【特约专题】
基于快速响应的红色ONOO−荧光探针及其细胞成像
张春香，张向阳，申有名，周紫乐
(湖南文理学院 化学与材料工程学院，湖南 常德 415000)
摘要：过氧亚硝酸盐（ONOO−）是机体内一种重要的活性氧物质，在众多生理和病理功能中扮演重要的角色。红色荧光探针具有背景荧光小、光毒性低和组织穿透性好等特点，在生物分析与成像方面具有明显优势。基于此，合成了一种红色ONOO−荧光探针HBSCN。在与ONOO−反应后，探针溶液迅速由无色变成红色，且展现出明显的荧光增强信号。通过高分辨质谱，证实该过程与探针中C=C氧化断裂有关。在PBS缓冲溶液（V(DMF): V(H2O) = 1:9, pH 7.4）中，探针HBSCN在649 nm处的荧光强度与0~20 μmol/L的ONOO−表现出良好的线性关系，检测下限为73 nmol/L。此外，该探针能够在生理pH下快速地检测ONOO−，且对ONOO−具有较大的Stokes位移和较高的选择性。更重要的是，HBSCN能够用于活细胞内ONOO−成像，表明其潜在的生物应用价值。
关键词：过氧亚硝酸盐；红色荧光探针；快速响应；细胞成像
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.2022.0915
Fast Responding Near-Infrared Fluorescent Probe for Peroxynitrite Detection and Living Cells Imaging ZHANG Chun-xiang, ZHANG Xiang-yang, SHEN You-ming, ZHOU Zi-le (College of Chemistry and Materials Engineering, Hunan University of Arts and Science, Changde 415000, China)
Abstract：Peroxynitrite (ONOO−) is one of important reactive oxygen species in the body, which plays a critical role in many physiological and pathological functions. Red fluorescent probes have recently attracted great interests in the fields of bioanalysis and bioimaging due to the lower background fluorescence, smaller phototoxicity and deeper tissue penetration. Based on these, we synthesized a red fluorescent ONOO− fluorescent probe HBSCN. After reacting with ONOO−, the probe solution quickly changed from colorless to red, and showed an obvious fluorescence enhancement signal. Through high-resolution mass spectrometry, it was confirmed that the sensing process was related to the oxidative cleavage of C=C in the probe. In PBS solution (V(DMF): V(H2O) = 1:9, pH 7.4), the fluorescence intensity at 649 nm of HBSCN were linearly proportional to the increasing of the concentration of ONOO− (0 ~ 20 μmol/L), and the low detection limit was 73 nmol/L. In addition, the probe can quickly detects (56 s) ONOO− under physiological pH, and displays large Stokes and high selectivity toward ONOO−. More importantly, HBSCN could be used for red fluorescent fluorescence imaging of ONOO− in living cells, indicating its high potential value in biological application.
Key words：peroxynitrite; red fluorescent probe; fast response; cell imaging
引用本文：张春香，张向阳，申有名，等. 基于快速响应的红色ONOO−荧光探针及其细胞成像[J]. 化学试剂，2023，45（4）：1-7.
新型近红外荧光探针成像细胞肺纤维化过程粘度变化
杨科，刘莹，王佩佩，李宋娇*，何隆薇*
(南华大学 药学院，湖南 衡阳 421001)
摘要：肺纤维化是一种致命疾病，患病率不断上升。肺纤维化的非放射性和无创性早期诊断可以改善预后，但却是艰巨的挑战。粘度的异常是肺纤维化的典型微环境特征。最近，粘度的精准可视化检测引起了人们的广泛兴趣。然而，由于其特性复杂，直接观察生物系统中的粘度仍然是一个巨大的挑战。线粒体粘度波动与肺纤维化、糖尿病、神经退行性疾病、癌症等多种疾病有关。在这里，报告了一种新型小分子荧光探针NIR-V-BR，用于检测线粒体粘度变化。NIR-V-BR对粘度变化具有近红外发射、优异的水溶性、良好的光稳定性、良好的膜通透性和低细胞毒性。共定位实验表明NIR-V-BR探针具有良好的线粒体靶向能力。NIR-V-BR成功应用于成像活细胞线粒体中粘度变化。最重要的是，NIR-V-BR探针荧光成像实验表明肺纤维化细胞中粘度水平升高。这些结果表明，NIR-V-BR将为生物医学诊断和成像应用提供新的机会。
关键词：近红外；粘度；肺纤维化；荧光探针；荧光成像
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.2022.0876
A Novel Near-infrared Fluorescent Probe for Visualizing Viscosity Fluxes in Live Cells and Idiopathic Pulmonary Fibrosis YANG Ke, LIU Ying, WANG Pei-pei, LI Song-jiao*, HE Long-wei* (Department of Pharmacy and Pharmacology, Hengyang Medical School, University of South China, Hengyang 421001, China.)
Abstract: Pulmonary fibrosis is a fatal disease with increasing prevalence. Nonradioactive and noninvasive diagnosis of pulmonary fibrosis at an early stage can improve the prognosis but represents a daunting challenge. Viscosity is a typical microenvironmental feature of pulmonary fibrosis. Recently, precise visualization of viscosity has begun to stimulate more and more interest. However, owing to the complicated character, it is still a huge challenge to directly observe viscosity in living systems. Mitochondria viscosity fluctuation is related to various diseases such as pulmonary fibrosis, diabetes, neurodegenerative diseases, and cancer. Herein, a novel viscosity probes NIR-V-BR was developed for monitoring the viscosity change of mitochondria. NIR-V-BR possessed a highly sensitive response toward viscosity change with near-infrared emission, excellent water solubility, good photostability, favorable membrane permeabilization, and low cytotoxicity. Colocalization study proved that NIR-V-BR probe exhibited good mitochondrion-targeting ability. NIR-V-BR is used for imaging of viscosity changes in mitochondrion of living cells. Most importantly, fluorescence imaging experiments with NIR-V-BR probe revealed that the level of intracellular viscosity increases in the pulmonary fibrosis cells. These results suggest that NIR-V-BR would provide new opportunities for biomedical diagnosis and imaging applications.
Key words: near-infrared; viscosity; pulmonary fibrosis; fluorescent probe; fluorescence imaging
引用本文：杨科，刘莹，王佩佩，等. 新型近红外荧光探针成像细胞肺纤维化过程粘度变化[J]. 化学试剂, 2023, 45(4): 8-13。
过氧化亚硝酸盐（ONOO-）荧光探针研究进展
何潞潞，田勇琪，李佳佳，曾竟*
（新疆师范大学 化学化工学院，新疆 乌鲁木齐 830054）
摘要：过氧化亚硝酸盐（ONOO-）是一种重要的活性氧，在生命系统的生理和病理过程中起着至关重要的作用，可以抵抗免疫系统中的外来病菌。但是过量的ONOO-可能会引起许多疾病，甚至癌症。因此有效的识别和检测ONOO-具有重要意义。近年来由于操作方便、选择性高、可实时性和无创性检测等优势，荧光探针法检测ONOO-的研究得到了快速的发展。基于探针设计原理根据不同的荧光母体进行分类，综述了近五年来用于检测ONOO-荧光探针的研究现状，评述了ONOO-荧光探针的优点和不足，探讨了该领域面临的挑战，展望了ONOO-荧光探针的研究和发展方向，为今后人们研究ONOO-在生理病理过程中的作用提供了一定的参考价值。
关键词：ONOO-；荧光探针；检测；识别；进展
中图分类号：O657.3 文献标识码：A 文章编号：0258-3283（2023）
DOI:10.13822/j.cnki.hxsj.2022.0889
Recent Progress on Peroxynitrite (ONOO-) Fluorescent Probes HE Lu-lu, TIAN Yong-qi, LI Jia-jia, ZENG Jing* (College of Chemistry and Chemical Engineering, Xinjiang Normal University, Urumqi 830054, China)
Abstract: Peroxynitrite (ONOO-) is an important reactive oxygen species that plays a crucial role in the physiological and pathological processes of the living system and is resistant to foreign bacteria in the immune system. However, excessive ONOO- may cause many diseases, or even cancer. Thus the effective identification and detection of ONOO- is of great importance. Recently, the detection of ONOO- by fluorescent probe detection has been rapidly developed due to the advantages of easy operation, high selectivity, real-time, and non-invasive detection. This review paper classifies different fluorescent matrix based on probe design principles, summarizes the research status of ONOO- fluorescent probes in the past five years, reviews the advantages and disadvantages of ONOO- fluorescent probes. We will also discuss the challenges faced by this field, the research and development direction of ONOO- fluorescent probe, and provides guidance for the future research on the role of ONOO- in the physiopathological process.
Key words: ONOO-; fluorescence probe; detection; recognition; progress
引用本文：何潞潞, 田勇琪, 李佳佳, 等. 过氧化亚硝酸盐（ONOO-）荧光探针研究进展[J]. 化学试剂, 2023, 45(4)：14-24.
DNA模板荧光金属纳米团簇的合成及应用
毛安丽*1，王海波2
（1. 信阳职业技术学院 基础医学部，信阳 4640000；2. 信阳师范学院 化学化工学院，信阳 464000）
摘要：荧光金属纳米团簇的尺寸介于金属原子和纳米颗粒之间，特殊的结构和尺寸赋予了金属纳米团簇一系列优异的荧光特性，如荧光强度高、抗光漂白性能强、较大的斯托克斯位移。脱氧核糖核酸（DNA）由于其独特的结构和可设计的序列而成为合成金属纳米簇的理想模板。DNA模板的金属纳米簇主要包括DNA模板的银纳米团簇（DNA-AgNCs）、铜纳米团簇（DNA-CuNCs）、金纳米团簇（DNA-AuNCs）等。DNA模板的金属纳米团簇作为一种新型的荧光纳米探针在生物传感和生物成像等领域具有较大潜在应用价值。基于先前对DNA模板的金属纳米团簇的研究，系统总结了DNA模板的金属纳米簇的制备、性质和在生物传感以及生物成像中的应用。最后，讨论了DNA模板的金属纳米簇的未来发展研究重点和前景。
关键词：DNA模板荧光金属纳米团簇；DNA模板银纳米团簇；DNA模板铜纳米团簇；DNA模板金纳米团簇；生物传感；生物成像
中图分类号：O657.39 文献标识码：A 文章编号：0258-3283(2023)--
DOI:10.13822/j.cnki.hxsj.2022.0918
Synthesis of DNA-Templated Metal Nanoclusters and Applications in Biosensing and Bioimaging MAO An-li*1, WANG Hai-bo2 (1. Basic Medical Department, Xinyang Vocational and Technical College, Xinyang 464000, China; 2. College of Chemistry and Chemical Engineering, Xinyang Normal University, Xinyang 464000, China)
Abstract: The size of fluorescent metal nanoclusters is between metal atoms and nanoparticles. The special structure and size endow fluorescent metal nanoclusters with a series of excellent fluorescence properties, such as strong fluorescence, good anti-photobleaching, and mega-Stokes shift. Deoxyribonucleic acid (DNA) is an ideal template for the synthesis of metal nanoclusters due to its unique structure and designable sequence. The metal nanoclusters of DNA template mainly include silver nanoclusters (DNA-AgNCs), copper nanoclusters (DNA-CuNCs) and gold nanoclusters (DNA-AuNCs). The metal nanocluster of DNA template as a new type of fluorescent nanoprobe has great application potentials in the fields of biosensing and biological imaging. Based on previous studies on DNA-templated metal nanoclusters, we focus on systematical summary of the preparations, property regulations and applications of DNA-templated metal nanoclusters in biosensing and bioimaging. Finally, the current research emphases and prospects of DNA-templated metal nanoclusters are also discussed.
Key words: DNA-templated fluorescent metal nanoclusters; DNA-templated silver nanoclusters; DNA-templated copper nanoclusters; DNA-templated gold nanoclusters; biosensing; bioimaging
引用本文：毛安丽，王海波. DNA模板荧光金属纳米团簇的合成及应用[J]. 化学试剂，2023，45（4）：25-33.
【综述与专论】
有机催化不对称aza-Henry反应研究进展
张振伟，黄红萍，谢钰航，陈泳乐，刘帆，邓延秋*
(广西中医药大学 药学院 广西壮瑶药工程技术研究中心，广西 南宁 530200)
摘要：不对称aza-Henry反应是重要的碳碳键形成反应，手性产物β -硝基胺是许多药物和天然产物的关键中间体，利用该反应构建手性化合物已有广泛报道，其中有机催化不对称aza-Henry反应已成为不对称催化领域的重要研究对象。催化不对称aza-Henry反应的有机小分子催化剂主要有硫脲类催化剂和相转移催化剂，其中硫脲类催化剂占主要部分，其次还有方酰胺类、胍酰胺类以及脲类等类型催化剂。本综述对近5年有机催化不对称aza-Henry反应的发展现状进行概述并作出总结与展望，以期为今后有机催化不对称合成研究提供参考。
关键词：有机催化；不对称aza-Henry反应；硝基烷烃；β-硝基胺；硫脲类催化剂；相转移催化剂
中图分类号：O621.3 文献标识码：A 文章编号：0258-3283（2023）--
DOI:10.13822/j.cnki.hxsj.2022.0853
Research Advances in Organocatalytic Asymmetric Aza-Henry Reaction ZHANG Zhen-wei, HUANG Hong-ping, XIE Yu-hang, CHEN Yong-le, LIU Fan, DENG Yan-qiu* (School of Pharmacy, Guangxi University of Traditional Chinese Medicine, Guangxi Zhuang Yao Medicine Center of Engineering and Technology, Nanning 530200, China)
Abstract: Asymmetric aza-Henry reaction is an important carbon-carbon coupling reaction, and the chiral product β -nitroamine is a key intermediate for many drugs and natural products. The construction of chiral compounds by this reaction has been widely reported. Among them, the organocatalytic asymmetric aza-Henry reaction has become important research subject in the field of asymmetric catalysis. The organic small molecule catalysts for asymmetric aza-Henry reaction mainly include thiourea catalysts and phase transfer catalysts. Among them, thiourea catalysts account for the main part, followed by squaramide, guanidine amide and urea catalysts. In this review paper, the development status of asymmetric aza-Henry reactions catalyzed by organocatalysts in the past five years is summarized and prospected to provide guidance for future researches relating organocatalytic asymmetric synthesis.
Key words: organocatalysis; asymmetric aza-Henry reaction; nitroalkanes; β -nitroamine; thiourea catalysts; phase transfer catalysts
引用本文：张振伟，黄红萍，谢钰航，等. 有机催化不对称aza-Henry反应研究进展[J]. 化学试剂, 2023, 45(4): 34-42。
用于卵巢癌标志物β-Gal检测的荧光探针研究进展
张亚涛，何杰芳*
（贵州师范大学 生命科学学院，贵州 贵阳 550000）
摘要：卵巢癌是最常见的妇科癌症之一，其患者大多数在晚期被诊断出，导致卵巢癌患者的死亡率高。因此，对隐匿症状的早期诊断是患者生存率提高的重要保障。β-半乳糖苷酶（β-Gal）在原发性卵巢癌中的过表达而被认定为卵巢癌生物标志物，所以快速精准的β-Gal检测技术对卵巢癌早期诊断至关重要。近年来，荧光探针技术已成为生物体内监测和可视化的有力工具。目前已经报道了大量的用于检测β-Gal的荧光探针，但是，用于卵巢癌β-Gal检测和可视化成像的荧光探针相对较少。主要综述用于卵巢癌细胞生物标志物β-Gal检测的荧光探针的研究进展，并对探针的发展进行展望。
关键词：荧光探针；β-Gal；卵巢癌；分子成像；生物标志物
中国分类号：R944 文献标识码：A 文章编号：0258-3283（2023）--
DOI:10.13822/j.cnki.hxsj.2022.0881
Progress of Fluorescent Probes for the Detection of Ovarian Cancer Marker β-Gal ZHANG Ya-tao, HE Jie-fang*(Guizhou Normal University, College of Life Sciences, Guiyang 550000, China)
Abstract: Ovarian cancer is one of the most prevalent gynecologic cancers, and the majority of its patients are diagnosed at an advanced stage, leading to its high mortality rate. Therefore, early diagnosis of occult symptoms is an important guarantee for improved patient survival.β-Gal has been identified as an ovarian cancer biomarker due to its overexpression in primary ovarian cancer, therefore rapid and accurate β-Gal detection technology is crucial for early diagnosis of ovarian cancer. In recent years, fluorescent probe technology has developed into a powerful tool for in vivo monitoring and visualization of organisms. A large number of fluorescent probes for β-Gal detection have been reported; however, only a few fluorescent probes have been used for β-Gal detection and visualization imaging of ovarian cancer. This article reviews the research progress of fluorescent probes for β-Gal detection of ovarian cancer as cell biomarkers and provides an outlook on the development of probes.
Keywords: fluorescent probes; β-Gal; ovarian cancer; molecular imaging; biomarkers
引用本文：张亚涛，何杰芳. 用于卵巢癌标志物β-Gal检测的荧光探针研究进展[J]. 化学试剂, 2023, 45(4): 43-51。
Burgess试剂在有机合成中的应用新进展
李健，滕大为，曹国锐*
(青岛科技大学 化工学院，山东 青岛 266042)
摘要：Burgess试剂（N-（三乙基铵磺酰）氨基甲酸甲酯）是一种温和的选择性脱水剂，可有效促进多种反应，在有机合成领域具有重要的应用价值，已广泛应用于药物及天然产物的合成。该综述简要介绍了Burgess试剂的合成方法，同时对近年来其应用进展进行了总结，主要包括醇脱水合成烯烃、酰胺脱水合成异氰或腈、诱导合成杂环化合物、醇的氧化反应、磺酸酯以及磺酰胺类化合物的合成，并对部分反应机理进行了介绍。期望Burgess试剂在官能团转化以及其他反应类型中的应用更加广阔，为有机合成领域的发展提供新的动力。
关键词：Burgess试剂；脱水反应；环化；有机合成；应用
中图分类号：O621.3 文献标识码：A 文章编号：0258-3283（2023）--
DOI:10.13822/j.cnki.hxsj.2022.0867
Recent Progresses on the Application of Burgess Reagent in Organic Synthesis LI Jian, TENG Da-wei, CAO Guo-rui* (College of Chemistry Engineering, Qingdao University of Science and Technology, Qingdao 266042, China)
Abstract: Burgess reagent (N-(triethylammonium sulfonyl) methyl carbamate) is a mild and selective dehydrating agent that can effectively promote a variety of reactions. It has important application value in organic synthesis and has been widely used in the synthesis of drugs and natural products. In this review, the synthesis methods of Burgess reagent are briefly introduced and the application progress in recent years is summarized. This review paper mainly includes the synthesis of olefin by alcohol dehydration, the synthesis of isocyanide and nitrile by amide dehydration, the synthesis of induced heterocycles, the oxidation of alcohols, and the synthesis of sulfonic esters or sulfonamide compounds. Mechanisms of some reactions are introduced. It is expected that Burgess reagent will be more widely used in functional group conversion and other type of reaction, providing new impetus for the development of organic synthesis.
Key words: Burgess reagent; dehydration reaction; cyclization; organic synthesis; application
引用本文：李健，滕大为，曹国锐. Burgess试剂在有机合成中的应用新进展[J]. 化学试剂, 2023, 45(4): 52-62。
【生化与药用试剂】
基于环糊精的刺激响应性药物递送系统
唐良健，黄绍德，王繁盛，吕焕能，吴建婷，黄雪秋，韦雪琴*
(广西医科大学 药学院，广西 南宁 530021)
摘要：刺激响应性超分子药物递送系统利用超分子丰富的药物分子识别位点、可逆的超分子作用力以及超分子组装体的刺激响应性等特点，可以实现药物的靶向和可控递送，有利于提高药物疗效并降低药物的毒副作用，在癌症治疗中展现了巨大的应用前景。环糊精具有特殊的空腔结构，以其经济易得、水溶性好、易于修饰、生物相容性好等优点，成为最广泛应用于构建刺激响应性药物递送系统的超分子主体之一。本文综述了近五年来基于环糊精的药物递送系统通过内源性刺激（pH、氧化还原环境和酶）和外源性刺激（温度、光和磁）实现药物可控释放的最新研究进展，重点阐述其功能设计、作用特点及机制，最后对基于环糊精的刺激响应性药物递送系统存在的问题及未来的发展进行了总结和展望。
关键词：环糊精；药物递送；主客体相互作用；刺激响应；可控释放
中图分类号：R943 文献标识码：A 文章编号：0258-3283（2023）--
DOI:10.13822/j.cnki.hxsj.2022.0888
Cyclodextrin-Based Stimuli-Responsive Systems for Drug Delivery TANG Liang-jian, HUANG Shao-de, WANG Fan-sheng, LV Huan-neng, WU Jian-ting, Huang Xue-qiu, WEI Xue-qin* (School of Pharmacy, Guangxi Medical University, Nanning 530021, China)
Abstract: Stimuli-responsive supramolecular drug delivery systems have been developed for achieving targeting and controlled drug delivery by virtue of sufficient drug recognition sites, reversible supramolecular interaction and stimuli response of supramolecular assembly, leading to improved therapeutic efficiency and reduced side-effects, which hold great promise for cancer treatment. Cyclodextrins are among the most extensively studied supramolecular hosts for the construction of stimuli-responsive drug delivery systems due to their unique cavities, ready availability, excellent water-solubility, easy modification and good biocompatibility. This review will focus on the recent progress on cyclodextrin-based drug delivery systems for controlled release of drugs in response to endogenous (pH, redox condition and enzyme) and exogenous (temperature, light and magnet) stimuli. The functional design, as well as features and mechanism of action of the cyclodextrin-based stimuli-responsive drug delivery systems will be emphatically introduced. Finally, this review provides an outlook on challenges and future perspectives in this field.
Key words：cyclodextrin; drug delivery; host-guest interaction; stimuli response; controlled release
引用本文：唐良健，黄绍德，王繁盛，等. 基于环糊精的刺激响应性药物递送系统[J]. 化学试剂, 2023, 45(4):63-73。
紫茎泽兰发酵前后挥发油成分变化及其抑菌活性
刘洋1a，胡世俊*1b，张东华1a，皋玉功2，闫晓慧*1a
(1.西南林业大学a.生物多样性保护学院 云南省森林灾害预警与控制重点实验室,b.林学院，云南 昆明 650224；2.紫茎泽兰中医农业科技云南有限公司，云南 昆明 650233）
摘要：紫茎泽兰适应性强、生长迅速是危害严重的入侵物种，目前没有理想的防除手段，如能资源化利用将有效推动其综合治理，具有重要意义。分析紫茎泽兰微生物发酵前、后挥发油成分及其抑菌作用，为利用紫茎泽兰开发发酵饲料提供依据。采用水蒸气蒸馏法提取挥发油，利用GC-MS分析挥发油成分，采用标准滤纸片法，研究挥发油对粪肠球菌（Enterococcus faecalis）、大肠杆菌（Escherichia coli）、铜绿假单胞菌(Pseudomonas aeruginosa)、沙门氏菌（Salmonella enterica）的抑菌活性，利用试管稀释法测定MIC、MBC。从紫茎泽兰发酵前、后挥发油中分别鉴定出40、43个化合物，其相对含量占挥发油总量的98.9%和98.84%，含氧单萜类成分含量发酵后明显降低，从发酵前的11.58%降低到发酵后的7.12%，倍半萜烯类成分以及含氧倍半萜烯类成分发酵后含量均有所升高，分别由发酵前的28.9%、41.89%上升为发酵后的34.72%和46.32%。其中发酵后挥发油中柠檬烯、石竹烯等抑菌活性成分含量有所升高；抑菌活性结果表明发酵后挥发油对粪肠球菌的抑菌活性较好，抑菌圈直径达到16.40 mm，发酵前、后挥发油对于粪肠球菌的抑菌活性要明显高于其他供试菌，而且发酵后挥发油对铜绿假单胞菌、大肠杆菌、粪肠球菌、沙门氏菌的抑菌圈直径都要高于发酵前；紫茎泽兰发酵前、后挥发油的MIC、MBC值范围为2.5～10.0 μL/mL。经微生物发酵后的紫茎泽兰挥发油出油率及化合物数量有增加，挥发油组成在发酵前后变化较大。紫茎泽兰经过微生物发酵后，对供试的四株细菌的抑菌活性有所增强，本研究为资源化利用紫茎泽兰提供了一定的科学依据。关键词：紫茎泽兰挥发油；微生物发酵；化学成分；抑菌活性
中图分类号：R284.1 文献标志码：A 文章编号：0258-3283（2023）--
DOI:10.13822/j.cnki.hxsj.2022.0814
Study of Volatile Oil Composition and Antibacterial Activity of Eupatorium Adenophorum Before and After Fermentation LIU Yang1a, HU Shi-jun*1b, ZHANG Dong-hua1a, Gao Yu-gong2, YAN Xiao-hui*1a (1.a.Key Laboratory of Forest Disaster Warning and Control in Yunnan Province, College of Biodiversity Conservation, b.College of Forestry，Southwest Forestry University, Kunming 650224, China; 2.Eupatorium adenophorum Technology (Yunnan) Co, Kunming 650233, China)
Abstract: The invasion of Eupatorium adenophorum has triggered serious harm, yet there is no ideal control methods at present. It is of great significance to make use of this plant comprehensively. The composition of volatile oil and its antibacterial effects before and after microbial fermentation of E. adenophorum were analyzed, which provided a basis for developing fermented forage with E. adenophorum. The volatile oil was extracted by hydrodistillation method, and the composition of volatile oil was analyzed by GC-MS. The antibacterial activity of volatile oil against Enterococcus faecalis, Escherichia coli, Pseudomonas aeruginosa and Salmonella enterica were studied by standard filter paper sheet method, and MIC and MBC were determined by test tube dilution method. 40 and 43 compounds were identified by GC-MS from the pre-fermentation and post-fermentation volatile oils, accounting for 98.9% and 98.84% of the total volatile oils, respectively; the content of the oxygenated monoterpenes decreased significantly after fermentation, from 11.58% to 7.12%，the contents of sesquiterpene and oxygen sesquiterpene increased after fermentation from 28.9% and 41.89% to 34.72% and 46.32%, respectively; and the concentration of limonene and sesquiterpene in the volatile oil increased after fermentation; the results of inhibition activity showed that the inhibition activity of the volatile oil on E. faecalis was potent after fermentation, and the diameter of the inhibition circle was 16.40 mm, which is more significant than those of the other tested bacteria After fermentation the diameter of inhibition circle of volatile oil on P. aeruginosa, E. coli, E. faecalis and S. enterica were larger than those before fermentation; the MIC and MBC values of volatile oil ranged from 2.5 to 10.0 μL/mL. The yield of volatile oil and the number of compounds increased after fermentation, and the composition of the volatile oil varied widely. The antibacterial activity of the volatile oil of E. adenophorum enhanced after fermentation against the four test strains of bacteria., This study provided a scientific basis for the utilization of E. adenophorum.
Keywords: volatile oil of Eupatorium adenophorum Spreng；microbial fermentation；chemical composition；antibacterial activity
引用本文：刘洋，胡世俊，张东华，等. 紫茎泽兰发酵前后挥发油成分变化及其抑菌活性[J]. 化学试剂, 2023, 45(4): 74-80。
含噻吩片段的三嗪类化合物的合成与抗肿瘤活性研究
饶念，龙志武，乐意，刘力*，鄢龙家*
(贵州大学 药学院，贵州 贵阳 550025)
摘要：以3-氨基噻吩-2-羧酸甲酯为原料设计合成了一系列含噻吩片段的结构新颖的三嗪类化合物。最终的22个化合物结构经1HNMR，13CNMR和HRMS确证。并且用MTT法评价了该系列化合物对人脑恶性星形胶质母细胞瘤细胞U87-MG的体外抗肿瘤活性。结果表明，化合物3-（（4-氯-6-（（4-（甲基磺酰基）苯基）氨基）-1,3,5-三嗪-2-基）氨基）-N-甲基噻吩-2-甲酰胺具有良好的抗肿瘤活性且优于阳性对照TAE-226，其对人脑恶性星形胶质母细胞瘤细胞U87-MG的IC50为9.528 µM。此研究以期为含1,3,5-三嗪骨架的抗肿瘤药物提供参考。
关键词：噻吩；三嗪；抗肿瘤；合成；MTT法
中图分类号： 文献标识码：A 文章编号：0258-3283（2023）
DOI:10.13822/j.cnki.hxsj.2022.0865
Synthesis and Antitumor Activity of Triazines Containing Thiophene Fragments RAO Nian, LONG Zhi-wu, LE Yi, LIU Li*, YAN Long-jia* ( School of Pharmaceutical Sciences, Guizhou University, Guiyang 550025, China)
Abstract： A series of novel triazines containing thiophene fragments were designed and synthesized from 3-aminothiophene-2-carboxylic acid methyl ester. The structures of the final 22 compounds were confirmed by 1H NMR, 13C NMR and HRMS. The anti-tumor activity of these compounds against human brain malignant astroblastoma cell line U87-MG in vitro was evaluated by MTT assays. The results show that the compound 3-((4-chloro-6-((4-(methylsulfonyl)phenyl)amino)-1,3,5-triazin-2-yl)amino)-N-methylthiophene-2-carboxamide has very good anti-tumor activity and is superior to the positive control TAE-226. Its IC50 to human malignant astroblastoma cell U87-MG is 9.528 µM. This study is expected to provide guidance for anti-tumor drugs containing 1,3,5-triazine skeleton.
Key words: thiophene; triazine; antineoplastic; synthesis; MTT assays
引用本文：饶念，龙志武，乐意，等. 含噻吩片段的三嗪类化合物的合成与抗肿瘤活性研究[J]. 化学试剂，2023，45（4）：81-90.
手性Cu2-xSe纳米材料的制备及其协同抗菌性能研究
施瑶1,2，邓业成∗1，艾福金∗2
(1. 广西师范大学 生命科学学院，珍稀濒危动植物生态与环境保护教育部重点实验室，广西 桂林 541006；2.深圳技术大学 健康与环境工程学院, 广东 深圳 518118)
摘要：利用手性半胱氨酸（L-/D-Cys）和铜的配位作用,设计合成了具有良好光热转换效率和类过氧化物酶活性的手性Cu2-xSe 纳米材料。其能够高效地催化过氧化氢分解生成羟基自由基等活性氧（ROS）而发挥杀菌作用。在光热效应促进下, Cu2-xSe有效地增强了 ROS的产生。抗菌实验结果表明,低浓度（10 μg/mL）的Cu2-xSe可抑制细菌生长，并且在表面手性修饰后,在过氧化氢和近红外激光共同处理下，L-/D-Cys-抗菌体系对大肠杆菌和金黄色葡萄球菌的抑菌活性几乎达到了100%，均表现出显著的抑菌活性。本研究通过手性修饰的方式优化了活性氧类抗菌剂Cu2-xSe的杀菌效果,拓展了新型手性抑菌材料的应用,对设计研发新型多功能的纳米抗菌剂具有参考价值。
关键词：手性Cu2-xSe纳米材料；光热效应；催化；抗菌活性
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.2022.0878
Preparation of Chiral Cu2-xSe Nanomaterials and Study of its Synergistic Antibacterial Properties SHI Yao1,2， DENG Ye-cheng1*，AI Fu-jin2* (1. Key Laboratory of Ecology of Rare and Endangered Species and Environmental Protection, Ministry of Education of China / College of Life Science, Guangxi Normal University，Guilin 541004，China; 2. Department of Health Science and Environmental Engineering, Shenzhen Technology University, Shenzhen 518118, China)
Abstract: A chiral nanoplatform with excellent photothermal conversion efficiency and peroxidase-like activity was designed and synthesized through the coordination of chiral cysteine (L-/D-Cys) and copper on the surface of Cu2-xSe nanoparticles (NPs). The chiral nanoplatform can efficiently catalyze the decomposition of hydrogen peroxide to generate highly toxic reactive oxygen species (ROS) such as hydroxyl radicals with effective anti-bactericidal properties. The Cu2-xSe NPs can effectively enhance the production of ROS promoted by photothermal effect. The results of antibacterial experiments showed that low concentration (10 μg/mL) of Cu2-xSe NPs could greatly inhibit bacterial growth. In addition, and after surface chiral modification of Cu2-xSe NPs, the bacteriostatic activity of L-/D-Cys-antibacterial system against Escherichia coli and Staphylococcus aureus reached almost 100%, all of which demonstrated significant bacteriostatic activity. In this study, the bactericidal effect of Cu2-xSe NPs as an active oxygen species antibacterial agent was optimized by chiral modification, and the application of new chiral antibacterial materials was expanded. Thus, this work can provide promising guide for the design and development of novel multi-functional nano-antibacterial agents.
Key Words: chiral Cu2-xSe NPs; photothermal effect; catalysis; antibacterial activity
引用本文：施瑶，邓业成，艾福金. 手性Cu2-xSe的制备及其协同抗菌性能研究[J]. 化学试剂，2023，45（4）：91-98.
【功能材料】
基于低共熔溶剂的磺胺二甲基嘧啶分子印迹聚合物制备及其性能评价
武曦*1，韩凰燕2，徐欣1
(1. 长治学院 化学系，山西 长治 046011；2. 山西师范大学 化学与材料科学学院，山西 太原 030000)
摘要：在低共熔溶剂（DES）-甲醇混合溶剂体系中，采用本体聚合法制备了磺胺二甲基嘧啶分子印迹聚合物（SMZ-MIPs）。通过一系列实验对聚合物的合成条件、吸附条件进行了优化。对SMZ-MIPs在水溶液中吸附磺胺二甲基嘧啶的性能进行评价，并通过扫描电镜和比表面积及孔径分析仪对其形态及结构进行表征。结果表明，在以丙烯酰胺为功能单体，氯化胆碱-硫脲DES-甲醇为致孔剂，模板分子与功能单体之比为1:4的条件下，制备的SMZ-MIPs具有最佳的特异性识别性能，在pH为8的条件下聚合物对水样中的SMZ的印迹因子达到2.74。在3水平加标浓度(1、5、10 mg/L)下的模板分子的平均回收率为84.0% ~ 93.4%，相对标准偏差（RSD）在4.3% ~ 6.2%之间，表明基于低共熔溶剂混合溶剂体系制备的分子印迹聚合材料对水溶液中的SMZ有良好的选择性吸附。
关键词：磺胺二甲基嘧啶；低共熔溶剂；分子印迹聚合物；水溶液
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.2022.0858
Preparation and Performance Evaluation of Sulfamethazine Molecularly Imprinted Polymer Based on Deep Eutectic Solvents WU Xi*1, HAN Huang-yan2, XU Xin1 (1. Chang Zhi University, Department of Chemistry Chang Zhi 046011,Shanxi China,2. Shanxi Normal University, School of Chemistry and Materials Science Taiyuan 030000)
Abstract：Sulfamethazine molecularly imprinted polymers (SMZ-MIPs) was synthesized by bulk polymerization in a deep eutectic solvent (DES)-methanol solvent system. A series of experiments were conducted to optimize the synthesis conditions and adsorption conditions. The adsorption of sulfamethazine from aqueous solution by SMZ-MIPs was investigated. The morphology and structure of SMZ-MIPs were characterized by scanning electron microscope and specific surface area analyzer. According to experimental results, the optimum synthesis condition of SMZ-MIPs was confirmed. The molar ratio of template and functional monomer was 1:4, the acrylamide was the optimal functional monomer and the mixed solvent of ethanol and choline chloride-thiourea DES was taken as porogen. The prepared polymer has good specific recognition to SMZ in an aqueous solution with pH 8 and the imprinting factor can reach 2.74. The average recoveries of the template at three spiked concentrations (1, 5, 10 µg/g) were 84.0%-93.4%, and the relative standard deviations were 4.3%-6.2%. The results indicate that the imprinted material based on DESs has good adsorption performance for SMZ in the water samples.
Key words：sulfamethazine; deep eutectic solvents; molecularly imprinted polymers; aqueous solution
引用本文：武曦，韩凰燕，徐欣. 基于低共熔溶剂的磺胺二甲基嘧啶分子印迹聚合物的制备及其性能评价[J]. 化学试剂，2023，45（4）：99-105.
沸石催化剂上四-氢双环戊二烯催化异构
冯汝明1，胡浩杰2，凌芳*2
（1. 国药集团化学试剂有限公司，上海 200002；2. 上海沃凯生物技术有限公司；上海 200235）
摘要：四氢双环戊二烯（TCD）在Y、β、ZSM-5与MOR沸石催化剂上的异构化反应表明，Y沸石具有更高的催化活性。TCD在Y沸石上异构化中，endo构型的TCD在180 ~ 220 ℃可以转化为exo构型的TCD，选择性超过95%，但反应产物中并未检测到金刚烷；在相同的温度区间exo构型TCD却不能异构化为endo构型TCD。相对于常规的Y沸石，小晶粒Y沸石表现出更高的催化活性，在260 ℃与0.5 MPa下，exo-TCD的转化率由10.5%提高到30.5%。经离子交换方法得到的La改性Y沸石，催化活性略有下降，但催化剂的稳定性明显提高，经过6次使用后，反应物转化率为22.1%，金刚烷的选择性仍保持在50%以上；再生后的催化剂与新鲜催化剂的性能接近。
关键词：四氢双环戊二烯；金刚烷；异构化；沸石
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.2022.0823
Isomerization of Tetrahydrodicyclopentadiene over Zeolite Catalyst FENG Ru-ming1, HU Hao-Jie2, LING Fang*2 (1. Sinopharm Chemical Reagent Co., Ltd., Jingan District, Shanghai 200002, China; 2. Shanghai Wokai Bio-technology company, Jinshan District, Shanghai 200235, China)
Abstract: Isomerization of tetrahydrodicyclopentadiene (TCD) over Y, β, ZSM-5 and MOR zeolites showed that Y zeolite exhibited the best catalytic activity. In the Y zeolite’s promoted TCD isomerization reaction, the endo-TCD was transformed to exo-TCD at the temperature range of 180 ℃ to 220 ℃ with a high exo-TCD selectivity exceeding 95%, no adamantane products were detected. Meanwhile, at the same condition the exo-TCD was not transformable to exo-TCD. The conversion of exo-TCD over small crystal particles of Y zeolite increased from 10.5% to 30.5% compared to the conventional Y zeolite in the isomerization in a condition of 260 ℃ and 0.5 MPa, better catalytic performance was gained over nanosized zeolites. After lanthanum ion-exchanging, Y zeolite showed a decreasing trend of catalytic activity while better stability. The total conversion was 22.1% and the selectivity of adamantane was kept above 50% after six cycles. The catalytic performance of the La-doped Y zeolite before and after regeneration was very close.
Key words：tetrahydrodicyclopentadiene; adamantane; isomerization; zeolite
引用本文：冯汝明, 胡浩杰, 凌芳. 沸石催化剂上四-氢双环戊二烯催化异构[J]. 化学试剂, 2023, 45（4）：106-112.
【电化学和新能源】
银修饰铜纳米阵列用于电催化还原CO2
乔华建1,2，李天治2，安赛1,2，刘德宇2，周扬*1
（1. 宁波大学 材料科学与化学工程学院，浙江 宁波 315211；2. 中国科学院宁波材料技术与工程研究所，浙江 宁波 315211）
摘要：二氧化碳的电化学转化为气态或液体燃料具有存储可再生能源以及减少碳排放的潜力。报道了一种Ag修饰Cu纳米阵列作为二氧化碳电化学还原催化剂的简单合成方法。首先，在铜箔上通过阳极氧化生成Cu(OH)2纳米阵列，然后经过原位电化学还原得到Cu纳米阵列，最后通过Cu纳米阵列和Ag+前驱体之间的电化学置换来生成Ag修饰的Cu纳米阵列。Ag修饰铜纳米阵列增强了电化学还原二氧化碳的催化性能，相较于未经修饰的铜纳米阵列，Ag修饰Cu纳米阵列电催化还原CO2生成C2H4的法拉第效率提升了158%，同时，修饰后的电极对于C2+产物的选择性提升了121%。其对CO2电催化性能的提升和对氢气的抑制归因于Ag和Cu的协同催化效应。
关键词：铜纳米阵列；协同作用；二氧化碳还原；电催化
中图分类号：O643.36 文献标识码：A 文章编号：0258-3283（2023）
DOI:10.13822/j.cnki.hxsj.2023.0002
Silver-Modified Copper Nanoarrays for Electrocatalytic Reduction of CO2 QIAO Hua-jian1,2, LI Tian-zhi2, AN Sai1,2, LIU De Yu2, ZHOU Yang*1 (1. School of Materials Science and Chemical Engineering, Ningbo University; 2. Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315211, China)
Abstract：Electrochemical conversion of carbon dioxide into gaseous or liquid fuels has the potential to store renewable energy and reduce carbon emissions. A simple synthesis method of Cu nanoarrays modified with Ag as catalyst for electrochemical reduction of carbon dioxide is reported. First, Cu(OH)2 nanoarrays were synthesized by anodizing on copper foil, and then by in-situ electrochemical reduction. Finally, the Ag-modified Cu nanoarrays were generated by Galvanic Replacement between the Cu nanoarrays and Ag+ precursors. Compared with unmodified copper foil, the Faraday efficiency of the electrocatalytic reduction of CO2 to C2H4 by Ag-modified Cu nanoarray was increased by 158%, at the same time, the selectivity of the modified electrode for C2+ products increased by 121%. The improvement of the electrocatalytic performance of CO2 and the inhibition of hydrogen were attributed to the synergistic catalytic effect of Ag and Cu.
Key words：copper nanoarray; synergy effect; carbon dioxide reduction; electrocatalysis
引用本文：乔华建，李天治，安赛，等. 银修饰铜纳米阵列用于电催化还原CO2[J]. 化学试剂，2023，45（4）：113-119.
【化学品与环境】
木质素基吸附剂制备及应用研究进展
王超1,2，冯雪贞1，张海波1，商士斌*1，宋湛谦1
(1.中国林业科学研究院林产化学工业研究所 林木生物质低碳高效利用国家工程研究中心 国家林业局林产化学工程重点开放性实验室 江苏省生物质能源与材料重点实验室，江苏 南京 210042；2.南京林业大学 林业资源高效加工利用协同创新中心，江苏 南京 210037）
摘要:木质素具有储量丰富、成本低、易于改性加工等优点，在废水处理中具有广阔的应用前景。重点综述了木质素基微球、木质素基水凝胶、木质素基炭材料等木质素基吸附剂的制备方法，及其在吸附有机染料、重金属以及抗生素等领域的应用，并对木质素基吸附剂的发展前景进行了展望。
关键词：木质素；吸附剂；制备；应用；进展
中图分类号：TQ424 文献标志码：A 文章编号：0258-3283（2023）
DOI:10.13822/j.cnki.hxsj.2022.0917
Progresses on the Preparation of Lignin-based Adsorbents and Its Applications. WANG Chao1,2, FENG Xue-zhen1, ZAHNG Hai-bo1, SHANG Shi-bin1*, SONG Zhan-qian1 (1. Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry; National Engineering Research Center for Low Carbon and Highly Efficient Utilization of Forest Biomass; Key and Open Lab on Forest Chemical Engineering, SFA; Jiangsu Province Key Laboratory of Biomass Energy and Material; Nanjing 210042, China; 2. Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Nanjing Forestry University, Nanjing 210037, China)
Abstract: Lignins have the advantages of plentiful sources, inexpensive cost, and effortless modification and processing, which has broad application prospects in wastewater treatment. This review paper focuses on the preparation of lignin-based adsorbents such as lignin-based microspheres, lignin-based hydrogels, and lignin-based carbon materials. The applications of lignin-based adsorbents in the adsorption of organic dyes, heavy metals and antibiotics. Finally, the prospects for the development of lignin-based adsorbents also are prospected.
Key words: lignin; adsorbent; preparation; application; progress
引用本文：王超，冯雪贞，张海波，等. 木质素基吸附剂制备及应用研究进展[J]. 化学试剂，2023，45（4）：120-127.
水滑石基苯酚选择性吸附材料的制备及再生研究
刘炬1,2，张柏源1,2，王思阳1，胡惠雯1，杨淼森*1，孙智勇*2，蔺存国2，张国新3
（1. 东北电力大学，吉林 吉林 132012；2. 中国船舶重工集团公司第七二五研究所，山东 青岛 266200；3. 山东科技大学，山东 青岛 266590）
摘要：目前，水资源短缺和污染已经成为制约世界各国经济发展的重要因素。因此，工业废水治理及再生利用就成为各国研究的热点。其中，含酚废水是当今世界上危害大、污染范围广的工业废水之一，也是环境中水污染的重要来源。利用改性β-环糊精（CMCD）插层到水滑石（LDHs）层间制备出CMCD/LDHs复合材料实现其对废水中苯酚的选择性吸附，揭示了LDHs不同的金属元素组成、比例以及溶液pH值对苯酚及硝基苯吸附的影响规律，获得了对苯酚选择性吸附最优的Mg2Al-CMCD LDH复合材料，并探讨了Mg2Al-CMCD LDH对苯酚与硝基苯吸附的等温吸附过程、动力学过程和再生循环能力。结果表明Mg2Al-CMCD LDH对苯酚具有显著的选择性吸附性能，当pH为6时，对苯酚的最大选择性吸附量为6.27 mg/g，而对干扰物硝基苯、苯胺及苯甲酸的吸附量分别为1.80、1.57、2.27 mg/g；吸附过程符合Freundlich等温吸附和二级吸附动力学；具有优异的循环再生能力，循环吸附5次后，吸附效率仍保持在85%以上。为废水中苯酚类物质选择性吸附材料的设计与制备提供了新的思路和途径。
关键词：水滑石；改性环糊精；苯酚；选择性吸附；再生利用
中国分类号：O69 文献标识码：A 文章编号：0258-3283（2023）
DOI:10.13822/j.cnki.hxsj.2022.0813
Preparation and Regeneration of Layered Double Hydroxide-Based Materials for Selective Phenol Adsorption LIU Ju1,2, ZHANG Bai-yuan1,2, WANG Si-yang1, HU Hui-wen1, YANG Miao-sen*1, SUN Zhi-yong*2, LIN Cun-guo2, ZHANG Guo-xin3 (1. Northeast Electric Power University, Jilin 132012, China; 2. Luoyang Ship Material Research Institute, Qingdao 266200, China; 3. Shandong University of Science and Technology, Qingdao 266590, China), Huaxue Shiji, 2023,
Abstract: At present, the shortage and pollution of water resources have become an important factor restricting the global economic development. Therefore, the treatment and recycling of industrial wastewater have aroused extensive research interests in various countries. Among them, phenol-containing wastewater is one of the most harmful and polluted industrial wastewater, it is also largely contributing the water pollution in the environment. In this work, CMCD/LDHs composites were prepared by intercalating β-cyclodextrin (CMCD) into layered double hydroxides (LDHs) and used for selective adsorption of phenol in wastewater. The effects of LDHs compositions and pH value of solution on the adsorption of phenol and nitrobenzene were evaluated. The optimal CMCD/ Mg2Al-LDH composite with the best selectivity for phenol adsorption was obtained. The isothermal adsorption process, kinetic process and regeneration cycle capability of CMCD/Mg2Al-LDH for the adsorption of phenol and nitrobenzene were discussed. The results showed that CMCD/Mg2Al-LDH had significant selective adsorption capacity for phenol. The maximum adsorption capacity for phenol is 6.27 mg/g at pH=6, while that for nitrobenzene, phenylamine and carboxybenzene are 1.80, 1.57 and 2.27 mg/g, respectively. The adsorption process is in accordance with Freundlich isothermal adsorption and two-stage adsorption kinetics. It also has excellent recycling capacity that the adsorption efficiency still remains above 85% after five cycles. This study has provided a new idea and approach for the design and preparation of LDH-based materials for selective adsorption of phenol in wastewater.
Key words: layered double hydroxides; carboxymethyl-β-cyclodextrin; phenol; selective adsorption; recyclin
引用本文：刘炬, 张柏源, 王思阳, 等. 水滑石基苯酚选择性吸附材料的制备及再生研究[J]. 化学试剂, 2023, 45(4)：128-135.
【分析与测试】
高效液相色谱-串联质谱法测定油菜籽和亚麻籽中16种真菌毒素
孙利东1，王震1，刘贺1，鲁婷婷1，娄婷婷*2
（1. 满洲里海关技术中心，内蒙古 满洲里 021400；2. 天津海关动植物与食品检测中心，天津 300461）
摘要：采用真菌毒素多功能净化柱（Mycotoxin multifunctional purification column，MFC）对样品进行前处理，建立了高效液相色谱-串联质谱法测定油菜籽和亚麻籽中16种真菌毒素及其代谢产物的检测方法。以50%乙腈水溶液对样品中目标物进行振荡提取，经MycoSpin TM 400多功能净化柱净化处理，采用EclipsePlus C18色谱柱分离，11种毒素采用电喷雾多反应离子监测正模式分析，5种毒素采用负模式分析，同位素内标法定量。16种真菌毒素在各自浓度范围内线性关系良好（R2 ＞ 0.995），在二种基质中进行3个水平添加实验（n = 6），回收率为65.1% ~ 97.3%，相对标准偏差为5.1% ~ 10.9%，方法检出限为0.2 ~ 11.5 μg/kg，定量限为0.6 ~ 30.0 μg/kg。本方法操作简单、准确性和灵敏度高，可用于油菜籽和亚麻籽中16种真菌毒素残留的检测分析。
关键词：真菌毒素；多功能净化柱；高效液相色谱串联质谱法；油菜籽；亚麻籽
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.2022.0812
Simultaneous Determination of 16 Mycotoxins in Rapeseed and Flaxseed by High Performance Liquid Chromatography-tandem Mass Spectrometry SUN Li-Dong1, WANG Zhen1, LIU He1, LU Ting-Ting1, LOU Ting-Ting*2 (1. Technology Center of Manzhouli Customs, Manzhouli 021400, Inner Mongolia, China; 2. Animal, Plant and Foodstuffs Inspection Center of Tianjin Customs, Tianjin 300461, China)
Abstract: The samples were treated with mycotoxin multifunctional purification column to establish an analytical method for simultaneous determination of 16 mycotoxins and their metabolites in rapeseed and flaxseed by high performance liquid chromatography-tandem mass spectrometry. 50% acetonitrile in water was selected as extraction solvent to extract sample via shaking and treated with MycoSpin TM 400 multifunctional purification column, and then filtrated. 11 mycotoxins were separated by EclipsePlus C18 chromatographic column and analyzed by electrospray reaction positive mode. 5 mycotoxins were analyzed by electrospray reaction negative mode, and quantitated by isotope internal stand method. Good linear relationships of 16 kinds of mycotoxins in rapeseed and flaxseed were obtained in respective linear ranges, their correlation coefficients (R2) were all greater than 0.995 and recoveries of 16 kinds of mycotoxins in rapeseed and flaxseed at 3 spiked levels were ranged from 65.1% ~ 97.3%, with precisions in a range of 5.1% ~ 10.9. The limits of detection are ranged from 0.2 ~ 11.5 μg/kg , and the limits of quantification are ranged from 0.6 ~ 30.0 μg/kg in different matrices, respectively. This method is simple to operate, of high accuracy and sensitivity, which is instantly available for the needs of quantitative analysis of 16 mycotoxins in rapeseed and flaxseed.
Key words：mycotoxins; multifunctional purification column; high performance liquid chromatography-tandem mass spectrometry; rapeseed; flaxseed
引用本文：孙利东, 王震, 刘贺, 等. 高效液相色谱-串联质谱法测定油菜籽和亚麻籽中16种真菌毒素[J]. 化学试剂，2023，45（4）：136-143.
【合成与工艺技术】
硼酸树脂的制备及其催化Biginelli反应性能研究
李文静，蔡楠，周宇涵*
（大连理工大学 化工学院药学系精细化工国家重点实验室，辽宁 大连 116024）
摘要：以苯乙烯、二乙烯基苯和4-乙烯基苯硼酸为原料，AIBN为引发剂，合成了含有硼酸基团的树脂，其活性硼酸基团含量可通过制备工艺调节。采用频哪醇吸附法，测定所合成树脂的活性硼酸基团含量，最高可达0.562 mmol/g。选取了几种活性硼酸基团含量较高的硼酸树脂催化Biginelli反应，优化了Biginelli反应条件。结果表明，以活性硼酸基团含量为0.486 mmol/g的硼酸树脂为催化剂，乙腈为溶剂，在催化剂的用量为0.412 g/(1 mmol乙酰乙酸乙酯)，回流36 h的条件下，催化乙酰乙酸乙酯、苯甲醛和尿素的Biginelli反应，分离收率高达71%。催化剂反复使用多次，仍具有一定的催化活性。该方法也适用于不同取代基的芳醛、2-噻吩甲醛或硫脲，以中等收率得到一系列3,4-二氢嘧啶-2-酮类衍生物（DHMPs）。
关键词：硼酸基树脂；制备；催化；Biginelli反应
中图分类号：TQ325/O626 文献标识码：A 文章编号：0258-3283（2023）
DOI:10.13822/j.cnki.hxsj.2022.0885
Preparation of Boric Acid Resin and Its Catalytic Performance Evaluation on the Biginelli Reaction LI Wen-jing, CAI Nan, ZHOU Yu-han* (State Key Laboratory of Fine Chemicals, School of Pharmaceutical Sciences, Dalian University of Technology, Dalian 116024, China)
Abstract: The resin containing boric acid group was synthesized using styrene, divinylbenzene and 4-vinylphenylboric acid as the starting materials and AIBN as the initiator. The content of active boric acid groups could be tuned by adjusting the preparation process. The content of active boric acid groups of the as-synthesized resin is up to 0.562 mmol/g, as determined by Pinna alcohol adsorption method. Several boric acid resins with high content of active boric acid groups were selected to catalyze the Biginelli reaction, and the reaction conditions were optimized. The results showed that the Biginelli reaction of ethyl acetoacetate, benzaldehyde and urea was catalyzed by boric acid resin with active boric acid group content of 0.486 mmol/g. Under the optimized conditions, 0.412 g/(1 mmol ethyl acetoacetate) of catalyst dosage, acetonitrile as solvent and reflux for 36 h, the product was isolated in a yield of 71%. The resin can be recycled and reused for several times with limitede decrease in activity. The method is also suitable for aromatic aldehydes with different substituents, 2-thiophene formaldehyde and thiourea, and a series of 3, 4-dihydropyrimidine-2-ketone derivatives (DHMPs) can be obtained in a moderate yield.
Key words：boric acid based resin; preparation; catalysis; Biginelli reaction
引用本文：李文静, 蔡楠, 周宇涵. 硼酸树脂的制备及其催化Biginelli反应性能[J]. 化学试剂，2023，45（4）：144-151.
二价铜催化下的硝酸铵对酚类化合物的单硝化反应研究
罗茂，陈淼，付效禹，徐泽锋，朱锦桃*
(浙江理工大学 理学院，浙江 杭州 310018)
摘要：硝基酚在生产生活中有着广泛的应用价值。以对羟基苯乙酮为原料,在二价铜盐作催化剂和硝酸铵作硝化剂条件下，考察了溶剂、温度、催化剂、投料比、投料方式对生成4-羟基-3硝基苯乙酮产率的影响，得到最佳反应条件：5 mmol%二价铜盐作催化剂，原料投料比n（对羟基苯乙酮）∶n（硝酸铵）＝1∶2.2，在V（乙酸）∶V（水）＝4∶1的混合溶液中100 ℃反应8 h能获得87.6%的收率。将该反应条件对酚类化合物进行拓展，结果显示带有吸电子取代基及卤素的酚类化合物以中等至高的产率生成了各种单硝化产物。本反应所用硝化剂硝酸铵廉价易得、反应条件温和、安全性好、工艺操作简单、有工业化应用的潜力。
关键词：硝化反应；硝酸铵；二价铜；芳烃；催化
中图分类号：O62 文献标识码：A 文章编号：0258-3283（2023）--
DOI:10.13822/j.cnki.hxsj.2022.0895
Mono-nitration Reaction of Ammonium Nitrate to Phenolic Compounds Catalyzed by Divalent Copper LUO Mao1, CHEN Miao2, FU Xiao-yu3, ZHU Jin-tao*（School of Science, Zhejiang Sci-Tech University, Hangzhou 310018, China）
Abstract: Nitrophenol has a wide range of applications in industry and life. Using 1-(4-hydroxyphenyl)-1-ethanone as the starting material, the effects of solvent, temperature, catalyst, feeding ratio and feeding mode on the yield of 1-(4-Hydroxy-3-nitrophenyl) ethan-1-one were investigated under the conditions of divalent copper salt as catalyst and ammonium nitrate as nitrating agent,. The optimal reaction conditions were obtained: 5 mmol% divalent copper salt as catalyst, feeding ratio of raw material n (1-(4-hydroxyphenyl)-1-ethanone): n (ammonium nitrate) =1:2.2, in V (acetic acid):V (water) =4:1 mixed solution reaction at 100 ℃ for 8 h, 87.6% yield can be obtained. The reaction conditions were extended to phenolic compounds. The results showed that phenolic compounds with electron-absorbing substituents and halogens produced various mono-nitrification products at medium to high yields. The nitrification agent used in this reaction, ammonium nitrate, is cheap and easy to obtain, and the reaction can be operated in mild conditions with good safety and processing simpleness, and thus has considerable potential for industrial applications.
Key words: nitration reaction ; ammonium nitrate; Cu(Ⅱ); arene; catalysis
引用本文：罗茂，陈淼，付效禹，等. 二价铜催化下的硝酸铵对酚类化合物的单硝化反应研究[J]. 化学试剂, 2023, 45(4): 152-159。
异补骨脂素酰胺类化合物的合成及其AKR1C3抑制活性
孙明娜1，江晓怡，曾思莹，黄萍，郑雪花，刘欢，张超*
(广州医科大学 a. 药学院 广东省分子靶标&临床药理学重点实验室与呼吸疾病国家重点实验室；b. 附属第五医院，广州 511436)
摘要：以7-羟基香豆素为初始原料，经Duff甲酰化反应、Rap-Stoermer反应、水解反应和缩合反应得具有酰胺侧链的角型呋喃香豆素（异补骨脂素）类化合物；利用HR-MS、1HNMR及13CNMR确证化合物的结构；通过中通量抑酶活性测试方法评价化合物对AKR1C3及AKR1C1的抑制作用。合成了7个新的异补骨脂素酰胺类化合物5a~5g；初步酶活性测试结果显示，化合物5e对AKR1C3具有一定的选择性抑制作用。合成异补骨脂素酰胺类化合物，评价其对AKR1C3的抑制作用。采用上述方法可成功合成异补骨脂素酰胺类化合物，化合物5e具有一定的选择性AKR1C3抑制作用，可为后续研究提供一定的依据。
关键词：异补骨脂素；酰胺；AKR1C3；呋喃香豆素；合成
中图分类号：R91 文献标识码：A 文章编号：0258-3283(2023)
DOI:10.13822/j.cnki.hxsj.2022.0794
Synthesis and AKR1C3 Inhibitory Activity of Angelicin Amides SUN Ming-na1, JIANG Xiao-yi, ZENG Si-ying, HUANG Ping, ZHENG Xue-hua, LIU Huan, ZHANG Chao* (a.Key Laboratory of Molecular Target & Clinical Pharmacology and the State Key Laboratory of Respiratory Disease, School of Pharmaceutical Sciences, b.The Fifth Affiliated Hospital, Guangzhou Medical University, Guangzhou 511436, China)
Abstract：This study is aiming at the synthesis of angelicin amides and evaluation of their inhibitory effect on AKR1C3. Methods are listed as followed: the angular furocoumarin (angelicin) compounds with amide side chain were prepared using 7-hydroxycoumarins as the initial materials through Duff formylation, Rap-Stoermer reaction, hydrolysis, and condensation in sequence. The structures of the compounds were confirmed by combining HR-MS, 1HNMR and 13CNMR characterizations. The medium flux enzyme activity inhibition tests were carried out to evaluate the inhibition of the compounds on AKR1C3 and AKR1C1. Seven new angelicin amides (5a~5g) are synthesized and confirmed. According to the preliminary enzyme activity results, compound 5e shows a certain selective inhibition effect on AKR1C3. The angelicin amides can be successfully synthesized by the method described above. Compound 5e exhibits a certain selective inhibitory effect on AKR1C3, which can provide some basis for subsequent research.
Key words：angelicin; amide; AKR1C3; furocoumarin; synthesis
引用本文：孙明娜，江晓怡，曾思莹，等. 异补骨脂素酰胺类化合物的合成及其AKR1C3抑制活性[J].化学试剂，2023，45（4）：160-166.-
粉体高纯偏磷酸铝的制备及表征
刘红梅*1,2，谷芳芳1,2，王保金1,2，李炳华1,2，杜荣光1,2，陈勉彬1,2
（1. 广州化学试剂厂，广东 广州 510288；2. 广东广试试剂科技有限公司，广东 肇庆 526238）
摘要：通过对磷酸和氢氧化铝制备的磷酸二氢铝，在不同制备方法下制备偏磷酸铝，使用化学分析和ICP-OS分析手段对其纯度进行了检测，并用XRD、SEM和TEM对其结构进行了表征。结果表明，单一微波制得的产品为无定型结构，易吸潮，含量为93.75%。单一焙烧法制得的偏磷酸铝，易聚合板结，取料耗时费力，一次性收率低。微波法与焙烧法连用制备偏磷酸铝，刚好避免了前两种制备方法的缺点，该法制备的产品不与培烧器皿粘结，易取出、易压碎，球形颗粒，大小均匀，粒径基本在18 ~ 35 nm之间。
关键词：高纯；偏磷酸铝；微波法；焙烧法；连用；制备；表征
中图分类号：TQ126.3 文献标识码：A 文章编号：0258-3283（2023）
DOI:10.13822/j.cnki.hxsj.2022.0769
Preparation and Characterization of High-purity Powder Aluminum Metaphosphate LIU Hong-mei*1,2, GU Fang-fang1,2, WANG Bao-jin1,2, LI Bing-hua1,2, DU Rong-guang1,2, CHEN Mian-bin1,2 (1. Guangzhou Chemical Reagent Factory, Guangzhou 510288, China; 2. Guangdong Guangshi Reagent Technology Co., Ltd, Zhaoqing 526238, China)
Abstract：Aluminum metaphosphate was prepared by different preparation methods from aluminum dihydrogen phosphate that were prepared using phosphoric acid and aluminum hydroxide. Its purity was detected by chemical analysis and ICP-OS analysis, and its structure and morphology was characterized by XRD, SEM and TEM. The results show that aluminum metaphosphate prepared by single-type microwave heating method is in amorphous structure, containing 93.75% aluminum metaphosphate, it shows high absorbance to moisture. Aluminum metaphosphate prepared by single baking method is easy to polymerize and harden, and the extraction of aluminum metaphosphate is time-consuming and laborious, thus attaining low one-time yield. The microwave method and baking method are combined to prepare aluminum metaphosphate, which avoid the shortcomings of the first two preparation methods. Aluminum metaphosphate prepared by this method do not bond with the baking utensils, hence being easy to take out and crush, showing spherical particle morphology with uniform size in between 18 ~ 35 nm.
Key words：high purity; aluminum metaphosphate; microwave heating; baking method; combination; preparation; characterization
引用本文：刘红梅, 谷芳芳, 王保金, 等. 粉体高纯偏磷酸铝的制备及表征[J]. 化学试剂，2023，45（4）：167-172.
