six months, -20 °C) stabilities of transgenic maize (Zea mays) plasmid DNA were evaluated using duplex digital PCR. Eight laboratories were combined for characterization analysis of reference materials, which were using MON863/ Adh1 duplex digital PCR. The obtained experimental results show that the reference substance has good homogeneity and the effective period is at least 6 months (-20 °C). The calculated average of all independent measurement results (8 laboratories) was assigned as the certified value. The uncertainty of the plasmid consisted of uncertainty components from characterization, homogeneity, and stability during short-term and long-term storages. The certified value of DNA copy number ratio was calculated to be 1.01 with an extended uncertainty of 0.04. DNA copy number was calculated to be 5.78×1010 copies/μL with an extended uncertainty of 0.29×1010 copies/μL. The plasmid reference material can be used for the qualitative detection, quantitative detection, and methodology establishment for GM MON863.
Key words: plasmidDNA; reference materials; droplet digital PCR; duplex digital PCR; transgenic maize（Zea mays）
引用本文：马丽侠，周李华，叶德萍，等.玉米MON863质粒DNA标准物质的研制[J].化学试剂，2021，43（12）：1729-1734.
Ca2+在邻苯二酚氧化过程中的作用机制
陈义鑫，尹俊钧，罗炜艳，王夺*
（厦门大学 能源学院，福建 厦门 361102）
摘要：以邻苯二酚为对象，通过抗氧化活性测试间接定量分析了Ca2+对邻苯二酚自氧化程度的影响。结果表明，随着在不同Ca2+浓度、反应时间、反应温度下，邻苯二酚的DPPH自由基清除能力分别下降了12.96%、26.32%和12.50%，说明邻苯二酚的自氧化程度均有所提高。选择了两种具有邻位羟基结构的酚类化合物，通过紫外-可见吸收光谱（UV-Vis）发现邻苯二酚、儿茶素和去甲肾上腺素的氧化程度均明显提高。此外，邻苯二酚与Ca2+之间发生了配位反应，在溶液中生成了不溶性的配合物。通过TGA、ICP-OES、元素分析等表征手段，发现邻苯二酚是以2 : 1的物质的量比与Ca2+进行配位。进一步对产物分析，证明了邻苯二酚与Ca2+是以两个酚羟基中的氧原子与Ca2+结合，螯合形成了邻苯二酚钙配合物，进而提出了Ca2+介导邻苯二酚氧化的路径。
关键词：邻苯二酚；抗氧化；钙离子；配合；配位反应
中图分类号：TQ35 文献标识码：A 文章编号：0258-3283（2021）
Effect and Mechanism of Ca2+ in the Oxidation Process of Catechol Substances CHEN Yi-xin, YIN Jun-jun, LUO Wei-yan, WANG Duo* (College of Energy, Xiamen University, Xiamen361102, China), HuaxueShiji, 2021, 43(12),
Abstract: The DPPH radical scavenging ability of Ca2+ on catechol under different conditions was studied, and the effect of Ca2+ on the degree of autoxidation of catechol was indirectly quantified by the antioxidant activity test method. The results showed that the DPPH radical scavenging ability of catechol decreased by 12.96 %, 26.32 %, and 12.50 % with the increases of the Ca2+ concentration from 0 to 2 mol/L, the reaction time from 0 to 120 min, and the reaction temperature from 4 to 90 °C, respectively, indicating that the degree of autoxidation of catechol was increased in all cases. Two phenolic compounds with an adjacent hydroxyl structure were selected and their oxidation levels in the presence or absence of Ca2+ were directly and qualitatively compared by UV-Vis analysis. The results showed that the degree of oxidation was significantly higher for catechol, catechin, and norepinephrine. In addition, the coordination between catechol and the calcium ions occurs, generating insoluble substances in the solution. After analysis with TGA, ICP-OES, and elemental analysis, it was found that the coordination between catechol and the calcium ion in a molar ratio of 2:1. The characterization of the coordinated complex demonstrated that catechol as a bidentate ligand coordinates through the oxygen atom of its phenolic groups, forming a stable chelating structure. Finally, a pathway for calcium ion-mediated oxidation of catechol was proposed for the application of phenolic compounds.
Key words: catechol; antioxidation; calcium ion; complexation; coordination reaction
引用本文：陈义鑫，尹俊钧，罗炜艳，等.Ca2+在邻苯二酚氧化过程中的作用机制[J].化学试剂，2021，43（12）：1735-1742.
响应面分析法优化啤酒花总多酚的提取工艺及抗氧化活性的研究
王诗瑶,吴欣恬,曹星星,王庆林,何文静*
（新疆医科大学 中医学院，新疆 乌鲁木齐 830017）
摘要：以新疆、云南、广西、安徽4种产地的啤酒花为研究对象，选择料液比、乙醇浓度、提取时间进行单因素试验，参照单因素试验结果，结合响应面法优化超声波提取啤酒花总多酚的提取工艺，通过测定啤酒花总多酚对DPPH自由基的清除率以及对Fe3+的还原能力，来评价其体外抗氧化活性。得到最佳提取工艺为：料液比1:30（g/mL），乙醇浓度60%，提取时间40 min，得出啤酒花总多酚提取率为62.86%，与理论值61.522%相近；啤酒花总多酚对DPPH自由基清除率以及对Fe3+的还原能力均与样品浓度呈正比，说明其有一定的抗氧化活性。4个产地的啤酒花中，以新疆啤酒花的总多酚含量和抗氧化活性最高。响应面法优化超声提取啤酒花总多酚的工艺研究准确可靠，为啤酒花的深入开发提供了理论依据。
关键词：啤酒花；总多酚；响应面分析法；DPPH；还原能力
中图分类号：R284.2 文献标识码：A
Optimization of the Extraction Process and Antioxidant Activity of Total Polyphenols from Hops by Response Surface Analysis WANG Shi-yao, WU Xin-tian, CAO Xing-xing, WANG Qing-lin, HE Wen-jing* (School of Traditional Chinese Medicine, Xinjiang Medical University, Xinjiang 830017, China)
Abstract: Hops from Xinjiang, Yunnan, Guangxi, and Anhui were used for the study. The single-factor test was conducted to select the material-to-liquid ratio, ethanol concentration, and extraction time, to optimize the extraction process of total polyphenols in hops by ultrasonic extraction with reference to the results of the single-factor test, and to evaluate their in vitro antioxidant activity by determining the scavenging rate of hops total polyphenols against DPPH free radicals and the reduction ability of Fe3+. The optimum extraction process was obtained as follows: the material-to-liquid ratio of 1:30 (g/mL), ethanol concentration of 60%, extraction time of 40 min, resulting in an extraction rate of 62.86% for hops total polyphenols, similar to the theoretical value of 61.522%. The scavenging of DPPH radicals and the reduction of Fe3+ by hops total polyphenols were both proportional to the sample concentration, indicating a certain antioxidant activity. Among the four origins of hops, the highest polyphenol content and antioxidant activity was found in Xinjiang hops. The response surface methodology for optimizing the process of the ultrasonic extraction of total polyphenols from hops is accurate and reliable, and provides a theoretical basis for the further development of hops.
Key words: hops; total polyphenols; response surface analysis; DPPH; reducing power
引用本文：王诗瑶,吴欣恬,曹星星，等. 响应面分析法优化啤酒花总多酚的提取工艺及抗氧化活性的研究[J]. 化学试剂，2021，43（12）：1743-1748.
Pd(II)-salen配合物的制备及水相催化Suzuki反应
鄢仲钰,何静远,史大斌*
（遵义医科大学 药学院 贵州省生物催化与手性药物合成重点实验室，贵州 遵义 563000）
摘要:以4-羟基-3-甲氧基苯甲酸为起始原料，经Duff反应、缩合和配位等反应步骤，合成了一个新型含羧基的Pd(II)-salen催化剂，该催化剂能溶于碱性水溶液中并在水溶液中有效催化溴代芳烃与芳基硼酸发生Suzuki偶联反应，反应使用0.5 mol % 催化剂，水为溶剂，空气环境中90 oC反应24 h，以良好产率生成联芳基化合物。合成的催化剂及偶联产物的结构经NMR和HRMS确证。实验结果表明，该催化反应在水相中进行，无需膦配体且水相能循环使用3次，具有操作方便及环境友好的特点。
关键词:绿色化学；Pd(II)-salen配合物；Suzuki偶联反应；联芳基化合物；水相
中图分类号：O621.3 文献识别码：A 文章编号：0258-3283（2021）
Preparation of Pd(II)-Salen Complex and Its Application as an Efficient Catalyst for Suzuki Reaction in Water YAN Zhong-yu, HE Jing-yuan, SHI Da-bin* (Key Laboratory of Biocatalysis & Chiral Drug Synthesis of Guizhou Province, School of Pharmacy, Zunyi Medical University, Zunyi 563000, China), Huaxue Shiji, 2021, 43(12),
Abstract: A new Pd(II)-salen complex I containing carboxylic acid groups was synthesized from 4-hydroxy-3-methoxybenzoic acid by the Duff reaction, condensation, and coordination. Compound I can be dissolved in an alkaline water solution and effectively catalyze the Suzuki coupling of aryl bromides and arylboronic acids in aqueous medium to produce biaryl compounds in good yields. The structures of biaryls were confirmed by NMR and HRMS analysis. The experimental results showed that the reaction was processed in the aqueous phase without phosphine ligand, and the aqueous phase was reused three times for the Suzuki reaction. This protocol provides several advantages such as simple operation and environment friendly.
Key words: green chemistry; Pd(II)-salen complex; Suzuki coupling reaction; biaryl compounds; aqueous media
引用本文：鄢仲钰，何静远，史大斌. Pd(II)-salen配合物的制备及水相催化Suzuki反应[J].化学试剂，2021，43（12）：1749-1754.
稳定同位素标记溴氰菊酯-d5的合成
徐仲杰1, 2，赵诚* 2，胡祖明* 1
(1. 东华大学 材料科学与工程学院 化纤与高分子材料改性国家重点实验室，上海 201620；2. 上海化工研究院有限公司，上海 200062)
摘要：氘标记合成标题化合物是从苯酚-d6出发，以甲苯为溶剂，碱选用氘氧化钠，进行脱水反应得到苯酚钠-d5，氘代苯酚钠再与间溴苯甲醛进行乌尔曼缩合得到间苯氧基苯甲醛-d5，催化剂选用氯化亚铜，最后通过氰化钠重水溶液构成无机相的相转移催化酯化反应，由间苯氧基苯甲醛-d5与溴氰菊酰氯反应得到标题化合物，以初始原料的物质的量计算产率为25.54%。所得终产品经NMR确认结构，HPLC外标法检测纯度﹥98%，MS检测丰度﹥98 atom % D。标题化合物作为内标试剂可以用于溴氰菊酯残留量的稳定同位素稀释质谱法（IDMS）检测。
关键词：溴氰菊酯-d5；同位素标记；拟除虫菊酯；内标试剂
中图分类号：O628.1 文献标识码：A 文章编号：0258-3283（2021）
Synthesis of Isotope-Labeled Deltamethrin-d5 XU Zhong-jie1, 2, ZHAO Cheng* 2, HU Zu-ming* 1 (1.State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Donghua University, Shanghai 201620, China; 2.Shanghai Research Institute of Chemical Industry Co., Ltd., Shanghai 200062, China) , Huaxue Shiji, 2021
Abstract: The deuterium-labeled synthesis of deltamethrin-d5 started from phenol-d6. Phenol-d6 reacted with sodium deuterium oxide in toluene as the solvent to obtain sodium phenolate-d5. 3-Phenoxy-benzaldehyde-d5 was obtained from sodium phenolate-d5 and 3-bromobenzaldehyde under the catalysis of CuCl through the Ullmann reaction. The phase transfer esterification reaction, of which inorganic phase is sodium cyanide in deuterium oxide aqueous solution, converted 3-phenoxy-benzaldehyde-d5 and 3-(2,2-dibromoethenyl)-2,2-dimethyl cyclopropane-
carbonyl chloride to deltamethrin-d5 in 25.4% yield. The structure of deltamethrin-d5 was confirmed by NMR. Its HPLC purity detected with the external standard method was＞98% with the abundance of element＞98% atom D in MS analysis. The final product as an internal standard reagent can be used for the detection of deltamethrin residues with IDMS.
Key words: deltamethrin-d5; isotope labelling; pyrethroid; internal standard reagent
引用本文：徐仲杰，赵诚，胡祖明. 稳定同位素标记溴氰菊酯-d5的合成[J]. 化学试剂，2021，，43（12）：1755-1761.
2-氨基查尔酮类化合物的简便合成
孙江凯，刘 坤，刘仁华*
（华东理工大学 药学院，上海 200237）
摘要：2-氨基查尔酮类化合物是一类重要的合成中间体，在药物化学、有机合成等领域有广阔的应用前景。现有合成方法大多存在原料不易得、底物范围窄、收率较低等问题。发展了一种利用查尔酮和叠氮钠制备2-氨基查尔酮类化合物的方法。该反应无需催化剂，在CO2氛围中，120 ℃反应5 h以较高收率获得2-氨基查尔酮类化合物。该合成方法体系简单，具有原料价廉易得、后处理操作简便、底物范围广等优点。
关键词：查尔酮；2-氨基查尔酮类化合物；叠氮钠；二氧化碳
中图分类号：O625.6 文献标识码：A 文章编号：0258-3283（2021）
Facile Synthesis of 2-Aminochalcones SUN Jiang-kai, LIU Kun, LIU Ren-hua* (School of Pharmacy, East China University of Science and Technology, Shanghai 200237, China), Huaxue Shiji, 2021, 43(12)
Abstract: 2-Aminochalcones are a class of important intermediates and have broad application prospects in the fields of medicinal chemistry and organic synthesis. Most of the existing synthetic methods have problems, such as difficult synthesis of raw materials, narrow substrate range, and low yield. A method for preparing 2-aminochalcones using chalcones and sodium azide has been developed. The method does not require a catalyst, and reacts at 120 ℃ for 5 h in CO2 atmosphere to obtain 2-aminochalcones in high yields. The synthetic method has the advantages of low cost, readily availability of raw materials, simple operation and workup, and wide substrate range.
Key words: chalcone; 2-aminochalcones; sodium azide; carbon dioxide
引用本文：孙江凯，刘 坤，刘仁华. 2-氨基查尔酮类化合物的简便合成[J]. 化学试剂，2021,43（12）：1762-1767.
