Fe3O4@TiO2@SiO2@Ag光催化剂的制备及其光催化活性研究
沈启慧1，朱自豪1，高汉良2，陈宇溪1，吕茉1，周新宇1，刘岩1*
(1.吉林化工学院 化学与制药工程学院，吉林 吉林 132022；2.中国石油吉林石化公司 丙烯腈厂，吉林 吉林 132021)
摘要：采用溶剂热法和溶胶-凝胶法合成了磁性Fe3O4@TiO2@SiO2复合光催化剂。再通过巯基改性，使二氧化硅表面原位合成银纳米颗粒，最终形成目标光催化剂。利用XRD、FTIR、XPS、SEM、VSM等分析测试手段对所该催化剂的组成、结构、形貌及其磁学性能进行表征。通过光催化降解40 mL罗丹明B溶液（pH 5.3，30 mg/L），催化剂按1 g/L加入反应体系，光照120 min时，罗丹明B溶液的降解率达96.22 %。相同条件重复循环实验10次，罗丹明B溶液降解率仅下降4.32 %，表明Fe3O4@TiO2@SiO2@Ag磁性光催化剂具有出色的光催化活性和循环使用性。
关键词：Fe3O4@TiO2@SiO2@Ag；光催化；磁性光催化剂；纳米材料
中图分类号：O657.32 文献标识码：A 文章编号：
Preparation and Photocatalytic Activities of Fe3O4@TiO2@SiO2@Ag SHEN Qi-hui1, ZHU Zi-hao1, GAO Han-liang2, CHEN Yu-xi1, LYU Mo1, ZHOU Xin-yu1, LIU Yan1*(1.Jilin Institute of Chemical Technology, Jilin 132022, China;2.Acrylonitrile Factory of Jilin Petrochemical Company, PetroChina, Jinlin 132021, China)
Abstract：Magnetic Fe3O4@TiO2@SiO2 composite photocatalyst was synthesized by solvothermal method and sol-gel method, and then modified by sulfhydryl to support silver nanoparticles which were synthesized in situ on the silica surface. The composition, structure, morphology and magnetic properties of the photocatalyst were confirmed by XRD, FTIR, XPS, SEM, VSM, etc. Photocatalytic degradation of 40 mL rhodamine B solution (pH 5.3, 30 mg/L), the catalyst was added to the reaction system at 1 g/L, the degradation rate of RhB solution was 96.22% under 120 min of light irradiation. Under the same conditions, the degradation rate of RhB solution only decreased by 4.32 % after 10 repeated cycles. The magnetic photocatalyst of Fe3O4@TiO2@SiO2@Ag has excellent photocatalytic activity and reusability.
Key words：Fe3O4@TiO2@SiO2@Ag; photocatalysis; magnetic photocatalyst；nanomater materials
引用本文：沈启慧，朱自豪，高汉良，等.Fe3O4@TiO2@SiO2@Ag光催化剂的制备及其光催化活性研究[J]. 化学试剂, 2021, 43(4):405-411.
三维WO3/rGO复合物的制备及光解水制氢性能研究
李抒洋，刘博涵，杨颖*，于辉*
（长春理工大学 化学与环境工程学院，吉林 长春 130022）
摘要：主要通过水热法制备出WO3/rGO复合物用于在可见光下光解水制氢。采用XRD和SEM表征手段对其组成、形貌进行研究，同时进行光解水制氢性能测试并对其机理进行探讨。研究结果表明：WO3样品呈海草状，具有丰富的空隙，可以更大程度上提升光解水制氢性能，WO3/rGO复合物与未复合石墨烯的WO3样品比较，其形貌没有明显变化。并且rGO的导电性在提高光感应电荷载流子分离效率中也起着关键作用。WO3/rGO复合物产氢速率为236 μmol/h，而WO3样品的产氢速率为212 μmol/h，氧化石墨与WO3复合后样品对光解水制氢性能得到提升。增强的光解水制氢性能归因于rGO的优异电导率和WO3/rGO复合物的纳米结构的协同作用。
关键词：水热法；石墨烯；三氧化钨；光解水制氢；光催化
中图分类号： TQ314 文献标识码： A 文章编号：0258-3283（2021）
Preparation of Three-dimensional WO3/rGO Composite and Its Performance for Photocatalytic Water Splitting LI Shu-yang, LIU Bo-han, YANG Ying*, YU Hui* (College of Chemistry and Environmental Engineering, Changchun University of Science and Technology, Changchun 130022, China), Huaxue Shiji, 2021, 43(4)
Abstract: In this work, WO3/rGO composite was prepared by hydrothermal method for photocatalytic water splitting under visible light. Its composition and morphology were confirmed by XRD and SEM. The performance of photocatalytic water splitting was tested and its mechanism was discussed. The WO3 sample was like seaweed and had abundant voidage, which could improve the hydrogen production performance of photolysis water to a greater extent. The morphology of WO3/rGO composite was not significantly changed compared with the WO3 sample of uncompounded graphene. The conductivity of rGO also plays a key role in improving the efficiency of photoinduced charge carrier separation. The hydrogen production rate of WO3/rGO composite was 236 μmol/h , while the hydrogen production rate of WO3 sample was 212 μmol/h . The enhanced hydrogen production performance is attributed to the synergistic effect of rGO's excellent conductivity and the nanostructure of WO3/rGO complexes.
Key words: hydrothermal; graphene; WO3; photocatalytic water splitting; photocatalysis
引用本文：李抒洋，刘博涵，杨颖，等. 三维WO3/rGO复合物的制备及光解水制氢性能研究[J]. 化学试剂，2021, 43（4）：412-416.
改性活性炭吸附甲醛的影响因素研究
金梧凤，刘旺，王志强*，只长明，王波
（天津商业大学 天津市制冷技术重点实验室，天津 300134）
摘要：利用浸渍法制备出以柱状活性炭为基材负载高锰酸钾（KMnO4）的复合型甲醛吸附材料，利用比表面积及孔隙度分析测试仪和场发射扫描电子显微镜观察活性炭改性前后的物理结构变化，搭建单通道滤料性能测试实验台研究高锰酸钾负载率、气体相对湿度、重复负载对改性活性炭吸附甲醛的性能影响。结果表明：未负载KMnO4的活性炭对甲醛的吸附性能最差，负载率5%、10%、20%、24%的改性活性炭比未改性活性炭吸附容量增大1.1、3.5、4.5、5.5倍，最佳负载率为24%；负载率10%的改性活性炭在相对湿度为20%、50%比相对湿度80%时，甲醛吸附容量增大1.5、1.3倍；改性活性炭失活后，重复负载KMnO4一次仍表现出良好的甲醛吸附性能。但重复负载两次后改性活性炭的甲醛吸附性能下降明显。
关键词：活性炭；高锰酸钾；甲醛；吸附性能
中图分类号：X511 文献标识码：A 文章编号：0258-3283（2021）
Factors Affecting the Adsorption of Formaldehyde by Activated Carbon Supported KMnO4 JIN Wu-feng, LIU Wang, WANG Zhi-qiang*, ZHI Chang-ming, WANG Bo (Tianjin Key Laboratory of Refrigeration Technology, Tianjin University of Commerce, Tianjin 300134, China), Huaxue Shiji, 2021, 43(4)
Abstract: A composite formaldehyde adsorption material loaded with potassium permanganate (KMnO4) using columnar activated carbon as the base material was prepared by the impregnation method. Observe the physical structure changes of activated carbon before and after modification with specific surface area and porosity analysis tester and field emission scanning electron microscope. A single-channel filter material performance test bench was built to investigate the effect of potassium permanganate loading rate, gas relative humidity, and repeated loading on the adsorption of formaldehyde by modified activated carbon. The results show that activated carbon without potassium permanganate has the worst formaldehyde adsorption performance. Modified activated carbon with a loading rate of 5%, 10%,20%, and 24% has an increased adsorption capacity of 1.1, 3.5, 4.5and 5.5 times compared with unmodified activated carbon. Modified activated carbon with a loading rate of 10% increases the formaldehyde adsorption capacity by 1.5 and 1.3 times when the relative humidity is 20% and 50% compared to 80% relative humidity. After the modified activated carbon was deactivated, KMnO4 was repeatedly loaded once and still showed good formaldehyde adsorption performance. However, the formaldehyde adsorption performance of the modified activated carbon decreased significantly after repeated loading twice.
Key words: activated carbon; potassium permanganate; formaldehyde; adsorption performance
引用本文：金梧凤，刘旺，王志强，等. 改性活性炭吸附甲醛的影响因素研究[J]. 化学试剂, 2021, 43(4):417-422。
基于银纳米簇的纳米传感平台用于丙酮酸的检测
肖利智，闫茹月，米继强，张阳，庞博，王淑敏，姜英男*
（长春中医药大学，吉林 长春 130117）
摘要：现有的丙酮酸（Pyruvate，Py）检测方法大都需要特殊仪器，并且受某些适用范围的影响而存在缺乏选择性等问题。提出一种基于荧光银纳米簇（Ag nanoclusters，AgNCs）构建纳米传感平台定量精确检测Py的方法。建立了AgNCs的荧光发射强度与Py浓度的线性定量关系，标准曲线方程为y = 116.714 + 0.306x，R2 = 0.991，Py浓度的线性检测范围为200～1400 μmol/L。并且，实验结果表明人体血液、尿液中的常见成分如葡萄糖（Glucose，GO）、尿酸（Uric acid，UA）、肌氨酸（Sarcosine，SO）、乳酸（Lactic acid，LA）等不会干扰该平台对于Py的测定。因此该方法具有很强的特异针对性，可实现对Py含量的高灵敏度和高选择性检测。
关键词：丙酮酸检测；银纳米簇；荧光传感；线性定量；纳米探针
Nano-sensing Platform Based on Silver Nanoclusters for Pyruvate Detection XIAO Li-zhi, YAN Ru-yue, MI Ji-qiang, ZHANG Yang, PANG Bo, WANG Shu-min, JIANG Ying-nan* (ChangChun University Of Chinese Medicine, Changchun 130117, China), Huaxue Shiji, 2021, 43(4), ～
Abstract：Most of the pyruvate (Py) detection methods require special instruments, and lack of selectivity due to the effect of certain application ranges. This work presents a method for quantitative and accurate detection of Py based on fluorescent silver nanoclusters (AgNCs) to construct a nano-sensing platform. The linear quantitative relationship between the fluorescence intensity of AgNCs and the Py concentration has been established. The standard curve equation is y = 116.714 + 0.306x, R2 = 0.991, and the linear detection range of Py concentration is 200 ~ 1400 μmol/L. Moreover, the results show that common components in human blood and urine such as glucose (GO), uric acid (UA), sarcosine (SO), lactic acid (LA), etc. Barely interfere the platform for the determination of Py. Therefore, this method has strong specificity and can realize high sensitivity, as well as high selectivity detection of Py content.
Key words：pyruvate detection; silver nanoclusters; fluorescence sensing; linear quantification; nano probe
引用本文：肖利智, 闫茹月, 米继强. 基于银纳米簇的纳米传感平台用于丙酮酸的检测[J]. 化学试剂, 2021, 43(4):423-427.
氮杂甾体吡啶类衍生物的合成及抗肿瘤活性
左前进1，蒋丽娟2，吴爱群*2,3
(1. 湖南科瑞生物制药股份有限公司，湖南 邵阳 422000；2. 广西民族大学 化学化工学院，广西 南宁 530008; 3. 林产化学与工程国家民委重点实验室 广西林产化学与工程重点实验室 广西林产化学与工程协同创新中心，广西 南宁 530006)
摘要：利用药物设计的拼合原理，以黄体酮为原料，经过氧化开环、闭环、还原及缩合反应等步骤，设计合成了9个目标化合物，其结构经IR、NMR和HRMS确证。以阿比特龙和5-氟脲嘧啶为阳性对照，采用MTT法初步评价目标化合物对体外人前列腺癌细胞PC-3、人卵巢癌细胞Skov3、人恶性黑色瘤细胞A375和人正常前列腺上皮细胞RWPE-1的抗增殖活性。结果显示，2-氨基-4-吡啶-4-基-6-（4′-氮杂孕甾-3′-酮-17′-基）烟腈、2-氨基-4-呋喃-2-基-6-（4′-氮杂孕甾-3′-酮-17′-基）烟腈对PC-3和Skov3细胞抗增殖活性优于阳性对照药阿比特龙和5-氟脲嘧啶。特别是2-氨基-4-吡啶基-6-（4′-氮杂孕甾-3′-酮-17′-基）烟腈对PC-3细胞的IC50值（2.73 ± 0.80）μmol/L，明显优于阿比特龙，值得进一步研究。
关键词：氮杂甾体吡啶；合成；抗肿瘤活性；5-氟脲嘧啶
中图分类号：R914.5 文献标识码：A 文章编号：0258-3283（2021）
Synthesis and Antitumor Activity Evaluation of Aza-steroidal Pyridines Derivatives ZUO Qian-jin1, JIANG Li-juan2, WU Ai-qun*2,3 (1. Hunan Kerui Bio-Pharmaceutical Co., Ltd., Shaoyang 422000, China; 2. College of Chemistry and Chemical Engineering, Guangxi University for Nationalities, Nanning 530008, China; 3. Key Laboratory of Chemistry and Engineering of Forest Products, State Ethnic Affairs Commission, Guangxi Key Laboratory of Chemistry and Engineering of Forest Products, Guangxi Collaborative Innovation Center for Chemistry and Engineering of Forest Products, Nanning 530006, China), Huaxue Shiji, 2021, 43(4)
Abstract: Utilizing the principle of pharmacophore flattening, nine of new aza- steroidal pyridines derivatives have been synthesized by cleavage of A-ring, ring-closure, reduction and three-component reaction by progesterone as starting material, and their structures were confirmed by IR, NMR and HRMS. The antitumor activity was evaluated against PC-3、Skov3、A375 and RWPE-1 cells in vitro by MTT assay，and abiraterone and 5-Fu was used as a positive control． The compounds 5f and 5i had higher activity to inhibit PC-3 cells and Skov3 than abiraterone and 5-Fu . The IC50 of compounds 5f (2.73 ± 0.80) μmol/L is worthy of further study.
Key words: aza-steroidal pyridines; synthesis; antitumor activity; 5-Fu
引用本文：左前进，蒋丽娟，吴爱群. 氮杂甾体吡啶类衍生物的合成及抗肿瘤活性[J]. 化学试剂, 2021, 43(4):428-433.
新型DPP-4抑制剂LGT-6在Caco-2细胞单层模型中的转运特性研究
张宇1，班玉娟1，王忠元2，张丽3，汤磊3，廖伟科1,3
（1. 贵州医科大学 药学院，贵州 贵阳 550004；2. 贵州省人民医院，贵州 贵阳 550002；3. 贵州省化学合成药物研发利用工程技术研究中心，贵州 贵阳 550004）
摘要：通过建立Caco-2细胞单层模型探究降糖化合物LGT-6的转运特性。采用MTS法测定LGT-6的安全浓度范围，通过测定跨膜电阻、碱性磷酸酶活力、高渗透性药物普莱洛尔与低渗透性药物荧光素钠通透性实验的表观渗透系数Papp(AP→BL)来验证Caco-2细胞单层模型的致密性。考察LGT-6在从Transwell顶端(AP)到底端(BL)及底端到顶端的转运特性，计算表观渗透系数和外排比。并分析转运时间、给药浓度和和P-gp抑制剂对LGT-6转运特性的影响。Caco-2细胞单层模型建立成功，可用于LGT-6的转运特性研究。LGT-6的转运量随时间的延长及浓度的增大而增加，不同浓度的LGT-6在双向转运随浓度变化而变化，从AP→BL的Papp值为3.55×10-6～5.64×10-6 cm/s，BL→AP的Papp为4.28×10-6～8.76×10-6 cm/s，外排比(ER)均大于1.2。降糖化合物LGT-6在体外Caco-2细胞模型上的口服吸收较好，其转运方式主要以被动扩散为主，可能有P-糖蛋白参与其转运。
关键词：Caco-2细胞单层模型；LGT-6；表观渗透系数；转运；P-糖蛋白；外排比
中图分类号：R96 文献标识码：A 文章编号：0258-3283（2021）--
Transport Characteristics of Novel DPP-4 Inhibitor LGT-6 in Caco-2 Cell Monolayer Model
ZHANG Yu1, BAN Yu-juan1,WANG Zhong-yuan2,ZHANG Li3, TANG Lei3, LIAO Wei-ke1,3(1. School of Pharmacy，Guizhou Medical University，Guiyang 550004，China；2. Guizhou Provincial People’s Hospital, Guiyang 550002;3. Guizhou Provincial Engineering Technology Research Center for Chemical Drug R&D，Guiyang 550004，China)
Abstract: To investigate the transport characteristics of hypoglycemic compound LGT-6, a Caco-2 cell monolayer model was established. MTS method was used to determine the safe concentration range of LGT-6.To verify the compactness of the Caco-2 cell monolayer model, transmembrane resistance, alkaline phosphatase activity and the apparent permeability coefficient Papp(AP→BL) of both high permeability drug Propranolol as well as low permeability drug fluorescein sodium was measured. Later investigation on the transport characteristics of LGT-6 from AP→BL and BL→AP obtained the apparent permeability coefficient (Papp) and reflux ratio (ER). Furthermore, the impact of drug concentration, transport time and P-glycoprotein inhibitor on LGT-6wasalso determined. The Caco-2 cell monolayer model was successfully established and can be used to investigate the transport characteristics of LGT-6. The transport volume of LGT-6 increases with the extension of time and concentration. The two-way transport of LGT-6 at different concentrations varies with the concentration. The Papp value from AP→BL is 3.55×10-6 to 5.64×10 -6 cm•s-1 as well as the Papp of BL→AP was 4.28×10-6 to 8.76×10-6 cm•s-1, the ER ratio (ER) was all greater than 1.2. The hypoglycemic compound LGT-6 exhibited a desirable oral absorption in an in vitro Caco-2 cell model, and the transport mode is mainly passive diffusion, P-glycoprotein may be involved in its transport.
Keywords: Caco-2 cell monolayer model; LGT-6; apparentpermeability coefficient; transport; P-glycoprotein; Outside row ratio
引用本文：张宇，班玉娟，王忠元，等.新型DPP-4抑制剂LGT-6在Caco-2细胞单层模型中的转运特性研究[J].化学试剂，2021，43（4）：434-440.
三种小檗碱衍生物的结构性质及与DNA作用的理论研究
蒲小华*1，吴艳波2
（1.宝鸡文理学院 化学化工学院，陕西 宝鸡 721013；2. 山西大学 分子科学研究所，山西 太原 030006）
摘要：运用 Materials Studio 程序的DMOL3模块对小檗碱衍生物，即 9-氧-二胺乙基小檗碱分别与乙醛、苯甲醛和1-萘醛发生缩合反应的产物的几何结构和性质(振动频率、反应活性及热力学性质)进行了理论研究，得到了分子的稳定几何构型、Fukui指数、前线分子轨道和热力学性质。通过计算得到的吉布斯自由能的改变量，预测了反应进行的可能性。同时，采用分子对接技术对三个模型与DNA之间的相互作用进行研究，揭示两者作用机制。此研究为抗癌药物的基础理论研究提供了新的视角和方法。
关键词：小檗碱衍生物；分子结构；性质；DNA；分子对接；作用模式
中图分类号：O642 文献标识码：A 文章编号：0258-3283（2021）--
Theoretical Study on Structure、Properties and DNA Interaction of Three Berberine Derivatives PU Xiao-hua*1，WU Yan-bo2 (1.College of Chemistry and Chemical Engineering, Baoji University of Arts & Sciences, Baoji 721013, China; 2. Institute for Molecular Science, Shanxi University, Taiyuan 030006, China), Huaxue Shiji, 2021, 43(4), ～
Abstract：Using materials studio program module of DMOL3, the structure and thermodynamic properties of berberine derivatives including the product of the condensation reaction of 9-oxy-diamineethylberberine with acetaldehyde, benzaldehyde and 1-naphtaldehydeof were investigated. The parameters of the geometry optimization, Fukui functions, frontier molecular orbital vibration frequencies and thermodynamics have been obtained. Then, the probability of the reaction is predicted by calculating the change in Gibbs free energy. At the same time, the interaction between the three models and DNA was investigated using molecular docking technology to reveal the mechanism of interaction. This work provides a new perspective and method for the basic theoretical research of anticancer drugs.
Key words: berberine derivatives; molecular structure; properties; DNA; molecular docking; interaction mode
引用本文：蒲小华, 吴艳波. 三种小檗碱衍生物的结构性质及与DNA作用的理论研究[J]. 化学试剂, 2021, 43(4):441-446.
分子噻蒽化修饰及偶联反应研究进展
田俊1，高文超*1 2，姜雪峰*2
(1.太原理工大学 生物医学工程学院，山西 太原 030024；2. 华东师范大学 化学与分子工程学院，上海 200062)
摘要：噻蒽鎓盐是近几年来研究较为热门的一个偶联模块，其具有制备简单、活性高、选择性好、转化模式多样等特点。该鎓盐可通过多种未活化的芳烃或者烯烃与噻蒽亚砜直接噻蒽化合成，并可兼容多种官能团，尤其适合多种复杂分子的后期噻蒽化修饰，所得到的噻蒽鎓盐结构可通过金属偶联以及光氧化还原偶联等模式引入多种重要官能团。综述了近三年噻蒽鎓盐的发现及发展过程、制备及反应机制，以及利用其为原料进行的芳烃的三氟甲基化、羟基化、氨基化、氟化、硼基化以及硅基化等转化。
关键词：噻蒽化；噻蒽鎓盐；光氧化还原；后期修饰
中图分类号：O622.7 文献标识码：A 文章编号：
Advances on the Thianthrenation for Molecular Decoration and Cross-coupling Reaction TIAN Jun1, GAO Wen-Chao*1 2, JIANG Xue-Feng*2 (1. College of Biomedical Engineering，Taiyuan University of Technology, Taiyuan 030024, China; 2. School of Chemistry and Molecular Engineering，East China Normal University, Shanghai 200062, China)
Abstract：As one kind of attractive coupling building blocks, thianthrenium salts features ready preparation, high reactivity, site-selective installation, and multiple transformations. Thianthrenium salts can be synthesized directly from the reaction of unactived arrenes or alkenes with thianthrene-S-oxide in the presence of acids, and this functionalization can be well tolerated with a series of functional groups, and especially for the late-stage thianthrenation of complex molecules. The thianthrenium salts can be transformed to diverse functional groups via photoredox catalysis or metal catalysis. This review summarized the discovery and development of thianthrenium salts, and the corresponding preparation and reaction mechanism. Furthermore, diverse transformations including trifluoromethylation, oxygenation, amination, fluorination, borylation, with thianthrenium salts were also discussed.
Key words：thianthrenation; thianthrenium salts; photoredox; late-stage modification
引用本文：田俊，高文超，姜雪峰. 分子噻蒽化修饰及偶联反应研究进展[J].化学试剂，2021，43（4）：447-453.
硫酰氟的制备及在有机合成中的应用
姜雪峰
(华东师范大学 化学与分子工程学院 上海市绿色化学与化工过程绿色化重点实验室，上海 200062)
摘要：硫酰氟作为广谱的熏蒸剂和杀虫剂，性能优异，应用较为广泛。而其独特的物理化学性质，在有机合成化学中的应用近年来也被相继报道。本文对硫酰氟物理化学性质进行介绍，并且对合成硫酰氟的方法、生产情况进行了简要的总结归纳，同时对以硫酰氟作为反应物及化学反应中间体，在有机合成中用于构建磺酰氟、烷基胺、脱氢化等应用进行介绍。期望通过硫酰氟反应特性的介绍，为有机合成工作者提供硫酰氟更多的使用策略。
关键词：硫酰氟；点击化学；合成应用；氟磺酰咪唑盐；氟磺酰叠氮
中图分类号：O62 文献标识码：A
Preparation of Sulfuryl Fluoride and Its Application in Organic Synthesis JIANG Xue-feng (Shanghai Key Laboratory of Green Chemistry and Chemical Process, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, China)
Abstract：As a broad-spectrum fumigation agent and insecticide, sulfuryl fluoride has excellent functions and has been widely used. Due to the unique physical and chemical properties of sulfuryl fluoride, its application in organic synthetic chemistry has been reported successively in recent years. This manuscript briefly introduces the physicochemical properties of sulfuryl fluoride, and summarizes the methods and production of the synthesis of sulfuryl fluoride, and makes a simple introduction to the application of sulfuryl fluoride as reactants and chemical reaction intermediates in organic synthesis for the construction of sulfonyl fluoride, alkylamine, dehydrogenation. It is expected that the introduction of the reactions of sulfuryl fluoride can provide more strategies for organic synthesis workers.
Key words：sulfuryl fluoride; click chemistry; synthesis application; imidazolium fluorosulfuryl salt; fluorosulfuryl azide
引用本文：姜雪峰.硫酰氟的制备及在有机合成中的应用[J].化学试剂，2021,43（5）：454-457.
电化学传感器检测植物生长调节剂的研究进展
张艳，杜海军*，杜科志，张欣月，艾纪星，胡华丽
（贵州民族大学 化学工程学院，贵州 贵阳 550025）
摘要：近年来，植物生长调节剂（PGRs）的检测方法备受研究者的广泛关注。由于电化学传感器具有较高的灵敏度和选择性、响应时间短、成本低、方便携带等优点，在现场快速检测中受到研究者的青睐。从电化学传感器检测PGRs的4个方面进行了总结：1）直接电化学行为传感，主要是通过不同的修饰材料对电极进行增敏，从而实现对具有电化学活性的PGRs进行直接检测；2）电化学生物传感，主要通过酶和免疫两种方法对PGRs进行特异性识别；3）光电化学传感，主要是利用具有光催化性能的材料实现对电化学活性较差的PGRs进行光电转化检测；4）分子印迹电化学传感，通过构建能够特异性识别PGRs的聚合物薄膜从而进行专属检测。并对现状进行了阐述以及对未来发展趋势进行展望。
关键词：植物生长调节剂；电化学传感器；电化学分析；修饰电极
中图分类号：O657.1 文献标识码：A 文章编号：0258-3283（2021）
Progress on the Detection of Plant Growth Regulators by Electrochemical Sensors ZHANG Yan, DU Hai-jun*, DU Ke-zhi, ZHANG Xin-yue, AI Ji-xing, HU Hua-li (School of Chemical Engineering, Guizhou Minzu University, Guiyang 550025, China), Huaxue Shiji, 2021, 43(4)
Abstract: In recent years, the detection methods of plant growth regulators (PGRs) have attracted extensive attention. Electrochemical sensors are favored in the field of rapid detection because of their high sensitivity and selectivity, short response time, low cost, and convenient carrying. This work summarizes the four aspects of PGRs detection by electrochemical sensors. (1) Direct electrochemical behavior sensing, which mainly uses different modified materials to sensitize the electrode, so as to realize the direct detection of electrochemically active PGRs. (2) Electrochemical biosensing, mainly through enzymes and immunity Two methods for specific identification of PGRs. (3) Photoelectrochemical sensing, which mainly uses materials with photocatalytic properties to achieve photoelectric conversion detection of PGRs with poor electrochemical activity.(4) Molecular imprinting electrochemical sensing. By constructing a polymer film that can specifically recognize PGRs for exclusive detection. And it was explained as well as the future development trends, prospect.
Key words: plant growth regulators; electrochemical sensor; electrochemical analysis; modified electrode
引用本文：张艳，杜海军，杜科志，等. 电化学传感器检测植物生长调节剂的研究进展[J]. 化学试剂, 2021, 43(4):458-465.
水滑石基电极材料的结构调控及电化学储能应用研究进展
石利泺，陈腾，宋明*
（徐州工程学院 材料与化学工程学院，江苏 徐州 221018）
摘要：水滑石是一种具有层板金属阳离子可搭配、层间客体可替代和高分散性的二维层板状纳米材料，在能量存储与转换应用领域获得广泛的关注和研究。但由于水滑石自身存在容易聚集和电导率差并且在电化学循环过程中易粉化的问题，因此需对水滑石基电极材料进行针对性结构设计，从而提高其电化学性能。本文系统介绍了水滑石材料的结构与性质特点和当下对其结构调控的研究进展。另外，还详细介绍了在电化学储能领域的应用进展，主要包括锂离子电池和超级电容器电极材料领域，并展望了今后的研究趋势。
关键词：水滑石；结构调控；电化学储能；锂离子电池；超级电容器
中图分类号：TB34 文献标识码：A 文章编号：0258-3283(2021)--
Progress on Structure Regulation and Electrochemical Energy Storage Application of Layered Double Hydroxides Based Electrode Materials SHI Li-luo，CHEN Teng, SONG Ming* (School of Materials and Chemical Engineering, Xuzhou University of Technology, Xuzhou 221018, China), Huaxue Shiji, 2021, 43(4), ～
Abstract: Layered double hydroxides (LDHs) are two-dimensional layered nanomaterial with high controllability of metal cations and interlayer guests, and high dispersion. Benefiting from their properties, LDHs have attracted many attentions in the field of energy storage and conversion. However, LDHs have the weakness of easy to aggregate and poor conductivity, and easily powdered during the electrochemical cycling process. Therefore, it is necessary to design the structure of LDHs-based electrode materials to improve their electrochemical performance. This work systematically introduces the structure and properties of LDHs and the current research progress of structural regulation. In addition, the application progress of LDHs materials for energy storage and conversion field is also introduced in detail, mainly including lithium-ion batteries and super-capacitors. Finally, the research trend in the future is prospected.
Keywords: layered double hydroxides; structure regulation; electrochemical energy storage; lithium ion battery; super-capacitor
引用本文：石利泺, 陈腾, 宋明. 水滑石基电极材料的结构调控及电化学储能应用研究进展[J]. 化学试剂, 2021, 43(4): 466-473.
基于磁性纳米材料显现潜在手印的研究进展
万敬伟*1,2，陈蕾3，崔胜峰1,2，李伟1,2，马学兵4
(1. 铁道警察学院 刑事科学技术系 郑州市刑事科学技术重点实验室，河南 郑州 450053；2. 郑州大学 公共安全研究院 环境与生态安全技术研究所，河南 郑州 450001；3. 河南医学高等专科学校 药学系，河南 郑州 451191；4. 西南大学 化学化工学院 重庆市应用化学重点实验室，重庆 400715)
摘要：手印作为指认犯罪嫌疑人的重要物证，通过对犯罪现场的潜在手印进行显现比对，为公安司法机关提供侦查线索和法庭证据。近年来，将新型磁性纳米材料应用于潜在手印显现技术的研究成为法庭科学研究者及刑侦人员关注的热点，与传统手印显现技术相比，磁性纳米手印显现技术具有可回收、低DNA毒性、高灵敏度、显现方式多样等突出优点。从显现原理、合成方法及对潜在手印的显现效果等方面重点阐述了常规磁性纳米粉末、磁性小颗粒悬浮（SPR）试剂、磁性掺杂纳米荧光材料、无机-有机杂化磁性纳米材料、具有核壳构型的磁性纳米材料、基于免疫反应的磁性纳米材料等6类磁性纳米材料，并对存在的问题进行了讨论，展望了新型磁性纳米材料应用的未来发展趋势，为犯罪现场潜在手印的显现提供了重要的参考和借鉴。
关键词：法庭科学；纳米材料；磁性；潜在手印；物证
中图分类号：DF794.1 文献标识码：A 文章编号：0258-3283（2021）
Development of Latent Fingerprints Based on Magnetic Nanomaterials WAN Jing-wei*1, CHEN Lei2, CUI Sheng-feng1, LI Wei1, MA Xue-bing3 (1. Zhengzhou Key Laboratory of criminal science and technology, Department of Public Security Technology, Railway Police College, Zhengzhou 450053, China; 2. Institute of Environmental and Ecological Safety Technology, Institute of Public Safety Research, Zhengzhou University, Zhengzhou 450001, China; 3. Department of pharmacy, Henan Medical College, Zhengzhou 451191, China; 4. Key Laboratory of Applied Chemistry of Chongqing Municipality, College of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, China).
Abstract: As an important evidence for the identification of criminal suspects, fingerprints can provide investigation clues and evidence for the public security and judicial organs by developed latent fingerprints at the crime scene. In recent years, the application of novel magnetic nanomaterials by which developed latent fingerprint has become the focus of forensic science researchers and criminal investigators. Compared with traditional technology developed by latent fingerprint, magnetic nanomaterials has the advantages of recyclability, low DNA toxicity, high sensitivity and multiple forms. This work focuses on the development principles, synthesis methods and effects of six types of magnetic nanomaterials, including conventional magnetic nanomaterials, magnetic Small Particle Suspension (SPR) reagent, magnetic doped nano-fluorescent material, inorganic-organic hybrid magnetic nanomaterials, magnetic nanomaterials with core-shell configuration, and magnetic nanomaterials based on immune reaction. The existing problems are discussed, and the future development trend of the application of new magnetic nanomaterials is prospected. The existing problems are discussed, and the future development trend of the application of novel magnetic nanomaterials is prospected, which provides an important reference for developed by latent fingerprints at crime scenes.
Key words：forensic science; nanomaterials; magnetic; latent fingerprints; evidence
引用本文：万敬伟，陈蕾，崔胜峰，等. 基于磁性纳米材料显现潜在手印的研究进展[J]. 化学试剂, 2021, 43(4):474-483.
浅谈药用辅料企业实验室管理体系的建立
王刚，郑琦，吴言言*，顾小焱
（国药集团化学试剂有限公司，上海 200002）
摘要：中国的药用辅料企业质量管理水平参差不齐，提高药用辅料企业的质量管理、提倡药用辅料企业建立实验室ISO/IEC 17025质量管理体系、把好企业的原料入厂检测关及过程质量控制和成品出货检测质量关尤为重要。通过实验室认可，提高企业实验室的检测能力、标准化管理水平及企业的市场竞争力。通过对药用辅料企业实验室管理体系的建立进行综述，阐述了药用辅料企业实验室管理体系的建立和运行，为药用辅料企业实验室建立质量管理体系提供相关参考。
关键词：药用辅料；实验室质量管理；ISO/IEC 17025；标准
中图分类号：G311 文献标识码：A 文章编号：0258-3283（2021）
Discussion on the establishment of laboratory management system in pharmaceutical excipients Enterprises WANG Gang, ZHENG Qi，WU Yanyan*，GU Xiaoyan (Sinopharm Chemical Reagents Co., Ltd., Shanghai 200002, China)
Abstract: The quality management level of pharmaceutical excipients enterprises in China is uneven. It is very important to improve the management level of enterprises, encourage enterprises to establish ISO / IEC 17025 management system, and ensure the incoming inspection of raw materials, process quality control and delivery inspection of finished products.If the enterprise passes the laboratory qualification recognition, it can help the enterprise to improve the laboratory testing ability, standardized management level and market competitiveness.This paper describes the establishment and operation of the ISO/IEC 17025for pharmaceutical excipients enterprisesand provides reference for the establishment of the laboratory management system.
Key words: medicinal auxiliary material; laboratory quality management; ISO/IEC 17025；standard
引用本文：王刚，郑琦，吴言言，等. 浅谈药用辅料企业实验室管理体系的建立[J].化学试剂，2021,43（4）：484-487.
高效液相色谱法测定小麦粉及面粉处理剂中三聚硫氰酸三钠盐的含量
周霞，国振，赵博，赵光亮，张庆合，李秀琴*
（中国计量科学研究院 化学分析与计量科学研究所，北京 100029）
摘要：建立了小麦粉及面粉处理剂中三聚硫氰酸三钠盐的高效液相色谱（HPLC）检测方法。对比了不同提取试剂及提取方式对三聚硫氰酸三钠盐回收率的影响，并考察了三聚硫氰酸三钠盐在样品提取液中的稳定性。在最优实验条件下，三聚硫氰酸三钠盐在0.05 ～ 2.0 µg/mL范围内线性良好，相关系数R2 > 0.9999，方法检出限为0.4 mg/kg，定量限为1.0 mg/kg。小麦粉中三聚硫氰酸三钠盐的加标回收率范围为80.4% ~ 84.8%，RSD为1.4% ~ 3.1%；面粉处理剂中三聚硫氰酸三钠盐的加标回收率为87.9% ~ 91.5%，RSD为2.2% ~ 3.2%。
关键词：小麦粉；面粉处理剂；三聚硫氰酸三钠盐；高效液相色谱
中图分类号：O652.1 文献标识码：A
Determination of Trithiocyanuric Acid Trisodium Salt in Wheat Flour and Flour Treatment Agent by High Performance Liquid Chromatography ZHOU Xia, GUO Zhen, ZHAO Bo, ZHAO Guang-liang, ZHANG Qing-he, Li Xiu-qin*（Division of Chemical Metrology, National Institute of Metrology, Beijing, 100029, China）
Abstract: A method for the determination of trithiocyanuric acid trisodium salt (TMT) in wheat flour and flour treatment agent was established based on high performance liquid chromatography (HPLC). The effects of different extraction reagents and extraction methods on the recovery of TMT were compared, and the stability of TMT in the sample extract was investigated. Under the optimal experimental conditions, a wide linearity range (0.05 ~ 2.0 µg/mL) was obtained with a correlation coefficient higher than 0.9999. The detection limit of the method was 0.4 mg/kg, and the quantitation limit was 1.0 mg/kg. The recovery of TMT from wheat flour was in the range of 80.4% ~ 84.8% with RSD being 1.4% ~ 3.1%; the recovery of TMT from flour treatment agent was in the range of 87.9% ~ 91.5%, with RSD being 2.2% ~ 3.2%.
Key words: wheat flour; flour treatment agent; trithiocyanuric acid trisodium salt (TMT) ; high performance liquid chromatography（HPLC）
引用本文：周霞，国振，赵博，等. 高效液相色谱法测定小麦粉及面粉处理剂中三聚硫氰酸三钠盐的含量[J].化学试剂，2021，43（4）：488-493.
儿童及成人头发皮质醇检测方法的建立及应用
张琦宗1,2，卢晓琳2，王硕文2，常韶燕2，刘蓓3，张霆2，张敏2，赵丽娇1，王理*2
（1. 北京工业大学 生命科学与生物工程学院，北京 100022；2. 首都儿科研究所 遗传科，北京100020；3. 中国发展研究基金会，北京 100011）
摘要：目前检测皮质醇主要的方法是通过检测血液、唾液以及尿液中的皮质醇浓度，但是这只能反映人体的应激压力，而头发皮质醇含量则可以反映人体慢性压力。建立了一种定量检测头发皮质醇含量的方法，比较了一步法与四步法测定头发皮质醇含量的差异，探讨了磷酸盐缓冲液（PBS）体积、样品放置时间等因素对测定结果的影响。结果表明，四步法比一步法更加有利于充分提取出头发中的皮质醇；溶解5 mg头发皮质醇的最佳PBS体积为170 μL；皮质醇溶液放置7 d后，会随时间的延长而降解，对最终检测结果造成影响。使用该方法对20例头发样本中的皮质醇含量进行了测定，结果表明儿童中女生头发皮质醇含量比男生高，成人中男性头发皮质醇含量比女性高。
关键词：头发皮质醇；定量分析；四步法；一步法
中图分类号： Q819 文献标识码：A 文章编号：
Establishment and Application for Determination Method of Cortisol in Hair ZHANG Qi-zong1,2, LU Xiao-lin2, WANG Shuo-wen2, CHANG Shao-yan2, LIU Bei3, ZHANG Ting2, ZHANG Min2, ZHAO Li-jiao1, WANG Li*2.(1College of Life Science and Bioengineering, Beijing University of Technology, Beijing 100022, China;2Genetic department, Capital Institute of Pediatrics, Beijing 100020, China;3China Development Research Foundation, Beijing 100011, China)
Abstract: At present, the main cortisol detection method is to detect the concentration of cortisol in blood, saliva and urine, but this can only reflect the stress pressure of the human body, and the cortisol content of the hair can reflect the chronic pressure of the human body. Therefore, this work established a method to quantitatively detect the cortisol content of hair. The difference between the one- and four-step methods for detecting the cortisol content of hair was compared, and the influence of the volume of phosphate buffered saline (PBS) and time of sample placement on the determined results were discussed. The four-step method is more conducive to fully extract cortisol from hair than the one-step method; the optimal PBS volume for dissolving 5 mg of cortisol in hair is 170 μL; the cortisol solution will degrade over time after being placed for 7 days, which finally influences the results. This method was used to determine the cortisol content in 20 hair samples, and the results showed that the cortisol content in the hair of girls was higher than that of boys in children, and the cortisol content in the hair of men was higher than that of women in adults.
Key words:Hair cortisol; quantitative analysis; four-step method; one-step method
引用本文：张琦宗，卢晓琳，王硕文，等.儿童及成人头发皮质醇检测方法的建立及应用[J].化学试剂，2021,43（4）：494-498.
磺胺甲基嘧啶纯度定值研究
孙余娟1，孙永跃*1，李蔚1，全灿2，陈刚3，王艺玮1，赵程祥1，尹伊1
（1.天津理工大学 化学化工学院 天津市药物靶向与生物成像重点实验室，天津 300384；2.中国计量科学研究院 化学计量与分析科学研究所，北京 100029；3.中国农业科学院 农业质量标准与检测技术研究所，北京 100081）
摘要：建立氢定量核磁共振法和质量平衡法对磺胺甲基嘧啶纯度进行定值。采用Bruker-Avance Ⅲ 400 型核磁共振波谱仪，noesyigld1d脉冲序列，以尼泊金乙酯为内标、氘代DMSO为溶剂，在恒温为298 K、谱宽为15×10-4%、中心激发偏置为5.41×10-4%、弛豫时间为7 s、扫描次数为32、空扫16次的条件下，采集1H-qNMR。以磺胺甲基嘧啶化学位移（δ 6.56）为定量峰，尼泊金乙酯化学位移（δ 4.25）为内标峰，1H-qNMR测得磺胺甲基嘧啶纯度为96.56%，测定精密度RSD为0.089%，重复性RSD为0.24%。质量比在2.014～4.051范围内，质量比Y（ms/mr）与峰面积比X（As/Ar）线性回归方程为y=0.6071x+0.0049（R2=0.9999）。结果表明，1H-qNMR与质量平衡法测定结果具有一致性。因此，氢定量核磁共振法可用于磺胺甲基嘧啶含量测定，该方法具有准确、简便的优势。
关键词：氢定量核磁共振法（1H-qNMR）；磺胺甲基嘧啶；质量平衡法；含量测定
中图分类号：O657.61 文献标识码：A 文章编号：007906
Purity Determination of Sulfadiazine SUN Yu-juan1, SUN Yong-yue*1,LI Wei1, QUAN Can2, CHEN Gang3, WANG Yi-wei1, ZHAO Cheng-xiang1, YIN Yi1 (1. Tianjin Key Laboratory of Drug Targeting and Bioimaging, School of Chemistry and Chemical Engineering, Tianjin University of Technology, Tianjin 300384, China; 2. Division of Metrology in Chemistry，National Institute of Metrology，Beijing 100029, China; 3. Key Laboratory of Agro-Product Quality and Safety, Institute of Quality Standards and Testing Technology for Agro-Products, Chinese Academy of Agricultural Sciences ( CAAS ) , Beijing 10008, China )
Abstract: Establish hydrogen quantitative nuclear magnetic resonance method and mass balance method to determine the purity of sulfamethazine. Bruker-Avance Ⅲ 400 nuclear magnetic resonance spectrometer, noesyigld1d pulse sequence, ethylparaben GBW(E)100064 as internal standard, deuterated DMSO as solvent, constant temperature is 298 K, spectrum width(SW) is 15 10-4%, the excitation bias（O1P） is 5.41 10-4%， the relaxation time（D1） is 7 s, a scan number of 32, and an empty scan of 16, 1H qNMR spectra were collected. The sulfamethazine chemical shift (δ 6.56) was used as the quantitative peak, and the paraben ethyl acetate chemical shift (δ 4.25) was used as the internal standard peak. The purity of sulfamethazine measured by 1H qNMR was 96.56%. The precision RSD was 0.089%, and the repeatability RSD was 0.24%. The mass ratio (ms/mr) is in the range of 2.014 to 4.051, and the linear regression equation of the mass ratio Y (ms/mr) and its peak area ratio X (As/Ar) is y=0.6071x+0.0049 (R2=0.9999). The results of 1H qNMR measurement are basically consistent with the mass balance method. Therefore, the hydrogen quantitative nuclear magnetic resonance method can be used for the determination of sulfamethazine content. This method has the advantages of accuracy and simplicity.
Key words: hydrogen quantitative nuclear magnetic resonance (1H-qNMR); sulfamethazine; mass balance method; content determination
引用本文：孙余娟，孙永跃，李蔚，等. 磺胺甲基嘧啶纯度定值研究[J].化学试剂,2021, 43（4）：499-504.
乙酸铵静置交换测定土壤阳离子交换量的方法优化
易田芳*，向勇，刘杰，吴文群
（广电计量检测（湖南）有限公司 农业农村部南方耕地污染防控重点实验室，湖南 长沙 410000）
摘要：针对现有土壤阳离子交换量测定标准的不足，为了提高分析效率，减少试剂消耗，采用乙酸铵静置交换对测定方法的前处理进行改进，结合全自动定氮仪测定土壤中阳离子交换量。结果表明，对不同酸碱性质的土壤标准样品进行测定，其结果均在允许误差范围内，相对误差为0.8%～1.0%，测定土壤标准样品及实际样品的相对标准偏差为1.4%～2.5%（n=7），乙醇用量至少减少50%，选用100目的土壤进行实验最方便。优化后的方法为准确、高效、经济的检测土壤中阳离子交换量提供了可靠依据。
关键词：乙酸铵；静置交换；阳离子交换量；土壤
中图分类号：O657 文献标识码：A 文章编号：0258-3283（2021）
Optimization of Method for Determination of Soil Cation Exchange Capacity by Static Exchange of Ammonium Acetate YI Tian-fang*, XIANG Yong, LIU Jie, WU Wen-qun (Key Laboratory of Southern Farmland Pollution Prevention and Contorl, Ministry of Agriculture and Rural Affairs, GRG Metrology & Test (HuNan) Co., Ltd., Changsha 410000, China), Huaxue Shiji, 2021, 43(4)
Abstract: To improve the efficiency of analysis and reduce the consumption of reagents of cation exchange capacity in soil, in view of the deficiency of the present standard, the pretreatment of the determination method was optimized and improved by using ammonium acetate to static exchange， and combining with Kjeltec Automatic Azotometer. The results indicate that the soil certified reference materials with different acidity and alkalinity were within the allowable error, which the relative error was 0.8%~1.0%. The relative standard deviation of real soil samples and soil standard sample was 1.4%~2.5% (n=7), and that the ethanol was reduced at least 50%. In addition, it is a better choice to use the soil of 100 mesh. Thus the optimized analysis method is accurate, efficient and economical, which could provide a reliable basis for the determination of the cation exchange capacity in soil.
Key words: ammonium acetate; static exchange; cation exchange capacity; soil
引用本文：易田芳，向勇，刘杰，等. 乙酸铵静置交换测定土壤阳离子交换量的方法优化[J]. 化学试剂，2021,43（4）:505-509.
氟化铵辅助消解结合ICP-MS测定滤棒中的7种元素含量
周浩，陈云璨，何春莉，秦子娴，朱玲，唐杰，朱立军，许嘉东*
（重庆中烟工业有限责任公司 技术中心，重庆 400060）
摘要：采用氟化铵辅助微波消解联合电感耦合等离子体质谱法测定卷烟滤棒中铬、镍、砷、硒、镉、汞和铅7种元素含量。使用氟化铵/硝酸消解体系消解样品，考察了氟化铵用量、消解温度、消解时间对滤棒样品消解效果的影响。结果表明，最佳前处理条件为0.2 g，滤棒样品在6 mL 60%硝酸和0.75 mL （12.66 mol/L） 氟化铵溶液中消解，消解温度为175 ℃，恒温保持20 min。对不同样品进行测定，7种元素检出限在0.007～0.044 mg/kg之间，样品的加标回收率为92.50%～108.36%，相对标准偏差为1.71%～5.65%。方法与传统方法同时测定滤棒样品7种元素含量相比较无显著性差异（P＞0.05）。方法使用试剂种类少，更加绿色环保，避免了大量直接使用氢氟酸带来的安全隐患，且能快速、准确的测定滤棒中7种元素的残留量。
关键词：滤棒；氟化铵；重金属；氢氟酸；电感耦合等离子体质谱法
中图分类号：O614 文献标识码：A 文章编号：0258-3283（2021）--
Determination of 7 Elements in Filter Rods by ICP-MS Combined with the Decomposition of Ammonium Fluoride ZHOU Hao, CHEN Yun-can, HE Chun-li, QIN Zi-xian, ZHU Ling, TANG Jie, ZHU Li-Jun, XU Jia-dong* (Technology Center, China Tobacco Chongqing Industrial Co., Ltd., Chongqing 400060, China), Huaxue Shiji, 2021, 43(4), ～
Abstract：The method was established for the quantitative analysis of 7 metal elements (Cr, Ni, As, Se, Cd, Hg, Pb) in filter rods using inductively coupled plasma mass spectrometry(ICP-MS) with ammonium fluoride. Samples were digested by the microwave system of ammonium fluoride and nitric acid. Decomposition temperature, time and the amount of ammonium fluoride were investigated in detail. The optimized experimental conditions was that 0.2 g samples of filter rods with a selected acid mixture of 6 mL of 60% HNO3 and 0.75 mL of 12.66 mol/L NH4F was digested in a constant temperature at 175 ℃ for 20 min.Different samples were determined, the limits of detection for 7 elements in filter rods were 0.007~0.029 mg/kg. The recoveries of the method ranged from 92.50% to 105.8%, and RSDs in the range of 1.71%~5.65%. There was no significant difference between this method and the traditional method for simultaneous determination of 7 elements in filter rod samples. The using of ammonium fluoride instead of hydrofluoric acid , contributes to environmental friendly and avoids the potential risk of hydrofluoric acid. Moreover, the method can quickly and accurately determine the residual amount of 7 elements in filter rods.
Key words: Filter rods; Ammonium fluoride; Heavy metal; Hydrofluoric acid; ICP-MS
引用本文：周浩, 陈云璨, 何春莉. 氟化铵辅助消解结合ICP-MS测定滤棒中的7种元素含量[J]. 化学试剂, 2021, 43(4): 510-514.
微波消解-ICP-MS测定海洋沉积物中的稀土元素
黄金松，李正鹤，王佳翰*
（中国人民武装警察部队黄金第九支队，海南 海口 571127）
摘要：建立了一种微波消解前处理样品，使用电感耦合等离 子体质谱测定海洋沉积物中14种稀土元素的方法。研究了称样量、微波消解程序、酸的配比及复溶酸对稀土元素测定的影响。试验结果表明，14种稀土元素的方法检出限为0.001～0.088 μg/g，精密度（RSD）均低于8%，实际样品加标回收率介于83.6%～113.7％之间，通过测定国家标准物质GBW07335、GWB07336、GBW07314、GBW07316，测定值与标准值一致，满足实际分析要求。
关键词：微波消解；海洋沉积物；稀土元素；电感耦合等离子体质谱；内标元素；选择
中图分类号：O657.3 文献标识码：A 文章编号：0258-3283（2021）--
Determination of Rare Earth Elements in Marine Sediments by Microwave Digestion ICP-MS HUANG Jin-song, LI Zheng-he, WANG Jia-han *(No.9 Geological Part of Chinese Armed Police Force, Haikou 571127, China), Huaxue Shiji, 2021, 43(4), ～
Abstract: A method of determination of 14 rare earth elements in marine sediments by inductively coupled plasma mass spectrometry with microwave digestion has been established. The effects of sample weight, microwave digestion procedure, acid ratio and resolution acid on the determination of rare earth elements were studied. The detection limit of 14 rare earth elements was 0.001-0.088 μg/g, the precision (RSD) was lower than 8%, and the recovery rate of the actual sample was between 83.6% - 113.7%. By measuring the national standard substances GBW07335, GBW07336, GBW07314 and GBW07316, the measured value was consistent with the standard value, which meet the actual analysis requirements.
Key words: microwave digestion; marine sediments; rare earth elements; inductively coupled plasma mass spectrometry; internal standard elements; selection
引用本文：黄金松，李正鹤，王佳翰. 微波消解-ICP-MS测定海洋沉积物中的稀土元素[J].化学试剂，2021，43（4）：515-519.
动态稀释法配制痕量一氧化氮气体标准物质的研究
李剑，夏春*，汪圣甲，程丽萍
（青岛市计量技术研究院，山东 青岛 266101）
摘要：建立了一套动态稀释法配制痕量一氧化氮气体标准物质的稀释系统。通过控制两个质量流量计的流量，按比例将1.00 μmol/mol的NO/N2标准气体稀释成浓度为9.9、19.8、48.4、78.2 nmol/mol的一氧化氮标准气体，并给出稀释后标准气体的相对扩展不确定度Ur=1.7%（k=2）。同比例稀释试验（99.6 μmol/mol NO/N2标准气体稀释100倍，与1.00 μmol/mol NO/N2标准气体进行比较）证明了稀释后的标准气体浓度准确可靠，结果表明本稀释系统配制的痕量一氧化氮标准气体适用于检校低量程化学发光法氮氧化物分析仪。
关键词：动态稀释法；痕量；一氧化氮；标准气体；化学发光法
中图分类号：O657.71 文献标识码：A
Preparation of Trace Nitric Oxide Standard Gas by Dynamic Dilution Method LI Jian，XIA Chun*，WANG Sheng-jia，CHENG Li-ping（Qingdao Institute of Measurement Technology，Qingdao，Shandong 266101）
Abstract：A dilution system for the preparation of trace nitric oxide standard gas by dynamic dilution method was established. By controlling the flow rates of the two mass flowmeters,1.00 μmol/mol NO/N2 standard gas was diluted to 9.9,19.8,48.4,78.2 nmol/mol NO standard gas. The relative expanded uncertainty was 1.7% (k = 2). The same proportion dilution test（99.6 μmol/mol NO/N2 standard gas was diluted 100 times and compared with 1.00 μmol/mol NO/N2 standard gas）proved that the concentration of diluted standard gas was accurate and reliable. The trace nitric oxide standard gas prepared by the dilution system was suitable for calibrating the low-range chemiluminescence nitrogen oxide analyzer.
Key words：dynamic dilution method；trace；nitric oxide；standard gas；chemiluminescence
引用本文：李剑，夏春，汪圣甲，等. 动态稀释法配制痕量一氧化氮气体标准物质的研究[J].化学试剂，2021，43（4）：520-523.
超声诊疗一体化的载药壳聚糖纳米微泡的制备
易夕圆，王生庚，杨增涛*
（重庆医科大学 生物医学工程学院 超声医学工程国家重点实验室 重庆市生物医学工程学重点实验室，重庆 400016）
摘要：载药微泡在超声诊疗一体化中具有广阔的应用前景。本文以壳聚糖为原料制备了一种能够实现超声诊疗一体化功能的载药壳聚糖纳米微泡，采用激光粒度仪、透射电镜、扫描电镜、紫外分光光度计、超声成像仪以及圆二色谱仪等检测方法对载药纳米微泡进行表征，研究了载药纳米微泡的稳定性，并验证了其体外超声显影和超声释放的能力。结果表明：载药纳米微泡平均粒径为136.54±4.46 nm，粒径均一且分散性好，药物的包封率和载药率分别为43.1%±1.3%和4.1%±0.01%，体外实验证实该载药纳米微泡具有的空核结构能够实现超声显影功能，且通过聚焦超声能实现对纳米微泡中包裹的药物进行体外定点释放。制备的载药纳米微泡有望在超声诊疗一体化的应用中提供参考。
关键词：诊疗一体化；载药纳米微泡；壳聚糖；超声造影
中图分类号：O636.1 文献标识码：A 文章编号：0258-3283（2021）
Preparation of Drug-loaded Chitosan Nano-microbubbles Integrated with Ultrasound Diagnosis and Treatment YI Xi-yuan, WANG Sheng-geng, YANG Zeng-tao* (1. State Key Laboratory of Ultrasound Medical Engineering, School of Biomedical Engineering, Chongqing Medical University, Chongqing Key Laboratory of Biomedical Engineering, Chongqing 400016, China)
Abstract: Drug-loaded microbubbles have good application prospects in the integration of ultrasound diagnosis and treatment. The drug-loaded chitosan nano-microbubble was prepared from chitosan as raw material, which has the function of realizing the integration of ultrasound diagnosis and treatment. The drug-loaded nano-microbubbles were characterized by particle size potentiometer, transmission electron microscopy, scanning electron microscopy, ultraviolet spectrophotometer, ultrasonic imager, and circular dichrograph. The stability of drug-loaded nano-microbubbles and the ability of external ultrasound imaging and ultrasound release were studied. The average particle size of the drug-loaded nano-microbubbles was (136.54±4.46) nm. The drug-loaded nano-microbubbles were spherical with uniform size and had good dispersibility. The drug encapsulation rate and drug loading rate were 43.1±1.3%, 4.1±0.01%, respectively. The drug-loaded nanobubbles had a core-shell structure, which can have the function of ultrasound imaging while loading drugs, and achieve the targeting of drugs loaded in the drug-loaded nanobubbles through focused ultrasound freed. The prepared drug-loaded nano-microbubbles are expected to provide reference for the application of integrated ultrasound diagnosis and treatment.
Key words: integrated diagnosis and treatment; drug-loaded nano-microbubbles; chitosan; ultrasound contrast
引用本文：易夕圆，王生庚，杨增涛. 超声诊疗一体化的载药壳聚糖纳米微泡的制备[J]. 化学试剂, 2021, 43(4):524-528.
基于4,4’-二苯醚二甲酸桥配体的一维Co(II)配位聚合物的制备、晶体结构及性质
张治良*1，晋杜娟2，张芳芳3，姚小强4
（1. 青海省产品质量监督检验所，青海 西宁 810000；2. 西宁(国家级)经济技术开发区甘河滩工业园区管委会，青海 西宁 810000；3. 西宁市第十四中学，青海 西宁 810000；4. 西北师范大学 化学化工学院，甘肃 兰州 730000）
摘要：以1-咪唑基-4-羟基吡啶基苯（4-(4-(1H-imidazol-1-yl)phenyl)pyridine，L）线性含氮配体和4,4'-二苯醚二甲酸（4,4'-diphenyl ether dicarboxylic acid，H2oba）羧酸配体、六水合氯化钴为原料，采用水热的方法在水热反应釜中得到一个新的蓝紫色配位聚合物{[Co(L)(odba)(H2O)]·H2O}n 。通过IR和PXRD对其进行了表征，并且用单晶衍射仪测定了配合物的晶体结构发现该化合物为是双核钴的结构，X-射线单晶衍射分析表明配位聚合物属于三斜晶系，P-1空间群，a=10.1697(11) Å、b=10.2756(8) Å、c=13.5456(12) Å、α=71.523(7)°、β=85.728(8)°、γ=68.084(9)°、V=1244.0(2) Å3、Z=2、F(000)=606、Rint=0.034、ωR2= 0.1200。在配合物中二价钴，分别与6个不同的原子进行了六配位，整个配合物的结构通过配位水分子和自由水分子分子与配体间形成的氢键连接成三维的超分子结构，自由水的氢键O—H···O对化合物的结构稳定性起到至关重要的作用，加强了化合物的稳定。并且对这个配合物的紫外吸收及结构的热稳定性进行了进一步研究。
关键词: 蓝紫色配位聚合物；水热反应合成；晶体结构；紫外光谱；热稳定性
中图分类号：O61 文献标识码：A 文章编号：0258-3283（2020）--
Synthesis, Crystal Structure and Properties of One-dimensional Co(II) Coordination Polymer Based on 4,4’-Diphenyl Ether Dicarboxylic Acid Bridged Ligand ZHANG Zhi-liang*1，JIN Du-juan2，ZHANG Fang-fang3 , YAO Xiao-qiang4 (1. Qinghai Products Quality Supervision and Inspection Institute, Xining 810000, China; 2. Xining (National) Economic Technological Development Zone Ganhe Industrial Park, Xining 810000, China; 3. Xining No.14 High School, Xining 810000, China; 4. college of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 73000, China), Huaxue Shiji, 2021, 43(4), ～
Abstract: One coordination polymer{[Co(L)(odba)(H2O)]·H2O}n with L (4-(4-(1H-imidazol-1-yl)phenyl)pyridine) and H2odba ligand (H2odba = 4,4'-4,4'-diphenyl ether dicarboxylic acid ) has been synthesized by hydrothermal conditions with CoCl2·6H2O. The complex was characterized by instrument methods. The complex belongs to triclinic system space group, P-1 space group, a=10.1697(11) Å，b=10.2756(8) Å，c=13.5456(12) Å，α=71.523(7)°，β=85.728(8)°，γ=68.084(9)°，V=1244.0(2) Å3， Z=2， F(000)=606 ，Rint=0.034，ωR2= 0.1200。 The center metal Co2+ is six-coordinated and has a slightly distorted octahedral coordination geometry. The whole structure of the complex is stabilized by the weak interactions. The hydrogen bond of free water and coordinated water O—H···O plays a vital role in the structural stability of the compound and strengthens the stability of the compound. Moreover, the UV absorption and thermal stability of the complex have been further investigated.
Key words: bluish violet coordination polymers; hydrothermal synthesis; crystal structure ultraviolet spectrum; thermal stability
引用本文：张治良, 晋杜娟, 张芳芳, 等. 基于4,4’-二苯醚二甲酸桥配体的一维Co(II)配位聚合物的制备、晶体结构及性质[J]. 化学试剂, 2021, 43(4)：529-533.
响应面法优化N-氨基甲酰谷氨酸的合成工艺
张昊昱，荣易，李静，黄双平，张朝峰*
（太原理工大学 生物医学工程学院，山西 太原 030024）
摘要：关于N-氨基甲酰谷氨酸的合成国内外已有许多报道，通过以L-谷氨酸和尿素为原料，研究了N-氨基甲酰谷氨酸的合成工艺。在单因素实验的基础上，采用响应面分析法的BOX-Behnken设计方法，利用软件Design-Expert 10 考察了反应温度、反应时间、物料物质的量比等因素以及因素之间的交互作用对合成N-氨基甲酰谷氨酸收率的影响。建立了N-氨基甲酰谷氨酸收率的二次线性回归方程，获得了最优工艺条件：反应时间2.05 h、反应温度119.83℃、n（L-谷氨酸）：n（尿素）=1：2.2，在此条件下NCG收率为82.47%，并进行了3次验证性实验，得N-氨基甲酰谷氨酸的产率为81.76%，与理论预测值相对误差较小，与响应面模型预测值非常吻合，说明采用响应面优化方案有效、可靠。
关键词：N-氨基甲酰谷氨酸；单因素；响应面优化法；box-behnken设计；最优工艺
中图分类号：TQ464.7 文献标识码：A 文章编号：0258-3283（2021）--
Optimization of Synthesis Process of N-carbamyl-l-glutamic Acid by Responses Surface Methodology
ZHANG Hao-yu, RONG Yi, LI Jing, HUANG Shuang-ping, ZHANG Chao-feng (College of Biomedical Engineering, Taiyuan University of Technology, Taiyuan 030024, China), Huaxue Shiji, 2021, 43(4), ～
Abstract: There have been many reports on the synthesis of N-carbamoyl glutamic acid. In this work, the synthesis process of N-carbamoyl glutamic acid was studied using L-glutamic acid and urea as raw materials. Based on the single factor experiment, the BOX-Behnken design method of response surface analysis was used, and the software Design-Expert 10 was used to examine the factors such as reaction temperature, reaction time, material molar ratio and the interaction between the factors on the synthesis of N- Effect of carbamoyl glutamate yield. A quadratic linear regression equation for the yield of N-carbamoyl glutamate was established, and the optimal process conditions were obtained: reaction time 2.05h, reaction temperature 119.83℃, raw material n (L-glutamic acid) : n (urea)=2.2 : 1. Under the condition, the yield of NCG is 82.47%. Under this optimal condition, three confirmatory experiments were carried out, and the yield of N-carbamoyl glutamic acid was 81.76%, which was relatively small relative to the theoretical prediction and very consistent with the predicted value of the response surface model, indicating that the response surface optimization scheme is effective and reliable.
Keyword: N-carbamylglutamate; single factor; response surface methodology; box-behnken design; optimal process
引用本文：张昊昱, 荣易, 李静. 响应面法优化N-氨基甲酰谷氨酸的合成工艺[J]. 化学试剂, 2021, 43(4): 534-539.
3-碘-6-卤代咪唑并[1,2-a]吡啶-8-甲酸酯的合成
程伟1，杨德亮1，张向龙2，陈本康1，郑爽1，张箫壬1，袁文鹏*1
(1.齐鲁工业大学（山东省科学院） 山东省科学院菏泽分院 山东省生物工程技术创新中心 山东 菏泽 274000；2.山东友帮生化科技有限公司，山东省小分子杂环化合物工程实验室 山东 菏泽 274000 )
摘要：标题化合物是一类重要杂环化合物，具有较高的生物活性，广泛应用于抗肿瘤药物、抗菌、抗病毒等药物的生产。报道了以2-氨基烟酸为起始原料,经过浓硫酸催化与醇类生成2-氨基烟酸酯，再与N-卤代丁二酰亚胺反应制备2-氨基-5-卤代烟酸酯，再与氯乙醛成环缩合生成6-卤代咪唑并[1,2-a]吡啶-8-甲酸酯，最后和N-碘代琥珀酰亚胺碘代共4步制得标题化合物，总收率为58.9%~67.7%。产物结构经 IR、 1H NMR、13C NMR、元素分析进行了表征。合成路线具有方法新颖、操作简单、收率高、避免柱层析分离纯化，更适合工业化放大生产的特点。
关键词：2-氨基烟酸；氯乙醛；N-碘代丁二酰亚胺；3-碘-6-卤代咪唑并[1,2-a]吡啶-8-甲酸酯；合成；抗癌药物
中图分类号：R914.5 文献标识码：A 文章编号：
Synthesis of 3-Iodo-6-haloimidazo [1,2-a] pyridines-8-carboxylic Acid Esters CHENG Wei1, YANG De-liang1, ZHANG Xiang-long2, CHEN Ben-kang1, ZHENG Shuang1, ZHANG Xiao-ren1, YUAN Wen-peng*1 (1.Heze Branch，Qilu University of Technology(Shandong Academy of Sciences)，Biological Engineering Technology Innovation Center of Shandong Province, Heze 274000, China; 2.Shandong Youbang Biochemical Technology Co., Ltd., Shandong Engineering Laboratory of Small Molecule Heterocyclic Compounds, Heze 274000, China)
Abstract：The title compounds are important heterocyclic compounds with high biological activity, which can be widely used in the production of anti-cancer drugs, anti-bacterial drugs and anti-virus drugs. In order to explore a new synthetic route, taking 2-aminonicotinic acid as the raw materials, the synthesis gradually went by the following four-step reaction processes with the total yield of 58.9% ~ 67.7%.Reaction with alcohols catalyzed by concentrated sulfuric acid to form 2-aminonicotinic acid esters, halogenation with N-halosuccinimide to form 2-amino-5-halonicotinic acid esters, ring-closing condensation with chloroacetaldehyde, and iodization with NIS to form 3-iodo-6-haloimidazo [1,2-a] pyridines-8-carboxylic acid esters. The structure was confirmed by IR、1HNMR、13CNMR and elemental analysis. The protocol takes the advantages of new synthetic route, easy operation, and high yield, avoiding column chromatography separation and suited for scale-up production.
Key words：2-aminonicotinic acid; chloroacetaldehyde; N-Iodosuccinimide; 3-iodo-6-haloimidazo [1,2-a] pyridines-8-carboxylic acid esters; synthesis; anti-cancer drugs
引用本文：程伟，杨德亮，张向龙，等.3-碘-6-卤代咪唑并[1,2-a]吡啶-8-甲酸酯的合成[J].化学试剂，2021,43（4）：540-545.
三氮唑螺氧化吲哚衍生物的合成及表征
王龙，张文静，曹国锐*
（青岛科技大学 化工学院，山东 青岛 266042）
摘要：以1-苄基-2-氧代吲哚-3-亚氨基甲酸叔丁脂和4-取代（Z）-N-苯基苯甲酰氯为底物通过1,3-偶极环加成反应合成了9种目标产物。通过比较目标产物的产率，对反应溶剂、碱及其用量、温度等因素进行了优化，确定了最佳反应条件，即在25 ℃下以二氯甲烷为溶剂、三乙胺为碱，且n(Et3N)∶n(1-苄基-2-氧代吲哚-3-亚氨基甲酸叔丁脂) = 2.0∶1.0时目标化合物最高产率可达94.4%。将具有生物活性的三氮唑骨架引入到螺环氧化吲哚骨架中，为更好地发现具有生物活性的该类新化合物提供借鉴。
关键词：1-苄基-2-氧代吲哚-3-亚氨基甲酸叔丁脂；4-取代（Z）-N-苯基苯甲酰氯；1,3-偶极环加成反应；三氮唑螺氧化吲哚化合物
中图分类号：O626.13 文献标识码：A 文章编号：0258-3283（2021）
Synthesis and Characterization of Spirotriazoline Oxindoles Derivatives WANG Long, ZHANG Wen-jing, CAO Guo-rui* (College of Chemistry Engineering, Qingdao University of Science and Technology, Qingdao 266042, China), Huaxue Shiji, 2021, 43(4)
Abstract：1-Benzyl-2-oxoindole-3-iminocarboxylic acid tert-butyl ester and 4-substituted (Z)-N-phenylbenzoyl chloride were used as substrates through 1,3-dipolar cycloaddition reaction to give nine spirotriazoline oxindoles compounds. The following 1,3-dipolar cycloaddition reaction was studied by exploring reaction solvent, base and its equivalent and temperature to found the optimized reaction conditions. The dichloromethane as the solvent and triethylamine as the base at 25°C, and n(Et3N) : n(1-benzyl-2-oxoindole-3-iminocarboxylic acid tert-butyl ester) =2.0 : 1.0，the highest yield of the target product was 94.4%. In this work, the triazole skeleton with biological activity is successfully introduced into the spiroepoxy indole skeleton, which provides a reference for better discovering such new compounds with biological activity.
Key words：1-benzyl-2-oxoindole-3-iminocarboxylic acid tert-butyl ester; 4-substituted (Z)-N-phenylbenzoyl chloride; 1,3-dipolar cycloaddition reaction; spirotriazoline oxindoles compounds
引用本文：王龙，张文静，曹国锐. 三氮唑螺氧化吲哚衍生物的合成及表征[J]. 化学试剂, 2021, 43(4):546-553.
