【特约专题】
稳定同位素在组学研究及临床诊断中的应用
赵雅梦1,2,3，范若宁1,3，李良君1，刘建军2，罗勇1，赵诚1，雷雯*1,3
（1. 上海化工研究院有限公司，上海 200062；2. 上海交通大学 医学院仁济医院核医学科，上海 200127；3. 上海市稳定同位素检测及应用研发专业技术服务平台）
摘要：稳定同位素因其具有可示踪性、良好的稳定性和与非标记试剂化学性质相近等特点，在农残检测、样品溯源等诸多研究中起着重要作用。近年来，随着生命科学的发展和分析检测技术的不断提高，稳定同位素在药物研发、精准诊疗等与人民健康息息相关领域的重要性日益突出。介绍了稳定同位素试剂在蛋白质定量、代谢机理确证和潜在生物标记物筛选等多组学研究中的应用，还介绍了其作为内标物或原料试剂在临床质谱、核医学成像等临床诊疗中的应用，并对其未来发展进行了展望。
关键词：稳定同位素；内标试剂；示踪剂；应用
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2023）--
DOI：10.13822/j.cnki.hxsj.2022.0701
Application of Stable Isotopes in Omics Studies and Clinical Diagnosis ZHAO Ya-meng1,2,3, FAN Ruo-ning1,3, LI Liang-jun1, LIU Jian-jun2, LUO Yong1, ZHAO Cheng1, LEI Wen*1,3 (1. Shanghai Research Institution of Chemical Industry Co. Ltd., Shanghai 200062, China; 2. Department of Nuclear Medicine, Renji Hospital, School of Medicine, Shanghai Jiaotong University, Shanghai 200127, China; 3. Shanghai Professional Technology Service Platform on Detection and Application Development for Stable Isotope)
Abstract：Stable isotope reagents have been essential tools in pesticide residue detection, origin tracking, and other environmental studies because of their good traceability, stability, and chemical compatibility with unlabeled reagents. In recent years, advances in life science and evolution of detection instruments have propelled stable isotope labeling to be more widely applied in pharmaceutical research, precision medicine, and other fields closely related to public healthcare. In this paper, we review the applications of stable isotope reagents in multi-omics research including protein quantification, metabolic pathway identification, and biomarker detection as well as their clinical uses such as clinical mass spectrometry and nuclear medical imaging. In the end, we give prospects for the future of stable isotope technologies.
Key words：stable isotope; internal standard reagents; tracer; application
引用本文：赵雅梦, 范若宁, 李良君, 等. 稳定同位素在组学研究及临床诊断中的应用[J]. 化学试剂, 2023, 45(3):1-9.
【综述与专论】
聂永欣，王繁盛，刘泽恩，屈馨甜，黄雪秋，韦雪琴*
（广西医科大学 药学院，广西 南宁 530021）
摘要：利用超分子识别与组装的基本原理，发展新型超分子催化剂以实现催化反应的超分子选择性调控是当今催化领域研究的热点和前沿。柱芳烃是一类具有刚性骨架结构的新型大环主体分子，其富电子的空腔和优异的主客体化学性质能够对客体分子进行选择性识别，使其在超分子催化中显示了独特的催化性能。综述了近十年来柱芳烃在超分子催化领域的应用研究进展，重点阐述主-客体相互作用对超分子催化选择性的调控作用，并对其存在问题进行总结及发展前景进行展望。
关键词：超分子催化；柱芳烃；主-客体相互作用；相转移催化；光催化；金属催化
中图分类号：O641.3 文献标识码：A 文章编号：0258-3283（2023）--
DOI：10.13822/j.cnki.hxsj.2022.0788
Advances in Supramolecular Catalysis based on Pillararenes NIE Yong-xin, WANG Fan-sheng, LIU Ze-en, QU Xin-tian, HUANG Xue-qiu, WEI Xue-qin* (School of Pharmacy, Guangxi Medical University, Nanning 530021, China)
Abstract：Supramolecular catalysts have been developing for controlling selectivity of supramolecular catalysis by virtue of the basic principles of supramolecular recognition and assembly, which has become a hot topic in the field of catalysis. Pillararenes is a novel macrocyclic host possessing rigid architecture. The electron-rich cavity and excellent host-guest property make pillararenes great supramolecular hosts with selective guest binding and unique catalytic performance in supramolecular catalysis. This review will focus on the recent progress in supramolecular catalysis based on the pilliararenes in recent decade. The manipulation of selectivity in supramolecular catalysis via host-guest interaction will be emphatically introduced. The existing problems of current study and the perspectives will also be discussed.
Key words：supramolecular catalysis; pillararenes; host-guest interaction; phase transfer catalysis; photocatalysis; metal catalysis
引用本文：聂永欣, 王繁盛, 刘泽恩, 等. 基于柱芳烃的超分子催化研究进展[J]. 化学试剂, 2023, 45（3）：10-21。
殷慧1，孟颖1，彭微1，白安琪1，李淑荣1,2，罗利霞1,2，冀华*1,2，孟佩俊*1,2
(1. 内蒙古科技大学 包头医学院 公共卫生学院，内蒙古 包头 014040；2. 内蒙古自治区卫生检测与评价工程技术中心，内蒙古 包头 014040)
摘要：随着农药应用的日益广泛，农药残留对人群健康和环境污染带来的潜在危害日益凸显出来。由于农药残留具有残留量低，样品基底成分复杂等特点，因此，构建对农药残留进行灵敏、准确、稳定、简便、快速的微量甚至痕量检测方法已成为一个热点研究领域。稀土掺杂上转换纳米材料（REEs-UCNPs）作为一种非常重要的具备反斯托克斯发光的稀土发光材料，化学稳定性和光稳定性好，具有发射峰窄、毒性低、量子产率高等显著优势，近些年来，用REEs-UCNPs作为荧光探针在分析检测领域备受关注。重点综述了基于REEs-UCNPs的免疫分析法和荧光分析法对农药残留进行检测的研究进展。以期为后续建立和发展灵敏、简单、快速以及低成本的农药残留检测方法提供思路，从而为人类健康、农业生产以及生态文明建设保驾护航。
关键词：稀土掺杂上转换纳米材料；农药残留；免疫分析法；荧光分析法；检测
中图分类号：O657 文献标识码：A 文章编号：0258-3283（2023）--
DOI：10.13822/j.cnki.hxsj.2022.0840
Application of rare-earth-elements-doped upconversion nanoparticles in the fields of pesticide residue detection YIN Hui1，MENG Ying1，PENG Wei1，BAI An-qi1，LI Shu-rong1,2，LUO Li-xia1,2，JI Hua*1,2，MENG Pei-jun*1,2 (1.Public Health School, Baotou Medical College, Inner Mongolia University of Science & Technology, Baotou 014040, China; 2.Engineering Technology Center of Hygienic Inspection and Assessment of Inner Mongolia Autonomous Region, Baotou 014040, China)
Abstract: With the increasingly widespread application of pesticides, the potential hazards of pesticide residues on human health and environmental pollution are increasingly highlighted.Since pesticide residues are characterized by low residue amounts and complex sample substrate components, the construction of sensitive, accurate, stable, simple and rapid methods for the detection of pesticide residues in trace amounts has become a hot research area. Rare-earth-elements-doped upconversion nanoparticles (REEs-UCNPs), as a very important rare earth luminescent material with anti-Stokes luminescence, have good chemical stability and optical stability, and have significant advantages such as narrow emission peak, low toxicity and high quantum yields. In recent years, REEs-UCNPs as a fluorescent probe has attracted much attention in the fields of analysis and detection. This paper focuses on the research progress of immunoassay and fluorescence analysis based on REEs-UCNPs for the detection of pesticide residues. It is expected to provide ideas for the subsequent establishment and development of sensitive, simple, rapid and low-cost pesticide residue detection methods, so as to guide agricultural production, protect human health, and promote the ecological civilization construction.
Key words: rare-earth-elements-doped upconversion nanoparticles(REEs-UCNPs); pesticide residues; immunoassay; fluorescence analysis; detection
引用本文：殷慧，孟颖，彭微，等. 稀土掺杂上转换纳米材料在农药残留检测中的应用[J].化学试剂, 2023, 45(3): 22-28。
新烟碱类杀虫剂的研究与开发进展
李昌兴1，刘东东1,3，高一星1,2，张静1,2,3，张立新*1,2,3
(1. 沈阳化工大学 功能分子研究所，辽宁省绿色功能分子设计与开发重点实验室，沈阳市靶向农药重点实验室，辽宁 沈阳 110142；2. 广西思钺生物科技有限责任公司，江苏 南宁 530000；
3. 辽宁科技大学 化学工程学院，辽宁 鞍山 114051）
摘要：自上世纪80年代吡虫啉上市以来，新烟碱类杀虫剂便受到广泛关注和应用，登记国家超120个，是全球用量最大的杀虫剂品种。新烟碱类杀虫剂是一种高效的内吸性杀虫剂，能有效控制刺吸式害虫以及部分双翅目、鞘翅目害虫。新烟碱类杀虫剂作用于昆虫烟碱乙酰胆碱受体，阻断昆虫中枢神经系统信号的正常传导，从而导致害虫麻痹而亡。具有杀虫谱广、低毒低残留的优点，并且具有胃毒和触杀等多重作用。概述了新烟碱类杀虫剂的发展历程、作用机理、结构分类、及其在农业害虫防治的应用。
关键词：新烟碱类杀虫剂；烟碱乙酰胆碱受体；结构分类；作用机理
中图分类号：TQ460 文献标识码：A 文章编号:0258-3283（2023）
DOI：10.13822/j.cnki.hxsj.2022.0644
Research and Development Progress of Neonicotinoid Insecticides LI Chang-xing1, LIU Dong-dong1,3, GAO Yi-xing1,2, ZHANG Jing1,2,3, ZHANG Li- xin*1,2,3 (1. Shenyang Key Laboratory of Targeted Pesticides, Liaoning Key Laboratory of Green Functional Molecule Design and Development, Institute of Functional Molecules, Shenyang University of Chemical Technology, Shenyang 110142, China; 2. Guangxi SiYue Biotechnology Co., Ltd., Nanning 530000, China; 3. School of Chemical Engineering, University of Science and Technology Liaoning, Anshan 114051, China)
Abstract: Since the listing of imidacloprid in the 1980s, neonicotinoid insecticides have received widespread attention and application, with more than 120 registered countries, making it the world's largest insecticide variety. Neonicotinoid insecticides are highly effective systemic insecticides for controling sucking pests and some diptera and coleoptera pests. Neonicotinoid insecticides act on the nicotinic acetylcholine receptor of insects, blocking the normal transmission of signals in the central nervous system of insects, resulting in paralysis and death of pests. It has the advantages of broad insecticidal spectrum, low toxicity and low residue, and multiple effects such as gastric toxicity and contact toxicity. This paper summarizes the development history, mechanism of action, structural classification， and its application in agricultural pest control.
Key word: neonicotinoid insecticides; nicotinyl acetylcholine receptor; structure classification; mechanism of action
引用本文：李昌兴, 刘东东, 高一星, 等. 新烟碱类杀虫剂的研究与开发进展[J]. 化学试剂, 2023, 45（3）：29-.36
【生化与药用试剂】
吲哚类抗抑郁药物的研究进展
凌芳*1，柯德宏1，罗强2，许胜2
(1. 国药集团化学试剂公司，上海 200002)
(2. 华东理工大学 化学与分子工程学院，上海 200237)
摘要：吲哚类化合物凭借其显著的生理活性而被广泛应用于靶向抗抑郁药物的研究。近年来，对于吲哚类抗抑郁药物的研究取得了较大的进展，这些新型抗抑郁药物主要针对单胺氧化酶、5-羟色胺转运体(SERT)和5-羟色胺(5-HT)受体等靶点发挥作用。按照药物与靶点的作用机制的分类，综述了近年来吲哚类抗抑郁药物的研究进展。
关键词：抗抑郁；吲哚类化合物；研究进展
DOI：10.13822/j.cnki.hxsj.2022.0868
Research Progress of Indole Antidepressants Ling Fang1，Ke De-Hong1，Luo Qiang2，Xu Sheng2 (1.Sinopharm Chemical Reagent Co., Ltd., Shanghai 200002, China; 2. School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, China）
Abstract: Indoles have been widely used in the research of targeted antidepressants because of their significant physiological activities. In recent years, great progress has been made in the research of indole antidepressants. These new antidepressants mainly target monoamine oxidase, serotonin transporter (SERT) and serotonin (5-HT) receptor. According to the classification of the mechanism of action between drugs and targets, the progress of indole antidepressants in recent years have been reviewed in this paper.
Key words: antidepressant；indoles；research progress
引用本文：凌芳，柯德宏，罗强，等. 吲哚类抗抑郁药物的研究进展[J]. 化学试剂, 2023, 45(3):37-46。
【功能材料】
负载芹菜素壳聚糖凝胶珠的制备及其性能研究
李慧卿*，曹叶霞，陈雪涛，郎悦
（忻州师范学院 化学系，山西 忻州 034000）
摘要：为实现芹菜素有效利用，以柠檬酸钠为交联剂，采用离子聚沉法制备了芹菜素水凝胶珠，通过FTIR、TGA和XRD等手段对其表征，并利用Uv-vis测定了芹菜素的包封率、负载率、溶胀度及其释药行为。实验条件下，芹菜素负载率为20.58%，包封芹菜素后，芹菜素形态未发生变化，但由于壳聚糖与芹菜素之间发生相互作用，热稳定性略降低。凝胶珠中芹菜素可持续释放，并且对pH有明显的响应性。其中在pH 8.0条件下8 h释放率最高。在0.1 mol/L酸度下，24 h后，空白和载药凝胶珠都可降解，但随着酸度增大到1、2 mol/L，降解反而减缓，负载芹菜素凝胶珠比空白凝胶珠更不易降解。这些为利用凝胶珠运载药物进一步提供了实验依据。
关键词：壳聚糖凝胶珠；芹菜素；pH响应；溶胀率；缓释
中图分类号：O632 文献标识码：A 文章编号：0258-3283（2023）--
DOI：10.13822/j.cnki.hxsj.2022.0807
Preparation and Properties of Apigenin-Loaded Chitosan Gel Beads LI Hui-qing*, CAO Ye-xia, CHEN Xue-tao, LANG Yue (Department of chemistry, Xinzhou Teachers’ Normal University, Xinzhou 034000, China)
Abstract：To utilize apigenin efficiently, hydrogel beads were prepared by ion polymerization method with sodium citrate as crosslinking agent. The synthesized beads were characterized by FTIR, TGA and XRD. UV-vis spectrophotometry was used to determine the encapsulation efficiency, loading rate, swelling degree and drug release behavior of apigenin encapsulated in hydrogel beads. Under the experimental conditions, the loading rate of apigenin in hydrogel beads was 20.58%. The crystal state of apigenin encapsulated has not changed, but the thermostability slightly fell due to the interaction between chitosan and apigenin. Apigenin can be released continuously from hydrogel beads and respond to different pH. The highest release rate lasting 8 h was obtained at pH 8.0. It was found that in 0.1 mol/L acidic solution, both blank and drug-loaded hydrogel beads were degraded after 24 h. With the increase of acidity to 1 mol/L and 2 mol/L, the degradation process slows down instead of speeding up. Apigenin-loaded chitosan hydrogel beads were more difficult to degrade than blank gel beads. All provides experimental basis for utilizing hydrogel beads to deliver drugs.
Key words：chitosan hydrogel beads; apigenin; pH response; swell rate; xsmmcontrolled-release
引用本文: 李慧卿, 曹叶霞, 陈雪涛, 等. 负载芹菜素壳聚糖凝胶珠的制备及其性能研究[J]. 化学试剂, 2023, 45(3):47-52。
过渡金属改性Ce-M-Ox（M=Cu, Co, Mn和Fe）催化剂在NH3-SCR反应研究
刘春宇1，宋忠贤2，张学军*1，刘威1，莫杜娟1，刘泽鹏1，李海洋1
（1. 沈阳化工大学 环境与安全工程学院，辽宁 沈阳 110142;
2. 河南城建学院 市政与环境工程学院，河南 平顶山 467036）
摘要:采用共沉淀法制备了CeO2上负载不同过渡金属元素Ce-M（M表示Fe、Mn、Cu、Co）催化剂，研究了不同金属负载对CeO2基催化剂脱硝活性影响。CeO2催化剂中加入适量的过渡金属可降低催化剂结晶度，提高催化剂的氧化还原性和表面酸性，从而影响催化剂在NH3-SCR中的催化性能。Ce-Fe、Ce-Mn催化剂中Fe3+和Mn3+的大量存在可提高催化剂的Lewis和Brønsted酸性位点，提升催化剂对NH3的吸附与活化性能，从而提升其催化性能。Ce-Mn催化剂具有优越的低温活性，Ce-Fe展现了较好的中高温活，这与其催化剂的表面酸性密切相关。
中图分类号：X511 文献标识码：A 文章编号：0258-3283（2023）
DOI：10.13822/j.cnki.hxsj.2022.0746
Transition-Metal-Modified Ce-M-Ox (M = Cu, Co, Mn, and Fe) Catalysts Were Studied in the NH3-SCR Reaction LIU Chun-yu1, SONG Zhong-xian2, ZHANG Xue-jun*1, LIU Wei1, MO Du-juan1, LIU Ze-peng1, LI Hai-yang1 (1. School of Environmental and Safety Engineering, Shenyang University of Chemical Technology, Shenyang 110142, China; 2. School of Municipal and Environmental Engineering, Henan University of Urban Construction, Pingdingshan 467036, China)
Abstract: Catalysts loaded with different transition metals Ce-M (M stands for Fe, Mn, Cu and Co) on CeO2 were prepared by co-precipitation method. The effects of different metal loads on the denitrification activity of CeO2 based catalysts were studied. Adding proper amount of transition metal to CeO2 catalyst can reduce the crystallinity of the catalyst, improve the oxidation reducibility and surface acidity of the catalyst, and thus affect the catalytic performance of the catalyst in NH3-SCR. The presence of Fe3+ and Mn3+ in Ce-Fe and Ce-Mn catalysts can improve the Lewis and Brønsted acid sites of the catalysts, improve the adsorption and activation properties of NH3, and thus improve the catalytic performance. Ce-Mn catalyst has superior activity at low temperature, and Ce-Fe exhibits better activity at middle and high temperature, which is closely related to the surface acidity of the catalyst.
Key words: nitrogen oxides; selective catalytic reduction; transition metal element; surface acidity
引用本文：刘春宇, 宋忠贤, 张学军, 等. 过渡金属改性Ce-M-Ox（M = Cu, Co, Mn和Fe）催化剂在NH3-SCR反应研究[J]. 化学试剂, 2023,45（3）：53-60.
6,7-二羟基香豆素温敏表面分子印迹材料制备及吸附性能
钟海艺*，罗健伟，李俊潮，蔡锦云
（广西中医药大学 药学院，广西 南宁 530200）
摘要：以6,7-二羟基香豆素为模板分子，纳米SiO2为表面载体，丙烯酰胺（AM）为功能单体，引入温敏单体N-异丙基丙烯酰胺（NIPAM），乙二醇二甲基丙烯酸酯（EGDMA）做交联剂，采用沉淀聚合法制备6,7-二羟基香豆素温敏表面分子印迹聚合物（T-SMIPs）。红外光谱（FTIR）和扫描电镜（SEM）对聚合物结构与形貌进行了表征验证；吸附性能研究显示，所得MIP2能有效地对6,7-二羟基香豆素进行选择性吸附，当吸附液浓度为0.8 mg/mL时，吸附量可达21.85 mg/g，吸附过程与Langmuir和Freundlich模型相符；此外，印迹材料具有一定的温度响应性，降低温度有利于吸附。该研究可为天然药物中香豆素类成分的分离纯化、富集提供新的方法与思路。
关键词：分子印迹聚合物；表面印迹；香豆素；温敏；吸附
中图分类号：O631.1 文献标识码：A 文章编号：0258-3283（2023）--
DOI：10.13822/j.cnki.hxsj.2022.0709
Preparation and adsorption properties of 6,7-dihydroxycoumarin thermosensitive surface molecularly imprinted polymer ZHONG Hai-yi*, LUO Jian-wei, LI Jun-chao, CAI Jin-yun (College of Pharmacy, Guangxi University of Chinese Medicine, Nanning 530200, China)
Abstract: 6,7-dihydroxycoumarin thermal-sensitive surface molecularly imprinted polymers (MIP2) were synthesized by precipitation polymerization which containing nano silica as a surface carrier, 6,7-dihydroxycoumarin as a template, acrylamide (AM) as a functional monomer, N-isopropylacrylamide (NIPAM) as a temperature sensitive monomer and ethylene glycol dimethacrylate (EGDMA) as a crosslinker. The structure and morphology of the polymers were characterized by FTIR and SEM. Static adsorption demonstrated that these imprinted polymers possessed well specific adsorption properties for 6,7-dihydroxycoumarin. The adsorbing capacity reached 21.85 mg/g when concentration of 6,7-dihydroxycoumarin was 0.8 mg/mL for MIP2, and the adsorption process accorded with Langmuir and Freundlich model. The MIP2 also exhibited temperature responsive behavior, which had a higher adsorption capacity at low temperature. This study could provide some new thoughts and methods to separate and purify coumarin from natural medicines.
Key words: molecularly imprinted polymers; surface imprinting; coumarin; thermal-sensitive; adsorption
引用本文：钟海艺，罗建伟，李俊潮，等. 6,7-二羟基香豆素温敏表面分子印迹材料制备及吸附性能[J]. 化学试剂, 2022, 44(3): 61-66。
【分离提取技术】
大孔树脂对二醇型、三醇型人参皂苷的纯化研究
王斌1,2，赵升铭1,2，袁松竹1,2，王义1,2，张美萍1,2，雷军*1,2，陈屏*1,2
（1. 吉林农业大学 生命科学学院，吉林 长春 130118；
2. 吉林省人参基因资源开发与利用工程研究中心, 吉林 长春 130118）
摘要：分析大孔树脂与人参皂苷之间的吸附行为，优化大孔树脂分离人参皂苷的条件。选用6种大孔树脂（D101、HPD-100、AB-8、NKA-9、ADS-7、DM130），以二醇型人参皂苷（Rg1、Re、Rg2）和三醇型人参皂苷（Rc、Rb1、Rd）的含量为评判指标，进行吸附率、解吸率与吸附容量比较，发现纯化人参皂苷的最适大孔树脂为HPD-100。然后对其静态吸附时间、吸附温度、吸附初始浓度与动态加载流速、加载量、洗脱溶剂等进行考察，筛选最佳纯化工艺。二醇型人参皂苷与三醇型人参皂苷在HPD-100大孔树脂上静态吸附量为109 mg/g，吸附率分别为99.93%与56%，解吸率分别为96.4%与98.5%，静态最佳吸附时间为190 min，吸附初始浓度为32 mg/mL，温度为35 ℃，动态加载流速为4 BV/H（4个柱体积每小时），加载量8 BV（柱体积），洗脱剂为40%和60%乙醇。最终三醇型皂苷的纯化率为66%，二醇型皂苷的纯化率为52%。表明HPD-100D大孔树脂可以用于二醇型人参皂苷和三醇型人参皂苷的分离纯化。
关键词：大孔树脂；人参皂苷；分离纯化；静态吸附；动态吸附
中图分类号： 文献标识码：A 文章编号：0258-3283（2023）
DOI：10.13822/j.cnki.hxsj.2022.0770
Purification of Diol and Triol Ginsenosides by Macroporous Resin WANG Bin1,2, ZHAO Sheng-ming1,2, YUAN Song-zhu1,2, WANG Yi1,2, ZHANG Mei-ping1,2, LEI Jun*1,2, CHEN Ping*1,2 (1. College of Life Science, Jilin Agricultural University, Changchun 130118, China; 2. Jilin Engineering Research Center for Ginseng Genetic Resources Development and Utilization, Changchun 130118, China)
Abstract: The adsorption behavior between macroporous resin and ginsenosides were analyzed and the conditions for the separation of ginsenosides from macroporous resin were optimized. In this paper, the adsorption rate, desorption rate and adsorption capacity of six macroporous resins (D101, HPD-100, AB-8, NKA-9, ADS-7, DM130) were compared with the content of diol-type ginsenosides (Rg1, Re, Rg2) and triol-type ginsenosides (Rc, Rb1, Rd) as the evaluation index. The most suitable macroporous resin for the purification of ginsenosides was found to be HPD-100. After that, the static adsorption time, adsorption temperature, initial concentration of adsorption and dynamic loading flow rate, loading volume and elution solvent were investigated to screen the best purification process. Statically, the adsorption of diol and triol ginsenosides on HPD-100 macroporous resin was 109 mg/g with 99.93% and 56% adsorption and desorption rates of 96.4% and 98.5%, respectively, with a static optimum adsorption time of 190 min, an initial concentration of 32 mg/g at 35 °C, a dynamic loading flow rate of 4 BV/H (4 column volumes per hour), loading volume of 8 BV (column volume), eluent of 40% and 60% ethanol. The purification rates were 66% for triol ginsenosides and 52% for diol ginsenosides. HPD-100D macroporous resin could be used for the isolation and purification of diol and triol ginsenosides.
Key words: macroporous resin; ginsenoside; separation and purification; static adsorption; dynamic adsorption
引用本文：王斌, 赵升铭, 袁松竹, 等. 大孔树脂对二醇型、三醇型人参皂苷的纯化研究[J]. 化学试剂, 2023, 45(3):67-73.
【电化学和新能源】
咔唑基化学传感器识别各种阴离子研究进展
温雨柔1，王浩洋1，赵翔1，温雅梅1，纪利春1，赵霜*2，杜玉英*1
（1. 内蒙古工业大学 a. 化工学院；b. 二氧化碳资源化利用自治区高等学校重点实验室，内蒙古自治区 呼和浩特 010051；2. 内蒙古农业大学 理学院，内蒙古自治区 呼和浩特 010018）
摘要：随着工业的快速发展，阴离子的数量在大幅上升，阴离子识别与检测面临着重大挑战。作为优异的给电子荧光团，咔唑特殊的含氮芳杂环结构，活跃的分子内电荷转移和优秀的空穴传输性能，以及独特的理化性质，使其在光化学传感领域有着广阔的应用前景，因此发展咔唑基衍生物作为化学传感器识别阴离子是一种有效的途径。根据不同的阴离子类型，将近十年各种咔唑衍生物的荧光性质及其在阴离子识别检测方面的研究成果进行了总结，并对未来的发展进行展望。
关键词：咔唑衍生物；化学传感器；荧光；阴离子识别；检测线；配合常数
中图分类号：O626 文献标识码：A 文章编号：0258-3283（2023）--
DOI：10.13822/j.cnki.hxsj.2022.0852
Progress in the Recognition of Various Anions by Carbazole-Based Chemical Sensors WEN Yu-rou1,#, WANG Hao-yang1,#, ZHAO Xiang1, WEN Ya-mei1, JI Li-chun1, ZHAO Shuang*2, DU Yu-ying*1 (1a. Chemical Engineering College, 1b. Inner Mongolia University of Technology, Key Laboratory of CO2 Resource Utilization at Universities of Inner Mongolia Autonomous Region, Hohhot 010051, China; 2. College of Science, Inner Mongolia Agricultural University, Hohhot 010051, China)
Abstract: With the rapid development of industry, the number of anions is increasing greatly, and the identification and detection of anions are facing great challenges. Carbazole is an important type of nitrogen organic compound containing aromatic heterocyclic ring. As the electron-rich fluorophore, carbazole derivatives are endowed with strong active intramolecular charge-transfer, excellent hole transporting ability, unique physical and chemical properties, which was applied to photophysical materials. Therefore, it is an effective way to develop carbazole derivatives as chemical sensors for the recognition of anions. According to the different kinds of anion, the fluorescence properties of carbazole derivatives and the relevant research in anion identification and detection in recent ten years are summarized in this paper. A perspective is also given in this review.
Key words: carbazole derivatives; chemical sensors; fluorescence; anion recognition; determination limit; assocation constant
引用本文：温雨柔, 王浩洋, 赵翔, 等. 咔唑基化学传感器识别各种阴离子研究进展[J]. 化学试剂, 2023, 45(3):74-84。
吴贤格1，陈京成2，姚锐洪1，谢春生*1
（1. 肇庆学院 a. 环境与化学工程学院；b. 广东省环境健康与资源利用重点实验室，广东 肇庆 526061；2. 广州谱临晟科技有限公司，广东 广州 510520）
摘要：氯霉素(CAP)是一种典型的广谱抗生素，然而其不恰当的使用对人体健康和环境安全产生显著的有害影响。电化学传感器检测食品与环境等样品中的氯霉素残留具有重要的意义。近年来，基于碳材料、金属复合材料、金属化合物复合材料、导电聚合物和金属有机骨架(MOFs)等纳米材料已成功地用于氯霉素抗生素检测的传感材料。通过对比基于这些新型纳米材料的氯霉素电化学传感器的特征及适用范围，为氯霉素分析选择检测方法及开发更高效的检测技术提供参考。最后，总结了氯霉素电化学传感器技术目前存在的问题并对其发展前景进行了展望。
关键词：电化学传感器；氯霉素；修饰材料；研究进展
中图分类号：O657. 1；O629. 8 文献标识码：A 文章编号：0258-3283（2023）--
DOI：10.13822/j.cnki.hxsj.2022.0832
Research progress of electrochemical sensor detection technology for chloramphenicol WU Xian-ge1, CHEN Jing-cheng2, YAO Rui-hong1, XIE Chun-sheng*1 (1a.School of Environmental and Chemical engineering, 1b. Provincial Key Laboratory of Environmental Health and Land Resource, Zhaoqing University, Zhaoqing 526061, China; 2.Guangzhou Prin-Cen Scientific Ltd, Guangzhou 510520, China)
Abstract：Chloramphenicol (CAP) is a typical broad-spectrum antibiotic, but its inappropriate use has significant harmful effects on human health and environmental safety. It is of great significance to detect CAP residues in food and environmental samples by electrochemical sensors. In recent years, nanomaterials based on carbon materials, metal composites, metal compound composites, conductive polymers and metal-organic frameworks (MOFs) have been successfully used as sensing materials for CAP detection. By comparing its feature and application scope of CAP electrochemical sensor based on these new nanomaterials, a reference was provided for the selection of detection methods for CAP and the development of more efficient detection technology. Finally, the existing problems of CAP electrochemical sensor technology were summarized and its development prospect was prospected.
Key words：electrochemical sensor；chloramphenicol；modified material；research progress
引用本文：吴贤格，陈京成，姚锐洪，等. 氯霉素电化学传感器检测技术的研究进展[J]. 化学试剂, 2023, 45（3）：85-93.
【化学品与环境】
空气中甲醛能力验证样品的研究及应用
宁远英，左泽浩，张智渊，孙自杰，刘涛*
（生态环境部环境发展中心环境标准样品研究所 国家环境保护污染物计量和标准样品研究重点实验室，北京 100029）
摘要：近年来，随着社会对室内外空气中甲醛污染情况的关注，实验室对空气中甲醛检测能力验证的需求也越来越多。为满足环境监测实验室的需求，配套《空气质量 甲醛的测定 乙酰丙酮分光光度法》（GB/T 15516-1995）、《居住区大气中甲醛测定 AHMT分光光度法》（GB/T 16129-1995）和《公共场所空气中甲醛测定方法：第一法 酚试剂分光光度法》（GB/T 18204.2-2014）相关标准及分析方法。制备了空气中甲醛能力验证样品，进行了均匀性和稳定性检验，表明样品的均匀性、稳定性良好。采用相同程序制备了6批空气中甲醛能力验证样品，成功实施了3次空气中甲醛检测能力验证项目，共有624家实验室参加，参加实验室分布广泛，满意率为76.5%～88.2%，并对实验室检测过程中出现的不满意结果的原因进行了分析。
关键词：空气中甲醛；均匀性；稳定性；能力验证
中图分类号： 文献标识码：A 文章编号：0258-3283（2023）--
DOI：10.13822/j.cnki.hxsj.2022.0756
Preparation and application of proficiency testing sample of formaldehyde in air NING Yuan-ying, ZUO Ze-hao, ZHANG ZHi-yuan, SUN Zi-jie, LIU Tao* (State Environmental Protection Key Laboratory of Environmental Pollutant Metrology and Reference Materials, Institute of Environmental Reference Materials, Environmental Development Center of the Ministry of Ecology and Environment, Beijing 100029, China)
Abstract: In recent years, with more and more attention to the pollution of formaldehyde in the air, there is an increasing demand for laboratories to verify the proficiency testing of formaldehyde in the air. In order to meet the needs of environmental monitoring laboratory, relevant standards and analytical methods are provided in the Air quality-Determination of formaldehyde-Acetylacetone spectrophotometric methd (GB/T15516-1995), Atandard method for hygienic examination of formaldehyde in air of residential areas-Spectrophotometric method (GB/T16129-1995) and Exanmination methods for public-Part 2: Chemical pollutants (GB/T18204.2-2014). Through the homogeneity test and stability test, the homogeneity and stability of sample was good.Six batches of samples were prepared as proficiency testing, and implemented three proficiency testing projects. 624 laboratories participated, and widely distributed. The satisfaction rate was 76.5%～88.2%. And the causes of unsatisfactory results in the process of testing were analyzed.
Key words：formaldehyde in the air; homogeneity; stability; proficiency testing
引用本文：宁远英，左泽浩，张智渊，等. 空气中甲醛能力验证样品的研究及应用[J].化学试剂，2023,45（3）：94-99
新型微波辅助-基质分散固相萃取技术结合HPLC测定土壤中塑化剂
韩凰燕1，武曦*1, 2，张鑫鑫3
(1. 山西师范大学 化学与材料科学学院，山西 太原 030000；2. 长治学院 化学系，山西 长治 046011；3. 太原海关技术中心，山西 太原 030024)
摘要：建立基于低共熔溶剂（DESs）的微波辅助-基质分散固相萃取技术结合高效液相色谱法（HPLC）测定土壤中邻苯二甲酸酯类塑化剂（PAEs）的方法。采用在土壤样品中分别加入不同的分散剂和DES研磨分散的方法进行目标物提取，并将混合物经微波萃取后装入固相萃取小柱并用正己烷洗脱，提取液采用高效液相色谱法（HPLC）检测PAEs。结果表明：在优化实验条件下，5种PAEs的线性范围分别为0.1 ~ 500、0.1 ~ 500、0.1 ~ 500、0.1 ~ 500、1 ~ 1000 μg/mL，检出限分别为0.01、0.01、0.01、0.01、0.02 μg/mL，DMP、DEP、DBP、DPP、DCHP的加标回收率分别为93.41%、93.43%、93.71%、97.98%、
97.58%。此方法操作快速、简便、灵敏度高，结果令人满意，可适用于土壤中PAEs的定量检测。
关键词：低共熔溶剂；基质固相分散萃取；邻苯二甲酸酯；土壤
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2023）
DOI：10.13822/j.cnki.hxsj.2022.0817
A Novel Microwave-Assisted Matrix Solid Phase Dispersion Extraction Technique with HPLC for the Determination of Phthalic Acid Esters in Soil HAN Huang-yan1, WU Xi*2 ZHANG Xin-xin3 (1. School of Chemistry and Materials Science, Shanxi Normal University, Taiyuan 030000, China; 2. Department of Chemistry, Chang Zhi University, Chang Zhi 046011, China; 3. Taiyuan Customs Technology Center, Taiyuan 030024, China)
Abstract： A microwave-assisted matrix dispersed solid phase extraction method based on deep eutectic solvents (DESs) with HPLC for the determination of phthalic acid esters (PAEs) in soil was established. The target was extracted by adding different dispersants and grinding and dispersing DES in the soil samples. The mixture was fully ground and extracted by microwave radiation. The homogenized mixture was then packed in an SPE cartridge and the SPE column was eluted with hexane. The extract was detected using high performance liquid chromatography (HPLC). The results showed that the linear ranges of the five PAEs were 0.1-500, 0.1-500, 0.1-500, 0.1-500, 1-1000 μg/mL, and the detection limits were 0.01, 0.01, 0.01, 0.01, 0.02 μg/mL, respectively, with the optimized experimental conditions. The recoveries of DMP, DEP, DBP, DPP and DCHP were 93.41%、93.43%、93.71%、97.98% and 97.58%, respectively. This method is rapid, simple and sensitive, and the results are satisfactory. The proposed method can be applied to the quantitative determination of PAEs in soil.
Key words：deep eutectic solvents; matrix solid phase dispersion; phthalic acid esters; soil
引用本文：韩凰燕, 武曦, 张鑫鑫．新型微波辅助-基质分散固相萃取技术检测土壤中塑化剂[J].2023，45（3）：100-105.
黄铁矿去除水中Cr(VI)的行为及机理
王小兵，胡雨晴，江丽娜，胡嘉盈，黄晴晴，胡月*
（韶关学院 化学与土木工程学院，广东 韶关 512000）
摘要：以广泛存在于土壤中的黄铁矿（FeS2）为还原剂，探究了Cr(VI)浓度、pH值、共存离子和溶解氧对FeS2还原去除水中Cr(VI)效率的影响，结合FeS2反应前后的表征和活性物种检测，揭示了FeS2高效去除Cr(VI)的机理。结果表明：FeS2具有在较宽pH值范围内（pH 3 ~ 10）高效去除Cr(VI)的性能，HR-XPS分析和铁溶出检测证明FeS2在水中溶解态的Fe(II)和S22-可以快速还原水中的Cr(VI)，而FeS2固相表面的Fe(II)、Sn2-和S22-能吸附溶液中的Cr(VI)，实现Cr(VI)的快速还原和固定。共存离子实验证明NaCl、NaNO3几乎不影响Cr(VI)的去除，而Na3PO4导致FeS2去除Cr(VI)的效率降低至32%，溶解氧则几乎不影响Cr(VI)的去除。最后，利用天然FeS2治理某铬渣污染土壤修复场地的洗脱废水，发现其具有较好的治理铬废水效果。该研究为黄铁矿治理实际铬废水的应用提供了理论支撑。
关键词：黄铁矿；Cr(VI)；还原；去除；固定
中图分类号：O647,O644 文献标识码：A 文章编号：0258-3283（2023） --
DOI：10.13822/j.cnki.hxsj.2022.0743
Behavior and Mechanism of Cr(VI) Removal in Water by Pyrite WANG Xiao-bing, HU Yu-qing, JIANG Li-na, HU Jia-ying, HUANG Qing-qing, HU Yue* (School of Chemistry and Civil Engineering, Shaoguan University, Shaoguan 512023, China)
Abstract：As a widely existing reductive iron mineral in soil, pyrite (FeS2) was employed to remediate Cr(VI) contaminated water. The influence of Cr(VI) concentration, initial pH, coexisting anions and dissolved oxygen on the efficiency of Cr(VI) removal by FeS2 was explored in detail, and the mechanism of Cr(VI) removal by FeS2 was discussed. The experimental results revealed that the high concentration of Cr(VI) in a wide range of pH values (pH = 3 ~ 10) could be removed efficiently by using FeS2. HR-XPS spectroscopic analysis and iron dissolution detection indicated that the dissolved Fe(II) and S(II) could quickly reduce Cr(VI) in water, and the solid-state FeS2 could be removed the adsorbed Cr(VI). In addition, coexisting anions experiments showed that NaCl and NaNO3 did not affect the removal efficiency of Cr(VI), while the presence of Na3PO4 reduced the removal efficiency of Cr(VI) to 32%, and dissolved oxygen did not affect the removal of Cr(VI). Finally, the natural pyrite was successfully applied to treat the eluting wastewater of Cr(VI) contaminated soil. This study provides theoretical and technical guidance for the application of pyrite in the treatment of practical chromium wastewater.
Key words：pyrite; hexavalent chromium; reduction; removal; immobilization
引用本文：王小兵, 胡雨晴, 江丽娜, 等. 黄铁矿去除水中Cr(VI)的行为及机理[J]. 化学试剂, 2023, 45（3）：103-111.
【分析与测试】
红外光谱结合化学计量学鉴别西红花的产地
王巧1，熊丰2，王游游2，张雯1，杨健*2
（1. 南京中医药大学，江苏 南京 210023; 2. 中国中医科学院 中药资源中心 道地药材国家重点实验室培育基地，北京 100700）
摘要：西红花不仅是在世界范围内广泛使用的传统香料，也是一味著名的中草药，其品质与产地密切相关。迫切需要寻找一种能快速对西红花进行产地判别的方法。基于不同产地西红花样品近、中红外光谱数据特征，采用Savitzky-Golay平滑、多元散射校正、标准正态变量变换、一阶导数和二阶导数等预处理算法对光谱数据进行降噪处理，可以减小试验样本、测定环境以及仪器噪音对光谱数据的影响。结合偏最小二乘判别分析（Partial least square-discriminant analysis，PLS-DA) 、决策树（Decision tree，DT）和支持向量机（Support vector machine，SVM）方法分别建立近红外光谱、中红外光谱、近中红外融合光谱分类模型，并采用移动窗口偏最小二乘法（Moving window partial least square method，MWPLS）提取光谱特征区间可以提升建模速度和分类精度。基于预测结果的准确率、混淆矩阵（Confusion matrix）和ROC曲线下面积AUC（Area under curve）以选择最优分类模型。结果显示：近红外光谱、中红外光谱与融合光谱的最佳模型组合均为基于Savitzky-Golay 平滑（SG平滑）预处理的偏最小二乘判别分析法（PLS-DA），其测试集准确率分别达到94.00%、94.00%和96.00%，ROC曲线下面积分别为0.9974、0.9963和0.9990，表明融合光谱可提升分类精度。特征波段的选择增强了单一光谱的分类准确率，但降低了融合光谱的分类性能。可见，结合移动窗口偏最小二乘法（MWPLS)的单一光谱技术可以精简、优化模型。所采用的方法实现了对不同产地西红花的快速准确鉴定，为西红花的产地判别提供一种新颖、快速的解决方案，有利于维护西红花市场的秩序，有助于其产业健康发展。
关键词：西红花；化学计量学；近中红外光谱；融合光谱；产地鉴别
中图分类号：R284.1 文献标识码：A 文章编号：0258-3283（2023）--
DOI：10.13822/j.cnki.hxsj.2022.0753
Identification of origin of crocus sativus by infrared spectroscopy combined with stoichiometry WANG Qiao1, XIONG Feng2, WANG You-you2, ZHANG Wen1, YANG Jian*2 (1.Nanjing University of Chinese Medicine, Nanjing 210023, China; 2.State Key Laboratory Breeding Base of Dao-di Herbs, National Resource Center for Chinese Materia Medica, China Academy of Chinese Medical Sciences, Beijing 100700, China)
Abstract: Crocus is not only a traditional spice widely used in the world, but also a famous Chinese herbal medicine. Its quality is closely related to the origin. It is urgent to find a method that can be used for quick identification of the origin of crocus.In this study, the near-mid-infrared data characteristics of saffron samples from different production areas were extracted. The data were preprocessed by Savitzky-Golay smoothing, multivariate scattering correction, standard normal variable transformation, first-order derivative and second-order derivative algorithms to reduce the test samples, environmental effect and instrument noise on spectral data.Combined with partial least square-discriminant analysis (PLS-DA), decision tree (DT) and support vector machine (SVM) methods were used to establish the classification models of near-infrared, mid-infrared, and near-mid-infrared fusion spectral, respectively. The moving window partial least square method (MWPLS) used for the extraction of the spectral feature interval can improve the modeling speed and classification accuracy. The optimal classification model is selected based on the accuracy of the prediction results, the confusion matrix and the area under the ROC curve (AUC). The results showed that the best model combination of near-infrared spectrum, mid-infrared spectrum and fusion spectrum was partial least squares discriminant analysis (PLS-DA) based on Savitzky-Golay smoothing (SG smoothing) preprocessing. The accuracies of the test sets reached 94.00%, 94.00%, and 96.00%, and the area under the ROC curve reached 0.9974, 0.9963, and 0.9990, respectively, indicating that the fusion spectrum could improve the classification accuracy. The selection of characteristic bands enhances the classification accuracy of single spectrum, but degrades the classification performance of fusion spectrum. It can be seen that the single spectral technique combined with moving window partial least squares (MWPLS) can simplify and optimize the model. The proposed method provides a novel and fast solution for the identification of origin of crocus, which is conducive to maintain the order of crocus market, and contributes to the healthy development of its industry.
Key words: Crocus; Chemometrics; Near/mid-infrared spectroscopy; Fusion spectral; Origin classification
引用本文：王巧，熊丰，王游游，等. 红外光谱结合化学计量学鉴别西红花的产地[J]. 化学试剂, 2023, 45( 3):112-119。
微波消解-ICP-OES法测定电子级硼铝掺杂源中多种金属元素
孟宪冬，王连旺，孟蓉*
（北京化学试剂研究所有限责任公司，北京 102607）
摘要：建立一种微波消解-电感耦合等离子体发射光谱法（ICP-OES）测定电子级硼铝掺杂源中多种金属元素的测试方法。称样量为2.0 g（精确至±0.001 g），样品中加入6 mL硝酸，升温速率10 ℃/min，消解温度为180 ℃，消解时间30 min。用ICP-OES标准加入法进行测定。硼铝掺杂源中钠元素在0～10 mg/L、其余11种金属元素在0～5 mg/L范围内与光谱强度线性关系良好，相关系数均大于0.9990。采用该方法，测定样品的精密度为1.73%～7.71%（n=7）,加标回收率为93.0%～106%，分析结果准确度高，稳定性好，适用于电子级硼铝掺杂源中多种金属元素的测定。
关键词：微波消解；ICP-OES；电子级；硼铝掺杂源；金属元素
中图分类号：O652.1 文献标识码：A 文章编号：0258-3283（2023）--
DOI：10.13822/j.cnki.hxsj.2022.0721
Determination of various metallic elements in electronic grade boron-aluminum spin-on dopant by microwave digestion-inductively coupled plasma optical emission spectrometry MENG Xian-dong, WANG Lian-wang, MENG Rong* (Lnstitute of Chemical Reagents Co. Ltd., Beijing 102607, China)
Abstract: A microwave digestion-inductively coupled plasma emission spectrometry (ICP-OES) method has been developed for the determination of various metallic elements in electronic-grade boron-aluminum spin-on dopant. The sample weight was 2.0 g (accurate to ± 0.001 g), 6 mL nitric acid was added into the sample, the heating rate was 10 °C/min, the digestion temperature was 180 °C, and the digestion time was 30 min. The determination was performed using ICP-OES standard addition method. Good linear relationship with the spectral intensity was observed in the range of 0～10 mg/L for the sodium element and 0～5 mg/L for the other 11 metal elements in the boron-aluminum spin-on dopant with the correlation coefficients greater than 0.9990. Using this method, the precision of the method was 1.73%～7.71% (=7), the recovery of standard addition was 93.0%～106%, and the analytical results had high accuracy and good stability. It is suitable for the determination of various metal elements in electronic-grade boron-aluminum spin-on dopant.
Key words:microwave digestion; ICP-OES; electronic grade;boron-aluminum spin-on dopant;metal element
引用本文：孟宪冬，王连旺，孟蓉. 微波消解-ICP-OES法测定电子级硼铝掺杂源中多种金属元素[J]. 化学试剂, 2023,45（3）：120-125.
高效液相色谱-串联质谱法测定人血清中5种抗真菌药物及相关代谢产物的测量方法
阎娜，于晓燕，陈武炼*
（上海义准生物有限公司，上海安谱实验科技股份有限公司，上海 201609）
摘要：建立了一种能同时测定人血清中伏立康唑（VRC）及伏立康唑氮氧化物（VNO）、泊沙康唑（PCZ）、伊曲康唑（ICZ）及羟基伊曲康唑（HICZ）、氟康唑（FCZ）、卡泊芬净（CPF）5种抗真菌药物及相关代谢产物的测量方法，并对基质匹配标准品和质控物的稳定性进行研究并优化，可应用于临床进行患者血清药物浓度检测。血清样本加入含同位素内标的萃取液进行蛋白沉淀处理后，稀释上清液并进样检测。采用甲酸-乙腈和甲酸-乙酸铵-水为流动相进行梯度洗脱，CNW Shell C18（2.1 mm ×100 mm，2.6 μm）色谱柱进行分离。采用高效液相色谱-串联质谱法（LC-MS/MS），电喷雾电离源正离子（ESI+），多反应监测扫描模式（MRM)，基质匹配标准品、内标法定量。结果表明：伏立康唑、伏立康唑氮氧化物、伊曲康唑、羟基伊曲康唑线性范围为0.1 ~ 10 μg/mL，泊沙康唑线性范围为0.05 ~ 5 μg/mL，氟康唑线性范围为0.5 ~ 50 μg/mL，卡泊芬净线性范围为0.2~20 μg/mL，各化合物线性相关系数大于0.995，准确度为91% ~ 115 %，批内和批间精密度变异系数（CV）均＜15%，混合基质效应偏差为-1.15% ~ 2.23%。方法操作简便，准确度高，稳定性好，可适用于临床对血清中上述抗真菌药物的血药浓度监测。
关键词：抗真菌药物；血药浓度监测；血清；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（2023）--
DOI：10.13822/j.cnki.hxsj.2022.0796
Determination of 5 Antifungal Drugs and Metabolites in Human Serum by High Performance Liquid Chromatography Tandem Mass Spectrometry YAN Na, YU Xiao-yan, CHEN Wu-lian*（ANPEL Laboratory Technologies Inc.; E-GEN (ShangHai) Diagnostics Inc., Shanghai 201609, China)
Abstract: A method was established for simultaneous determination of the concentration of 5 antifungal drugs and metabolites in human serum. The 5 kinds of antifungal drugs and metabolites are voriconazole (VRC), Voriconazole N-Oxide (VNO), posaconazole (PCZ), itraconazole (ICZ), hydroxyitraconazole (HICZ), fluconazole(FCZ) and caspofungin (CPF). The stability of calibrators and quality control products were studied and optimized, which can be applied to clinical detection of serum drug concentration in patients. The serum samples were precipitated to remove the proteins by adding extract containing isotope internal standards, and the supernatant was diluted and tested. The supernatant was analyzed by a CNW Shell C18 (2.1*100 mm, 2.6 μm) column and eluted with a gradient mobile phase containing formic acid-acetonitrile and formic acid-ammonium acetate-water. The method was established using LC-MS/MS under MRM mode and positive ESI+ mode. The concentration of the sample was quantified by the addition of matrix matching standards and internal standards. The results indicated that the calibration calibration curves were linear (r2 > 0.995) in the range of 0.1 ~ 10 μg/mL for VRC, VNO, ICZ and HICZ, 0.2 ~ 20 μg/mL for PCZ, 0.5 ~ 50 μg/mL for FCZ and 0.2 ~ 20 μg/mL for CPF. The accuracy was between 91% ~ 115%. The intra-day and inter-day coefficient of variation (CV) were lower than 15%. The deviation of mixed matrix effect was between -1.15% ~ 2.23%. The method is simple and has a high accuracy and good stability. It is suitable for the clinical monitoring of the concentration of the 7 antifungal drugs and metabolites in human serum.
Key words: antifungal drugs; therapeutic durg monitoring; serum; high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS)
引用本文：阎娜，于晓燕，陈武炼. 高效液相色谱-串联质谱法测定人血清中5种抗真菌药物及相关代谢产物的测量方法[J]. 化学试剂, 2023, 45(3):126-131.
刺梨果汁类产品品质分析与综合评价
王红林1，解璞1，尚雪英1，王梦柳2，宁祎2，罗会1，陈健*2
（1.贵州省农业科学院果树科学研究所，贵州 贵阳 550006；2.贵州省六盘水市农业科学研究院，贵州 六盘水 553001）
摘要：建立刺梨果汁类产品品质综合评价体系，为贵州刺梨加工产品推广宣传提供参考。以贵州不同地区生产的14份刺梨果汁产品为试材，测定了包含可溶性固形物、蛋白质、可溶性糖及可滴定酸在内的基础品质指标，以及6种有机酸和超氧化物歧化酶（Superoxide Dismutase, SOD）、类黄酮和总酚3种活性物质含量，对21个品质指标进行相关性、主成分分析及系统聚类。综合21个指标分析共获得4个主成分，累积贡献率达92.77%，包含了所检品质中绝大部分指标信息，建立了刺梨类果汁产品品质综合评价模型为F = 0.640×F1 + 0.142×F2 + 0.090×F3 + 0.056×F4；在类间距离为18时，14份供试样品被聚为3类，第1类聚集了7份样品，其抗坏血酸、活性物质SOD、类黄酮和总酚以及元素含量较高，糖含量较低；第2类仅有1份样品，但其活性物质、可滴定酸和可溶性蛋白质含量最高；第3类聚集了其余6份样品，特点是固酸比、糖酸比较高，其余指标排名较为靠后。14份样品综合品质由高到低依次为：YPC > JHJ > YGT > YAJ > YGW > YSY> YSC > YPT > JPY > JPL > JPS >JGS > JSQ >JSJ。
关键词：刺梨果汁；品质指标；主成分分析；相关性分析；聚类分析
中图分类号： 文献标识码：A 文章编号：0258-3283（2023）--
DOI：10.13822/j.cnki.hxsj.2022.0820
Quality analysis and comprehensive evaluation of Rosa Roxburghii Tratt. juices WANG Hong-lin1, XIE Pu1, SHANG Xue-ying1, WANG Meng-liu2, NING Yi2, LUO Hui1, CHEN Jian*2 (1. Institute of Pomology, Guizhou Academy of Agricultural Sciences, Guiyang 550006, China; 2. Liupanshui Academy of Agricultural Sciences, Liupanshui 553001, China)
Abstract: To provide reference for promotion and publicity, establish a comprehensive evaluation system for the juice quality of Rosa roxburghii Tratt. The basis of quality indexes, including soluble solids, protein, soluble sugar and titratable acid, and 6 kinds of organic acids and 3 kinds of active materials (superoxide dismutase, flavonoids and total phenols), were determined. The principal component analysis, correlation analysis and systematic clustering of 21 quality indexes were carried out. The results showed that, by principal component analysis, four principal components were obtained, and the cumulative contribution rate reached 92.77%. The comprehensive evaluation model was established as F = 0.640×F1 + 0.142×F2 + 0.090×F3 + 0.056×F4. In addition, the 14 Samples were grouped into three categories when the interclass distance was 18. Furthermore, category I contained 7 samples, which had higher content of ascorbic acid, SOD, flavonoids, total phenols and elements, but lower content of sugar. The second type had only one sample, but its active substance, titratable acid and soluble protein content was the highest.The remaining 6 samples were clustered in category Ⅲ, characterized by high solid-acid ratio and high sugar-acid ratio, however, the other indexes were ranked relatively low. Based on the comprehensive quality score, the ranking of the 14 samples was: YPC > JHJ > YGT > YAJ > YGW > YSY> YSC > YPT > JPY > JPL > JPS >JGS > JSQ >JSJ.
Key words: juice of Rosa roxburghii Tratt.; quality indexes; principal component analysis; correlation analysis; clustering analysis
引用本文：王红林, 解璞, 尚雪英, 等. 刺梨果汁类产品品质分析与综合评价[J]. 化学试剂, 2023, 45(3): 132-140。
有机磷农药检测方法研究及进展
王志刚*，费荣杰
（南京化学试剂股份有限公司，江苏 南京 210047）
摘要：有机磷农药（Organophosphorus pesticides，OPPs）是蔬菜水果中检出率最高、危害最严重的化学性残留危害物之一，世界各国对其最大残留限量都做了严格规定。检测技术是有机磷农残监管的关键环节，目前OPPs残留检测主要是色谱法或色谱-质谱联用法，用于快速初筛的快速检测方法尚且有限，OPPs的多残留快速检测技术仍是当前农残快速检测领域的急需技术，但是准确性和抗干扰能力等关键问题尚需研究解决。综述了常见的有机磷农残快速检测方法，分析了它们的主要特点和适用领域，讨论了当前的主要问题，并展望了OPPs快速检测方法的发展方向和前景。
关键字：有机磷农药；最大残留限量；快速检测方法；食品安全；色谱法；多残留免疫分析
中图分类号：O657 文献标识码：A 文章编号：0258-3283（2023）--
DOI：10.13822/j.cnki.hxsj.2023.0036
Research progress of organophosphorus pesticide detection methods WANG Zhi-gang*, FEI Rong-jie (Nanjing Chemical Reagent Co., Ltd., Nanjing 210047, China)
Abstract：Organophosphorus pesticides (OPPs) are one of the chemical residue hazards with the highest detection rate and the most serious harm in vegetables and fruits. Countries around the world have made strict regulations on their maximum residue limits, and the detection technology plays important roles in the supervision of organophosphorus pesticide residues. At present, the method of residue detection of OPPs is mainly chromatography or chromatography-mass spectrometry. The rapid detection methods used for rapid primary screening are still limited. The multi-residue rapid detection technology of OPPs is still an urgent technology in the field of rapid detection of pesticide residue. However, some key issues such as accuracy and anti-interference ability still need to be studied and solved. The common rapid detection methods of organophosphorus pesticide residues were summarized, their main characteristics and application fields were analyzed, the current main problems were discussed, and the development direction and prospects of OPPs rapid detection methods were look forward.
Key words：organophosphorus pesticide; maximum residue limit; rapid detection method; food safety; chromatography; multiresidue immunoassay
引用本文：王志刚, 费荣杰. 有机磷农药检测方法研究与进展[J]. 化学试剂, 2023, 45（3）：141-147.
【合成与工艺技术】
氯铝酸盐离子液体催化二叔丁基蒽的合成研究
武虎建1，王琪1，张晓昕2，王涛*1
（1. 北京化工大学 化学学院，北京 100029；2. 中国石油化工股份有限公司 石油化工科学研究院，北京 100083）
摘要：为将离子液体代替三氟乙酸制备二叔丁基蒽，设计合成了2种Bronsted酸性离子液体与3种Lewis酸性氯铝酸盐离子液体，并将其用于蒽与叔丁醇的烷基化反应。研究发现，Bronsted酸性离子液体无催化活性，在L酸性离子液体存在时反应可以快速进行，且通过控制[Et3NH][Al2Cl7]离子液体用量得到了目标产物二叔丁基蒽，并采用单因素实验进行工艺优化，在最佳工艺条件下，蒽的转化率为99.5%，二叔丁基蒽的产率为94.1%，反应效果明显好于三氟乙酸，为工业化应用提供了新思路。
关键词：离子液体；蒽；叔丁醇；烷基化；二叔丁基蒽
中图分类号： 文献标识码：A 文章编号：0258-3283（2023）--
DOI：10.13822/j.cnki.hxsj.2022.0810
Synthesis of Di-tert-butyl Anthracene Catalyzed by Aluminochloride Ionic Liquid WU Hu-jian1, WANG Qi1, ZHANG Xiao-xin2, WANG Tao*1 (1. School of Chemistry, Beijing University of Chemical Technology, Beijing 100029, China; 2. Research Institute of Petrochemical Science, China Petrochemical Corporation, Beijing 100083, China)
Abstract: In this study, two Bronsted acidic ionic liquids and three Lewis acidic aluminochloride ionic liquids were designed and synthesized. These ionic liquids instead of trifluoroacetic acid were used for the alkylation of anthracene with tert butyl alcohol. It was found that Bronsted acidic ionic liquids had no catalytic activity, but the reaction could be carried out quickly in the presence of aluminochloride ionic liquids. By controlling the amount of [Et3NH][Al2Cl7] ionic liquid, di-tert-butyl anthracene was prepared successfully. Under the optimal reaction conditions, the conversion rate of anthracene was 99.5%, the yield of di-tert-butyl anthracene was 94.1%. The good results from using these ionic liquids replace trifluoroacetic acid will provides a new idea for industrial application.
Key words: ionic liquid; anthracene; tert-butanol; alkylation; di-tert-butyl anthracene
引用本文：武虎建, 王琪, 张晓昕, 等. 氯铝酸盐离子液体催化二叔丁基蒽的合成研究[J]. 化学试剂, 2023, 45(3):148-153.
TMSN3/NfF：一种有机胺叠氮化试剂的制备和应用
石磊a，刘慧丽b，孙自强a，任德豪a，赵湲湲a，郑钧a，刘义*a
(烟台大学 a.化学化工学院；b.药学院，分子药理和药物评价教育部重点实验室, 山东 烟台 264006)
摘要：伯胺的重氮转移反应是制备有机叠氮化物的重要手段。高毒、易爆的金属叠氮化物（NaN3）一直是制备重氮转移试剂的必需原料。以安全性更高的TMSN3和NfF为原料，制备得到重叠转移试剂NfN3，进而开发出一种制备有机叠氮化合物的新方法。该TMSN3/NfF试剂制备有机叠氮的方法，具有良好的底物适用性、官能团兼容性和安全性，且放大至10克级规模，产率无明显下降。所有15个芳香胺、脂肪胺、氨基酸衍生底物都以60%～95%的收率得到了目标叠氮产物。
关键词：重氮转移反应；TMSN3；有机叠氮化物；制备；克级制备
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2022）--
DOI：10.13822/j.cnki.hxsj.2022.0795
TMSN3/NfF: Preparation and application of an organic amine azide reagent SHI Leia, LIU Hui-lib, SUN Zi-qianga, REN De-haoa, ZHAO Yuan-yuana, ZHENG Juna, LIU Yi*a (a. School of Chemistry and Chemical Engineering, b. Key Laboratory of Molecular Pharmacology and Drug Evaluation, Ministry of Education, College of medicine, Yantai University, Yantai 264005, China)
Abstract: Diazo-transfer reaction of primary amine is an important synthetic tool for the preparation of organic azides. The highly toxic and explosive metal azide (NaN3) is a necessary raw material for the preparation of almost all diazo transfer reagents. Therefore, a new method was developed for the preparation of organic azide compounds by preparation of diazo-transfer reagent NfN3 from comparatively safe azide source TMSN3 and NfF. This diazo transfer reaction showed wide substrate applicability, good functional group compatibility, safety and facile scalability. All 15 aromatic amines, aliphatic amine, and amino acid-derived substrates were transformed to desired azides in 60%～95% yields.
Key words：diazo-transfer reaction; TMSN3; synthesis; gram-scale
引用本文：石磊，刘慧丽，孙自强，等. TMSN3/NfF：一种有机胺叠氮化试剂的制备和应用[J]. 化学试剂, 2022, 45(3): 154-159。
阿伐那非合成中的工艺杂质分析
孙允凯*1,2，赵梦梦2，吴小霞2,3，禹曾达3，刘钊3
(1. 常州工学院 化工与材料学院，江苏 常州 213032；2. 南华大学 化学化工学院，湖南 衡阳 421001；3. 嘉实（湖南）医药科技有限公司，湖南 长沙 410220)
摘要：作为治疗勃起功能障碍的有效药物，阿伐那非在国内已有药企获批生产，但国内外药典并没有具体方法可用于评估。根据阿伐那非的原研路线，研究了合成过程中的四种工艺杂质（Imp-A，Imp-B，Imp-C，Imp-D），利用超高效液相色谱（UPLC）、液质联用（LC-MS）、核磁共振（NMR）、元素分析（EA）等手段，分析了杂质的结构，结合合成路线，推断出杂质来源。通过有机合成的方式，制备出对应的四种杂质，验证了推理的正确性。该研究为后续建立阿伐那非原料药的评估和质量控制提供有力参考。
关键词：阿伐那非；工艺杂质；合成；分析
中图分类号：O621.3 文献标识码：A 文章编号：0258-3283（2022）--
DOI：10.13822/j.cnki.hxsj.2022.0790
Analysis of process impurities in the synthesis of avanafil SUN Yun-kai*1,2, ZHAO Meng-meng2, WU Xiao-xia2,3, YU Zeng-da3, LIU Zhao3 (1. School of Chemical Engineering and Materials, Changzhou Institute of Technology, Changzhou 213022, China; 2. School of Chemistry and Chemical Engineering, University of South China, Hengyang 421001, China; 3. Harvest Pharmaceutical Co., Ltd, Changsha 410000, China)
Abstract: Avanafil, as an effective drug for the treatment of erectile dysfunction, has been approved for production in China, but there is no specific method for evaluation in domestic and foreign pharmacopoeia. According to the original research route of avanafil, four kinds of process impurities (IMP-A, IMP-B, IMP-C, IMP-D) were studied. The structures of impurities were analyzed by ultra-high performance liquid chromatography (UPLC), liquid chromatography-mass spectrophotometry (LC-MS), nuclear magnetic resonance (NMR), elemental analysis (EA) and other means, and the source of the impurities were inferred combined with the synthetic route. The corresponding four kinds of impurities were prepared by means of organic synthesis, which verified the correctness of the reasoning. This study provides a strong support for the subsequent establishment of evaluation and quality control for avanafil.
Key words: avanafil; process impurity; synthesis; analysis
引用本文：孙允凯，赵梦梦，吴小霞，等. 阿伐那非合成中的工艺杂质分析[J]. 化学试剂, 2023, 44(3): 160-166。
