重氮化合物的合成方法
袁鑫，许家喜*
（北京化工大学 化学学院 有机化学系，北京 100029）
摘要：重氮化合物是重要的高活性有机合成中间体，可用来制备烯酮、环丙烷和三元杂环衍生物、环庚三烯衍生物、叶立德、金属卡宾、酮和偶氮类化合物等，因此，广泛应用于有机合成化学、药物合成化学和农用化学品的合成，其合成方法和应用也都得到了很大发展。目前合成重氮化合物的方法主要分为重氮转移法、其他官能团的重氮化法和重氮化合物的修饰法3种。对重氮化合物的合成方法，特别是近十余年发展的新合成方法进行了综述，并预测和讨论了重氮化合物合成今后的发展方向。
关键词：重氮化合物；重氮转移；重氮化；衍生化
中图分类号：O623.7 文献标识码：A 文章编号：0258-3283(2022)--
Synthetic Methods of Diazo Compounds YUAN Xin, XU Jia-xi* (Department of Organic Chemistry, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, China), Huaxue Shiji, 2022, 44(2), ～
Abstract：Diazo compounds are important active organic synthetic intermediates and have been used in preparations of ketenes, cyclopropane and three-membered heterocycle derivatives, cycloheptatriene derivatives, ylides, metaloocarbenes, ketones, and azocompounds, and so on. They have been widely applied in organic synthetic chemistry, pharmaceutical synthetic chemistry, and agrochemical synthesis. Their synthetic methods and applications have been well developed. Three synthetic methods have been developed, including diazo transfer, diazotization of other functional groups, and derivatization of diazo compounds, to date. The synthetic methods, especially new synthetic methods developed in recent decades, of diazo compounds are summarized. New development direction on synthesis of diazo compounds in the future is predicted and discussed.
Key words：diazo compound; diazo transfer; diazotization; derivatization
引用本文：袁鑫，许家喜. 重氮化合物的合成方法[J]. 化学试剂，2022，44(2):161-168。
基于半导体量子点的电致化学发光试剂的研究进展
张连梅*，王宇红，赵英杰，刘璐，毛雪，邸萌婕
(兰州市疾病预防控制中心 微生物实验室，甘肃 兰州 730030)
摘要：电致化学发光因为不需要激发光源，没有杂散光的干扰，实验设备简单且具有背景信号低、灵敏度高的优点，近年来在环境监测、食品安全分析、生物传感和成像等领域都引起了科学家们广泛地关注。在电致化学发光技术中，发光试剂无疑是最重要的组成部件。随着纳米科学和技术的迅猛发展，半导体量子点由于尺寸调控带隙、表面易于改性和表面态依赖性的电子转移、良好的发光强度和单色性而成为一类理想的电致化学发光试剂。首先简要介绍电致化学发光及其机理，接着重点总结各类半导体量子点的电致化学发光特性，最后对基于半导体量子点的电致化学发光试剂存在的挑战和机遇进行讨论。
关键词：电致化学发光；发光试剂；纳米颗粒；半导体量子点
中图分类号：O646 文献标识码：A 文章编号：0258-3283（2022）
Recent Advances in Semiconductor Quantum Dots as Electrogenerated Chemiluminescence Reagents ZHANG Lian-Mei*, WANG Yu-Hong, ZHAO Ying-Jie, LIU Lu, MAO Xue, DI Meng-Jie (Laboratory of Microbiology, Lanzhou Center for Disease Control and Prevention, Gansu, Lanzhou 730030,China), Huaxue Shiji, 2022, 44(2)
Abstract: Benefitting from no requirement of excitation light sources, no presence of background emissions from unexpected photoexcitation, simple instruments and apparatus, along with its high sensitivity and low signal-to-noise ratio, electrogenerated chemiluminescence (ECL) has been a superior analytical tool and attracts widespread interests from scientists in the areas of environmental monitoring, food safety analysis, biosensing and bioimaging. With the rapid development of nanoscience and nanotechnology, the novel semiconductor quantum dots (QDs) are affording a new opportunity for exploring ideal nanomaterial based ECL reagents due to their size-regulated band gap, easy surface modification and surface state-dependent electron transfer, excellent emission intensity and monochromaticity. In this review, we firstly provide a brief overview of ECL fundamentals, and then place emphasis on the ECL characteristics of different kinds of semiconductor QDs. The current challenges and perspectives on semiconductor QDs based ECL reagents are finally discussed as well.
Key words:electrogenerated chemiluminescence; luminophore; nanoparticle; semiconductor quantum dots
引用本文：张连梅，王宇红，赵英杰，等. 基于半导体量子点的电致化学发光试剂的研究进展[J]. 化学试剂，2022，44（2）:169-177.
基于超临界萃取技术的泰国青柠果皮精油成分解析及其抗肿瘤活性研究
郑莹1,2,3，李天娇1,2,3，包永睿1,2,3，王帅1,2,3，杨欣欣1,2,3，赵国斌4，孟宪生*1,2,3
（1. 辽宁中医药大学 药学院，辽宁 大连 116600；2. 辽宁省中药多维分析专业技术创新中心，辽宁 大连116600；3. 辽宁省现代中药研究工程实验室，辽宁 大连 116600；4. 大连卓尔超临界科技发展有限公司，辽宁 大连 116600）
摘要：主要研究泰国青柠果皮精油成分组成及其抗肿瘤活性。采用超临界二氧化碳萃取技术提取青柠果皮精油，经超高效液相-飞行时间质谱联用仪（UPLC-QTOF-MS）和气相色谱-质谱联用仪（GC-MS）进行成分分析，经与数据库及参考文献比对，鉴定化学成分；采用CCK-8法测定青柠果皮精油抗肝癌细胞株HepG2和结直肠癌细胞株SW620的体外抗肿瘤活性。经UPLC-QTOF-MS指出泰国青柠果皮精油中香豆素类14个、黄酮类12个、萜类6个、鞣质类1个、脂肪酸类1个；经GC-MS指出挥发性成分58个，包括醇类34个、烯烃类12个、酯类5个、醛类2个、芳香烃类2个、醚类2个和酮类1个。细胞实验证明泰国青柠果皮精油对HepG2和SW620细胞株具有不同程度的抑制作用，IC50分别为0.53mg/mL和0.77mg/mL，表明其具有较好的抗肿瘤活性。为泰国青柠果皮精油抗肿瘤应用开发提供数据支撑。
关键词：泰国青柠果皮精油；超临界流体萃取；抗肿瘤；UPLC-QTOF-MS；GC-MS
中图分类号：R9 文献标识码：A 文章编号：0258-3283（2022）--
Component Analysis and Antitumor Activity of Oil fromKaffir Lime PeelBased on Supercritical Fluid Extraction ZHENG Ying1,2,3, LI Tian-jiao1,2,3, BAO Yong-rui1,2,3, WANGShuai1,2,3, YANG Xin-xin1,2,3, ZHAO Guo-bin4, MENG Xian-sheng*1,2,3(1. College of Pharmacy, Liaoning University of Traditional Chinese Medicine, Dalian 116600, China; 2. Liaoning Multi-dimensional Analysis of Traditional Chinese Medicine Technical Innovation Center, Dalian 116600, China; 3. Liaoning Province Modern Traditional Chinese Medicine Research and Engineering Laboratory, Dalian 116600, China; 4. Dalian Zhuoer supercritical technology development Co., Ltd, Dalian 116600), Huaxue Shiji, 2022, 44(2), ～
Abstract: To study the composition and antitumor activity of oil from KaffirLime peel, oil from KaffirLime peel was extracted by supercritical carbon dioxide extraction technology. The components were analyzed by UPLC-QTOF-MS and GC-MS. These components were estimated by comparing with database and references. The antitumor activity of oil from KaffirLime peel against hepatocellular carcinoma cell line HepG2 and colorectal cancer cell line SW620 in vitro was investigated by CCK-8 assay. The results showed that by using UPLC-QTOF-MS, 14 coumarins, 12 flavonoids, 6 terpenoids, 1 tannin and 1 fatty acid were identified in the oil from KaffirLime peel. A total of 58 volatile compounds were identified by GC-MS, including 34 alcohols, 12 alkenes, 5 esters, 2 aldehydes, 2 aromatic hydrocarbons, 2 ethers and 1 ketone. Cell experiments showed that the oil from KaffirLime peel had different degree of inhibitory effects on HepG2 and SW620 cell lines, with IC50 of 0.53 and 0.77mg/mL, respectively, indicating that it had good antitumor activity. This paper provides the data support for the development of antitumor application of oil from KaffirLime peel.
Key words: Oil from KaffirLime peel; Supercriticalfluid extraction;Antitumor;UPLC-QTOF-MS;GC-MS
引用本文：郑莹，李天娇，包永睿，等. 基于超临界萃取技术的泰国青柠果皮精油成分解析及其抗肿瘤活性研究[J]. 化学试剂, 2022,44(2):178-185。
齐墩果酸-川芎嗪衍生物的合成及抗肿瘤活性研究
王璇，姜晓晔，黎七雄*
（武汉城市学院 医学部，湖北 武汉 430083）
摘要: 以川芎嗪为原料，经过氧化、Boekelheide重排、水解、Ing-Manske等反应制得了两个川芎嗪衍生物2-羟甲基-3,5,6-三甲基吡嗪和2-甲胺基-3,5,6-三甲基吡嗪，再利用药物拼合原理将其与齐墩果酸及其衍生物通过酯化或酰胺反应合成了8个新型齐墩果酸-川芎嗪衍生物，其结构通过1HNMR和MS确证。初步的生物活性结果表明，所合成的目标化合物对PC-3、MCF-7、HepG2和HeLa 4种肿瘤细胞均展现出了良好的抑制活性，半数抑制浓度 (IC50)值均在20 mmol/L以内，其抗肿瘤活性明显的强于先导化合物齐墩果酸与川芎嗪。构效关系研究表明，齐墩果酸与川芎嗪的拼接方式对活性影响不大，而齐墩果酸A环的修饰方式对活性影响较大，其中在齐墩果酸A环具有1-烯-3-氧代官能团的化合物对MCF-7展现出了最强的抑制活性，其IC50分别为3.4、2.2 mmol/L。此外，这些齐墩果酸-川芎嗪衍生物对正常MCF-10A和LO2细胞没有毒性。
关键词: 齐墩果酸；川芎嗪；拼合原理；抗肿瘤活性
中图分类号：R914； 文献标记码：A 文章编号：0258-3283（2022）--
Synthesis and Anti-tumor Activity Evaluation of Oleanolic acid-Ligustrazine Derivatives WANG Xuan, JIANG Xiao-ye, LI Qi-xiong* (School of Medicine, Wuhan City College, Hubei, Wuhan 430083, China), Huaxue Shiji, 2022, 44(2), ～
Abstract: Initially, 2-hydroxymethyl-3,5,6-trimethylpyrazine (3) and 2-aminemethyl-3,5,6- trimethylpyrazine (6) were synthesized with ligustrazine as starting materials by oxidation reaction, Boekelheide rearrangement reaction, hydrolysis reaction, and Ing-Manske reaction. After that, eight noveloleanolic acid-ligustrazine derivatives were obtained by esterification reaction or amidation reaction of intermediate 3 or 6 with oleanolic acid or its derivatives. Their chemical structures were confirmed by 1HNMR and Mass spectra. The preliminary biological results indicated that these derivatives showed potent inhibitory activities against PC-3, MCF-7, HepG2 and HeLa cells, and their half maximal inhibitory concentration (IC50) values were less than 20 mM, which were better than that of the lead compound oleanolic acid and ligustrazine. The structure-activity relationship showed that the coupling method of oleanolic acid with ligustrazine had little effect on the antiproliferative activity, while the modification of A ring of oleanolic acid unit had obvious effect on the activity. Among them, the derivatives 17~18 with 1-en-3-oxo group in A ring of oleanolic acid unit exhibited the greatest potency against MCF-7 with the IC50 values were 3.4 and 2.2 mM, respectively. Moreover, all derivatives were nontoxic to both health MCF-10A and LO2 cells.
Key words: oleanolic acid; ligustrazine; combination; anti-tumor activity
引用本文：王璇， 姜晓晔，黎七雄.齐墩果酸-川芎嗪衍生物的合成及抗肿瘤活性研究[J].化学试剂，2022，44（2）：186-194.
白术-白芍活性成分治疗肠易激综合征的网络药理学研究
丁凌1，孙九许1，侯思瀚1，乌恩奇2，令亚琴2，裴凌鹏*1,2
（1. 中央民族大学 药学院，北京 100081；2. 教育部 民族医药重点实验室，北京 100081）
摘要：基于网络药理学的方法预测白术-白芍中活性成分治疗肠易激综合征的作用靶点、信号通路、分子机制。检索TCMSP数据库查找白术、白芍活性成分及其作用靶点。检索OMIM、Genecard和Drugbank数据库富集疾病靶点并筛查交集靶点。采用String数据库与Cytoscape软件进行蛋白相互作用分析、靶点网络构建。通过Metascape数据库进行通路富集分析与功能注释。最终筛选出活性成分20个，作用靶点73个，交集靶点61个。活性成分包括3β-乙酰氧基苍术酮、β-谷甾醇、山萘酚等。作用到的核心靶点包括白细胞介素-6 (IL-6)、蛋白激酶1 (AKT1)、肿瘤坏死因子 (TNF)等。通路富集分析得到121条信号通路，包括肿瘤坏死因子信号通路、白介素-17信号通路、Toll样受体信号通路等，以晚期糖基化终产物及其胞膜受体信号通路最为显著。功能注释分析得到生物进程条目261个，以调节蛋白同源二聚体的活性最为显著；分子功能条目62个，以对脂多糖、细菌来源分子等成分的反应为主。白术-白芍发挥治疗肠易激综合征的作用是多成分、多靶点、多途径作用的结果。
关键词：网络药理学；活性成分；肠易激综合征；白术；白芍；潜在靶点；信号通路
中图分类号：R282.71 文献标识码：A 文章编号：0258-3283（2022）- -
Study on Effective Substances of Atractylodes macrocephala Koidz - Paeonia lactiflora Pall in Treatment of Irritable Bowel Syndrome Based on Network Pharmacology DING Ling1, SUN Jiu-xu1, HOU Si-han1, WU En-qi2, LING Ya-qin2, PEI Ling-peng*1,2(1.School of Pharmacy, Minzu University of China, Beijing, 100081, China; 2. Key Laboratory of Ethnomedicine, Ministry of Education, Beijing, 100081, China), Huaxue shiji, 2022, 44(2), ～
Abstract：Based on network pharmacology, the potential targets, signaling pathways and molecular mechanism of active components among Atractylodes macrocephala Koidz and Paeonia lactiflora Pall in the treatment of irritable bowel syndrome are predicted. The active components and potential targets of Atractylodes macrocephala Koidz and Paeonia lactiflora Pall were retrieved by the TCMSP database, while the potential targets of irritable bowel syndrome were screened by OMIM, GeneCards and Drugbank databases. By finding common targets among the above potential targets, a protein-protein interaction network has been analyzed and constructed through String database and Cytoscape software. KEGG pathway enrichment analysis and GO biological function module analysis of key targets were performed by Metascape database. Totally 20 active components of Atractylodes macrocephala Koidz and Paeonia lactiflora Pall were screened out, including 3β-acetoxyatractylone, β-sitosterol, kaempferol, etc. 73 relative targets were found from the components above, and 61 targets of the massociated with diseases. The core targets mainly included IL-6, AKT1, TNF, etc. KEGG analysis revealed 121 signaling pathways like TNF, IL-17 and Toll-like Receptor with the AGE-RAGE signaling pathway being the most significant. GO analysis revealed 261 biological process entries, among which protein homodimerization activity were the most significant one. Moreover, 62 molecular function entries were being revealed,the response of which to lipopolysaccharide and molecule of bacterial origin were the most important. Atractylodes macrocephala Koidz and Paeonia lactiflora Pall performs the role of multiple-components, multiple-targets, and multiple-pathways in treatment of irritable bowel syndrome.
Key words: network pharmacology; active components; irritable bowel syndrome; Atractylodes macrocephala Koidz; Paeonia lactiflora Pall; potential targets; signaling pathway
引用本文：丁凌，孙九许，侯思瀚，等. 白术-白芍活性成分治疗肠易激综合征的网络药理学研究[J]. 化学试剂，2022，44(2):195-202。
基于1,8-萘酰亚胺的甲醛荧光探针研究进展
曹碧霞1,2，刘 荣*1,2，高玉清1，刘婷1，岳胜利1
(1. 甘肃省化工研究院有限责任公司，甘肃 兰州 730020；2. 甘肃省精细化工重点实验室，甘肃 兰州 730020)
摘要：甲醛广泛存在于工业生产和日常生活中，是常见的环境污染物和人体致癌物。1,8-萘酰亚胺是重要的双光子荧光基团，具有良好的光稳定性、大的stocks位移以及高的荧光量子产率。近年来，大量基于1,8-萘酰亚胺基团的甲醛荧光探针被开发出来，并在环境监测及生命科学等领域有了较为初步的应用。对甲醛与识别基团的反应类型分类，综述了近年来具有代表性的基于1,8-萘酰亚胺基团的甲醛荧光探针的最新研究进展，并展望了其未来设计与发展趋势。
关键词：甲醛；1,8-萘酰亚胺；荧光探针；设计；进展
中图分类号：O65 文献标记码：A 文章编号：0258-3283（2022）--
Research Progress of Formaldehyde Fluorescent Probes Based on 1,8-naphthimide CAO Bi-xia1,2, LIU Rong*1,2, GAO Yu-qing1, LIU Ting1, YUE Sheng-li1 (1. Gansu Research Institute of Chemical Industry Co., Ltd., Lanzhou, 730020, China; 2. Gansu Key Laboratory of Fine Chemicals, Lanzhou, 730020, China), Huaxue Shiji, 2022, 44(2), ～
Abstract: Formaldehyde widely exists in industrial production and daily life, which is a common environmental pollutant and human carcinogens. 1,8-naphthimide is an important two-photon fluorescence group, which has good photostability, large stocks shift and high fluorescence quantum yield. In recent years, a large number of formaldehyde fluorescent probes based on 1,8-naphthimide groups have been developed, and they had been preliminary applied in the fields of environmental monitoring and life sciences. This article categorizes the reaction types of formaldehyde and recognition groups, summarizes the latest research progress of representative formaldehyde fluorescent probes based on 1,8-naphthimide in recent years, and gives the prospect in future design and development trends.
Key words: formaldehyde; 1,8-naphthimid; fluorescent probes; design; progress
引用本文：曹碧霞，刘 荣，高玉清，等.基于1,8-萘酰亚胺的甲醛荧光探针研究进展[J].化学试剂，2022，44（2）:203-211.
基于碳纳米点荧光试纸可视化探针的构建及应用
黄诚*1，张帅帅1，权一鸣1，任科旭1，田燕琳1，朱森强2，刘睿2
（1. 东南大学成贤学院 制药与化学工程学院，江苏 南京 210088；2. 南京工业大学 化学与分子工程学院，江苏 南京 211816）
摘要：以吩噻嗪为原料，经硝化反应合成出3,7-二硝基吩噻嗪，并以此为前驱体，制备出两种N、S掺杂的碳纳米点材料，通过多种手段对所合成材料结构和组成进行表征。将碳纳米点应用于Cu2+的快速定性/定量可视化检测，并基于碳纳米点荧光试纸结合智能手机的颜色分析识别，构建Cu2+可视化检测传感器，展现出高效、准确、灵敏和便捷的优势。在0～5 µmol/L范围内的碳纳米点荧光差值和Cu2+浓度的相关系数R2 = 0.9976，Cu2+检出限可达0.26 µmol/L；在0～15 µmol/L范围内，试纸荧光颜色的B/R值与Cu2+浓度呈现较好的线性关系，相关系数R2 = 0.9213，Cu2+检出限可达1.28 µmol/L。该荧光试纸的开发和应用为功能化碳纳米点材料提供了有益思路，并有望应用于现场和实时检测中。
关键词：硝化反应；碳纳米点；荧光试纸；智能手机；可视化传感
中图分类号：O69 文献标识码：A 文章编号：0258-3283(2022)--
Construction and Application of Visual Sensor Based on Carbon Nanodots Fluorescent Test Paper HUANG Cheng*1, ZHANG Shuai-shuai1, QUAN Yi-ming1, REN Ke-xu1, TIAN Yan-lin1, ZHU Sen-qiang2, LIU Rui2 (1. Department of Chemical and Pharmaceutical Engineering, Southeast University Chengxian College, Nanjing 210088, China;2. College of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing 211816, China), Huaxue Shiji,2022, 44(2), ～
Abstract: Aromatic nitro compounds were synthesized through nitration reaction by using phenothiazine, and used to preparetwo N, S-doped carbon nanodots (CNDs). These synthesized materials were characterized by various methods. The obtained CNDs were applied to the rapid qualitative, quantitative visualization detection of Cu2+. Based on the fluorescent test paper of CNDs and the color analysis and recognition of smart phones, a visual detection sensor for Cu2+ is constructed, which is effective, accurate, sensitive and convenient. Thefluorescence difference of CNDs and Cu2+ concentration in the range of 0～5 µmol/L show a good linearity, the correlation coefficient R2 = 0.9976, and the detection limit can reach 0.26µmol/L. In the range of 0～15 µmol/L, the B/R value of fluorescent test paper shows a good linear relationship with Cu2+ concentration, the correlation coefficientR2 = 0.9213, and the detection limit of Cu2+ can reach 1.28 µmol/L. The development and application of the test paper provides a useful idea for functionalized CNDs materials, and is expected to be applied to field and real-time detection.
Keywords: nitration reaction; carbon nanodots; fluorescent test paper; smart phone; visual sensing
引用本文：黄诚，张帅帅，权一鸣，等. 基于碳纳米点荧光试纸可视化探针的构建及应用[J]. 化学试剂，2022，44(2):212-218。
基于萘酚席夫碱结构的荧光增强型铝离子探针
刘玉村*，于晓凡，赵妍，吴淼，王媛，赵际涵
(吉林师范大学 化学学院，吉林 四平 136000)
摘要：金属离子Al3+在生命系统中起着非常重要的作用并影响着人类的健康，荧光分子探针由于方法简单、选择性和灵敏度高、现场实时监测、检出限低等优点吸引了更多的研究关注。通过一步缩合反应制备了基于萘酚席夫碱结构的荧光分子探针，该分子探针在DMSO/H2O溶液中对Al3+具有较好的选择性。加入Al3+后分子探针溶液的荧光强度明显增强，且溶液发射出明显的蓝绿色荧光。同时，分子探针对Al3+表现出较好的灵敏度，其检测限为1.58×10-8 mol/L。分子探针与Al3+以2 ：1结合模式进行配位，pH实用范围为6 ~ 9，且具有可逆性。此外，分子探针可对实际饮用水中的Al3+进行定量检测。
关键词：萘酚；席夫碱；荧光增强；铝离子；探针
中图分类号：O655.9 文献标识码：A 文章编号：0258-3283（2022）
A Fluorescence Enhancement Al3+ Probe Based on Naphthol Schiff Structure Liu Yu-cun*, YU Xiao-fan, Zhao Yan, Wu Miao, Wang Yuan, ZhaO Ji-han (College of Chemistry, Jilin Normal University, Siping 136000, China), HuaxueShiji, 2022
Abstract: The metal ion Al3+ plays very important roles in living system and affects human health. Fluorescence probes with simple method, high selectivity and sensitivity, real-time monitoring and low detection limit have aroused more attention. A fluorescent probe based on naphthol Schiff base structure was prepared by one-step condensation reaction. The probe showed good selective for the detection of Al3+ in DMSO/H2O solution. Upon the addition of Al3+, the fluorescence intensity of solution was significantly enhanced, and the solution emitted obvious blue-green fluorescence. In addition, the probe also exhibited good sensitivity to Al3+ with a detection limit of 1.58×10-8 mol/L. The probe was found to bind with Al3+in a 2:1 (probe: metal) stoichiometric fashion. The probe had good recognition performances for Al3+ in the range of pH = 6 ~ 9, and the sensing process was chemically reversible by adding EDTA. Furthermore, the probe could be successfully practiced for the quantitative analysis of Al3+ in actual water samples.
Key words: naphthol; Schiff base; fluorescence enhancement; Al3+; probe
引用本文：刘玉村，于晓凡，赵妍，等.基于萘酚席夫碱结构的荧光增强型铝离子探针[J]. 化学试剂，2022, 44(2):219-223.
新型咔唑衍生物的合成及发光性能研究
曹建华*1，李敏2，赵雷1，韩洪波1，田会强1，邓师勇1
（1. 北京八亿时空液晶科技股份有限公司，北京 102500；2. 中国政法大学 商学院 工商管理系，北京 100088）
摘要：基于螺二芴的大位阻结构和咔唑的高三线态能级，设计了一种在咔唑的3、4和5、6位并入两个高位阻的螺二芴结构，以4,4’-二甲基联苯为起始原料，经过硝化反应、Bucherer反应、偶联反应、卤化、Suzuki偶联反应和关环等反应成功制备了咔唑衍生物CzSF2，产物结构经过1H NMR、13C NMR、MS确证。其在二氯甲烷溶液中的最强发射峰位于384 nm，磷光发射峰位于450 nm，CzSF2的ES1和ET1分别为3.4 eV和2.88 eV。分别以CzSF2和mCBP（3,3’-Di(9H-carbazol-9-yl)biphenyl）为磷光主体材料，分别掺杂3%、6%和10%的GD030（（2-氘甲基-8-（2-吡啶基）苯并呋喃[2,3-b]吡啶）双（2-苯基吡啶）铱（III））制备了绿色磷光电致发光器件（PhOLEDs），在较低（3%）掺杂浓度下，实现了较高的电流效率、功率效率和外量子效率，分别为98.5 cd/A、83.0 lm/W和25.2%，与mCBP作为主体材料相比，驱动电压低约11%、发光效率高约4%。研究结果表明：利用高度扭曲的螺二芴共轭结构和位阻优势以及高π-π共轭的咔唑设计合成的材料CzSF2具有高的热稳定性，高的三线态能级，非常适用于有机电致发光二极管的发光层，用于磷光主体材料，本征光电性能良好，其设计思路对实现低浓度铱配合物的掺杂具有借鉴意义。
关键词：4,4’-二甲基联苯；螺二芴；咔唑；有机电致发光材料；磷光主体材料
中图分类号：O626.2 文献标识码：A 文章编号：0258-3283（2022）--
Synthesis and Luminescent Properties of New Carbazole Derivatives CAO Jian-hua*1, LI Min2, ZHAO Lei1, HAN Hong-bo1, TIAN Hui-qiang1, DENG Shi-yong1 (1. Beijing Bayi Space LCD Technology Co., Ltd., Beijing 102500, China; 2. Department of Business Administration, Law Business School, China University of Political Science, Beijing 100088, China), Huaxue Shiji, 2022, 44(2), ～
Abstract：Based on the large steric hindrance of spirobifluorene and the high triplet energy level of carbazole, we designed a carbazole derivative, structure of which has two spirobifluorenes at 3,4 and 5,6 positions of carbazole. By using 4,4'-dimethylbiphenyl as starting material, the double 9,9'-spirobifluorenes and one carbazole derivative CzSF2 was synthesized via sequential reactions of nitration, Bucherer reaction, coupling, halogenations, Suzuki-Miyaura coupling, cyclization reaction and other reactions. All compounds were identified by 1H NMR, 13C NMR and MS spectra. The optical and electronic properties have been investigated by molecular simulation and calculation. The emission spectrum of CzSF2 showed a maximum peak at 384 nm and a shoulder peak at 403 nm, and the phosphorescence emission peak located at 450 nm at low temperature, therefore, the ES1 and ET1 were calculated to be 3.4 eV and 2.88 eV, respectively. CzSF2 and mCBP are used asthe phosphorescent host materials, and the green phosphorescent organic light-emitting diodes devices (PhOLEDs) were fabricated by doping with ω＝3%, ω＝6% and ω＝10% of iridium complex GD030 (2-(methyl-d3)-8-(pyridin-2-yl)benzofuro[2,3-b] pyridine)bis[2-phenylpyridinato-C2,N]Ir(III)), respectively. The highest current efficiency, power efficiency and external quantum efficiency were achieved in low (3%) doping concentrations, which were 98.5 cd/A, 83.0 lm/w and 25.2%, respectively, under current density of 0~100 mA/cm2.Compared with mCBP as the host material, the driving voltage is 11% lower and the luminous efficiency is about 4% higher. These results indicate that the material of CzSF2,designed by taking advantages of the highly twisted spirobifluorene conjugated structure, steric hindrance and the high π-π conjugated carbazole, has high thermal stability and high triplet energy level, which is suitable for organic electroluminescence. The light-emitting layer of the OLEDs is used as the phosphorescent host material that has good intrinsic photoelectric performance. The design ideas of host material have reference significance to realize the dopant with lower concentrations of iridium complex.
Key words: 4,4'-dimethylbiphenyl; spirobifluorene; carbazole; organic electroluminescent materials; phosphorescent host material
引用本文：曹建华，李敏，赵雷，等. 新型咔唑衍生物的合成及发光性能研究[J]. 化学试剂, 2022, 44(2):224-232。
Cu-N/C单原子催化剂用于芳基硼酸羟基化反应
李晓怡1，朝飞1，麦悦贤1，梁广锋1，郎睿*1，吴传德*2
（1.广东工业大学 轻工化工学院，广东 广州 510006；2.浙江大学 化学学院，浙江 杭州 310027）
摘要：单原子催化剂中所有金属原子都能作为活性位点，故表现出极高的原子利用率和优异的催化性能。以铜-乙二胺四乙酸配合物作为前驱体，高比表面的活性炭作为载体，通过简单的吸附浸渍-高温焙烧法制备了一系列Cu-N/C催化剂。结果发现，当铜负载量为0.2wt%时，铜以单原子的状态分散在载体上，得到0.2wt%Cu-N/C(1:1)单原子催化剂。该催化剂在芳基硼酸羟基化制苯酚的反应中具有优异的活性，可以直接用氧气作为氧化剂，反应效率达到3250 mmol产物/gCu，高于铜纳米颗粒催化剂6倍。此外，该单原子催化剂稳定性较好，并且该反应对各种带有吸电子或给电子基团的芳基硼酸都具有良好的底物适用性。
关键词：铜；单原子催化；苯硼酸；羟基化反应；炭载体
中图分类号：O643 文献标识码：A 文章编号：0258-3283（2022）--
Ipso-hydroxylation of Aryl boronic Acids Catalyzed by Cu-N/C Single-Atom Catalyst LI Xiao-yi1, CHAO Fei1, MAI Yue-xian1, LIANG Guang-feng1, LANG Rui*1, WU Chuan-de*2 (1.School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, China; 2.Department of Chemistry, Zhejiang University, Hangzhou 310027, China), Huaxue Shiji, 2022, 44(2), ～
Abstract: Single-atom catalysts can improve the catalytic performance by maximizing the atomic efficiency of active metal species, thus exhibiting high catalytic performance. In this paper, a series of Cu-N/C catalysts were prepared by impregnating active carbon material with Cu-EDTA complex precursor and the subsequent calcination. The composition and morphology of the catalyst were characterized by the combination of XRD, AC-STEM, and BET techniques. The synthesized 0.2wt%Cu-N/C(1:1) single-atom catalyst carries out the ipso-hydroxylation of phenylboronic acid to produce phenol under O2 atmosphere with a catalytic efficiency of 3250 mmolproduct/gCu, which was6 times higher than that of Cu nanoparticle catalyst. In addition, this single-atom catalyst shows good stability and wide functional-group tolerance, because various arylboronic acids with electron withdrawing/donating groups can be transformed to the corresponding phenolic compounds under mild conditions.
Key words:copper; single-atomcatalysis; phenylboronic acid; ipso-hydroxylation; carbon support
引用本文：李晓怡，朝飞，麦悦贤，等. Cu-N/C单原子催化剂用于芳基硼酸羟基化反应[J]. 化学试剂，2022，44(2):233-238.
星点设计-效应面法优化羧甲基壳聚糖包覆纳米粒处方工艺
黄欣瑜，何李浩，姜佳妙，夏晓静*
（浙江医药高等专科学校药学院，浙江宁波 315100）
摘要：为获得包封率高且稳定的载齐墩果酸的羧甲基壳聚糖包覆纳米制剂。采用星点设计-效应面法进行优化，以粒径、电位、包封率为评价指标，非线性数学模型拟合，并对优选出的条件制成的纳米粒进行粒径、电位等评价，HPLC法进行载药量测定及体外释放评价。优化后条件为醇水比为0.105，单硬脂酸甘油酯与硬脂酸比为1.656，羧甲基壳聚糖与硬脂酸比为1.458，制备所得纳米粒包封率93.4纳米粒包封，载药量为9.1量为米粒包，粒径362.3米粒包封nm，电位-44.8米粒包封mV，体外释放也说明纳米粒能维持48h以上载药稳定。该法优化后所得测量值与预测值偏差较小，相关性好，为齐墩果酸壳聚糖包覆纳米粒的处方设计提供了可靠的依据。
关键词：星点设计-效应面法；羧甲基壳聚糖；纳米粒；齐墩果酸
中图分类号：R944；R975文献标识码：A文章编号：0258-3283（2022）
Optimiazation of Formulation and Preparation Technology of Carboxymethyl Chitosan-Coated Nanoparticle by Central Composite Design and Response Surface Methodology HUANG Xin-yu, HE Li-hao, JIANG Jia-miao, XIA Xiao-jing* (Department of Pharmaceutics, Zhejiang Pharmaceutical College, Ningbo315100, China), Huaxue Shiji, 2022, 44(2), ～
Abstract: To obtain stable carboxymethyl chitosan-coated nanoparticles loading oleanolic acid with high encapsulation efficiency, the central composite design response surface method was used to optimize the formulation and preparation of the nanoparticles which take particle size, potential, and encapsulation efficiency as evaluation indexes. And also a nonlinear mathematical model was fitted. The particle size and potential of the optimized formulation were evaluated, and the drug loading andthe in-vitro release were determined by HPLC. The optimized conditions were as follows: the alcohol-water ratio was 0.105,the proportion of glyceryl monostearate(GM) to stearic acid(SA) was 1.656, and that carboxymethyl chitosan(C-Cs) to SA was 1.458. Encapsulation efficiency of the optimized nanoparticles was 93.4 ± 2.8%, drug loading was 9.1 ± 1.6%, particle size was 362.3 ± 7.2nm, and zetapotential was - 44.8 ± 0.9mv. The in vitro release showed that the nanoparticles were stable enough for more than 48h. This optimized method provides a reliable basis for the formulation design of oleanolic acid chitosan-coated solid lipid nanoparticles.
Key words: central composite design and response surface methodology; carboxymethyl chitosan; nanoparticle; oleanolic acid
引用本文：黄欣瑜，何李浩，姜佳妙，等. 星点设计-效应面法优化羧甲基壳聚糖包覆纳米粒处方工艺[J]. 化学试剂, 2022, 44(2): 239-244.
光诱导锰羰基化合物释放一氧化碳研究
张俊蝶，王雪梅，潘滢滢，吴晓君，李爱云，姜秀娟*
(嘉兴学院 生物与化学工程学院，浙江 嘉兴 314001)
摘要：通过合成可见光诱导的一氧化碳释放分子，实现可见光作用下的一氧化碳释放。通过Mn(CO)5Br和邻菲罗啉衍生物反应合成得到了一种光敏感的锰羰基化合物[Mn(CO)3(L)Br] ，并进一步通过红外光谱和紫外光谱技术研究了该化合物在不同可见光作用下的一氧化碳（CO）释放性能。结果表明，目标化合物在可见光作用下即可分解释放CO，可以作为潜在的光诱导一氧化碳释放分子。进一步研究其CO释放动力学表明该过程符合准一级反应模型，而且CO释放速率可通过选用不同光源进行调控。因此，通过得到一种速率方便调控的可见光诱导的一氧化碳释放剂，预期该化合物在医药领域具有潜在的应用前景。
关键词：一氧化碳释放剂；锰羰基化合物；光诱导；邻菲罗琳衍生物
中图分类号：O614.8 文献标识码：A 文章编号：0258-3283(2022)--
The Study of Photo Initiation Carbon Monoxide releasing from Manganese Carbonyl Complex ZHANG Jun-die, WANG Xue-mei, PAN Ying-ying, Wu Xiao-jun, LI Ai-yun, JIANG Xiu-Juan* (, College of Biological and Chemical Sciences and Engineering, Jiaxing University, Jiaxing 314001, China), Huaxue Shiji, 2022, 44(2), ～
Abstract：Photoinduced carbon monoxide releasing agent has attracted extensive attention of scientists because of its easy controllability. In this paper, we have synthesized visible light induced carbon monoxide releasing molecule to realize carbon monoxide releasing under visible light. Alight-sensitive manganese carbonyl compound [Mn(CO)3(L)Br] (1) was synthesized by the reaction of Mn(CO)5Br and phenanthroline derivative. Its carbon monoxide releasing ability under different visible light were studied by infrared and ultraviolet spectroscopy. The results showed that compound 1 could decompose and release CO under visible light, and be used as a potential photoinduced carbon monoxide releasing molecule (photoCORMs). Further study of the CO release kinetics revealedthat the process conforms to the quasi-first-order reaction model, and the CO release rate can be controlled by selecting different light sources. This work provides a visible light induced carbon monoxide releasing agentwith easy rate regulation, which is expected to have a potential application in the medical field.
Key words：CO-releasing molecule（CORMs）; manganese carbonyl complex; photo initiation; phenanthroline derivatives
引用本文： 张俊蝶，王雪梅，潘滢滢，等. 光诱导锰羰基化合物释放一氧化碳研究[J].化学试剂，2022，44（2）：245-249.
金属酞菁/卟啉分子电催化CO2还原的研究进展
曹茂启，吴大旺，李晓凤，向丁玎，罗骏，李云萍，代虹镜*
（黔南民族师范学院 化学化工学院，贵州 都匀 558000）
摘要：大气中日益增加的CO2浓度导致了气候变化等环境问题。将CO2催化转化为有价值的化学品具有重要意义。利用太阳能、风能等可再生能源产生的电能，通过电化学方法将CO2还原转化为有价值的碳基化合物是最具有应用前景的方式。分子催化剂具有明确的结构和清晰的活性位点，可实现基于机理的性能优化。综述了近年来金属酞菁/卟啉分子在电催化CO2还原为CO的实验和理论方面的最新研究进展。首先，介绍了金属酞菁/卟啉分子电催化CO2还原为CO的详细机理。然后，重点介绍了如何通过分子分散和配体修饰提升金属酞菁/卟啉分子电催化CO2还原为CO的活性和选择性。最后，讨论了金属酞菁/卟啉分子电催化CO2还原存在的挑战及其可能的解决方案。
关键词：金属酞菁/卟啉基分子；碳纳米材料；电催化CO2还原；反应机理；活性和选择性
中图分类号：O643.3 文献标识码：A 文章编号：0258-3283（2022）--
Research Progress of Electrocatalytic Reduction of CO2 by Metal Phthalocyanine/Porphyrin Molecules CAO Mao-qi, WU Da-wang, LI Xiao-feng, XIANG Ding-ding, LUO Jun, Li Yun-ping, DAI Hong-jing* (School of Chemistry and Chemical Engineering, Qiannan Normal University for Nationalities, Duyun 558000, China), Huaxue Shiji, 2022, 44(2), ～
Abstract: The increasing concentration of CO2 in the atmosphere contributes to environmental problems such as climate change. The catalytic conversion of CO2 into valuable chemicals is of great significance. It is the most promising way to use the electric energy provided by solar energy, wind energy and other renewable energy to reduceCO2 into valuable carbon-based compounds by electrochemical method. The molecular catalyst has distinct structures and clear active sites, which is conducive to the optimization of performance based on the mechanism. The latest experimental and theoretical research in the electrocatalytic reduction of CO2 to CO by metal phthalocyanine/porphyrin molecules in recent years was reviewed. Firstly, we introduced the detailed mechanism of electrocatalytic of CO2 to CO. And then, we focused on how to improve the activity and selectivity of electrocatalytic of metal phthalocyanine/porphyrin molecules for reducingCO2 to CO through molecular dispersion and ligand modification. Finally, we discussed the challenges and possible solutions of metal phthalocyanine/porphyrin molecular in the process of electrocatalytic CO2 reduction.
Key words: metal phthalocyanine/porphyrin molecules; carbon nanomaterials; electrocatalytic reduction of carbon dioxide; reaction mechanism; activity and selectivity
引用本文：曹茂启，吴大旺，李晓凤，等. 金属酞菁/卟啉分子电催化CO2还原的研究进展[J]. 化学试剂, 2022, 44(2)：250-258。
改性花生壳吸附亚甲基蓝动力学与机理研究
吕东灿，王志敏，姜广策，王佳雯，李演鑫，朱乾臣，李鑫*
（河南农业大学 理学院，河南 郑州 450002）
摘要：吸附法是去除水中有机污染物的一种重要方式。以农业废弃物花生壳为原料，通过稀酸改性制备对亚甲基蓝吸附性能良好的生物质基吸附材料。FTIR分析表明改性花生壳表面含有羟基、羧基等有利于吸附的官能团，SEM和孔结构分析结果显示稀硫酸改性花生壳表面形成大量孔结构。亚甲基蓝浓度为100 mg/L时，改性花生壳的去除效率为91.5%。亚甲基蓝吸附过程符合准二级动力学，热力学数据符合Langmuir和Redlich-Peterson模型，表明改性花生壳对亚甲基蓝是化学吸附为主的单分子层吸附过程，氢键、范德华力和电子作用是吸附的主要机理。Langmuir拟合可知稀硫酸改性花生壳对亚甲基蓝的最大吸附量为174.9 mg/g。这种价廉、高效的生物质基吸附材料为低成本、环境友好地利用废弃生物质资源提供了理论依据。
关键词：花生壳；硫酸预处理；动力学；亚甲基蓝；机理
中图分类号：S52；TQ352 文献标识码：A 文章编号：0258-3283（2022）--
Adsorption Kinetics and Mechanism of Sulfuric Acid Modified Peanut Husk for Removal of Methylene Blue LV Dong-can, WANG Zhi-min, Jiang Guang-ce, WANG Jia-wen, LI Yan-xin, ZHU Qian-chen, LI Xin* (College of Science, Henan Agricultural University, Zhengzhou 450002, China), Huaxue Shiji, 2022, 44(2), ～
Abstract: Adsorption is an important pathway for removal of organic pollutant from water. The present study aimed at the removal of methylene blue (MB) using peanut hull modified by sulphuric acid treatment. FTIR showed that there are plenty of hydroxyl and carboxyl groups, as well as other functional groups, conducive to adsorption. Scanning electron microscope (SEM) results showed that a rough surface with pore structure was presented on the modified peanut hull surface, which was confirmed by specific surface area analysis. The removal efficiency was 91.5% under the MB initial concentration of 100 mg/L. For H2SO4 modified sorbents tested, pseudo-second-order model was more suitable for fitting adsorption, and MB adsorption followed both Langmuir and Redlich-Peterson model. The MB removal was a monolayer adsorption process dominated by chemisorption, which was also a spontaneous and endothermic process. Adsorption mechanisms involve hydrogen bonds, electrostatic, and Van der Waals force. The maximum absorption capacity is 174.9 mg/g by Langmuir model. The results suggest that the modified agricultural waste is an environmentally friendly and low-cost bio-sorbent for effective removal of MB from aqueous solutions.
Key words: peanut hull; sulphuric acid pretreatment; adsorption kinetics; methylene blue; mechanism
引用本文：吕东灿，王志敏，姜广策，等. 改性花生壳吸附亚甲基蓝动力学与机理研究[J]. 化学试剂，2022，44(2)：259-265.
基于高分辨质谱技术的植物源性药食同源特色农产品中10种农药残留的测定和快速筛查
谢昊臻1，胡婷婷2，王佳慧2,付瑶2，陈光宇2，李爱军2，荣会2，张勋*2，张哲*1
（1. 长春中医药大学吉林省人参科学研究院，吉林 长春 130118；2. 长春海关技术中心，吉林 长春 130062）
摘要：建立了人参、五味子、刺五加、人参花、灵芝和灵芝孢子粉基质中10种农药残留的高分辨液相质谱检测及筛查方法，样品中残留的农药采用乙腈提取，经氯化钠及乙酸钠盐析分层，提取液经无水硫酸镁、N-丙基乙二胺(PSA)和石墨化炭黑（GCB）吸附剂分散固相萃取净化，用高效液相色谱-高分辨质谱定性。在上述检测方法条件下，所测的10种农药的定量限为10 μg/kg，平均回收率为73.2%～98.5%，线性范围为10～1000 μg/L（R2>0.9986）。本研究所建立的方法前处理简单快捷，能够快速筛查出样品中的10种农药并对目标物进行准确的定性分析，为药食同源特色农产品中的农药残留的风险评估提供了技术支持。
关键词：药食同源；农药；高效液相色谱；高分辨质谱；快速筛查法
中图分类号：O657.63 文献标识码：A 文章编号：0258-3283（2022）--
Determination and Rapid Screening of 10 Pesticide Residues in Agricultural Products of Plant Origin Medicine Homologous Food by High Resolution Mass Spectrometry XIE Hao-zhen1, HU Ting-ting2, WANG Jia-hui2, FU Yao2, CHEN Guang-yu2, LI Ai-jun2, RONG Hui2, ZHANG Xun*2, ZHANG Zhe*1 (1.Jilin Ginseng Academy, ChangChun University Of Chinese Medicine, Changchun 130117; 2. Changchun Customs Technology Center, Changchun 130062, China), Huaxue Shiji, 2022, 44(2), ～
Abstract: A high-resolution liquid chromatography-mass spectrometry (HPLC-MS) method was developed for the detection and screening of 10 pesticide residues in ginseng, Schisandrachinensis, acanthopanaxsenticosus, ginseng flower, Ganodermalucidum and Ganodermalucidum spore powder. The pesticide residues were extracted with acetonitrile, salted out by sodium chloride and sodium acetate, and then purified by solid phase extraction with anhydrous magnesium sulfate, PSA and GCB. The samples were identified by high performance liquid chromatography high resolution mass spectrometry. Under the above conditions, LOQ of 390 pesticides was 10 μg/kg. The average recovery was 80.5%～96.6% and the linear range was 10～1000 μg/L (R2> 0.9986). This established method was simple and rapid. Quickly screening out samples of 10 kinds of pesticides and accurately qualitative analysis provides a technical support for the medicine edible characteristic agricultural products pesticide risk assessment.
Key words: medicine homologous food; pesticide; high performance liquid chromatography (HPLC); high resolution mass spectrometry; rapid screening method
引用本文：谢昊臻，胡婷婷，王佳慧，等.基于高分辨质谱技术的植物源性药食同源特色农产品中10种农药残留的测定和快速筛查[J]. 化学试剂, 2022, 44(2): 266-272。
固相萃取法与GC-FPD联用分析海水中13种有机磷
彭诗琪1,2,3，赵嘉辉1,3，黄晓玲1,3，吴志鹏1,3，张傲1,3，陈婷2，赖华杰*1,3
(1. 中科检测技术服务（广州）股份有限公司，广东 广州 510650；2. 中科广化（重庆）新材料研究院有限公司，重庆 400700；3. 中国科学院广州化学有限公司，广东 广州 510650）
摘要：有机磷农药的广泛使用导致其不可避免地进入到环境中，不仅会影响生态环境，而且还会通过食物链富集进入到人体中，对人类健康造成影响。建立了固相萃取与GC-FPD联用的方法，并成功用于海水样品中敌敌畏等13种有机磷的分析。在中性条件下，100 mL水样经过HLB固相萃取小柱富集后，以二氯甲烷为洗脱溶剂进行洗脱，以HP-5柱为分离色谱柱，FPD为检测器，实现了对13种有机磷的分离及检测。对固相萃取柱和洗脱溶剂的种类、仪器条件等进行了探究，比较了C18、HLB、PSD 3种固相萃取柱对有机磷的吸附性能以及丙酮、二氯甲烷、乙酸乙酯3种溶剂的洗脱能力，考察了海水的基质效应对有机磷分析的影响。在最优的分析条件下，13种有机磷可实现基线分离，线性良好，相关系数均大于0.995，回收率在58.3%~114%之间，所建方法适用于海水样品中敌敌畏等13种有机磷的同时测定。
关键词：有机磷；海水；固相萃取；气相色谱；基质效应；敌敌畏
中文分类号：O657.7 文献标识码：A 文章编号：0258-3283（2022）--
Determination of 13 Kinds of Organophosphorus Pesticides in Seawater by Solid Phase Extraction Coupled with Gas Chromatography-flame Photometric DetectorPENG Shi-qi1,2,3, ZHAO Jia-hui1,3, HUANG Xiao-ling1,3, WU Zhi-peng1,3, ZHANG Ao1,3, CHEN Ting2, LAI Hua-jie*1,3 (1. CAS Testing Technical Services （Guangzhou）Co., Ltd., Guangzhou 510650, China; 2. New Materials Research Institute of CASCHEM（Chongqing）Co., Ltd., Chongqing 400700, China; 3. Guangzhou Institute of Chemistry, Chinese Academy of Science, Guangzhou 510650, China), Huaxue Shiji, 2022, 44(2), ～
Abstract: The widespread abuse of organophosphorus pesticides leads to the inevitable release into environment, which not only affects the ecological environment, but also causes harm to human health through the enrichment of the food chain. The method of solid phase extraction (SPE) coupled with GC-FPD was established and successfully applied for the determination of 13 kinds of organophosphorus pesticides in seawater samples such as dichlorvos, etc. Under neutral condition, 100mL water sample was enriched by HLB column, and then dichloromethane was used for elution. The separation and determination of 13 kinds of organophosphorus pesticides was completed by using HP-5 as the chromatography column and FPD as the detector. The types of solid phase extraction column, elution solvent, and instrument condition were optimized. The adsorption performance of C18, HLB and PSD solid phase extraction columns for organophosphorus pesticides and the elution capacity of acetone, dichloromethane and ethyl acetate were compared, and the matrix effect was investigated. Under the optimized conditions, the separation baseline of analytes was achieved. The linear coefficients of analytes were more than 0.995, and the recovery rates were between 58.3~114%. The established method was suitable for simultaneous determination of 13 kinds of organophosphorus pesticides.
Key words: organophosphorus pesticides; seawater; solid phase extraction; gas chromatography; matrix effect; dichlorvos
引用本文：彭诗琪，赵嘉辉，黄晓玲，等. 固相萃取法与GC-FPD联用分析海水中13种有机磷[J]. 化学试剂，2022，44(2):273-278。
基于近红外光谱快速测定雪菊的总黄酮含量
冯昱龙，彭娟，贺小刚，于佳萍，韩想，楚刚辉*
（喀什大学 化学与环境科学学院 新疆特色药食用植物资源化学实验室，新疆 喀什844000）
摘要：建立了一种近红外漫反射光谱快速测定不同产地雪菊中总黄酮含量的方法。以10个不同产地的100份雪菊样品为对象，采用NaNO2-Al（NO3）3比色法对来自不同产地的雪菊进行总黄酮含量测定；通过不同产地雪菊样品的近红外光谱图和对应的总黄酮含量，运用偏最小二乘法(PLS)建立了雪菊总黄酮含量的快速测定模型并对模型进行了验证。试验结果表明，采用连续小波变换与标准正态变换的方法进行光谱预处理，所建立的定量模型稳健有效，模型的相关系数为0.9862，交叉验证均方根误差为0.6259，预测残差值为4.0907，预测回收率为93.06%～104.64%。说明通过近红外漫反射光谱结合化学计量学方法能够实现快速测定不同产地雪菊中总黄酮的含量，该方法预测效果良好，结果准确，对快速、无损地测定其他植物样品中总黄酮的含量具有一定的借鉴意义。
关键词：雪菊；近红外光谱；总黄酮；快速测定
中图分类号：O657.39;TQ460.7+2 文献标识码：A 文章编号：0258-3283（2022）--
Rapid Determination of Total Flavonoids in Snow Chrysanthemum Based on Near Infrared Spectroscopy Feng Yu-long, Peng Juan, He Xiao-gang, Yu Jia-ping, Han Xiang, CHU Gang-hui* (Xinjiang Special Medicine and Edible Plant Resources Chemistry Laboratory, School of Chemistry and Environmental Science, Kashgar University, Kashgar 844000, China), Huaxue Shiji, 2022, 44(2), ～
Abstract: A method for the rapid determination of total flavonoids in snow chrysanthemum from different places by near-infrared diffuse reflectance spectroscopy was established. Taking 100 samples of snow chrysanthemum from 10 different producing areas as the research object, NaNO2-Al(NO3)3 colorimetric method is used to determine the total flavonoid content of snow chrysanthemum from different producing areas. Based on the near-infrared spectra and the corresponding total flavonoid content data of the snow chrysanthemum samples from different origins, a rapid determination model of snow chrysanthemum total flavonoids by using partial least squares (PLS)was established and verified. The correlation coefficient R of the established model is 0.9862, the cross validation of root mean square error RMSECV is 0.6259, the predicted residual value is 4.0907, and the predicted recovery rate is 93.06-104.64%.Therefore, the method of near-infrared diffuse reflectance spectroscopy combined with chemometrics can quickly determine the content of total flavonoids in snow chrysanthemum of different origins. This method has the advantages of good prediction effect and accurate results, and it has certain reference significance for the rapid and non-destructive determination of total flavonoids in other plant samples.
Key words: snow chrysanthemum; near infrared spectroscopy; total flavonoids; rapid determination
引用本文：冯昱龙，彭娟，贺小刚，等. 基于近红外光谱快速测定雪菊的总黄酮含量[J]. 化学试剂，2022，44(2): 279-284。
液相色谱串联质谱与通过式固相萃取结合测定人体血液和血清中的伏立康唑和卡马西平
杨飞1，鞠华波2，刘卫3，杨进1，王颖1，邓惠敏1，范子彦1，纪元1，唐纲岭*1
（1. 国家烟草质量监督检验中心，河南 郑州 450001；2. 西北烟草质量监督检测站，甘肃 兰州 730030；3. 郑州大学 药学院，河南 郑州 450001）
摘要：采用通过式固相萃取建立高效液相色谱-串联质谱（HPLC-MS/MS）快速测定人体血液和血清中伏立康唑和卡马西平的方法。样品经蛋白沉淀后过PRiME HLB通过式固相萃取柱净化，以Poroshell 120 EC-C18（4.6 mm×50 mm，2.7 μm）为色谱柱，0.01 mol/L醋酸铵水溶液-乙腈（含0.1%甲酸）为流动相进行梯度洗脱。在电喷雾离子源正离子模式下电离，以多反应监测模式（MRM）下扫描。同时采用基质匹配标准曲线和同位素内标法进行定量分析。结果表明：待测化合物的回收率在85.5% ～ 106.6%之间，日内RSD和日间RSD均小于10.0%，所有化合物线性关系良好（R2≥0.9968），检出限（LOD）和定量限（LOQ）范围分别为0.02 ～ 0.65和0.07 ～ 2.12 ng/mL。该方法专属性强、操作简单、分离速度快、稳定性好、灵敏度高，适用于人体血液和血清中伏立康唑和卡马西平含量的测定，为不同种类药物的同时检测提供了借鉴。
关键词：通过式固相萃取；卡马西平；伏立康唑；高效液相色谱-串联质谱
中图分类号：R917 文献标识码：A 文章编号：0258-3283（2022）--
Determination of Voriconazole and Carbamazepinein Human Blood and Serum by Liquid Chromatography Tandem Mass Spectrometry Combined with Pass-Through Solid Phase Extraction YANG Fei1, JV Hua-bo2, LIU Wei3, YANG Jin1, WANG Ying1, DENG Hui-min1, FAN Zi-yan1, JI Yuan1, TANG Gang-ling* 1 (1. China National Tobacco Quality Supervision & Test Center, Zhengzhou 450001, China; 2. North-west Tobacco Test Centre, Lanzhou 730030, China; 3. School of Pharmacy, Zhengzhou University, Zhengzhou 450001, China), Huaxue Shiji, 2022, 44(2), ～
Abstract: This method established a high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) for the determination of voriconazole and carbamazepine in human blood and serum by pass-through solid-phase extraction. Human whole blood/serum samples were purified by acetonitrile precipitation and PRiME HLB pass-through solid-phase extraction column. Poroshell 120 EC-C18 (4.6 mm×50 mm, 2.7 μm) was used as the chromatographic column, and0.01 mol/L ammonium acetate-acetonitrile aqueous solution (containing 0.1% formic acid)was used as the mobile phase for gradient elution. The samples were scanned in the multiple reaction monitoring (MRM) mode with positive ion mode of electrospray ionization. At the same time, the quantitative analysis of the sample was carried out using matrix matching standard curve and isotope internal standard method. The recoveries of the tested compounds were between 85.5% and 106.6%, and the intra-day relative standard deviation (RSD) and inter-day RSD were both less than 10.0%. All compounds have a good linear relationship (R2≥0.9968), while the limit of detection (LOD) and limit of quantification (LOQ) range from 0.02 to 0.65 ng/mL and 0.07 to 2.12 ng/mL, respectively. This method has strong specificity, simple operation process, fast separation speed, good stability and high sensitivity, which is suitable for the determination of voriconazole and carbamazepine in human whole blood and serum.
Key words: pass-through solid phase extraction; carbamazepine; voriconazole; high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS)
引用本文：杨飞，鞠华波，刘卫，等. 液相色谱串联质谱与通过式固相萃取结合测定人体血液和血清中的伏立康唑和卡马西平[J]. 化学试剂，2022, 44(2):285-292.
ICP-OES法测定不同水源地饮用矿泉水中35种矿物质元素
贡慧1，杨震2，窦培谦1，孟燕华1，赵秋生1，任国友1，徐桂芹1
（1. 中国劳动关系学院 安全工程学院，北京 100048；2. 中国绿色食品发展中心，北京 100081)
摘要：采用湿法消解为前处理方法，ICP-OES为检测手段建立了天然饮用矿泉水中35矿物质种元素的检测方法，优化了前处理方法，确定了35种元素的ICP-OES分析线；建立了35种元素的适合浓度范围的标准曲线，线性相关系数均在0.995以上；检出限在0.04 ~ 10.50 μg/L之间，定量限在0.12 ~ 35.00 μg/L之间。对35种元素的标准样品进行了测定，相对标准偏差在0.50% ~ 8.00%之间，加标回收率在90% ~ 108%之间，方法简便省时，精密度和准确度较高。对6个水源地的天然饮用矿泉水实际样品进行了35种矿物质元素测定，检测结果发现天然矿泉水具有低钠、钾，高钙、镁，富有锶、硅等有益元素的特点，但因水源地不同，各元素含量差异较大，消费者可根据自身情况加以选购。
关键词：ICP-OES；矿泉水；矿物质元素；湿法消解；不同水源地
中图分类号：O657.3 文献标识码：A 文章编号: 0258-3283（2022）
Determination of 35 Mineral Elements in Drinking Water from Different Water Sources by ICP-OES GONG Hui1*, YANG Zhen2, DOU Pei-qian1, MENG Yan-hua1, ZHAO Qiu-sheng1, REN Guo-you1, XU Gui-qin1 (1. China University of Labor Relations School of Safety Engineering, Beijing 100048, China; 2. China Green Food Development Center, Beijing 100081, China), Huaxue Shiji, 2022, 44(2), ～
Abstract: The detection method of 35 mineral elements in natural drinking mineral water was established by wet digestion as pretreatment method and ICP-OES as detection method. The pretreatment method was optimized, and the ICP-OES analysis line of 35 elements was determined. The standard curves suitable for the concentration range of 35 elements were established, and the linear correlation coefficients were more than 0.995. The detection limit was 0.04-10.50 μg/L, and the quantitative limit was 0.12-35.00 μg/L. The relative standard deviation was 0.50%-8.00%, and the recovery was 90%-108%. The method was simple, time-saving and had high precision and accuracy. 35 kinds of mineral elements were determined in the actual samples of natural drinking mineral water from 6 water sources. The results showed that natural mineral water had the low ion concentration of sodium, potassium, while high ion concentration of calcium, magnesium, strontium, silicon and other beneficial elements. Notably, due to the difference in water sources, the content of each element varies greatly. In this case, consumers are suggested to choose and buy the water according to their own situation.
Key words: ICP-OES; mineral water; mineral elements
引用本文：贡慧，杨震，窦培谦，等. ICP-OES法测定不同水源地饮用矿泉水中35种矿物质元素[J]. 化学试剂，2022，44（2）：293-297.
柱串联凝胶色谱分离表征多分散聚乙二醇羧酸衍生物的
方法研究
张安林1, 2，马宁2，张径*1, 2，张爱玲*1, 3
（1. 长沙创新药物工业技术研究院有限公司，湖南 长沙 410006；2. 长沙医学院 药学院，湖南 长沙 410219；3. 华中科技大学同济医学院附属协和医院，湖北 武汉 430022）
摘要：药用聚乙二醇（PEG）由于具有多分散特性而导致其衍生物之间的分离表征极其困难。常规的基于分子排阻（SEC）的凝胶色谱对于相同平均分子量（Mn）的PEG衍生物很难实现良好的分离效果。对平均分子量为2000和5000的直链聚乙二醇（PEG）及其羧酸衍生物进行了色谱分析。在低离子强度下，采用示差折光检测器和3种OHpark KF型色谱柱串联对一系列多分散PEG衍生物进行了分离表征，解决了聚乙二醇及其羧酸衍生物分离表征难题。结果表明，这些PEG衍生物在OHpark KF色谱柱上的保留机制主要是离子交换相互作用。当流动相中的盐浓度增加时，保留体积减小，并且保留体积和保留时间随着洗脱液的溶剂比例以及柱温的变化而变化。此外，PEG链的链长度和末端基团对PEG化合物的色谱行为也会产生明显影响。
关键词：聚乙二醇；羧酸衍生物；分子排阻色谱；保留体积；离子交换
中图分类号：0626.24 文献标识码：A 文章编号：0258-3283（2022）--
Separation and Characterization of Polyethylene Glycol Carboxylic Acid Derivatives by Gel Chromatography with Tandem Gel Columns ZHANG An-lin1, 2, MA Ning2, ZHANG Jing*1, 2, ZHANG Ai-ling*1, 3 (1. Changsha Institute of Innovative Pharmaceutical Industry Technology, Changsha 410006, China; 2. School of Pharmacy, Changsha Medical College, Changsha 410219, China; 3. Union Hospital, Tongji Medical College, Huazhong University of Science and Technology, Wuhan 430022, China), Huaxue Shiji, 2022, 44(2), ～
Abstract: Due to the polydispersion characteristics of medicinal polyethylene glycol (PEG), it is extremely difficult to separate and characterize PEG derivatives. Conventional gel chromatography based on size exclusion chromatography (SEC) is difficult to achieve a good separation effect for PEG derivatives with the same average molecular weight (Mn). This research describes achromatographic analysis of straight-chain polyethylene glycol (PEG) and their carboxyl-substituted derivatives (Mn=2000 or 5000). A series of polydisperse PEG derivatives were separated by tandem OHpark KF column under low ionic strength with refractive index detection (RID). The problem inseparation and characterization of carboxylic functionalized and unfunctionalized polyethylene glycol (PEG) due to its polydispersion property was solved. The results showed that the retention mechanism of these PEG derivatives on the OHpark KF column was mainly the ion exchange interactions, because the retention volume decreased with the increase of salt concentration in the mobile phase, and the retention time and volume changed with the solvent content and column temperature. Moreover, the size and the end functional groups of the PEG chain also have an obvious effect on the chromatographic behavior of PEG compounds.
Key words: poly(ethyleneglycol); carboxylic acid derivatives; size-exclusion chromatography; retention volume; ion exchange
引用本文：张安林，马宁，张径，等. 柱串联凝胶色谱分离表征多分散聚乙二醇羧酸衍生物的方法研究[J]. 化学试剂，2022，44(2)：298-305.
电感耦合等离子体串联质谱法测定高纯氧化钆中20种痕量元素含量
胡芳菲*1，刘鹏宇2，于磊1，王长华1，陈雄飞1
(1. 国标（北京）检验认证有限公司，北京 101407 ；2. 国合通用测试评价认证股份公司，北京 101407)
摘要：建立了电感耦合等离子体串联质谱法（ICP-MS/MS）直接测定高纯氧化钆中20种痕量元素含量的分析方法。在优化的实验条件下，分别采用He碰撞模式和NH3原位质量模式消除了Fe、As、Yb、Lu受到的质谱干扰，考察了基体效应以及不同内标元素的校正效果，方法定量限在0.003～0.63 μg/g之间，RSD（n=7）＞5%，加标回收率在90%～115%之间。本方法可以用于高纯氧化钆中包括Yb和Lu在内的痕量元素含量的直接测定。
关键词：电感耦合等离子体串联质谱；氧化钆；痕量元素；镱；镥
中图分类号：O657.63 文献标识码：A 文章编号：0258-3283（2022）--
Determination of 20 trace elements in high purity gadolinium oxide by inductively coupled plasma-tandem mass spectrometry HU Fang-fei*1, LIU Peng-yu2, YU Lei1, WANG Chang-hua1, CHEN Xiong-fei1 (1.Guobiao(Beijing) Testing & Certification Co., Ltd.; 2. China United Test & Certification Co., Ltd., Beijing 101407, China), Huaxue Shiji, 2022, 44(2), ～
Abstract: An analytical method was proposed to determine 20 impurity elements in high pure gadolinium oxide by inductively coupled plasma-tandem mass spectrometry. This work was finished under optimal conditions. He collision mode and NH3 in-situ mass mode were used to eliminate mass interference of Fe, As, Yb and Lu contents. Matrix effect and correction results of different internal standards were investigated. The limits of quantitation for each element were 0.003～0.63 μg/g, and the relative standard deviation (RSD, n=7) was below 5%. The recoveries for the testing spiked samples were between 90% and 115%. This method can be used to measure trace element contents in high purity gadolinium oxide directly, including Yb and Lu.
Key words: inductively coupled plasma-tandem mass spectrometry; gadolinium oxide; trace elements; Ytterbium; Lutetium
引用本文：胡芳菲，刘鹏宇，于磊，等. 电感耦合等离子体串联质谱法测定高纯氧化钆中20种痕量元素含量[J]. 化学试剂,2022,44(2): 306-309。
氮杂环基取代丙氨酸及其衍生物的合成、晶体结构及荧光性能研究
雷红琴1,2，王吉德*1，史岷山1
（1. 新疆大学 石油天然气精细化工教育部重点实验室，新疆 乌鲁木齐 830046；2. 伊宁海关技术中心， 新疆 伊宁 835000）
摘要：采用2-（二苯亚甲氨基）乙酸甲酯和3种2-/4-溴甲基取代的含氮杂环化合物分别进行烷基化、水解反应得到了3-(1H-苯并[d]咪唑-2-基)-2-氨基丙酸、3- (吡啶-2-基)-2-氨基丙酸及3-(噻唑-4-基)-2-氨基丙酸。所合成化合物的结构经过元素分析、1HNMR、13CNMR、IR和质谱确认，并用X射线衍射法测定了化合物2-(二苯亚甲氨基)-3-(1-叔丁氧羰基-1H-苯并[d]咪唑-2-基)丙酸甲酯及 2-(二苯亚甲氨基)-3-(噻唑-4-基)丙酸甲酯晶体结构。同时测试了标题化合物及其前体化合物的荧光性质，通过测试发现上述几种化合物具有很强的荧光，增大了其作为荧光材料的应用可能性。
关键词：杂芳基氨基酸；烷基化；合成；荧光性能；晶体结构
中图分类号：O625.63 文献标识码：A 文章编号：0258-3283(2022)--
Synthesis, Crystal Structure and Fluorescent property of Several N-Containing Heteroaromatic Amino Acids and Derivatives LEI Hong-qin1,2,WANG Ji-de*1, SHI Min-shan1 (1. Key Laboratory of Oil and Gas Fine Chemicals, Ministry of Education & Xinjiang Uyghur Autonomous Region, Xinjiang University, Urumqi 830046, China; 2 Yining Customs Technical Centre, Yining 835000, China), Huaxue Shiji, 2022, 44(2), ～
Abstract; 2-amino-3-(1H-benzo[d]imidazol-2-yl)propanoic acid, 2-amino-3-(pyridin-2-yl) propanoic acid and 2-amino-3- (thiazol-4-yl)propanoic acid have been synthesized by alkylation of N-(diphenyl methylene) glycine methyl ester with 3 kinds of nitrogen containing heterocycles and hydrolization subsequently. The target compounds were characterized by elemental analysis, 1H NMR, 13C NMR, IR, MS technique.Moreover, the crystal structures of methyl 2-(diphenylmethyleneamino)-3-(1 -tert-butoxycarbonyl-1H-benzo[d]imidazol-2-yl)propanoate and methyl 2-(diphenylmethyleneamino)-3-(thiazol-4-yl)propanoate were also determined by X-ray diffraction.Besides, we found that these compounds have strong fluorescence, which increases their potential application as fluorescent materials.
Key words: heteroaromatic amino acids; alkylation; synthesis; fluorescent property; crystal structure
引用本文：雷红琴, 王吉德, 史岷山. 氮杂环基取代丙氨酸及其衍生物的合成、晶体结构及荧光性能研究[J].化学试剂，2021，44(2)：310-316.
