新型冠状病毒核酸标准物质现状分析
杨雪a, b，梁文a，杨镇洲a，徐勤a，李妍a，闻艳丽a，刘刚a，许丽*a
（上海市计量测试技术研究院 a. 生物计量实验室，b. 上海市在线检测与控制技术重点实验室，上海 201203）
摘要：新型冠状病毒肺炎是由严重急性呼吸综合征冠状病毒2（SARS-CoV-2）引起的，其传染性高、致病性强，已在全球蔓延。核酸检测技术为新冠病人确诊和治疗提供科学依据，有效推动“早发现早治疗早隔离”的疫情防控策略。自新冠疫情爆发以来，我国陆续研制出来各种新型冠状病毒核酸检测试剂，为疫情防控提供了重要支撑，而新型冠状病毒核酸标准物质为核酸检测质量控制提供了有力保障。本文简单介绍了国内存在的3种不同形式的标准物质的原理和优缺点，列举了国内现有的新型冠状病毒核酸标准物质，对它们的研究现状及面临的挑战进行了阐述，并展望了未来的发展方向，为新冠病毒核酸标准物质的研制和使用提供了参考。
关键词：新型冠状病毒；标准物质；核酸检测；体外转录RNA；基因组RNA；假病毒
中图分类号：Q78 文献标识码：A 文章编号：0258-3283（2021）
Research Status of SARS-CoV-2 Nucleic Acid Reference Materials YANG Xue1, 2, LIANG Wen1, YANG Zhen-zhou1, XU Qin1, LI Yan1, WEN Yan-li1, LIU Gang1, XU Li1* (a. Biometrology Laboratory, b. Shanghai Key Laboratory of Online Test and Control Technology, Shanghai Institute of Measurement and Testing Technology, Shanghai 201203, China), Huaxue Shiji, 2021, 43(6)
Abstract：The Coronavirus Disease 2019 is caused by severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2), which is highly infectious and pathogenic, and has spread globally. Nucleic acid detection technology provides scientific basis for the diagnosis and treatment of patients, and effectively promotes the epidemic prevention and control strategy of "early detection, early treatment and early isolation". Since the outbreak of the epidemic, China has successively developed various SARS-CoV-2 nucleic acid testing reagents, which provide important support for the prevention and control of the epidemic, and the SARS-CoV-2 nucleic acid reference materials provide a strong guarantee for the quality control of nucleic acid testing. This article briefly introduces the principles, advantages and disadvantages of the three different forms of reference materials in China, lists the existing domestic SARS-CoV-2 nucleic acid reference materials, and explains their research status and challenges, and development direction. It provides a reference for the development and application of the SARS-CoV-2 nucleic acid reference materials.
Key words: SARS-CoV-2; reference materials; nucleic acid detection; in vitro transcription of RNA; genomic RNA; pseudovirus.
引用本文：杨雪，梁文，杨镇洲，等. 新型冠状病毒核酸标准物质现状分析[J]. 化学试剂, 2021, 43(6):711-717。
氮掺杂还原氧化石墨烯/多壁碳纳米管负载Ag@C的制备及在电化学传感器检测甲硝唑的应用
李瑜，陈瑞雪*
(锦州医科大学 药学院，辽宁 锦州 121000)
摘要：通过水热反应制备碳包银(Ag@C)核壳纳米粒子，以尿素作为氮源制备氮掺杂还原氧化石墨烯/多壁碳纳米管（N-RGO/MWCNTs），通过超声混合将Ag@C负载于N-RGO/MWCNTs形成复合材料Ag@C/N-RGO/MWCNTs。利用透射电子显微镜（TEM）、X射线衍射仪（XRD）、能量色散X射线谱（EDS）对材料进行表征。结果表明，氮元素成功掺杂于RGO/MWCNTs，Ag@C呈明显的核壳结构。将该复合材料用于甲硝唑的电化学检测，结果显示甲硝唑浓度在0.1～150 μmol/L范围内与还原峰电流呈现良好的线性关系，相关系数r=0.9976，检出限(S/N=3)为4.41×10-8 mol/L。该传感器对甲硝唑有良好的选择性，可用于药品中甲硝唑的检测。
关键词：碳包银；氮掺杂还原氧化石墨烯；甲硝唑；电化学传感器
中图分类号：O657.1 文献标识码：A 文章编号：0258-3283（2021）
Preparation of Nitrogen-doped Reduced Graphene Oxide/Multi-walled Carbon Nanotubes Loaded Ag@C and Its Application in Electrochemical Sensors for Detection of Metronidazole LI Yu, CHEN Rui-xue* (College of Pharmacy, Jinzhou Medical University, Jinzhou 121000, China), HuaxueShiji, 2021, 43(6)
Abstract: Ag@Ccore-shell nanoparticles were synthesized by hydrothermal method and urea was used as nitrogen source to prepare nitrogen-doped reduced graphene oxide/multi-walled carbon nanotubes (N-RGO/MWCNTs). Ag@C was loaded on N-RGO/MWCNTs by ultrasonic mixing to form composite Ag@C/N-RGO/MWCNTs. Transmission electron microscope(TEM), X-ray diffraction (XRD) and X-ray energy dispersive spectroscopy (EDS) were used to characterizethe material.The results showed that nitrogenwas successfully doped into RGO/MWCNTs and Ag@C showed a clear core-shell structure.The composite material was used for the electrochemical detection of metronidazole. The results showed that the metronidazole concentration in the range of 0.1～150 μmol/L showed a good linear relationship with the reduction peak current,the correlation coefficientwas 0.9976and the detection limit (S/N=3) was 4.41×10-8mol/L.The sensor has good selectivity to metronidazole and it can be used formetronidazole analysis in pharmaceutical samples.
Key words: Ag@C; nitrogen-doped reduced graphene oxide; metronidazole; electrochemical sensor
引用本文：李瑜，陈瑞雪. 氮掺杂还原氧化石墨烯/多壁碳纳米管负载Ag@C的制备及在电化学传感器检测甲硝唑的应用[J]. 化学试剂，2021，43（6）：718-723.
过氧甾醇-17-缩氨基硫脲类衍生物的合成及抗肿瘤活性评价
王佳丰，吴佳乐，韩迎龙，张杰，王明宇，王静*，卜明*
(齐齐哈尔医学院 药学院，黑龙江 齐齐哈尔 161006)
摘要：以天然过氧麦角甾醇为先导结构，脱氢表雄酮为原料，经6步反应合成7个全新的过氧化甾醇17位偶联苯基异硫氰酸酯侧链衍生物。采用1HNMR、13CNMR和HR-MS对所合成的7个衍生物进行结构表征。另外，选择人乳腺癌细胞（MCF-7）、人肝癌细胞（HepG2）和人结直肠癌细胞（HCT-116）作为受试细胞评价所合成化合物的抗肿瘤活性。结果表明，3β-羟基-5α,8α-过氧化雄甾-17-(3-氟-苯基)氨基硫脲对3种肿瘤细胞株均具有显著的抑制活性；与先导化合物过氧麦角甾醇相比，上述化合物活性提高明显。可为新型甾体类抗肿瘤药物的研发提供思路。
关键词：甾体；过氧化物；异硫氰酸酯；缩氨基硫脲；抗肿瘤活性
中图分类号：O626 文献标识码：A 文章编号：0258-3283（201*）
Synthesis and Antitumor Activity Evaluation of Peroxide Steroid 17-Thiosemicarbazone Derivatives WANG Jia-feng, WU Jia-le,HAN Yinglong,ZHANG Jie,WANG Ming-yu,WANG Jing*,BU Ming* (School of Pharmacy, Qiqihar Medical University, Qiqihar 161006, China)
Abstract：Using natural ergosterol peroxide as the lead structure and dehydroepi and rosterone as raw materials, seven steroidal endoperoxide derivatives with different thiosemicarbazone side chains have been synthesized in six steps. The structures of seven new compounds were characterized by 1H NMR, 13C NMR and HRMS. The cytotoxicity of all compounds were evaluated against human breast cervical cancer cells (MCF-7), human liver carcinoma cells (HepG2) and human colorectal cells (HCT-116). The results showed that 5α,8α-epidioxy-17-(3-fluoro-phenyl) thiosemicarbazide (7b) displayed significant cytotoxic activity against all three kinds of the tested cancer cells. Compared with the lead compound ergosterol peroxide, the activity of compound 7b increased significantly. This work can provide ideas for the development of new steroidal anti-tumor drugs.
Key words：sterol; endoperoxide; isothiocyanate; thiosemicarbazone; antitumor activity
引用本文：王佳丰，吴佳乐，韩迎龙，等. 过氧甾醇-17-缩氨基硫脲类衍生物的合成及抗肿瘤活性评价[J]. 化学试剂，2021, 43（6）：724-728.
BiOI纳米片电极的光电化学性能及对苯酚的检测
李梦岩，李永宇*，屈星含，丁梦瑶，赵金燕，陈建军
(郑州师范学院 化学化工学院 环境与催化工程研究所，河南 郑州 450044)
摘要：通过恒电位电沉积法制备了BiOI纳米片光电极，利用XRD、SEM和DRS等手段对其进行了表征，考察了偏置电压和沉积时间对BiOI电极的物相、光吸收以及电化学性能的影响，优化出最佳制备条件为偏置电压-0.14 V、沉积时间300 s。建立了基于该BiOI纳米片电极的光电化学检测苯酚的方法，在30～420 μmol/L的浓度范围内，光电流的倒数与苯酚浓度呈现良好的线性关系，线性方程为1/△I = -0.00109 c + 1.43753 (R2= 0.99781)。该方法成功应用于实际水样中苯酚的检测，取得了良好的回收率和较低的相对标准偏差(RSD)。
关键词：电化学沉积法；BiOI纳米片；苯酚；光电流；检测
中图分类号：O649.3 文献标识码：A 文章编号：0258-3283（2021）
Photoelectrochemical Performance of BiOI Nanosheet Electrode and Its Detection of Phenol LI Meng-yan, LI Yong-yu*, QU Xing-han, DING Meng-yao, ZHAO Jin-yan, CHEN Jian-jun (Institute of Environmental ＆ Catalytic Engineering, School of Chemistry and Chemical Engineering, Zhengzhou Normal University, Zhengzhou 450044, China), Huaxue Shiji, 2021, 43(6)
Abstract: BiOI nanosheet photoelectrodes were prepared by potentiostatic electrodeposition method and characterized by using XRD, SEM and DRS characterizations. The effects of deposition voltage and time on the phase, light absorption and electrochemical performance of BiOI electrodes were investigated. The optimized preparation conditions were the deposition voltage of -0.14 V and the time of 300 s. A photoelectrochemical detection method for phenol based on the BiOI nanosheet electrode was established based on the BiOI nanosheet electrode. The reciprocal of the photocurrent and the phenol concentrations showed a good linear relationship within the concentration range of 30～420 μmol/L, and the linear equation was 1/△I = -0.00109 c+ 1.43753 (R2= 0.99781), this method was successfully applied to the detection of phenol in real actual water samples, and achieved good recovery and low RSD.
Key words: electrochemical deposition; BiOI nanosheets; phenol; photocurrent; detection
引用本文：李梦岩，李永宇，屈星含，等. BiOI纳米片电极的光电化学性能及对苯酚的检测[J]. 化学试剂, 2021, 43(6):729-735。
肿瘤氧化还原荧光探针的研究进展
覃柳馨a，陈卫卫a，王刚*b，王洋*c
（广西中医药大学 a. 药学院, b. 广西壮瑶药工程技术研究中心, c. 人事处，广西 南宁 530200）
摘要：癌症威胁着人类的生命健康，其治疗进展与肿瘤的氧化还原环境密切相关，主要表现为活性氧水平和谷胱甘肽水平异常增高及氧化胁迫。氧化还原敏感探针是指能对肿瘤氧化还原环境敏感物质进行选择性荧光检测进而评价肿瘤的进展阶段的一类分析试剂，因其具有高灵敏性和高分辨能力能实现肿瘤诊断和治疗的作用已成为肿瘤相关研究的热点，有良好的临床应用前景。综述了肿瘤微环境氧化还原探针的研究进展，重点介绍了荧光探针的机理、设计、效果及存在的问题，并展望了该类探针的发展方向。
关键词：氧化还原；荧光探针；谷胱甘肽；活性氧
中图分类号：R944；R945 文献标识码：A 文章编号：0258-3283(2021)
Research Progress of Tumor Redox Fluorescent Probes QIN Liu-xina, CHEN Wei-weia, WANG Gang*b, WANG Yang*c (a. College of Pharmacy, b. Guangxi Zhuang Yao Medicine Center of Engineering and Technology, c. Personnel Department, Guangxi University of Chinese Medicine, Nanning 530200, China), Huaxue Shiji, 2021, 43(6)
Abstract: Cancer is a threat to human life and health. The progression of cancer treatment is closely related to the redox environment of tumor, characterized by abnormal increase of reactive oxygen species, glutathione levels and oxidative stress. Redox sensitive probe is a kind of analytical reagent which can detect the sensitive substances of redox environment selectively and evaluate the progress of tumor. Because of its high sensitivity and high resolution, redox sensitive probe has become a hot spot in tumor related research and has a good clinical application prospect. In this paper, the research progress of redox probes in tumor microenvironment is reviewed. The mechanism, design, effect and existing problems of fluorescent probes are mainly introduced, and the development direction of these probes is prospected.
Key words: redox; fluorescent probe; glutathione; reactive oxygen species
引用本文：覃柳馨，陈卫卫，王刚，等. 肿瘤氧化还原荧光探针的研究进展[J]. 化学试剂, 2021, 43(6):736-746。
工业烟气脱硝技术国内外研究进展
赵琳*1,2，刘庆岭1，周伟2，胡芝娟2，彭学平2，张利娜2，刘旭月2
（1. 天津大学 环境科学与工程学院，天津 300350；2. 天津水泥工业设计研究院有限公司，天津 300400）
摘要：随着超低排放政策的制定和逐步实施，各项法律法规、国家标准和行业标准对氮氧化物的排放浓度和排放总量均作出要求，氮氧化物减排迫在眉睫，迫切的需要发展更加适合我国国情、适应不同行业烟气特点的多元化脱硝技术，各种脱硝技术的研发与应用也受到了国内外工业和学术界的广泛关注。脱硝技术分为干法和湿法两类，干法脱硝主要包括吸附法、还原法、分解法和氧化法等。湿法脱硝技术包括溶液吸收、气相氧化吸收、液相氧化吸收等技术，还可耦合紫外、微波、电化学等技术提高脱硝效率。对各种技术逐一进行了介绍，并通过对国内外最新研究进展的报道做出具体阐述和简要评价比较最后对烟气湿法脱硝技术进行总结和展望，旨在为各项脱硝新技术的进步及早日实现工业应用提供参考。
关键词：干法脱硝；湿法脱硝；还原法；氧化吸收法；生物法
中图分类号：X5 文献标识码：A 文章编号：0258-3283(2021)
Research Progress of Industrial Flue Gas Denitrification Technology ZHAO Lin*1,2, LIU Qing-ling1, ZHOU Wei2, HU Zhi-juan2, PENG Xue-ping2, ZHANG Li-na2, LIU Xu-yue2 (1. School of Environmental Science and Engineering, Tianjin University, Tianjin 300350, China; 2. Tianjin Cement Industry Design and Research Institute Co., Ltd., Tianjin 300400, China), Huaxue Shiji, 2021, 43(6)
Abstract：With the formulation and gradual implementation of the ultra-low emission policy, various laws and regulations, national standards, and industry standards have been launched to set requirements for the concentration and total emission of nitrogen oxides. The reduction of nitrogen oxides is imminent, and the urgent need for development is more suitable for our nation. Diversified denitrification technologies have been adapted to the characteristics of flue gas in different industries, and the development and applications of various denitrification technologies have also received extensive attention from domestic and international industries and academia. Denitrification technology can be divided into two categories: dry methods and wet methods. Dry denitrification methods mainly include adsorption method, reduction method, decomposition method, and oxidation method. Wet denitrification technology mainly include solution absorption, gas phase oxidation absorption, liquid phase oxidation absorption, and other technologies. It can also be coupled with ultraviolet, microwave, electrochemistry, and other technologies to improve the denitrification efficiency. This article introduces various technologies one by one, and provides specific explanations and brief evaluation comparisons through the latest research progress reports at home and abroad. Finally, summaries and prospects regarding the wet denitrification technologies of flue gas were given, aiming at providing references for the progresses of various new denitrification technologies and the early realization of industrial applications.
Key words：dry denitrification; wet denitrification; reduction method; oxidation absorption method; biological method
引用本文：赵琳，刘庆岭，周伟，等. 工业烟气脱硝技术国内外研究进展[J]. 化学试剂, 2021, 43(6):747-756。
植物源提取物抑制亚硝胺致癌作用的研究进展
陈玉贺，尹方正，赵丽娇*，孙国辉，张娜，任婷，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：亚硝胺是一类对人体危害极大的致癌物，是引发肝癌、肺癌和食管癌等癌症的重要因素。植物源提取物近年来逐渐成为抗癌研究的热点，例如黄酮类、多酚类、维生素类以及生物碱类化合物都具有良好的抗肿瘤效果。一些植物源提取物可以通过清除亚硝酸盐或阻断亚硝化反应来抑制亚硝胺在体内的形成；还可以通过抑制亚硝胺代谢活化、促进肿瘤细胞凋亡、抑制肿瘤细胞增殖和调节肿瘤细胞周期来阻断亚硝胺的致癌作用。对近年来国内外关于植物源提取物抑制亚硝胺诱导癌症的研究进展进行了综述，为植物源提取物的临床应用及癌症防治提供参考。
关键词：植物源提取物；亚硝胺；致癌作用；癌症防治
中图分类号：R730.1 文献标识码：A 文章编号：0258-3283(2021)
Research Progress of Natural Extracts on Inhibiting the Carcinogenesis of Nitrosamines CHEN Yu-he, YIN Fang-zheng, ZHAO Li-jiao*, SUN Guo-hui, ZHANG Na, REN Ting, ZHONG Ru-gang (Beijing Key Laboratory of Environmental & Viral Oncology, Faculty of Environment and Life, Beijing University of Technology, Beijing 100124, China), Huaxue Shiji, 2021, 43(6), ～
Abstract: Nitrosamines are a class of carcinogens that are extremely harmful to humans and are the main cause of cancers such as liver cancer, lung cancer and esophageal cancer. In recent years, natural plant extracts, such as polyphenols, vitamins and alkaloids, have become a hot spot in anti-cancer research because of their satisfying anti-tumor activity. Some natural extracts can inhibit the formation of nitrosamines in vivo by eliminating nitrite or blocking nitrosation. Moreover, they can also inhibit the carcinogenesis of nitrosamines by suppressing the metabolic activation of nitrosamines, promoting tumor cell apoptosis, inhibiting tumor cell proliferation and regulating tumor cell cycle. In this paper, the research progress of natural plant extracts inhibiting nitrosamine-induced cancers in recent years is reviewed, which is expected to provide references for the clinical application of natural plant extracts and cancer prevention.
Key words: plant extracts; nitrosamines; carcinogenesis; cancer prevention
引用本文：陈玉贺，尹方正，赵丽娇，等. 植物源提取物抑制亚硝胺致癌作用的研究进展[J]. 化学试剂, 2021, 43(6): 757-766.
壳聚糖-透明质酸支架用于低氧靶向性抗癌药物筛选的研究
李君，刘琪，赵丽娇*，孙国辉，张娜，任婷，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：三维细胞培养近年来正被逐渐广泛地应用于抗肿瘤药物筛选，与传统二维细胞培养相比，三维细胞培养模型中的细胞形态、结构和功能与实体瘤更加接近，有利于模拟肿瘤微环境，从而提高药物筛选的准确度。本研究以壳聚糖和透明质酸为原料制备了一种三维多孔支架，并使用该支架构建了人脑胶质瘤SF763细胞的三维肿瘤模型。在此基础上，使用该三维肿瘤球和普通二维细胞评价了尼莫司汀（ACNU）与替拉扎明（TPZ）的体外抗肿瘤活性；并探讨了在常氧和低氧条件下两种药物的活性差异。结果表明，不论在常氧还是低氧条件下，经ACNU处理的三维细胞均比二维细胞表现出更强的耐药性，这说明三维细胞在抗癌药物耐药性评价中具有更高的灵敏性。对于肿瘤低氧敏感药物TPZ，其对三维细胞的毒性与低氧条件下二维细胞的毒性接近，且显著高于在常氧条件下对二维细胞的毒性，这说明三维肿瘤球模拟了肿瘤组织的低氧微环境，使TPZ发生低氧启动从而发挥了抗肿瘤活性。本研究表明，三维细胞培养可作为抗肿瘤药物体外活性评价的有效模型，为抗肿瘤药物筛选提供了更加可靠的方法。
关键词：壳聚糖-透明质酸支架；三维细胞培养；低氧靶向抗癌药物；耐药性
中图分类号：TQ469 文献标识码：A 文章编号：0258-3283（2021）
Chitosan-hyaluronic Acid Scaffolds for Screening Hypoxia-targeted Anticancer Drugs LI Jun, LIU Qi, ZHAO Li-jiao*, SUN Guo-hui, ZHANG Na, REN Ting, ZHONG Ru-gang (Beijing Key Laboratory of Environmental & Viral Oncology, Faculty of Environment and Life, Beijing University of Technology, Beijing 100124, China), Huaxue Shiji, 2021, 43(6)
Abstract: The three-dimensional (3D) cell culture has been widely used for screening of anticancer agents. Compared with traditional two-dimensional (2D) cell culture, the cell morphology, structure and function of 3D tumor culture model are more similar to solid tumors, which is beneficial to simulate the tumor microenvironment and to improve the accuracy of drug screening. In this study, chitosan and hyaluronic acid (HA) were used to synthesize 3D porous scaffolds, which were applied for establishing a 3D tumor model of human brain glioma SF763 cells. Based on the 3D model, the anticancer activity of nimustine (ACNU) and tirapazamine (TPZ) were investigated in vitro using 3D tumor spheres and 2D cells. Besides, the activity of the two drugs under normoxia and hypoxic conditions was compared. The results showed that the 3D cells treated with ACNU showed higher drug resistance than the 2D cells under both normal and hypoxic conditions, indicating that 3D cells possess higher sensitivity in the evaluation of drug resistance to chemotherapies. Tirapazamine, a tumor hypoxia-sensitive drug, exhibited similar toxicity to 3D and 2D cells under hypoxic condition, which was significantly higher than that under normoxic condition. This indicated that the 3D tumor spheres simulating the hypoxic microenvironment of tumors tissue enabled the hypoxic activation of TPZ, thus exerting its anti-tumor activity. This study showed that 3D cell culture could be used as an effective model for in vitro activity evaluation of anti-tumor drugs, and provided a reliable method for screening anti-tumor drugs.
Key words: chitosan-hyaluronic acid scaffolds; three-dimensional cell culture; hypoxia targeted anticancer agents; drug resistance
引用本文：李君，刘琪，赵丽娇，等. 壳聚糖-透明质酸支架用于低氧靶向性抗癌药物筛选的研究[J]. 化学试剂，2021，43（6）：767-774。
肿瘤靶向性多功能亚硝基脲的合成及抗肿瘤活性评价
刘琪，王娇娇，赵丽娇*，孙国辉，任婷，张娜，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：氯乙基亚硝基脲（CENUs）是临床上重要的抗肿瘤药物，该类药物通过诱导形成DNA股间交联（dG-dC交联）发挥抗肿瘤作用。但O6-烷基鸟嘌呤-DNA烷基转移酶（O6-alkylguanine-DNA alkyltransferase, AGT）介导的细胞耐药性及明显的毒副作用降低了其抗癌效果。通过合成了一种肿瘤靶向性多功能亚硝基脲，该化合物由具有低氧选择活性的偶氮苯衍生物、能够抑制AGT活性的O6-苄基鸟嘌呤衍生物和氯乙基亚硝基脲三部分组成。该化合物能够特异性地在低氧肿瘤区域被还原，释放AGT抑制剂和氯乙基亚硝基脲，从而发挥靶向抗肿瘤作用。多功能亚硝基脲及其各中间产物的化学结构经高分辨质谱、1HNMR、13CNMR及IR数据确证。用CCK-8法评价了上述化合物对人脑神经胶质瘤SF763细胞的增殖抑制活性；并用荧光成像法评价了该化合物对SF763细胞的促凋亡活性。结果表明，与临床一线亚硝基脲类抗肿瘤药物尼莫司汀相比，多功能亚硝基脲能够更有效地抑制肿瘤细胞增殖、促进肿瘤细胞凋亡，并具有明显的低氧靶向性。
关键词：氯乙基亚硝基脲；肿瘤靶向性；肿瘤低氧；耐药；化疗药物
中图分类号：R914 文献标识码：A 文章编号：0258-3283(2021)
Synthesis and Antitumor Activity Evaluation of Tumor-targeting Multifunctional Nitrosourea LIU Qi, WANG Jiao-jiao, ZHAO Li-jiao*, SUN Guo-hui, REN Ting, ZHANG Na, ZHONG Ru-gang (Beijing Key Laboratory of Environmental & Viral Oncology, Faculty of Environment & Life, Beijing University of Technology, Beijing 100124, China), Huaxue Shiji, 2021, 43(6)
Abstract: In order to select the best processing technology, the changes of active ingredients in Polygonatum kingianum Coll. et Hemsl were studied by the method "nine steaming and nine making" of traditional Chinese medicine. The samples were processed by steaming, and then the contents of polysaccharides, total saponins and anthraquinones in them were measured with UV-VIS spectrophotometry. The results showed that the changes of polysaccharide content in Polygonatum kingianum Coll. et Hemsl first decreased and then stabilized with the increase of steaming time. In contrast, the content of anthraquinones showed a decreasing trend. The content of total saponins first increased and then stabilized. The active ingredients in Polygonatum kingianum Coll. et Hemsl were affected by the steaming time, which indicated that excessive steaming time was adverse. The results provided a basis for the processing technology and the way of getting high-quality Polygonatum kingianum Coll. et Hemsl.
Key words: chloroethylnitrosoureas; tumor targeting; tumor hypoxia; drug resistance; chemotherapy drugs
引用本文：刘琪，王娇娇，赵丽娇，等. 肿瘤靶向性多功能亚硝基脲的合成及抗肿瘤活性评价[J]. 化学试剂, 2021, 43(6):775-782。
基于网络药理学分析中药半夏的药理作用分子机制
乔新荣, 蔡静, 陈琼*
（信阳农林学院 生物与制药工程学院，河南 信阳 464000）
摘要：基于网络药理学方法探讨中药半夏主要活性成分的药理活性，预测和分析其潜在的分子作用机制。首先使用TCMSP数据库筛选半夏的有效活性成分及作用靶点，并用Uniprot数据库将作用于人源靶点转成相应的基因名，而后运用STRING平台结合Cytoscape软件构建蛋白互作网络，再利用DAVID数据库进行GO生物学过程分析和KEGG信号通路富集分析，最后构建主要活性成分-靶点-通路可视化网络图。结果表明，半夏有12种主要有效成分作用于169个人源靶点，其中半夏的主要活性成分为黄芩素、β-谷甾醇、豆甾醇、松柏苷等。他们主要通过调控核心基因AKT1、FOS、JUN、TP53、VEGFA、MMP9、ESR1、CASP3、HSP90AA1、AR、PTGS2、RELA、PPARG、CYCS 和PGR及关键基因PIK3CG、PRKACA、BCL2、ADRA1A，ADRA1B和ADRB2等靶点，经钙信号、激酶信号等途径，在治疗癌症、神经性疾病、内分泌代谢性疾病等方面发挥较强的作用。研究揭示了中药半夏具有多成分、多靶点、多途径的药理作用特点，将为进一步对其药理药效作用机制的研究奠定了基础。
关键词：半夏；网络药理学；活性化合物；数据库；信号通路
中图分类号：R285 文献标识码：A 文章编号：0258-3283（2021）--
Study on the Molecular Mechanism of Pharmacological Effects in Pinellia Ternate (Thunb.) Breit. Based on Network Pharmacology QIAO Xin-rong, CAI Jing, CHEN Qiong* (College of Biological &Pharmaceutical Engineering, Xinyang College of Agriculture and Forestry, Xinyang 464000, China), Huaxue Shiji, 2021, 43(6), ～
Abstract: This study was aimed to explore pharmacological activities of the main active compounds in Pinellia ternate, and to predict and analyze their potential molecular mechanism based on network pharmacology methods. Firstly, the main components in Pinellia ternata and related targets were collected and screened using TCMSP database, and these targets of acting on homo species were transformed into gene names in Uniprot database. Then, STRING online platform and Cytoscape software were applied to construct protein interaction network. Enrichment analysis of GO biological process and KEGG pathway were performed by DAVID online software. Finally, a network interaction diagram of the main compound-target-signaling pathway of Pinellia ternate was established by Cytoscape software. The results showed that 12 main active components, including baicalein, beta-sitosterol, stigmasterol, coniferin and so on, acted on 169 targets from homo species, and played a certain role in the treatment of cancer, neurodegenerative diseases, endocrine and metabolic diseases by regulating hub genes such as AKT1, FOS, JUN, TP53, VEGFA, MMP9, ESR1, CASP3, HSP90AA1, AR, PTGS2, RELA, PPARG, CYCS, PGR and key genes including PIK3CG, PRKACA, BCL2, ADRA1A, ADRA1B and ADRB2 that mediate calcium and kinase signals. This study provides fully reflected pharmacologic action characteristics of the multiple components, multiple targets and multiple pathways in Pinellia ternata, and provided a theoretical reference for further understanding its pharmacological effects mechanism.
Key words: Pinellia ternate (Thunb.) Breit.; network pharmacology; active compound; database; signaling pathway
引用本文：乔新荣, 蔡静, 陈琼. 基于网络药理学分析中药半夏的药理作用分子机制[J]. 化学试剂, 2021, 43(6): 783-789.
不同炮制方式对黄精有效成分含量的影响
田先娇1，罗雪维2，杨新周1，张薇*2
(1. 德宏师范高等专科学校，民族医药研究所，云南 德宏，678400；
2. 红河学院，生命科学与技术学院，云南 蒙自 661100)
摘要:以滇黄精为对象，研究“九蒸九制”过程中有效成分含量的变化，探究出滇黄精的最佳炮制工艺。试验中选取蒸制处理方法，采用紫外-可见分光光度法，研究九蒸九制过程中，多糖、总皂苷和蒽醌类化合物的含量变化。结果表明，随着蒸制处理次数的增加，滇黄精多糖的含量呈现出先下降后趋于稳定的变化，蒽醌类化合物含量呈下降趋势，总皂苷含量呈现出先上升后趋于稳定的变化。蒸制处理对滇黄精有效成分含量产生了一定影响，蒸制时长和次数并不是越多越好。研究结果为黄精的炮制工艺和高品质黄精产品开发提供了依据。
关键词：滇黄精；蒸制；多糖；皂苷；蒽醌
中图分类号：R283 文献标识码：A 文章编号：0258-3283（2021）--
The Effects of Different Processing Methods on Components in Polygonatum kingianum Coll. et Hemsl TIAN Xian-jiao1, LUO Xue-wei 2, YANG Xin-zhou 1, ZHANG Wei*2 (1.The Research Institute of Ethnic Minority Medicine, Dehong Teachers’ College, Dehong 678400, China；2. College of Life Science and Technology, Honghe University, Mengzi 661100, China), Huaxue Shiji, 2021, 43(6), ～
Abstract：In order to choose the best processing technology,the change of active ingredient in Polygonatum kingianum Coll. et Hemsl were researched with a traditional Chinese medicine method “nine steaming and nine making”. The samples were processed by steaming, and then the content of polysaccharides, total saponins and anthraquinones in them were measured with UV-VIS spectrophotometry. The results show that the change of content of polysaccharide in Polygonatum kingianum Coll. et Hemsl were decreased firstly and then tended to be stable with the steaming times increasing;the content of anthraquinones showed a downward trend;The content of total saponins were increased firstly and then tended to be stable.The active ingredient in Polygonatum kingianum Coll. et Hemsl were affected by steaming times. The more times of steaming were not the better. The The results provided a basis for the processing technology and the way of getting high quality Polygonatum kingianum Coll. et Hemsl.
Key words: Polygonatum kingianum Coll. et Hemsl; steam; Polysaccharide; Saponins; anthraquinone
引用本文：田先娇，罗雪维，杨新周，等. 不同炮制方式对黄精有效成分含量的影响[J]. 化学试剂, 2021, 43(6): 790-794.
固相萃取-气相色谱质谱法同时测定环境水体中79种半挥发性有机污染物
王燕*1，朱卫平2
(1. 青海省地质矿产测试应用中心，青海 西宁 810000；
2. 青海省固体废物污染防治中心，青海 西宁 810000)
摘要：建立了固相萃取-气相色谱质谱法（SPE-GC-MS）同时检测环境水体中不同极性范围的79种半挥发性有机污染物的分析方法。样品经膜片式固相萃取装置，以50 mL/min速率通过Empore C18膜片（47 mm）净化和富集后GC-MS检测，内标法定量。研究表明，79种半挥发性有机污染物在1～1000 μg/L线性范围内相关系数R2>0.99；检测限和定量限分别为0.009～0.077 ng/L和0.076～0.31 ng/L；在3个添加水平下（10、100、500 ng/L）79种半挥发性有机污染物在3种不同水体环境中的平均回收率为60.6%～137.3%，相对标准偏差（RSD）为0.8%～8.8%。该方法操作简便，前处理流程快、方法灵敏度和准确度高、环保和通用性强，适用于河流、水库和化工污水样品的检测，在环境监测工作中有很强的实际应用价值。
关键词：气相色谱质谱；固相萃取；半挥发性有机污染物；环境水体
中图分类号：X8 文献标识码：A 文章编号：0258-3283（2021）06
Simultaneous Determination of 79 Semi-volatile Organic Pollutants in Environmental Water by Solid Phase Extraction-gas Chromatography-mass Spectrometry WANG Yan*1, ZHU Wei-ping2
(1. Application of Geology and Mineral Resources Test Center in Qinghai Province, Xining 810000, China; 2. Solid Waste Pollution Prevention and Control Center in Qinghai province, Xining 810000, China), Huaxue Shiji, 2021, 43(6)
Abstract: A solid-phase extraction gas chromatography mass spectrometry (SPE-GC-MS) method was developed for the simultaneous determination of 79 semi-volatile organic pollutants (SVOCs) with different polar ranges in environmental waters. The sample was first purified and enriched by 3M Empore C18 membrane (47 mm) at rate of 50 mL/min. The sample was detected by GC-MS and quantified by internal standard method. The results showed that the correlation coefficient (R2) of 79 SVOCs pollutants was greater than 0.99 in the linear range of 1～1000 μg/L. The MDL and LOQ were 0.009～0.077 ng/L and 0.076～0.31 ng/L, respectively. The average recoveries and relative standard deviations (RSDs) of the 79 SVOCs pollutants in two kinds of different environmental waters were 60.6%～137.3% and 0.8%～8.8%, respectively, at 3 additive levels (10, 100, and 500 ng/L). The method is easy to operate, fast in pretreatment process, high in sensitivity and accuracy, versatile in environmental protection. It is suitable for the detection of river, reservoir, and chemical wastewater samples, and has strong practical application values in monitoring environmental waters.
Key words: gas chromatography mass spectrometry (GC-MS); solid phase extraction; SVOCs; environmental water
引用本文：王燕，朱卫平. 固相萃取-气相色谱质谱法同时测定环境水体中79种半挥发性有机污染物[J]. 化学试剂，2021，43(6)：795-800.
柱前衍生-高效液相色谱法测定新鲜烟叶中游离氨基酸
许永1，黄丽佳1,2，刘欣1，李晶1，宋春满*1, 杨光宇1，李雪梅1
（1. 云南中烟工业有限责任公司技术中心，云南 昆明 650106；2. 昆明医科大学 药学院，云南 昆明 650504）
摘要：建立了柱前衍生-高效液相色谱检测新鲜烟叶中18种游离氨基酸的分析方法。0.2 g样品用5 mL超纯水超声提取30 min，过滤后取0.5 mL滤液以异硫氰酸苯酯（PITC）衍生，以Waters SunFire C18色谱柱为分析柱，80%乙腈和0.1 mol/L乙酸钠水溶液为流动相，梯度洗脱，在254 nm处检测，外标法定量。结果表明，18种氨基酸的线性范围介于2～50 μg/mL，定量限为0.03～0.10 mg/g，3个水平加标平均回收率在84.6%～105%之间，相对标准偏差为1.7%～5.5%。该方法简便快速，适用于新鲜烟叶中18种游离氨基酸的含量分析。
关键词：柱前衍生；高效液相色谱；烟叶；游离氨基酸
中图分类号：O652 文献标识码：A 文章编号：0258-3283（2021）--
Determination of Free Amino Acids in Fresh Tobacco Leaves by High Performance Liquid Chromatography with Pre-column Derivatization XU Yong1, HUANG Li-jia1,2, LIU Xin1, LI Jing1, SONG Chun-man*1, YANG Guang-yu1, LI Xue-mei1 (1. Technology Center of China Tobacco Yunnan Industrial Co., Ltd, Kunming 650106, China; 2. School of Pharmacy, Kunming Medical University, Kunming 650504, China), Huaxue Shiji, 2021, 43(6), ～
Abstract: A method was developed for the determination of 18 free amino acids in fresh tobacco leaves by pre-column derivatization-high performance liquid chromatography. 0.2 g Sample was extracted by ultrasonication with 5 mL ultrapure water for 30 min, filtrated and then 0.5 mL of the filtrate was derived with phenyl isothiocyanate (PITC) and analyzed on a Waters Sun Fire C18 column with 80% acetonitrile and 0.1 mol/L aqueous sodium acetate solution as mobile phase. Derivatives were detected at the wavelength of 254 nm and quantified with external standard method. The results showed that the linear ranges of 18 free amino acids were 2～50 μg/mL, and the limits of quantitation were 0.03～0.10 mg/g, and the average recoveries of 18 free amino acids were in the range of 84.6%～105% with relative standard deviations of 1.7%～5.5%. The method is simple and suitable for the analysis of 18 free amino acids in fresh tobacco leaves.
Key words: pre-column derivatization; high performance liquid chromatography; tobacco leaves; free amino acids
引用本文：许永, 黄丽佳, 刘欣, 等. 柱前衍生-高效液相色谱法测定新鲜烟叶中游离氨基酸[J]. 化学试剂, 2021, 43(6): 801-805.
盐酸吉西他滨中甲磺酸酯类基因毒性杂质的GC-MS/MS测定
姚彤1，程青芳*2
(1. 连云港杰瑞药业有限公司，江苏 连云港 222000；2. 江苏海洋大学 药学院，江苏 连云港 222005)
摘要：建立了盐酸吉西他滨中2种甲磺酸酯类基因毒性杂质甲磺酸甲酯和甲磺酸乙酯的气相色谱串联质谱（GC-MS/MS）检测方法。采用VF-WAX ms 毛细管色谱柱（30 m×0.25 mm×1.0 μm）对这两种甲磺酸酯类化合物进行分离。结果显示，两种化合物在所测浓度范围内线性关系良好；甲磺酸甲酯、甲磺酸乙酯定量限分别为0.0096、0.0087 μg/mL，检测限分别为0.0026、0.0029 μg/mL。平均加样回收率为97%～100%，RSD≤3%（n=9），且对照品溶液和供试品溶液在25 ℃放置24 h稳定，RSD≤1.2%。将所建方法应用于检测3批盐酸吉西他滨样品，检出了甲磺酸甲酯和甲磺酸乙酯，检出范围分别为0.22～0.40 mg/L 和 0.12～0.28 mg/L。所建立的分析方法灵敏度高、专属性和准确度好，适用于同时测定盐酸吉西他滨中两种甲磺酸酯类基因毒性杂质，为该药品的质量控制提供参考。
关键词：盐酸吉西他滨；基因毒性杂质；甲磺酸酯；气相色谱串联质谱法
中图分类号：R917 文献标识码：A 文章编号：0258-3283（2021）
Simultaneous Determination of Genotoxic Methanesulfonate Impurities in Gemcitabine Hydrochloride by GC-MS/MS YAO Tong1, CHENG Qing-fang*2（1. Lianyungang JerryPharm. Co., Ltd., Lianyungang 222000, China; 2. School of Pharmacy, Jiangsu Ocean University, Lianyungang 222005, China), Huaxue Shiji, 2021, 43(6), ～
Abstract: A GC-MS method was established for the determination of two genotoxic mesylate impurities in gemcitabine hydrochloride: methyl methanesulfonate and ethyl methanesulfonate. The separation of methyl methanesulfonate and ethyl methanesulfonate was performed in a VF-WAXms capillary column (30 m×0.25 mm×0.5 μm). The results showed that the linearities of methyl methanesulfonate and ethyl methanesulfonate in the test concentration ranges are good. The quantification limits of methyl methanesulfonate and ethyl methanesulfonate were 0.0096 μg/mL and 0.0087 μg/mL, respectively. Their detection limits were respectively 0.0026 μg/mL and 0.0029 μg/mL. The average recoveries of methyl methanesulfonate and ethyl methanesulfonate were 97% and 100% with RSDs (n = 9) no more than 3%. The reference solution and test solution were stable for at least 24 h at 25 ℃. The proposed method was applied to detect three gemcitabine hydrochloride samples, and the detection range of methyl methanesulfonate and ethyl methanesulfonate were 0.2～0.4 ppm and 0.1～0.3 ppm, respectively. With high sensitivity, good specificity and accuracy, the method established in this work is suitable for the simultaneous determination of methyl methanesulfonate and ethyl methanesulfonate in gemcitabine hydrochloride and provides a reliable method for the quality control of related drugs.
Key words: gemcitabine hydrochloride; genotoxic impurity; methanesulfonate; GC-MS/MS
引用本文：姚彤，程青芳. 盐酸吉西他滨中甲磺酸酯类基因毒性杂质的GC-MS/MS测定[J].化学试剂，2021,43（6）：806-810.
自动电位滴定法测定电池级碳酸锂中痕量氯
王裕生，廉芒芬，柳春月，林丽美，孙伟丽*
（宁波容百新能源科技股份有限公司，浙江 余姚 315400）
摘要：建立了自动电位滴定法测定电池级碳酸锂等化学品中痕量氯的测试方法。优化溶液总体积、溶剂、pH以及滴定参数后，碳酸锂中氯离子测试加标回收率96.3～103.5%，平均回收率99.1%，并通过加标测试避免高电位处可能出现的峰干扰。在样品测试中，电位滴定法与分光光度法的测试结果绝对差值≤0.0005%，并且测试时间通常低于10 min。优化后的电位滴定法氯离子测试检出限0.2876 μg，碳酸锂中氯离子测试绝对误差在±0.0001%范围内。此外，该方法也适用于氢氧化锂、硝酸铝等其他化学品中氯离子量的测定。
关键词：电位滴定法；碳酸锂；氯离子；氢氧化锂；硝酸铝
中图分类号：O655.24 文献标识码：A 文章编号：0258-3283（2021）--
Determination of Chloride Ion in Battery Grade Lithium Carbonate by Automatic Potentiometric Titration WANG Yu-sheng, LIAN Mang-fen, LIU Chun-yue, LIN Li-mei, SUN Wei-li* (Ningbo Ronbay New Energy Technology Co., Ltd., Ningbo 315000, China), Huaxue Shiji, 2021, 43(6), ～
Abstract: An automatic potentiometric titration method for the determination of trace chlorine in battery grade lithium carbonate and other chemicals was established. After optimizing total solution volume, solvent, pH and titration parameters, the recovery of standard addition of chloride ion test in lithium carbonate was 96.3～103.5%, the average recovery was 99.1%, and the standard addition method was used to eliminate the possible peak interference at high potential. In sample tests, the absolute difference between potentiometric titration method and spectrophotometry method was not larger than 0.0005%, and the testing duration was usually less than 10 min. The detection limit of the optimized potentiometric titration for chloride ion test was 0.2876 μg, and the absolute error of chloride ion test in lithium carbonate was within ±0.0001%. In addition, our method is also suitable for the determination of chloride ion in lithium hydroxide, aluminum nitrate and other chemicals.
Key words: potentiometric titration；lithium carbonate；chloride ion；lithium hydroxide；aluminum nitrate
引用本文：王裕生, 廉芒芬, 柳春月,等. 自动电位滴定法测定电池级碳酸锂中痕量氯[J]. 化学试剂, 2021, 43(6): 811-815.
库仑滴定法测定枸杞中二氧化硫的残留量
牛鹤丽
（白城医学高等专科学校，吉林 白城 137000）
摘要：建立库仑滴定法测定枸杞中二氧化硫残留量的分析方法。采用铂片电极为电解电极和指示电极，0.8 mol/L碘化钾为电解质溶液，经恒定电流电解生成I2后，与预处理的样品溶液中SO32-定量发生氧化还原反应，记录滴定时间，通过法拉第电解定律，测得样品中二氧化硫含量。采用不同分析方法分别测定硫磺熏蒸后样品的二氧化硫残留量，结果无显著性差异。由于该方法操作简便、快速，结果的准确度与精密度较好，因此适于枸杞中二氧化硫残留的监督检验。
关键词：枸杞；库仑滴定；碘化钾；二氧化硫；残留量
中图分类号：O 657.12 文献标识码：A 文章编号：0258-3283（2021）
Determination of Residual Sulfur Dioxide in Wolfberry by Coulometric Titration NIU He-li (Baicheng Medical College, Baicheng 137000, China), Huaxue Shiji, 2021, 43(6), ～
Abstract: A coulometric titration analytical method for sulfur dioxide residue in Wolfberry was established. The platinum electrode was used as the electrolysis electrode and the indicating electrode, and 0.8 mol/L potassium iodide solution was used as the electrolyte. The iodine titrant was electrolytically generated through constant current electrolysis. It further reacted with the SO32- in pretreated sample solution, which was a quantitative oxidation-reduction reaction. By recording the titration time, the sulfur dioxide residue was determined by Faraday’s law calculation. The sulfur dioxide residue of samples after sulphur fumigation were assayed by different analytical methods, and results indicated no significant difference. Because our proposed method is simple, fast, and the accuracy and precision of the results are very good, therefore it is suitable for the supervision and inspection of sulfur dioxide residues in Chinese Wolfberry.
Key words: Wolfberry; coulometric titration; potassium iodide; sulfur dioxide; residue
引用本文：牛鹤丽. 库仑滴定法测定枸杞中二氧化硫的残留量[J]. 化学试剂，2021, 43（6）：816-819.
醋酸可的松及其代谢物与牛血清白蛋白相互作用机制的研究
顾佳丽*1，刘璐1，黄曦瑶1，何茜1，李响2
(1. 渤海大学 化学与材料工程学院，辽宁 锦州 121013；
2. 沈阳感光化工研究院有限公司，辽宁 沈阳 110141)
摘要：采用荧光光谱法和紫外-可见吸收光谱法研究了醋酸可的松（CA）及其代谢产物氢化可的松（HS）与牛血清白蛋白（BSA）之间的作用机理。实验结果表明，CA和HS均通过疏水作用与BSA形成复合物，其结合常数分别为2.04×104 L/mol和2.02×103 L/mol。CA/HS对氨基酸残基周围的微环境没有显著影响。HS会使CA与BSA作用的结合常数减小，结合距离增大，但没有改变其主要作用力类型。
关键词：醋酸可的松；氢化可的松；牛血清白蛋白；相互作用
中图分类号：O657 文献标识码：A 文章编号：0258-3283(2021)
Study on the Interaction Mechanism of Cortisone Acetate and Its Metabolite with Bovine Serum Albumin GU Jia-li1, LIU Lu1, HUANG Xi-Yao1, HE Qian1, LI Xiang2 (1. College of Chemistry and Chemical Engineering, Bohai University, Jinzhou 121013, China; 2. Shenyang Photosensitive Chemical Research Institute Co., Ltd., Shenyang 110141, China), Huaxue Shiji, 2021, 43(6)
Abstract: The interaction mechanisms between cortisone acetate (CA) and its metabolite hydrocortisone (HS) with bovine serum albumin (BSA) were studied by fluorescence spectroscopy and UV-vis absorption spectroscopy. The results showed that CA and HS formed complex with BSA through hydrophobic interaction, and their binding constants were 2.04×104 L/mol and 2.02×103 L/mol, respectively. The micro-environment around the amino acid residues engaged no significant change in the present of CA/HS. As shown, the HS decreases the binding constant and increases the binding distance for the CA-BSA interaction, but does not change its main force type.
Key words: cortisone acetate; hydrocortisone; bovine serum albumin; interaction
引用本文：顾佳丽，刘璐，黄曦瑶，等. 醋酸可的松及其代谢物与牛血清白蛋白相互作用机制的研究[J]. 化学试剂，2021, 43（6）:820-824.
不同类型生物质秸秆燃烧特征研究
魏鑫1，周宇峰1，李清清1，成亚1，李娜1，韩维峥*2
（1. 吉林建筑大学 松辽流域水环境重点实验室，吉林 长春 130118；2. 长春市城乡规划设计研究院，吉林 长春 130000）
摘要：东北地区作为我国主要农业省份，其粮食产量高的同时亦产生大量的生物质，露天燃烧是去除生物质的高效而便捷的方式，但生物质燃烧过程会产生释放包括PM2.5、CO、VOCs等空气污染物，对区域环境质量、大气能见度、人类健康等均产生一定程度的影响。同时，生物质类型繁多，其燃烧产物和影响不尽相同，收集花生壳、稻壳、秸秆、木质颗粒物4种生物质，利用实验室环境模拟舱进行室外模拟燃烧实验，测定其燃烧产物中的无机元素、水溶性离子以及形貌分析。4种生物质燃烧后的8种无机元素中，均呈现出Zn含量较高，而致癌元素含量较低的趋势；小麦秸秆和木质颗粒物的水溶性离子排放因子较花生壳和稻壳较大，且水溶性离子以K+和Cl-排放较多；通过燃烧产物的形貌分析可以看出，不同类型生物质燃烧后形貌各异，以条状、柱状及颗粒状为主。该结果为研究地方生物质燃烧特点奠定了理论，并对地方生物质燃烧排放特征的确定提供了数据支撑。
关键词：生物质；无机元素；水溶性离子；形貌分析
中图分类号：TK6 文献标识码：A 文章编号：0258-3283（2021）--
Study of Characteristics through Biomass Burning WEI Xin1, ZHOU Yu-feng1, LI Qing-qing1, CHENG Ya1, LI Na1, HAN Wei-zheng*2 (1. Key Laboratory of Songliao Aquatic Environment, Ministry of Education, Jilin Jianzhu University, Changchun 130118, China; 2. Changchun Institute of Urban Planning & Designing, Changchun 130031, China), Huaxue Shiji, 2021, 43(6), ～
Abstract: As a major agricultural province in China, the northeast China produces a large amount of biomass along with high grain production. Open burning is an efficient and convenient way to remove biomass. However, atmospheric pollutants (PM2.5, CO, VOCs) are released in the process of biomass combustion, which has an impact on regional environmental quality, atmospheric visibility, and human health. Because of the various type of biomass, their combustion products and effects are different. In this study, peanut shells, rice husks, straw and wood pellets were collected and simulated combustion experiments were carried out in a laboratory environmental simulation chamber. Determination of the combustion products of inorganic elements, water-soluble ions and morphology analysis were conducted. The results showed that the content of Zn was higher than that of carcinogenic elements after combustion among eight main inorganic elements. The water-soluble ion emission factors of wheat straw and wood pellets were larger than those of peanut shells and rice husks, and the water-soluble ions are mainly K+ and Cl-. The morphological analysis of combustion products showed that that the morphology of different types of biomass after combustion was different, mainly in the form of strips, columns, and particles. The results lay a theoretical foundation for the study of local biomass combustion, and provide data for the determination of local biomass combustion emission characteristics.
Key words: biomass; inorganic elements; water-soluble ions; morphological analysis
引用本文：魏鑫, 周宇峰, 李清清, 等. 不同类型生物质秸秆燃烧特征研究[J]. 化学试剂, 2021, 43(6): 825-829.
污泥生物质混合燃料燃烧特性分析
何萍*，张京京，潘懿，刘说，高爽，朱宝伟
（营口理工学院 化学与环境工程学院，辽宁 营口 115014）
摘要：能源危机和环境问题加速了环境友好、可再生替代能源的发展。使用热重分析方法对北方常见5种农业废弃生物质、污泥以及玉米秸秆和污泥混合燃料的燃烧特性进行了研究，并考察了混合燃料各组分间相互作用。结果表明：5种生物质燃料中玉米秸秆燃烧特性最好，污泥燃烧性能明显低于生物质；混合燃料燃烧时，分阶段展现出玉米秸秆和污泥的燃烧特性；随着混合燃料中污泥含量的增高，会出现不易燃尽，放热量低，以及组分间相互抑制作用。
关键词：污泥；生物质；热重分析；燃烧特性
中图分类号：X705 文献标识码：A 文章编号：0258-3283（2021）--
Analysis of Co-combustion Characteristics of Sludge and Biomass HE Ping*, ZHANG Jing-Jing, PAN Yi, LIU Shuo, GAO Shuang, ZHU Bao-Wei (College of Chemistry and Environmental Engineering, Yingkou Institute of Technology, Yingkou 115014, China), Huaxue Shiji, 2021, 43(6), ～
Abstract: Due to the energy crisis and environment issues, the development of alternative energy sources that are environmentally friendly and renewable has been ever accelerated. In this paper, the combustion characteristics of five agricultural waste biomass, sludge, corn stalk and sludge mixed fuels in northern China were studied using thermogravimetric analysis. The interactions between the components of the mixed fuels were investigated. The results showed that the combustion characteristics of corn straw were the best among the five biomass fuels, and the sludge combustion performance was significantly lower than that of biomass. When the mixed fuels were burned, the combustion characteristics of corn straw and sludge were exhibited in stages. With the increase of the sludge content in the mixed fuels, there will be non-burnout, low heat release, and mutual inhibition between components.
Key words: sludge; biomass; thermogravimetric analysis; combustion characteristic
引用本文：何萍, 张京京, 潘懿, 等. 污泥生物质混合燃料燃烧特性分析[J]. 化学试剂, 2021, 43(6): 830-835.
双光子镉离子荧光探针TPCN合成及光谱性质研究
魏凯，刘永友*
（南京医科大学康达学院，江苏 连云港 222000）
摘要：双光子荧光探针具有长波激发、短波发射的特点，可以有效避免样品本底荧光和散射光的干扰，在生物分析中有较多应用。通过Wittig-Horner反应合成了发光机理为分子内电荷转移（ICT）型，分子构型为D-A-D型（A表示电子受体，D表示电子给体）的双光子镉离子荧光探针TPCN，探针随镉离子浓度增加，荧光强度呈线性下降并伴随红移现象发生，检测线性范围为3.00×10-6～1.00×10-4 mol/L，检测限可以达到4.00×10-7 mol/L，并由于探针荧光团中心存在吸电子能力较强的氰基，增加了分子内的电荷迁移能力，使探针有较大的双光子吸收截面。
关键词：双光子荧光探针；分子内电荷转移；镉离子；重金属检测；D-A-D型
中图分类号：O625 文献标识码：A 文章编号：0258-3283（2021）
Synthesis and Spectral Properties of Two-photon Fluorescent Probe TPCN for Cadmium Ion WEI kai, LIU Yong-you* (Kangda College of Nanjing Medical University, Lianyungang 222000, China), Huaxue Shiji, 2021, 43(6)
Abstract: Two-photon fluorescent probe can be excited in the NIR region to give emission in the visible region, therefore one can effectively reduce autofluorescence of biomolecules and the scattered light of the sample, which has been widely used in biological analysis. In this study, through Wittig-Horner reaction, a new two-photon fluorescent probe TPCN for cadmium ion with internal charge transfer (ICT) mechanism was synthesized. The structural type of the TPCN belongs to D-A-D (where A is an electron acceptor and D is an electron donator) quadruples configuration. With the increase of cadmium ions concentration, the fluorescence intensity of the fluorescent probe TPCN decreased linearly and accompanied by the phenomenon of red-shifting. The detection linear range was 3.00×10-6～1.00×10-4 mol/L, and the detection limit could reach 4.00×10-7 mol/L. Due to the cyano-group introduced in the central phenyl groups, the internal charge transfer (ICT) ability was enhanced, allowing the probe to achieve a larger two-photon cross section.
Key words: two-photon fluorescent probe; internal charge transfer (ICT); cadmium ion; heavy metal detection; D-A-D type
引用本文：魏凯，刘永友. 双光子镉离子荧光探针TPCN合成及光谱性质研究[J]. 化学试剂, 2021, 43(6):836-841。
藏茶多糖的提取工艺优化及其抗氧化活性研究
章斌1，姚永秀1，张恒1，卢勇2，袁野*1
（1. 雅安职业技术学院 药学与检验学院，四川 雅安 625000；2. 雅安市中医医院，四川 雅安 625000）
摘要：优化藏茶多糖(TTP)的提取工艺，并评价其体外抗氧化活性。在单因素试验基础上，以液料比、提取温度、提取时间为影响因素，TTP提取率为评价指标，采用响应面法(RSM)和遗传算法-人工神经网络(GA-ANN)优化提取工艺，并考察TTP对DPPH自由基和ABTS自由基的清除作用。结果表明，TTP最优提取工艺设置为液料比42 :1（mL/g），提取温度81 ℃，提取100 min，提取率为5.72%(n=3，RSD=2.45%)。TTP清除DPPH自由基和ABTS自由基的IC50值分别为102.52 、578.11 μg/mL。基于RSM和GA-ANN优选所得工艺提取效率高、稳定性好，可用于提取具有良好抗氧化活性的TTP，为藏茶资源的进一步开发利用提供参考。
关键词：藏茶多糖；提取工艺优化；响应面法；遗传算法-人工神经网络；抗氧化活性
中图分类号： 文献标识码： 文章编号：0253-3283（2021）06--
Study on Extraction Technology Optimization and Antioxidant Activity of Tibetan Tea Polysaccharides ZHANG Bin1, YAO Yong-xiu1, ZHANG Heng1, LU Yong2, YUAN Ye*1(1. School of Pharmacy and Medical Laboratory Science, Ya′an Polytechnic College, Ya'an 625000, China; 2.Ya'an Hospital of Traditional Chinese Medicine, Ya'an 625000, China), Huaxue Shiji, 2021, 43(6), ～
Abstract: This work was conveyed to optimize the extraction technology of Tibetan tea polysaccharides (TTP), and to study its antioxidant activity. Using the liquid-solid ratio, extraction temperature, extraction time as the influencing factors, and TTP yield as an evaluation index, the extraction technology was optimized by response surface method (RSM) and genetic algorithm-artificial neural network (GA-ANN) based on single factor test. The scavenging effect of TTP on DPPH and ABTS free radical was investigated. The optimal technology parameters of TTP were liquid-solid ratio of 42:1 (mL/g), extraction temperature of 81 ℃, and extraction time of 100 min. The yield of TTP was 5.72% (n = 3, RSD = 2.45%). TTP revealed a certain scavenging capacity on DPPH and ABTS free radical with the IC50 of 102.52 μg/mL and 578.11 μg/mL, respectively. The process of TTP with strong antioxidant activity obtained from RSM and GA-ANN has high extraction efficiency and good stability, which provides a reliable reference for the subsequent development and utilization of Tibetan tea.
Key words: Tibetan tea polysaccharides; extraction technology optimization; response surface methodology; genetic algorithm; artificial neural network; antioxidant activity
引用本文：章斌，姚永秀，张恒，等. 藏茶多糖的提取工艺优化及其抗氧化活性研究[J].化学试剂，2021，43（6）：842-847.
13C同位素标记DDT、DDD、DDE的简便合成
王智楠，全海源，胡宇钊，王留洋，蒋志福，梅向东，宁君，折冬梅*
(中国农业科学院植物保护研究所，北京 100193)
摘要：有机氯农药滴滴涕（双对氯苯基三氯乙烷，DDT）作为一种持久性有机污染物，在环境中长时间滞留，并逐步代谢为更加稳定的滴滴伊（1，1-二氯-2，2-双(4-氯苯基)乙烯，DDE）和滴滴滴（双(6-羟基-2-萘)二硫，DDD）。首次报道了13C12标记p,p’-DDT、p,p’-DDD和p,p’-DDE的合成。以13C6苯为同位素标记原料，通过氧氯化（oxychlorination）得13C6-氯苯，13C6-氯苯分别与三氯乙醛水合物和二氯乙醛水合物经浓硫酸催化缩合制得13C12-DDT和13C12-DDD，以聚乙二醇-600位相转移催化剂，13C12-DDT脱氯化氢制得13C12-DDE。该方法产率高，产品纯度高、操作简便，可为同位素标记的二氯二苯基三氯乙烷类化合物（DDTs）的合成提供参考。
关键词：13C标记；13C6-氯苯；DDTs；标记合成
中图分类号：TQ421.6 文献标识码：A 文章编号：0258-3283（2021）--
Facile Synthesis of Isotopically 13C12-labeled p,p’-DDT, p,p’-DDD and p,p’-DDE WANG Zhi-nan, QUAN Hai-yuan, HU Yu-zhao, WANG Liu-yang, JIANG Zhi-fu, MEI Xiang-dong, NING Jun, SHE Dong-mei* (Institute of Plant Protection, Chinese Academy of Agricultural Sciences, Beijing 100193, China), Huaxue Shiji, 2021, 43(6), ～
Abstract：As a persistent organic pollutant, the organochlorine pesticide dichlorodiphenyltrichloroethane (DDT) stays in the environment for a long time and is gradually metabolized into more stable 1,1-dichloro- 2,2-bis(p-chlorophenyl) ethylene (DDE)) and 1,1-dichloro-2,2-bis(p-chlorophenyl) ethane (DDD)). Isotope dilution mass spectrometry (IDMS) is a benchmark method for testing trace substances in the environment. Stable isotope-labeled standards are the material basis for this assay. The 13C12-labeled p,p′-DDD and p,p′-DDE were first reported in this paper. 13C6-Chlorobenzene was produced via oxychlorination from 13C6-benzene, and subsequent sulphuric acid-catalyzed condensation with chloral hydrate and dichloroacetaldehyde hydrate yielded 13C12-p,p′-DDT and 13C12-p,p′-DDD, respectively. Then 13C12-p,p′-DDE was synthesized by catalytic dehydrochlorination method from 13C12-p,p′-DDT using polyethylene glycol 600 as phase transfer catalyst. This method has a higher yield, fewer by-products and an easier handling process, which provides a reference for the isotope-labeled synthesis of isotope-labeled dichlorodiphenyltrichloroethane compounds (DDTs).
Key words：13C-labeled; 13C6-chlorobenzene; DDTs; labeled synthesis
引用本文：王智楠，全海源，胡宇钊，等. 13C同位素标记DDT、DDD、DDE的简便合成[J]. 化学试剂, 2021, 43(6): 848-851.
低共熔溶剂中2-氨基-7-羟基-3-氰基-4-芳基-4H-色烯的绿色合成
王英磊*，李文欢，宋晓静，黄可心，杜朝军
(南阳理工学院 生物与化学工程学院，河南 南阳 473004)
摘要：通过氯化胆碱和乳酸的混合制备了低共熔溶剂，并将其作为反应介质和催化剂应用于目标化合物的合成。研究结果表明，在氯化胆碱-乳酸用量2.0 g、反应温度90℃时，不同取代基的芳香醛均可与丙二腈、间苯二酚顺利完成缩合反应，目标产物的产率达85% ～ 93%。低共熔溶剂氯化胆碱-乳酸具有原料价格低廉、制备方法简单、生物相容性良好、分离与回收使用方便等优势，满足可持续发展化学的要求，具有潜在工业应用价值。
关键词：低共熔溶剂；色烯；绿色化学；多组分反应；重复使用
中图分类号：TQ612.6 文献标识码：A 文章编号：0258-3283（2021）--
Green Synthesis of 2-Amino-7-hydroxy-3-cyano-4-aryl-4H-chromenes in Deep Eutectic Solvent
WANG Ying-lei*, LI Wen-huan, SONG Xiao-jing, DU Chao-jun (School of Biological and Chemical Engineering, Nanyang Institute of Technology, Nanyang 473004, China), Huaxue Shiji, 2021, 43(6), ～
Abstract: The deep eutectic solvent was prepared by mixing choline chloride and lactic acid, and used as reaction medium and catalyst for the synthesis of 2-amino-7-hydroxy-3-cyano-4-aryl-4H-chromenes. The results showed that the condensation reaction of different substituent aryl aldehydes with malononitrile and resorcinol could be successfully completed and the target product yields could reach 85%～93%, under the conditions of 2.0 g of choline chloride-lactic acid and reaction temperature of 90 ℃. The major merits of deep eutectic solvent of choline chloride-lactic acid are low raw material price, simple preparation method, good biocompatibility, easy separation, and reusability, which meet the requirements of sustainable development of chemistry and possess potential industrial application values.
Key words: deep eutectic solvent; chromene; green chemistry; multi-component reaction; reuse
引用本文：王英磊, 李文欢, 宋晓静, 等. 低共熔溶剂中2-氨基-7-羟基-3-氰基-4-芳基-4H-色烯的绿色合成[J]. 化学试剂, 2021, 43(6): 852-856.
