有机磷农药中毒患者体内有机磷检测研究进展
沙鸥*1a，姚佳伟1b，许丽2，陈晓兵2，朱雨情1b，刘华1a
（1.江苏海洋大学 a.化学工程学院，b.药学院，江苏 连云港 222005；
2.连云港第一人民医院，江苏 连云港 222005；）
摘要：有机磷农药是全球最广泛使用的农药之一，每年因有机磷中毒的患者达数十万。然而，中毒患者体液基质复杂且有机磷农药含量低，因此选取合适的前处理方法与现代分析仪器联用对有机磷中毒患者体内药物浓度进行检测，一直是临床诊疗中亟需解决的关键问题。综述了临床诊疗中常见有机磷农药的分类、危害，以及国内外文献报道的中毒患者体液中有机磷农药的前处理和检测方法，同时对有机磷样品前处理以及检测方法分别进行了优缺点对比，以期为临床中毒患者快速确定血药浓度的方法改进提供思路。
关键词：有机磷农药；检测；前处理；有机磷中毒
中图分类号：R595.4 文献标识码：A
Research Progress on Organophosphorus Detection in Patients with Common Organophosphorus Pesticide Poisoning in Diagnosis SHA Ou*1a, YAO Jia-wei1b, XU Li2, CHEN Xiao-bing2, ZHU Yu-qing1b, LIU Hua1a（1.a.School of Chemistry and Chemical Engineering, b.School of Pharmacy, Jiangsu Ocean University, Lianyungang 222005, Jiangsu China; 2. The First People’s Hospital of Lianyungang City, Lianyungang 222005, Jiangsu China;)
Abstract：Organophosphorus pesticides (OPPs) are one of the most widely used pesticides in the world, with hundreds of thousands of patients suffering from organophosphorus poisoning every year. Because of complex humoral matrix and low concentration of organophosphorus pesticides residue, it is critical to develop an appropriate pretreatment method combined with analytical instrument to detect the pesticide concentration in patients. This review presents the classifications and hazards of common clinical OPPs, as well as the pretreatment and determination methods of OPPs in serum and whole blood reported in domestic and international literatures. At the same time, the advantages and disadvantages of different detection methods and pre-processing methods are compared. These results could provide guidance for the development of rapid determination of blood concentration in clinical OPP-poisoned patients in the future.
Key words: organophosphorous pesticide; determination; pretreatment methods; organophosphate poisoning
引用本文：沙鸥，姚佳伟，许丽，等.有机磷农药中毒患者体内有机磷检测研究进展[J].化学试剂，2021,43（7）:857-864.
CeO2负载RhCu纳米催化剂的制备及其催化氨硼烷水解性能的研究
郭亚君，刘林昌，朱红林*
（宁波大学 材料科学与化学工程学院 化学合成与绿色应用研究所，浙江 宁波 315211）
摘要：氨硼烷被认为是一种理想的储氢材料，由于氨硼烷本身不仅稳定无毒，还具有较高的氢含量，因此关于氨硼烷水解析氢研究引起广泛关注。选择在CeO2载体上原位还原制备一系列RhCu/CeO2双金属催化剂，并通过XRD、SEM、EDS、XPS、TEM、ICP-OES等测试方法表征催化剂的组成及结构，并在298K条件下作为氨硼烷水解的催化剂进行了测试。结果表明，当n(Rh) :n (Cu)=3 : 1时，制备的双金属催化剂Rh1.5Cu0.5/CeO2对氨硼烷水解析氢表现出最高的催化活性，反应的活化能Ea低至31.97 kJ/mol，转化效率TOF值为300.48 min-1，这说明双金属合金催化剂在氨硼烷水解析氢方面具有潜在的应用前景。
关键词：氨硼烷、产氢、 二氧化铈、催化反应
中图分类号：O643 文献标识码：A
Preparation and catalytic performance for ammonia borane hydrolysis of CeO2 Supported RhCu Nanocatalyst GUO Ya-jun, LIU Lin-chang, ZHU Hong-lin* ( Insitute of Chemical Synthesis and Green Applications, College of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, China)
Abstract: Ammonia borane (AB) has been regarded as an ideal hydrogen storage material due to its stability, non-toxicity and high hydrogen content, which has attracted tremendous attention from the application of hydrolysis dehydrogenation of AB. In this work, a series of RhCu/CeO2 bimetallic catalysts were successfully synthesized by in-situ reduction on CeO2 support. RhCu/CeO2 are characterized using the XRD, SEM, EDS, XPS, TEM, and ICP-OES techniques and tested as catalysts for the hydrolysis of ammonia borane at 298 K. At the ratio of Rh/Cu of 3:1, the bimetallic Rh1.5Cu0.5/CeO2 catalyst showed the highest catalytic activity. The activation energy (Ea) is 31.97 kJ mol-1, and the turnover frequency (TOF) is 300.48 min-1, rendering the bimetallic Rh1.5Cu0.5/CeO2 to be promising catalyst practical applications for the generation of hydrogen from AB.
Key words：ammonia borane, H2 generation, CeO2, catalytic reaction
引用本文：郭亚君，刘林昌，朱红林. CeO2负载RhCu纳米催化剂的制备及其催化氨硼烷水解性能的研究[J].化学试剂，2021，43（7）：865-871.
霉酚酸钠和吗替麦考酚酯与人血清蛋白相互作用机制的比较研究
马晓莉*1，马坚*2，刘春晖1，江志波1，李潇1,3
（1. 北方民族大学 化学与化学工程学院，宁夏 银川 750021；2. 宁夏医科大学总医院，宁夏 银川 750002；3. 四川大学 生物治疗国家重点实验室，四川 成都 610041）
摘要：利用荧光光谱法和分子对接比较研究了新型免疫抑制剂霉酚酸的两个前药吗替麦考酚酯和霉酚酸钠与人血清蛋白（HSA）相互作用。结果表明两种药物与HSA之间以1∶1结合形成复合物，猝灭机制均为静态猝灭。不同温度下荧光猝灭实验计算了结合参数，结果显示两种药物对HSA均有猝灭，且霉酚酸钠猝灭更为显著。三维和同步荧光结果表明两个药物单体的加入均对HSA的构象产生了影响。分子对接结果显示配体和蛋白间有氢键生成，结合热力学结果说明药物与HSA之间的相互作用力主要是氢键和范德华力，且霉酚酸钠的结合能力更强。综上结果表明霉酚酸钠能更好的结合HSA从而在体内运转和代谢的更快。相关研究工作不仅从分子层面阐明了两种药物单体与蛋白的结合机制，而且可为免疫抑制剂类药物的临床用药选择提供一定的理论依据。
关键词：人血清蛋白（HSA）；霉酚酸钠（MPS）；吗替麦考酚酯（MMF）；相互作用
中图分类号：O657.3 文献标识码：A
Comparative Study on the Interaction Mechanism of Mycophenolate Sodium and Mycophenolate Mofetil with Human Serum Albumin MA Xiao-li*1, MA Jian*2, LIU Chun-hui1, JIANG Zhi-bo1, LI Xiao1,3 (1. School of Chemistry and Chemical Engineering, North Minzu University, Yinchuan 750021, China; 2. General Hospital of Ningxia Medical University, Yinchuan 750002, China; 3. State Key Laboratory of Biotherapy, Sichuan University, Chengdu 610041, China), Huaxue Shiji, 2021
Abstract：This study evaluated the interaction between mycophenolate mofetil (MMF) and sodium mycophenolate (MPS) with human serum albumin (HSA) using fluorescence spectrometry and docking simulation. Results revealed that complexes were formed between MMF/MPS and HSA, and the quenching mechanism was static quenching. The binding parameters calculated at different temperatures showed MPS had stronger capability than MMF to quench the fluorescence of HSA. Furthermore, three-dimensional and simultaneous fluorescence spectra indicated that the conformation of HSA was changed with the addition of drug monomers. In addition, the acting forces for the binding were hydrogen bonds and van der Waals forces through molecular docking simulation and thermodynamic parameters. All the above results showed that MPS was the stronger quencher and bound to HSA with higher affinity than MMF, therefore it can be better transferred and metabolized in body system. The mechanism of MPS/MMF-HSA interaction has been elucidated, which provides valuable theoretical basis for the clinical use of immunosuppressive drugs.
Key words: human serum albumin (HSA); mycophenolate mofetil (MMF); sodium mycophenolate (MPS); interaction
引用本文：马晓莉，马坚，刘春晖，等. 霉酚酸钠和吗替麦考酚酯与人血清蛋白相互作用机制的比较研究[J]. 化学试剂，2021，43（7）：872-877.
基于网络药理学分析金英黄归汤治疗乳腺炎的作用机制
彭俊超a,b，杨会a,b，何绪华a，蔡亚玲a,b，廖加美a,b，龙利a,b，王鲁*a,b
（贵州大学 a.药学院，b.西南特色药用生物资源开发利用教育部工程研究中心，贵州 贵阳 550025）
摘要：构建金英黄归汤干预乳腺炎的“中药-活性成分-靶点-炎症通路”网络关系，预测其治疗乳腺炎的靶点及机制。方法：采用网络药理学方法。通过数据库收集金英黄归汤中化合物，以口服利用度（OB）和类药性（DL）作为限定条件筛选活性成分，收集其作用靶点，并应用Cytoscape软件拓补分析主要靶点，利用GeneCards等数据库获取乳腺炎疾病靶点，应用韦恩分析获取活性成分治疗乳腺炎的交集靶点；STRING数据库构建交集靶点之间的交互网络，利用DAVID数据库对作用的乳腺炎靶点进行GO和KEGG通路富集，最后构建“活性成分-靶点-炎症通路-疾病”网络。金英黄归汤中满足筛选条件的活性成分有62个，相对应的预测靶点有229个，主要靶点144个，乳腺炎疾病靶点有139个，金英黄归汤活性成分作用乳腺炎的靶点有23个，其通过调控Toll样受体（TLR）、TNF、NF-κB以及NOD样受体（NLRs）信号通路来治疗乳腺炎。金英黄归汤针对乳腺炎的药理作用是通过多成分、多靶点、多途径进行，这将为深入研究药效物质基础和作用机制提供理论指导。
关键词：金英黄归汤；网络药理学；活性成分；靶点；乳腺炎
中图分类号：R285.5 文献标识码：A
Analysis of the Mechanism of JinyingHuanggui Decoction in the Treatment of Mastitis Based on Network Pharmacology Peng Jun-chaoa,b, Yang Huia,b, He Xu-huaa, Cai Ya-linga,b, Liao Jia-meia,b, Long Lia,b, Wang Lu*a,b (a.School of Pharmacy, b. Engineering Research Center of the Ministry of Education for the Development and Utilization of Southwestern Featured Medicinal Biological Resources, Guizhou University, Guiyang 550025, China), Huaxue Shiji
Abstract: Network pharmacology method was used to construct a network of "Traditional Chinese Medicine-Active Ingredients-Targets-Inflammatory Pathway" for JinyingHuanggui Decoction to interfere with mastitis, and to predict its targets and mechanisms in the treatment of mastitis. We collected compounds in JinyingHuanggui Decoction in the database, screened the active ingredients with oralavailability (OB) and drug-like properties (DL) as limited conditions, collected their targets, and used Cytoscape software to top up and analyzed the main targets. GeneCards and other databases were used to obtain mastitis disease targets.Wayne analysis was used to obtain the intersection targets of active ingredients for the treatment of mastitis. We used STRING database to construct an interactive network between the intersection targets, used DAVID database to perform GO and KEGG on the active mastitis targets enrichment of pathways, and finally built a network of "active ingredients-targets-inflammatory pathways-disease". Results were as follows: there are 62 active ingredients in JinyingHuanggui Decoction that meet the screening conditions, 229 corresponding prediction targets, 144 main targets, 139 mastitis disease targets, and JinyingHuanggui Tang active ingredients. There are 23 targets for mastitis, which can treat mastitis by regulating Toll-like receptor (TLR), TNF, NF-κB and NOD-like receptors (NLRs) signaling pathways. The pharmacological action of JinyingHuanggui Decoction against mastitis was carried out through multiple components, multiple targets, and multiple pathways, which provided theoretical guidance for in-depth research on the material basis and action mechanism.
Key words: JinYingHuanggui Decoction; Network Pharmacology; Active Ingredient; Target; Mastitis
引用本文：彭俊超, 杨会, 何绪华, 等. 基于网络药理学分析金英黄归汤治疗乳腺炎的作用机制[J]. 化学试剂.2021，43（7）：878-883.
不同pH值下表面活性剂对污泥脱水性能影响的研究
刘说*，何萍，张京京
(营口理工学院 化学与环境工程学院，辽宁 营口 115014)
摘要：通过测定比阻、滤饼含水率、污泥胞外聚合物（EPS）中蛋白质和多糖、污泥沉降体积和污泥毛细吸水时间（CST），研究不同pH值下表面活性剂对污泥脱水性能的影响，采用十二烷基硫酸钠（SDS）作为表面活性剂，在不同pH值下对污泥脱水性能进行了研究。考察了调理污泥的脱水速率、脱水程度、沉降性和滤失性四个方面。结果表明，在原污泥20g、SDS投加量为污泥干重8%、用浓硫酸调节溶液pH 3的条件下，比阻0.44×109 m/kg、滤饼含水率65.10%、污泥胞外聚合物中蛋白质526.2 mg/g和多糖87.7 mg/g、污泥沉降体积55.4 mL和污泥毛细吸水时间80 s，污泥脱水效果较好。
关键词：污泥；表面活性剂；脱水性能；pH值；调理
中图分类号：X705 文献标识码：A 文章编号：0258-3283（2021）--
Effect of Surfactants on Sludge Dewatering Performance under Different pH Values LIU Shuo*, HE Ping, ZHANG Jing-jing (College of Chemistry and Environmental Engineering, Yingkou Institute of Technology, Yingkou 115014, China), Huaxue Shiji, 43(7), ～
Abstract: The effects of pH values on the dewatering performance of sludge were studied by measuring the specific resistance, the moisture content of filter cake, protein and polysaccharide in sludge extracellular polymer (EPS), sludge settling volume, and sludge capillary water absorption time (CST).Sodium dodecyl sulfate was used as surfactant to study the sludge dewatering performance under different pH values. The dewatering rate, dehydration degree, sedimentation and filtration of the conditioning sludge were investigated. The original sludge was 20 g, the dosage of SDS was 8% of sludge dry weight, and solution of pH 3 was adjusted by concentrated sulfuric acid. The results showed that the specific resistance was 0.44×109 m/kg, the moisture content of filter cake was 65.10%, protein and polysaccharide in EPS were 526.2 mg/g and 87.7 mg/g, sludge settling volume was 55.4 mL, and sludge capillary water absorption time was 80 s resulted the best sludge dewatering performance.
Key words: sludge; surfactant; dewatering performance; pH value; conditioning
引用本文：刘说, 何萍, 张京京, 等. 不同pH值下表面活性剂对污泥脱水性能影响的研究[J]. 化学试剂, 2021, 43(7): 884-888.
基于纳米混悬技术的黄芩素制剂研究
严红梅，祁秀秀*，秦海芳
（常州工程职业技术学院 化工与制药工程学院，江苏 常州 213164)
摘要：采用高压均质法制备黄芩素纳米混悬剂（BA-NS），以粒径及其分布作为评价指标，通过星点设计-效应面法优化BA-NS的处方为：黄芩素浓度是3.92 g/L、磷脂浓度是1.13 g/L、波洛沙姆浓度是1.04 g/L。体外溶出试验表明，将黄芩素制备成纳米混悬剂可有效改善其溶解性；以浓度为5%的甘露醇作为保护剂，冷冻干燥制备得到的BA-NS冻干粉，能显著提高制剂的稳定性。
关键词：黄芩素；纳米混悬剂；溶解性；冻干粉；稳定性
中图分类号：R944 文献标识码：A
Evaluation on thePreparation Process of Baicalein Nanosuspensions YAN Hong-mei, QI Xiu-xiu*，QIN Hai-fang (College of Chemical and Pharmaceutical Engineering ,Changzhou Vocational Institute of Engineering, Changzhou 213164, China)
Abstract: The baicalein nanosuspensions (BA-NS) were prepared using high-pressure homogenization method to improve the solubility of baicalein. The average particle size and polydispersity index (PDI) were used as the indexes to determine the single factor. By optimizing the formulation parameters using central composite design-response surface methodology, the optimal prescription was obtained: the concentrations of baicalein, phospholipid and poloxamer were 3.92, 1.13, 1.04 g/L, respectively. The apparent solubility and dissolution test in vitro showed that the BA-NS can effectively improve the solubility of BA. Then the BA-NS was freeze-dried assisted with 5% mannitol as the cryoprotectants to improve the stability. The stability test confirmed that freeze-dried powder had improved stability compared with the liquid of BA-NS.
Key words: baicalein; nanosuspensions; solubility; freeze-dried powder; stability
引用本文：严红梅，祁秀秀，秦海芳. 基于纳米混悬技术的黄芩素制剂研究[J]. 化学试剂, 2021, 43(7):889-894.
QSAR建模及其在抗病毒药物设计与筛选中的研究进展
陈硕，李非凡，孙国辉*，赵丽娇，钟儒刚
（北京工业大学 环境与生命学部 环境与病毒肿瘤学北京市重点实验室，北京 100124）
摘要：新药研发往往是一件过程漫长且人力物力投入极大的事情。随着日益严重的环境污染问题对人类生命健康形成的挑战，快速研发高效低毒的药物成为当务之急。定量构效关系（QSAR）在历经几十年的发展后，广泛应用于药物科学领域中，作为药物筛选及其生物活性预测的高效工具，在药物活性、毒性和渗透性预测以及作用机制等研究中发挥重要作用。重点介绍了QSAR建模过程及其近年来在抗病毒药物设计与筛选中的研究进展，并对现阶段QSAR应用的局限性问题进行了分析，展望了其未来的发展方向。
关键词：定量构效关系；抗病毒药物设计；新型冠状病毒；肝炎病毒；人类免疫缺陷病毒
中图分类号：R99 文献标识码：A 文章编号：
QSAR Modeling and Its Advances in Antiviral Drug Design and Screening CHEN Shuo, LI Fei-fan, SUN Guo-hui*, ZHAO Li-jiao, ZHONG Ru-gang (Beijing Key Laboratory of Environmental and Viral Oncology, Faculty of Environment and Life, Beijing University of Technology, Beijing 100124, China)
Abstract: The development of new drugs is very time-consuming, labor-intensive and costly. With the environmental pollution, human life health issues becoming more and more severe, rapid development of highly effective and low-toxic drugs has become an urgent task. In the past few decades, quantitative structure -activity relationship(QSAR) modeling has been widely used in the field of pharmaceutical sciences, this method can be used as an efficient tool for drug screening and biological activity prediction, and plays an important role in drug activity prediction, toxicity prediction, drug permeability prediction, mechanism study of action, and so on. In this paper, we highlighted the progresses of recent researches on the QSAR modeling process and its recent advances in antiviral drug design, and we also analyzed the limitations of QSAR applications at this stage, as well as perspectives of its future development.
Keywords: quantitative structure-activity relationship(QSAR);anti-viral drug design; SARD-CoV-2; hepatitis virus; HIV
引用本文: 陈硕，李非凡，孙国辉，等.QSAR建模及其在抗病毒药物设计与筛选中的研究进展[J].化学试剂，2021,43（7）：895-905.
五环三萜类化合物的口服吸收与代谢研究进展
班玉娟1,陈瑞2,张宇1,张丽2,刘婉霞1,朱高峰2,汤磊*1,2
（1.贵州医科大学 药学院，贵州 贵阳550004；2.贵州省化学合成药物研发利用工程技术研究中心，贵州 贵阳 550004）
摘要：五环三萜类化合物在自然界中分布广泛、资源丰富，我国多种传统中草药如甘草、柴胡、远志、人参、三七、白头翁和积雪草等皆含有五环三萜类化合物，且大量研究表明该类化合物是上述中草药的有效成分之一。国内外研究者发现五环三萜类化合物具有多种优良的药理活性，如抗肿瘤、抗糖尿病、抗炎、抗菌和抗病毒等，但由于其口服生物利用度偏低，极大地影响了进一步的开发及在临床上的应用。药物的吸收与代谢对生物利用度和药效的影响很大。因此，就近年来国内外有关五环三萜类化合物的口服吸收特征以及体内外代谢途径研究工作进行综述，以期对该类化合物的进一步研究及开发利用提供参考。
关键词：五环三萜；生物利用度；吸收；代谢；细胞色素P450
中图分类号：R969 文献标识码：A
Advances in studies on oral absorption and metabolism of pentacyclic triterpenoids BAN Yu-juan1, CHEN Rui2, ZHANG Yu1, ZHANG Li2, LIU Wan-xia1, ZHU Gao-feng2, TANG Lei*1,2(1.School of Pharmacy, Guizhou Medical University, Guiyang 550004, China Guizhou; 2.Provincial Engineering Technology Research Center for Chemical Drug R&D, Guiyang 550004, China）
Abstract: Pentacyclic triterpenoids, having abundant resources, are widely distributed in nature. Many traditional Chinese herbal medicines such as Licorice, Bupleurum, Polygala, ginseng, notoginseng, Pulsatilla, and Centellaasiatica contain Pentacyclic triterpenoids, and a large number of studies have shown that such compounds are the main effective ingredients in these Chinese herbal medicines. Researchers found that these compounds have a variety of excellent pharmacological activities such as anti-tumor, anti-diabetes, anti-inflammatory, antibacterial and anti-viral. However, due to their low oral bio-availability, further clinical applications of this kind of compounds have been greatly restrained. The absorption and metabolism of drugs greatly influence on its bio-availability and efficacy, so this article aims to review the studies on the oral absorption characteristics and metabolic pathways of pentacyclic triterpenes in vitro and in vivo in recent years, and to give a reference for further research and development of this kind of compounds.
Key words: pentacyclic triterpenes; bioavailability; absorption; metabolism; cytochrome P450
引用本文：班玉娟,陈瑞,张宇，等.五环三萜类化合物的口服吸收与代谢研究进展[J].化学试剂，2021,43（7）：906-916.
适配体AS1411功能化纳米材料的合成和生物应用进展
杜悦溶1，爱军*1, 2
（1. 内蒙古师范大学 化学与环境科学学院，内蒙古 呼和浩特 010022; 2. 内蒙古自治区环境化学重点实验室，内蒙古 呼和浩特 010022）
摘要：纳米技术的发展，给一些重大疾病的诊断和治疗提供了新方法，人们发现利用寡核苷酸可以靶向各种癌蛋白。AS1411是一种富含26个碱基的鸟嘌呤寡核苷酸，可形成稳定的二聚G-四链体结构。由于它的特异性高、亲和力强、免疫原性小，不仅可以特异性结合癌细胞上过度表达的靶核仁素受体，还可以和其他卟啉类衍生物特异性结合，有望用于肿瘤治疗及诊断，目前在II期临床试验中评估为抗癌药。结合近几年国内外学者的相关研究，对AS1411功能化纳米材料的合成与在生物领域的应用进展进行了综述。
关键词：AS1411；纳米材料；癌症；药物
中图分类号:O65 文献标识码:A
Progress in the Synthesis and Biological Applications of AptamerAS1411-functionalized Nanomaterials DU Yue-rong1, AI Jun*1,2 (1.College of Chemistry and Environmental Science, Inner Mongolia Normal University, 010022, Hohhot 2. Inner Mongolia Key Lab of Environmental Chemistry, Inner Mongolia Normal University, 010022, Hohhot)
Abstract：The development of nanotechnology has provided new methods for the diagnosis and treatment of some major diseases. It has been found that oligonucleotides can be used to target various cancer proteins. AS1411 is a 26-base guanine oligonucleotide that can form a stable dimeric G-quadruplex structure. Because of its high specificity, strong affinity, and low immunogenicity, it can realize specifical bindings to the target nucleolin receptor overexpressed on cancer cells, and to other porphyrin derivatives. Therefore, it is of great promisefor tumor treatment and diagnosis, and currently being evaluated as an anticancer drug in phase II clinical trials.
In this paper, the synthesis and applications of AS1411-functionalized nanomaterials are reviewed with respect to the current related researches from domestic and international scholars.
Key words：AS1411; nanomaterials; cancer; drug
引用本文：适配体AS1411功能化纳米材料的合成和生物应用进展[J].杜悦溶,爱军.化学试剂，2021,43（7）：917-924.
锰基催化剂在脱硝反应中的研究进展
任婉婷1，魏远航1，张庭基1，吴英含1，张卓夫1，宋忠贤2，张学军*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：低温脱硝催化剂近些年成为研究重点，锰基催化剂因其优异的低温性能在脱硝领域被广泛应用。为研究MnOx基低温脱硝催化剂的催化活性与抗中毒性能，综述了纯MnOx、过渡金属掺杂MnOx、和锰基分子筛在脱硝反应中的应用进展，综合比较了MnOx基催化剂抗中毒等性能，发现过渡金属掺杂MnOx和锰基分子筛这两类催化剂具备较好的催化性能和使用寿命。进一步对锰基催化剂的优缺点进行了分析，阐述了锰基催化剂是低温脱硝技术未来的发展方向，为低温脱硝技术奠定了理论基础。
关键词：锰基催化剂；脱硝；中毒机制；分子筛
中国分类号：X511 文献标识码:A
Research progress of MnOx-based catalysts in the selective catalytic reduction of NO by NH3 REN Wan-ting1, WEI Yuan-hang1,ZHANG Ting-ji1, WU Ying-han1, ZHANG Zhuo-fu1, SONG Zhong-xian2, ZHANG Xue-jun*1(1. School of Environmental and Safety Engineering, Shenyang University of Chemical Technology , Shenyang, 110142；2. School of municipal and environmental engineering, Henan University of urban construction, Pingdingshan, 467036)
Abstract：Low temperature denitrification catalysts have become one very hot research topic in recent years. Manganese-based catalysts have been widely used in the denitrification fields due to their excellent performance at low temperatures. In order to investigate the catalytic activity and poison resistance of MnOx-based catalysts at low temperatures, this review summarizes the recent research progresses on poison resistance and other properties of pure MnOx, transition metal-doped MnOx and manganese molecular sieve for the catalysis of denitrification reaction . The results indicated that transition metal-doped MnOx and Mn-based molecular sieve exhibited the excellent catalytic performance and service life. The advantages and disadvantages of Mn-based catalysts were further analyzed, and the low-temperature denitrification performance using Mn-based catalysts was provided for the guidance of future catalyst development, which lays a good theoretical foundation for the low-temperature denitrification technology.
Key words: manganese based catalyst; denitration; poisoning mechanism; molecular sieve
引用本文：任婉婷，魏远航，张庭基，等.锰基催化剂在脱硝反应中的研究进展[J].化学试剂，43（7）：925-929.
用于快速检测化妆品中重金属的样品前处理方法
张京1,2，薛雯蔚1，王颖1，朱海燕1，陈昌云*1
(1. 南京晓庄学院 环境科学学院，江苏 南京 211171；2. 徐州久强检测技术有限公司，江苏 徐州 221000)
摘要：通过以下几种前处理方案对化妆品中的重金属样品进行消解：1) 国标前处理：通过加硝酸和过氧化氢，静置过夜后在沸水浴中加热2 h，使化妆品中重金属被消解；2) 通过向样品中加入硝酸后在超声波作用下对化妆品样品进行快速消解；3) 通过向样品中加入硝酸和过氧化氢后在超声波作用下对化妆品样品进行快速消解；4) 通过在样品中加入王水、EDTA与离子液体在超声波作用下对化妆品样品进行快速消解。从准确度、消耗时间、回收率、精密度这4个指标着手，评价不同前处理方案。结果显示，采用超声辅助王水、离子液体消解法进行化妆品样品前处理时消耗的时间最短、回收率最高、精密度最好，是可用于快速检测防晒霜中铅含量测定的理想前处理方案。
关键词：离子液体；重金属；快速检测；前处理
中图分类号：O611.5 文献标识码：A
Sample Pretreatment Method for the Rapid Detection of Heavy Metals in Cosmetics ZHANG Jing1,2, XUE Wen-wei1, WANG Ying1, ZHU Hai-yan1,CHEN Chang-yun*1 (1. School of Environmental Science, Nanjing Xiaozhuang University, Nanjing 211171, China; 2. Xuzhou Joy Quality Testing Technology Co., Ltd., Xuzhou 221000, China), Huaxue Shiji, 2021, 43(7)
Abstract：Four typical pre-treatment procedures were used for the digestion of heavy metal in cosmetic samples: 1) Adding nitric acid and hydrogen peroxide, and let the mixture stand overnight heated in boiling water bath for 2 hours (GB pre-treatment). 2) Adding nitric acid under ultrasonication for rapid digestion. 3) Adding nitric acid and hydrogen peroxide under sonication for rapid digestion. 4) Adding aqua regia, EDTA, and ionic liquids under sonication for rapid digestion. Four indicators of accuracy, consumption time, recovery rate, and precision were used to evaluate different pre-treatment procedures. The results showed that the digestion method using ultrasonication, aqua regia, and ionic liquid obtained the shortest time, the highest recovery rate, and the best precision, which is an ideal pre-treatment method for the rapid detection of heavy metal like lead in sunscreen.
Key words: ionic liquid; heavy metal; rapid detection; pretreatment
引用本文：张京，薛雯蔚，王颖，等. 用于快速检测化妆品中重金属的样品前处理方法[J]. 化学试剂, 2021, 43(7): 930-935.
液态危废中总氟、总氯、总溴及总硫含量的测定
王晓军，梁炜耀，夏梦薇，杨瑛，周兰庭，肖娟，翟立红*
（湖北文理学院 基础医学院，湖北 襄阳 441053）
摘要：建立了液态危废中总氟、总氯、总溴及总硫含量的氧弹燃烧-离子色谱法快速测定的方法。液态危废种类多且成分复杂，采用充有高压氧气的氧弹可将其灼烧完全并且防止了目标物的挥发，灼烧后产生的挥发物在密闭体系中被一定比例的碳酸钠、碳酸氢钠及双氧水的混合吸收液充分吸收，转化为氟化物、氯化物、溴化物及硫酸盐，此吸收液进离子色谱仪可以同时将氟离子、氯离子、溴离子及硫酸根快速测出，通过计算可得到总氟、总氯、总溴及总硫的含量。试验表明，该方法中总氟、总氯、总溴及总硫的线性相关系数均高于0.999；方法的检出限分别为27.30、25.14、3.70、10.11 mg/kg；样品加标回收率均在93.64%～105.45%之间；RSD均在1.7%～3.1%之间。该方法操作简单、准确性高、精密度好，实现了液态危废中总氟、总氯、总溴及总硫含量的同步快速测定。
关键词：氧弹燃烧；离子色谱法；液态危废；总氟；总氯；总溴；总硫
中图分类号：TK6 文献标识码：A
Determination of Total Fluorine、Total Chlorine、Total Bromine and Total Sulfur in Liquid Hazardous Waste WANG Xiao-jun, LIANG Wei-yao, XIA Meng-wei, YANG ying, ZHOU Lan-ting, XIAO juan, ZHAI Li-hong* (School of Basic Medicine, Hubei University of Arts and Science, Xiangyang 441053, China), Huaxue Shiji, 2021, 43(7), ～
Abstract：A rapid determination method of total fluorine, total chlorine, total bromine, and total sulfur in liquid hazardous waste was established by using oxygen bomb combustion and ion chromatography techniques. The liquid hazardous waste in high pressure oxygen during oxygen bomb combustion could by completely burnt and the volatilization of the targets could be prevented. The volatiles produced after burning were fully absorbed by a certain proportion of sodium carbonate, sodium bicarbonate, and hydrogen peroxide in a sealed system and converted into fluoride, chloride, bromine, and sulfur. The content of total fluorine, total chlorine, total bromine, and total sulfur could be obtained by calculations. The results showed that the linear correlation coefficients were all higher than 0.999; the detection limits of the method for total fluorine,total chlorine,total bromine, total sulfur were 27.30, 25.14, 3.70, and 10.11 mg/kg; the recoveries of the method at different concentrations were all between 93.64% and 105.45%; the relative standard deviation (RSD) were all between 1.7% and 3.1%. This method was simple, accurate, and precise, it can realize simultaneous and rapid determination of total fluoride, total chlorine, total bromine and total sulfur in liquid hazardous wastes.
Key words: oxygen bomb combustion; ion chromatography; liquid hazardous waste; total fluorine; total chlorine; total bromine; total sulfur
引用本文：王晓军，梁炜耀，夏梦薇，等. 液态危废中总氟、总氯、总溴及总硫含量的测定[J].化学试剂，2021，43(7): 936-940.
基于特征肽的超高效液相色谱-串联质谱法测定复方胃蛋白酶颗粒的溶出度
杭宝建，巩丽萍*，陈晓，咸瑞卿，石峰*
（山东省食品药品检验研究院 山东省食品药品检验研究院国家药品监督管理局仿制药研究与评价重点实验室山东省仿制药一致性评价工程技术研究中心，山东 济南 250101）
摘要：建立以特征肽为指标的自身对照法测定复方胃蛋白酶颗粒中胃蛋白酶溶出度的方法。选择多肽GTIGIGTPAQDF作为胃蛋白酶的特征肽，建立超高效液相色谱-质谱多反应监测方法测定胃蛋白酶含量的方法。以水作为溶出介质，浆法，转速为50 r/min，采用自身对照法计算溶出度。特征肽在0.0105～0.525 μg/mL内线性关系良好，精密度和重复性均良好，回收率101.2%。7个厂家产品的溶出度均大于80%，溶出度相似度f2因子值均大于40%，溶出行为相似。方法准确、可靠，可用于测定该制剂的溶出度。
关键词：复方胃蛋白酶颗粒；特征肽；超高效液相色谱-串联质谱；自身对照法；溶出度
中文分类号：R917 文献标识码：A 文章编号：0228-3283（2021）--
Dissolution determination of compound saccarated pepsin granules with peptide marker based on UPLC-MS/MS HANG Baojian, GONG Liping*,CHEN Xiao, XIAN Ru-iqing, SHI Feng* (Shandong Institute for Food and Drug Control, National Medical Products Administration（NMPA）Key laboratory for Quality Evaluation of Gelatin Products, Shandong Research Center of Engineer and Technology for Consistency Evaluation of Generic Drugs, Shandong Institute for Food and Drug Control, Jinan 250101, China), Huaxue Shiji, 2021, 43(7), ～
Abstract: In this work, we established the self-control method for the determination of dissolution of pepsin in compound saccarated pepsin granules with peptide marker. Pepsin was quantified by its marker peptide GTIGIGTPAQDF using LC-MS/MS technique in multiple reaction monitoring mode. Paddle method was adopted with water as the dissolution medium. The rotation speed was 50 r/min. The dissolution was calculated by using self-control method. The linear range of marker peptide concentration was 0.0105～0.525 μg/mL (R2=0.996). The average recovery was 101.2%.
Key words:Compound saccarated pepsin granules;marker peptide; high performance liquid chromatography and quadrupole tandem mass spectrometry (HPLC-MS/MS);Self-comparison method; dissolution
引用本文：杭宝建，巩丽萍，陈晓，等.基于特征肽的超高效液相色谱-串联质谱法测定复方胃蛋白酶颗粒的溶出度[J].化学试剂，2021,43（7）：941-944.
HPLC-MS/MS法测定养殖场土壤中6种常见抗生素微量残留
毛娜1，孙志洪*2，张丽2
（1. 沧州市生态环境保护科学研究院，河北 沧州 061000；2. 河北省沧州生态环境监测中心，河北 沧州 061000）
摘要：采用全自动快速溶剂提取法将养殖场土壤中四环素、氯霉素、氟苯尼考、磺胺二甲基嘧啶、磺胺嘧啶和磺胺甲恶唑提取出来，建立液相色谱-三重四级杆串联质谱法定性、定量检测的分析方法。取畜禽养殖场土壤样品，风干后粉碎机粉碎，过60目筛网，准确称取15 g，置全自动快速溶剂萃取池中，加20 g硅藻土，以甲醇与乙腈混合溶剂进行提取。提取完毕后，将提取液氮吹至近干，加1.0 mL甲醇溶解残渣，涡旋1 min后，用0.22 μm滤膜过滤，上液相色谱-质谱仪定性、定量检测。四环素、氯霉素、氟苯尼考、磺胺二甲基嘧啶、磺胺嘧啶和磺胺甲恶唑在0.02～8.0 µg/mL范围内线性关系良好，相关系数（r）均大于0.995；检测限分别为0.021、0.033、0.046、0.018、0.022和0.010 µg/kg；平均回收率在83.9%～104.7%之间；重复性RSD分别为2.80%、3.17%、3.63%、2.27%、4.22%和3.93%（n = 6）。实验建立的方法具有快速、准确等特点，适用于养殖场土壤等样品的检测，为指导养殖户合理使用药物提供了技术依据。
关键词：快速溶剂萃取；HPLC-MS/MS；养殖场土壤；四环素；磺胺嘧啶
中图分类号：X833 文献标识码：A
Determination of 6 Antibiotics Residues in Farm Soil by HPLC-MS/MS MAO Na1, SUN Zhi-hong*2, ZHANG Li2 (1. Cangzhou Research Institute of Ecological Environment Protection, Cangzhou 061000, China; 2. Cangzhou Ecological Environment Monitoring Center of Hebei Province, Cangzhou 061000, China), Huaxue Shiji, 2021
Abstract：An ASE extraction method was developed for the determination of 5 antibiotics (tetracycline, chloramphenicol, florfenicol, sulfamethazine, sulfadiazine and sulfamethoxazole) residues in farm soil by using HPLC-MS/MS techniques. Farm soil samples were air-dried, curshed, and sieved by 60 mesh screen first. 12.0 g crushed sample was submitted to solvent extraction tank with the addition of 20 g diatomite, then the mixture was extracted by methanol-acetontrile solution. The extracted solution was blown to nearly dry. The residue was dissolved by 1 mL methanol, volex for 1 min, filtered by 0.22 μm membrane, then qualitatively and quantitatively detected by HPLC-MS/MS. The detection of tetracycline, chloramphenicol, florfenicol, sulfamethazine, sulfadiazine, and sulfamethoxazole showed good linear relationships in the concentration ranges of 0.02~8.0 µg/mL, with correlation coefficients (r) all larger than 0.995. The detection limits for tetracycline, chloramphenicol, florfenicol, sulfamethazine, sulfadiazine and sulfamethoxazole were 0.021, 0.033, 0.046, 0.018, 0.022, and 0.010 µg/kg, respectively. The average recoveries were 83.9~104.7%. The Relative standard deviation (RSD) of repeatability were 2.80%, 3.17%, 3.63%, 2.27%, 4.22%, and 3.93% (n=6). The experimental method was provn to be rapid and accurate, which is suitable for the detection of soil samples in farm and provided a technical basis for guiding the farmers to use drugs reasonably.
Key words: ASE; HPLC-MS/MS; farm soil; tetracycline; sulfadiazine
引用本文：毛娜, 孙志洪, 张丽. HPLC-MS/MS法测定养殖场土壤中6种常见抗生素微量残留[J].化学试剂，2021，43(7)：945-950.
原位顶空-气质联用仪测定可膨胀聚合物微球受热释放易燃挥发性物质的方法
蒋凯1，薛晓康*2，商照聪1
（1. 上海化工研究院有限公司 上海化学品公共安全工程技术研究中心，上海 200062；2. 上海化工院检测有限公司，上海 200062）
摘要：建立了顶空-气质联用仪测定可膨胀聚合物微球受热释放易燃挥发性物质的方法。通过将可膨胀聚合物微球恒温处理14 d，以模拟在密封容器中装卸、储存和运输的环境，测定释放出来的易燃挥发性物质的含量。结果表明，该方法的工作曲线具有良好的线性关系，相关系数均在0.9991~0.9995之间，方法检出限在0.0186～0.0542 mL/m3之间，定量限在0.0621~0.1806 mL/m3之间，加标回收率为86.7%~96.5%，RSD为5.3%~8.1%。该方法简便、准确、快速、灵敏度高，可满足可膨胀聚合物微球受热所释放的易燃挥发性物质的检测要求，值得推广。
关键词：可膨胀聚合物微球；顶空-气质联用仪；易燃挥发性物质
中图分类号：O65 文献标识码：A
In-Situ HS-GC/MS Method for Measuring Flammable and Volatile Substances Released by Expandable Polymer Microspheres JIANG Kai1, XUE Xiao-kang*2, SHANG Zhao-cong1（1. Shanghai Engineering Research Center of Chemicals Public Safety; Shanghai Research Institute of Chemical Industry Co., Ltd., Shanghai 200062; 2. Shanghai TECH. Chemical Industry Testing Co., Ltd., Shanghai 200062, China）
Abstract: A in-situ HS-GC/MS method was established to determine the flammable volatile substances released from expandable polymer microspheres during heated. By treating the expandable polymer microspheres at a constant temperature for 14 days to simulate the environment of loading, unloading, storage and transportation in a sealed container, the content of flammable volatile substances released are determined. The results show that the working curve of this method has a good linear relationship. The correlation coefficients are all between 0.9991 and 0.9995. The limit of detection (LODs) of the method are between 0.0186～0.0542 mL/m3. The limits of quantification (LOQs) of the method are between 0.0621~0.1806 mL/m3. The recovery ratios are between 86.7%~96.5%, and the relative standard deviation(RSDs) are between 5.3%~8.1%. This method is simple, accurate, fast, and sensitive. Therefore, our established method can meet the detection requirements of flammable volatile substances released from the expandable polymer microspheres during heated, and used for practical detections.
Keywords: expandable polymer microspheres; HS-GC/MS; flammable volatile substances
引用本文：蒋凯，薛晓康，冷远鹏.原位顶空-气质联用仪测定可膨胀聚合物微球受热释放易燃挥发性物质的方法[J].化学试剂，2021,43（7）：951-953.
基于电导率法测量水中CO2溶解性的研究
于得水*，孙喜荣，高旭辉，李域，邢轲
（陕西省计量科学研究院，陕西 西安 710100）
摘要：通过实验对CO2-水气液两相传质体系中CO2溶解性的研究，证明基于电导率的测量结果来表征CO2气体在水中的溶解度的可行性；筛选从戊烷到十六烷12种液态烷烃的7项物理性质，选择正己烷作为阻止CO2溶解于水的油封材料；通过对纯水和化学标准溶液使用油封前后电导率测量显示：正己烷作为油封材料可有效隔绝空气中CO2，纯水电导率变化由使用前的12倍降至使用后2.8倍，化学标准溶液电导率的变化由使用前1.5 µS/cm降至使用后0.12 µS/cm。结果表明利用电导率检测方法和正己烷油封材料，能有效的解决CO2气体溶解污染问题。
关键词：CO2；电导率；溶解度；油封；正己烷
中图分类号：O657.11 文献标识码：A 文章编号：0258-3283（2021）--
Measurement of CO2 solubility in water based on conductivity method YU De-shui*，SUN Xi-rong，Gao Xu-hui，LI Yu，XING Ke(Shaanxi Institute of Metrology Science, Xi’an 710100, China), Huaxue Shiji, 43(7), ～
Abstract: The solubility of CO2 in CO2/water gas-liquid two-phase mass-transfer system was studied experimentally, and the feasibility of characterizing the CO2 solubility in water was proven based on the measurement of conductivity. Seven physical properties of 12 liquid alkanes from Pentane to Hexadecane were selected, and n-hexane was selected as the oil seal material to prevent CO2 from dissolving in water; The conductivities of pure water and chemical standard solution before and after oil seal was collected. The results showed that using n-hexane as oil seal material can effectively isolate CO2 in air, the change of pure water conductivity is reduced from 12 times before use to 2.8 times after use, and the change of chemical standard solution conductivity is reduced from 1.5 µS/cm before use to 0.12 µS/cm after use. The results showed that the use of conductivity detection method and n-hexane oil seal material can effectively solve the problem of CO2 dissolved pollution.
Key words: CO2; conductivity; solubility; oil seal; n-hexane
引用本文：于得水，孙喜荣，高旭辉，等.基于电导率法测量水中CO2溶解性的研究[J]. 化学试剂, 2021, 43(7): 954-958.
导数离子色谱法在水质分析中的应用
王玲燕*，李珍，张国辉，朱瑞龙，胡静，南粉益，颜瑜秀
（陕西省石油化工研究设计院 陕西省工业水处理工程技术研究中心，陕西 西安 710054)
摘要：建立了一种一阶导数离子色谱法测定水样中钙镁离子的方法，该方法在测定前无须对水样进行处理。考察了pH、温度、离子强度等对该方法的影响，实验选择在pH为中性、室温下进行。由实验测定得到钙、镁离子的离子色谱图，并对谱图进行一阶求导，分别在钙离子和镁离子一阶离子色谱导数的零交点为6.5 min和7.5 min处读取另一离子的导数值dσ/dt，该数值与钙离子或者镁离子浓度呈现良好的线性。采用该方法测定的结果与滴定法测定的结果相一致，表明该方法准确、可靠。
关键词：导数离子色谱法；工业循环水；钙离子；镁离子
中图分类号：O661 文献标识码：A
Application of Derivative Ion Chromatography in Water Quality Analysis WANG Ling-yan*, LI Zhen, ZHANG Guo-hui, ZHU Rui-long, HU Jing, NAN Fen-yi, YAN Yu-xiu (Shaanxi Research Design Institute of Petroleum and Chemical Industry, Shaanxi Industry Watertreament Research Centre of Engineering & Technology, Xi'an 710054, China), Huaxue Shiji, 2021
Abstract: A first-order derivative ion chromatography method was established for the determination of calcium and magnesium ions in water samples, compared with previous study, this method requires not pre-treatment of water samples. The effects of pH, temperature and ionic strength on this method were investigated. The experiment was carried out at room temperature in neutral pH. The chromatograms of Ca2+ and Mg2+ were determined under the optimal conditions of ion chromatography. The first-order derivation of the spectrum was carried out, and the derivative value of another ion was read at the zero intersection point of the first order ion derivative of Ca2+ and Mg2+ at 6.5 min and 7.5 min, respectively. The derivative value showed good linearity with the concentration of Ca2+ or Mg2+. The results obtained by this method were consistent with those obtained by titration method, indicating this method to be accurate and reliable.
Key words: derivative ion chromatography; industrial circulating water; calcium; magnesium
引用本文：王玲燕，李珍，张国辉，等. 导数离子色谱法在水质分析中的应用[J]. 化学试剂, 2021, 43(7): 959-962.
基于罗丹明B的光“关-开”型Fe3+荧光探针的构建研究
代婉婷a，张军a，杨梅b，刘昂a，李琳a，于春伟*a
（海南医学院 a.热带医学与检验医学院, b.公共卫生学院，海南 海口 571199）
摘要：过渡金属离子Fe3+在生命体系的发展过程中担当重要角色，荧光探针因其具有操作简便、灵敏度高、时空分辨能力强等特点得到了广泛。自主设计合成了一类新型的Fe3+荧光探针。详细考查了其对不同金属离子的光谱分辨能力，结果表明：在中性乙醇–水溶液中，探针只对Fe3+表现出选择性的荧光增强和颜色变化（从无色到粉色），检测限达到10-7 mol/L的水平，这一变化是源于从内酰胺环（无荧光/off型）到开环胺（荧光/on型）的转化过程，对其它金属离子没有反应。利用等物质的量连续法测得探针与Fe3+的结合比是1:1，同时EDTA实验证明该结合模式具有可逆性。
关键词：Fe3+；罗丹明B；荧光探针；荧光增强；化学传感器
中图分类号：O655.9 文献标识码：A 文章编号：0258-3283(2021)--
Construction of a highly Fe3+-selective fluorescent probe derived from rhodamine B DAI Wan-tinga, ZHANG Juna, YANG Meib, LIU Anga, LI Lina, YU Chun-wei*a, (a. School of Tropical and Laboratory Medicine; b. School of Public Health, Hainan Medical University, Haikou 571199, China), Huaxue Shiji, 2021, 43(7), ～
Abstract: A fluorescent probe for sensing Fe3+ was designed and synthesized based on rhodamine B. It can selectively recognize Fe3+ with a detection limit down to 10-7 mol/L, whereas no significant spectral changes were observed toward other metal ions in ethanol-water solution at pH 6.5. Fe3+-specific binding would form the opening spirolactam ring, and consequently caused the appearance of the strong absorption at visible range accompanied by an obvious and characteristic color from colorless to pink. Furthermore, the 1:1 binding mode was proposed based on Job’s method. Meanwhile, the coordination mode was reversible, as investigated by EDTA experiment.
Key words: Fe3+; rhodamine B; fluorescent probe; fluorescence enhancement; chemosensor
引用本文：代婉婷, 张军, 杨梅, 等. 基于罗丹明B的光“关-开”型Fe3+荧光探针的构建研究[J].化学试剂, 2021, 43(7): 963-967.
5-异硫氰酸酯荧光素的合成与荧光性能研究
刘建武*1，马艳1，刘涛2，严生虎1，张跃1，辜顺林1，马晓明1
(1. 常州大学 药学院，江苏 常州 213164；2. 浙江万丰化工股份有限公司，浙江 绍兴 312073)
摘要：对5-异硫氰酸酯荧光素的合成进行了系统的研究。以4-硝基邻苯二甲酸、间苯二酚为原料，甲磺酸为缩合剂，乙酸酐为酰化剂、九水硫化钠为还原剂，经缩合、乙酰化、还原制得5-氨基荧光素，再在二硫化碳-三乙胺-铁盐体系下经异硫氰酸化制得5-异硫氰酸酯荧光素。目标产物结构经1HNMR，13CNMR、MS及IR表征，并测试了其荧光性能。与文献报道醇碱皂化再还原路线相比，采用“一锅法”合成5-氨基荧光素，减少分离纯化合成步骤与设备数量，具有效率高、成本低、绿色环保等优点。
关键词：5-氨基荧光素；5-异硫氰酸酯荧光素；合成；荧光性能
中图分类号： O643.3 文献标识码：A 文章编号：0258-3283（2021）--
Synthesis and Fluorescence Properties of 5-Isothiocyanate Fluorescein LIU Jian-Wu*1, MA Yan1, LIU Tao2, YAN Sheng-hu1, ZHANG Yue1, GU Shun-lin1, MA Xiao-ming1(1. School of pharmacy, Changzhou University, Changzhou 213164, China; 2. Zhejiang Wanfeng Chemical Co. Ltd, Shaoxing 312073, China), Huaxue Shiji, 2021, 43(7), ～
Abstract: The synthesis of 5-isothiocyanate fluorescein was studied systematically. 5-aminofluorescein was synthesized from 4-nitrophthalic acid and resorcinol by using CH3SO3H as the condensation agent, acetic anhydride as the acylation agent, and Na2S•9H2O as the reducing agent. Then, 5-aminofluorescein was prepared by isothiocyanation in carbon disulfide triethylamine iron salt system. The structure was characterized by 1HNMR,13CNMR, MS and IR, besides, its fluorescence properties was tested,compared with reported hydrolysis and afterward reduction step-by-step method, this article reported that 5-aminofluorescein can be obtained in a one-pot way, which simplified the separation and purification steps and equipment, and hold the advantages of high efficiency, low cost, and environmental friendliness.
Key words: 5-aminofluorescein; 5-isothiocyanate fluorescein; synthesis; fluorescence properties
引用本文：刘建武, 马艳, 刘涛, 等.5-异硫氰酸酯荧光素的合成与荧光性能研究[J]. 化学试剂, 2021, 43(7):968-972.
杨树桑黄多糖提取工艺与测定
长城1，赵俊华2，于文杰3，陈庆红1，秦立武1，吴秀玲1，刘凤霞1，范宇光*3
（1.长白山科学研究院 长白山生物群落与生物多样性吉林省联合重点实验室，吉林 延边朝鲜族自治州 133613；2.白城市食品药品检验所，吉林 白城 137000；3.海南医学院 海南省热带药用植物研究开发重点实验室 热带环境与健康实验室 海南 海口 571199）
摘要：通过比较微波提取、超声提取、加热回流提取，70 ℃水浴浸提4种方式对桑黄子实体中多糖工艺的提取，参考多糖含量以及遵循科学环保的原则选定最佳提取方法，以响应面法优化多糖提取工艺。比较苯酚-硫酸法与蒽酮-硫酸法测定多糖含量。结果表明，超声提取法可用于杨树桑黄的多糖提取，响应面法优化的最佳提取条件为：超声时间25 min、液料比400 : 1（mL/g）、超声功率60 kHz；蒽酮-硫酸法和苯酚-硫酸法均可用于杨树桑黄中多糖含量的测定。基于“多糖”测定以及实验的稳定性，证明苯酚-硫酸法更适合测定杨树桑黄中多糖的含量，该结果可为其建立质量控制标准做以参考。
关键词：杨树桑黄；紫外-可见分光光度法；响应面法；蒽酮-硫酸法；苯酚-硫酸法
中图分类号：R917 文献标识码：A
Studies on The Extraction Technology and Determination of Polysaccharide from Sanghuangporus vaninii CHANG Cheng1,ZHAO Jun-hua2 ,YU Wen-jie3,CHEN Qing-hong1,QIN Li-wu1，WU Xiu-ling1，LIU Feng-xia1， FAN Yu-guang*3（1. Jilin Provincial Joint Key Laboratory of Changbai Mountains Biocoenosis & Biodiversity，Changbai Mountain Academy of Sciences，Yanbian 133613，China 2. Baicheng Food and Drug Testing Institute，Baicheng 137000，China Abstract:Promoting the establishment of the quality evaluation technology of Sanghuangporus. 3. Hainan Provincial Key laboratory of R & D on Tropical medicinal Herbs，Hainan Medical University，Haikou 571199， China.）
Abstract: This work preliminarily screens the methods for the extraction of polysaccharides from Sanghuangporus vaninii fruiting bodies combining technologies including microwave extraction, ultrasonic extraction, heating reflux extraction, and 70 ℃ water bath. The optimal extraction methods are selected based on the content and environment-friendliness factors by response surface analysis. Phenol-sulfuric acidand the anthrone-sulfuric acid methods are used to determine the polysaccharide content. The results showed that the optimum conditions for ultrasonic extraction method is as follows: ultrasonic time 25 min, liquid-to-material ratio 400:1 (mL/g), ultrasonic power of 60 kHz. Both the anthrone-sulfuric acid and phenol-sulfuric acid methods are suitable for the determination of the content of polysaccharides in Sanghuangporus vaninii. However, the phenol-sulfuric acid method is preferred due to the durability of the experiment. These results could be used as a reliable reference to establish quality control standards of polysaccharides from Sanghuangporus vaninii.
Key words: Sanghuangporus vaninii；UV-vis spectrophotometry; response surface methodology; anthrone-sulfuric acid method; phenol-sulfuric acid method
引用本文：长城，赵俊华，于文杰，等. 杨树桑黄多糖提取工艺与测定[J].化学试剂，2021，43（7）：973-978.
醉鱼草总黄酮的提取及抗氧化活性研究
赵雨晴，王宝庆*，徐汉，刘楠楠
（哈尔滨商业大学 省预防治疗老年病药物研究重点实验室 财政部中央与地方共建实验室，黑龙江 哈尔滨 150076）
摘要：以醉鱼草为对象，选择料液比、超声功率、微波功率和提取时间进行单因素实验，以单因素试验结果为参考利用响应面试验设计对超声波-微波联合提取醉鱼草中总黄酮的工艺进行筛选优化，并对DPPH自由基及羟自由基进行体外抗氧化活性研究。修正最佳工艺条件为：料液比1：48 （g/mL），超声功率389 W，微波功率446 W，提取时间45 min。试验测得总黄酮得率为12.212%，与预测值12.247%相接近。在0.05～0.30 mg/mL的浓度范围内，醉鱼草总黄酮对DPPH自由基及羟自由基均有较强的清除作用，表明其具有一定的抗氧化能力。因此，响应面法优化超声波-微波提取醉鱼草总黄酮的工艺研究具有可行性，为醉鱼草的综合利用及形成产业化提供一定的理论及技术支持。
关键词：醉鱼草；总黄酮；响应面法；抗氧化活性
中图分类号：R284 文献标识码：A
Study on Extraction and Antioxidant Activity of Total Flavonoids from Buddleia lindleyana fort ZHAO Yu-qing, WANG Bao-qing*, XU Han, LIU Nan-nan(Harbin Univercity of Commerce, Key Laboratory of Drug Research on Prevention and Treatment of Geriatric Diseases, Key Laboratory of Ministry of Finance and Local Co-construction, Harbin 150076, China)
Abstract: We took the Buddleia as the research object, selected the ratio of material-to-liquid, ultrasonic power, microwave power, and extraction time for single-factor experiments. We used the single-factor test results as references and applied response surface test design to analyze the effect of ultrasonic-microwave combined extraction of total flavonoids in Buddleia The process was screened and optimized, and the in vitro antioxidant activities of DPPH free radical and hydroxyl free radical were studied. The optimized process conditions were improved as follows: material-liquid ratio of 1:48 g/mL, ultrasonic power of 389 W, microwave power of 446 W, extraction time of 45 min. The total flavonoid yield was 12.212%, which was close to the predicted value of 12.247%. In a concentration range of 0.05 ～ 0.30 mg/mL, the Buddleia flavonoids have a strong scavenging effect on DPPH free radicals and hydroxyl free radicals, indicating that it has a certain antioxidant capability. Therefore, it is feasible to optimize the ultrasonic-microwave extraction process of total flavonoids from Buddleia by using response surface methodology, providing certain theoretical and technical supports for the comprehensive utilization and industrialization of Buddleia.
Key words: Buddleia lindleyana fort; total flavonoids; response surface methodology; antioxidant activity
引用本文：赵雨晴, 王宝庆,徐汉,等. 醉鱼草总黄酮的提取及抗氧化活性研究[J]. 化学试剂, 2021, 43(7): 979-985.
响应面优化蝙蝠葛根生物碱的提取工艺
岑忠用*1，苏江1，高丽霞1，严军2，黄喜苗1
（1. 河池学院 化学与生物工程学院，广西 宜州 546300；2. 广西民族大学 化学化工学院，广西 南宁 530008）
摘要：为确定从蝙蝠葛根中提取生物碱的最佳工艺，以蝙蝠葛根为材料、乙醇溶液为提取剂，利用超声波辅助提取蝙蝠葛根生物碱。在超声功率175w的条件下，通过单因素试验考察乙醇浓度、超声温度、超声时间、料液比对超声提取蝙蝠葛生物碱提取量的影响。应用Box-Benhnken中心组合方法进行4因素3水平设计，以蝙蝠葛根生物碱提取量为响应值，采用响应面法优化蝙蝠葛根生物碱的提取工艺。结果表明超声波辅助提取蝙蝠葛根中生物碱的最佳工艺为料液比1:40、乙醇浓度70%、超声温度40 ℃、超声时间2 h，在此工艺条件下，蝙蝠葛根生物碱的提取量为9.067mg/g。说明该工艺条件切实可行，可用于控制和预测蝙蝠葛根中生物碱的提取。
关键词：蝙蝠葛；超声波；生物碱；响应面优化；提取工艺
中图分类号：O629.3 文献标识码：A 文章编号：0258-3283（2021）--
Optimization of the Extraction Process of Alkaloids from Menispermum dauricum by Response Surface Methodology CEN Zhong-yong*1, SU Jiang1, GAO Li-xia1, YAN Jun2, HUANG Xi-miao1 (1. College of Chemistry and Bioengineering, Hechi University, Yizhou 546300, China; 2. School of Chemistry and Chemical and Engineering, Guangxi University for Nationalities, Nanning 530008, China), Huaxue Shiji, 2021, 43(7), ～
Abstract：In this study, the extraction of alkaloids from the roots of Menispermum dauricum was carried out under ultrasonication using Menispermum dauricum (MD) roots as the target material and ethanol solution as the extractant. In order to determine the best process for extracting alkaloids from the roots of MD, under the condition of ultrasonic power of 175 W, the effects of ethanol concentration, ultrasonic temperature, ultrasonic time, and material-to-liquid ratio on the amount of alkaloids extracted by ultrasonic extraction were investigated by single-factor experiment. The Box-Benhnken central combination method was used to carry out a 4-factor 3-level design, with the extraction amount of the alkaloids of MD root as the response value, and the response surface method was used to optimize the extraction process of the alkaloids of MD root. The results showed that the best process for ultrasonic-assisted extraction of alkaloids from MD root is 1:40 ratio of material to liquid, 70% ethanol concentration, ultrasonic temperature of 40 ℃, ultrasonic time of 2 h. With this process condition, the extraction amount of alkaloids from MD root is 9.067 mg/g, showing high potential for the feasible and reliable extraction of alkaloids from MD roots.
Key words：Menispermum dauricum；ultrasonic；alkaloids；response surface methodology; extraction process
引用本文：岑忠用, 苏江, 高丽霞, 等. 响应面优化蝙蝠葛根生物碱的提取工艺[J].化学试剂, 2021, 43(7): 986-991.
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大黄素-硒（IV）配合物的合成、表征及抗氧化活性研究
黄九林*a,b，彭博a，丁瑜瑜a，赵小龙a
（安康学院 a. 化学化工学院, b. 秦巴中药资源研发中心，陕西 安康 725000）
摘要：研究了大黄素-硒（IV）配合物的合成，并对比配体和配合物体外抗氧化活性。采用单因素实验和正交试验研究大黄素-硒（IV）配合物的最佳合成条件：以无水乙醇为溶剂、n（大黄素）∶n（四氯化硒）= 1∶2、pH 3～4、反应温度40～45 ℃。通过红外光谱法、紫外-可见光谱法和基质辅助激光解吸-飞行时间质谱对大黄素-硒（IV）配合物的结构进行表征；运用紫外-可见分光光度法测定配体和配合物对DPPH的清除率。结果显示大黄素-硒（IV）配合物抗氧化活性相对于配体大黄素有显著提高，大黄素与硒之间存在协同抗氧化作用。
关键词：大黄素；大黄素-硒（IV）配合物；结构表征；抗氧化活性
中图分类号：R285.5 文献标识码：A
Synthesis, Characterization and Antioxidant Activity of Emodin-Selenium(IV) Complex HUANG Jiu-lin*a,b, PENG Boa, DING Yu-yua, ZHAO Xiao-longa (a. College of Chemistry and Chemical Engineering, b. Qinba Chinese Medicine Resources R&D Center, Ankang University，Ankang 725000, China)
Abstract: Emodin-selenium (IV) complex was synthesized using emodin and their in vitro antioxidant activities were comparatively studied. The optimum synthesis conditions of emodin-selenium (IV) complex were studied using single factor and orthogonal test. Its structure was characterized by using IR, UV-Vis and MALDI-TOF-MS techniques. The scavenging rates of DPPH by ligand and complex were detected by using UV-Vis. The optimum conditions for the synthesis of emodin-selenium (IV) complex were: the ethanol as solvent, n(emodin): n(selenium tetrachloride) = 1 : 2, pH 3～ 4, reaction temperature of 40 ～ 45 ℃. The possible structure of emodin-selenium (IV) complex was analyzed, and its antioxidant activity was significantly higher than the ligand emodin, suggesting a beneficial synergistic antioxidant effect between emodin and selenium.
Key words: emodin; emodin-selenium (IV) complex; structure characterization; antioxidant activity
引用本文：黄九林，彭博，丁瑜瑜，等. 大黄素-硒（IV）配合物的合成、表征及抗氧化活性的研究[J].化学试剂, 2021,43（7）：992-995..
微波促进合成4-(3-吡啶基)哌啶二盐酸盐
杜会茹
（河北化工医药职业技术学院 制药工程系 河北省手性药物技术创新中心，河北 石家庄 050026）
摘要：以N-叔丁氧羰基-4-哌啶酮为起始原料，经微波促进反应探讨了3-吡啶硼酸、Pd(PPh3)4、H2O、反应温度和反应时间等对叔丁基-4-(3-吡啶基)-5,6-二氢吡啶-1(2H)-羧酸酯反应产率的影响，再经催化氢化、脱去N原子的Boc保护基以及成盐等5步反应合成了4-(3-吡啶基)哌啶二盐酸盐。中间体叔丁基-4-(3-吡啶基)-5,6-二氢吡啶-1(2H)-羧酸酯最佳反应条件为1.8 mmol 3-吡啶硼酸、5 mmol碳酸钾、0.08 mmol Pd(PPh3)4、15 mL甲苯和2.4 mL H2O、130 °C下微波反应20 min，产率达到74.9%。该方法具有条件温和、操作简单以及环境友好等优点。
关键词：4-(3-吡啶基)哌啶；3-吡啶硼酸；Suzuki-Miyaura交叉偶联反应；微波促进反应
中图分类号：O626 文献标识码：A
Microwave-assistde Synthesis of 4-(Pyridine-3-yl)piperidin DU Hui-ru (Project Supported by Hebei Technological Innovation Center of Chiral Medicine, Pharmaceutical Engineering, Hebei Chemical & Pharmaceutical College, Shijiazhuang 050026, China), Huaxue Shiji, 2021
Abstract: A fast and efficient method for the synthesis of tert-butylcarbonyl-1,2,3,6-tetrahydro-4- [(trifluoromethyl) sulfonyloxy] pyridine-1-carboxylateswas established based on microwave-assisted reaction. It is found that the amounts of 3-pyridineboronic acid, Pd(PPh3)4, and H2O, the reaction temperature and time duration influenced the synthesis yields significantly. Then, the 4-(pyridine-3-yl)piperidin was synthesized through five steps including the catalytic hydrogenation, deprotection, and salt formation. tert-butylcarbonyl-1,2,3,6-tetrahydro-4- [(trifluoromethyl) sulfonyloxy] pyridine-1-carboxylateswas was obtained using the optimized condition of 3-pyridineboronic acid (1.8 mmol), Pd(PPh3)4 (0.08 mmol), H2O (2.4 mL) at 130 °C for 20 min, resulting in an isolated yield of 74.9%. This method possesses the advantages of mild synthesis, simple operation and environmental friendliness.
Key words: 4-( pyridine-3-yl)piperidin; 3-pyridinylboronic acid; Suzuki-Miyaura coupling reaction; microwave assisted reaction
引用本文：杜会茹. 微波促进合成4-(3-吡啶基)哌啶二盐酸盐[J].化学试剂, 2021, 43(7): 996-999.
