【特约专题】
基于金属有机框架的TiO2-NiO高效催化剂构建及光催化产氢性能研究
安阳*1，姜为易2，吕新玲1，王玲玲1，庞欢1
（1. 扬州大学 a.化学化工学院；b.创新材料与能源研究院，江苏 扬州 225009；
2. 山东大学 晶体材料研究院品系，山东 济南 250100）
摘要：设计和制备绿色高效的水分解产氢光催化剂是当前能源领域的迫切需求。首先通过溶剂热法合成金属有机框架材料（MOFs）NH2-MIL-125(Ti)，再利用Ni2+与-NH2的配位作用制备出Ni-NH2-MIL-125(Ti)，最后对所制备的前驱体进行高温煅烧成功获得颗粒小、分散性高、亲水性强TiO2-NiO高效光催化剂。采用X射线衍射（XRD）、X射线光电子能谱（XPS）、高分辨率透射电镜（HR-TEM）、红外光谱（FI-IR）、比表面积分析、紫外-可见漫反射光谱（UV-Vis DRS）及光致发光光谱（PL）等手段对催化剂进行表征，并通过光催化实验测试了其产氢活性。结果表明，制备TiO2-NiO光催化剂的最佳条件为镍钛比为0.6:1、煅烧温度为600 ℃，合成的TiO2-NiO光催化剂比表面积为51.064 m2/g，较溶胶-凝胶法合成的光催化剂粒径更小且分散度更高，其产氢速率最高可达1396 μmol·h-1·g-1，是传统光催化材料的11倍。实验证明了MOFs作为合成TiO2-NiO反应前驱体的优越性，为生产高效光催化剂提供了新的思路。
关键词：光催化；MOF；TiO2-NiO；产氢；机理研究
中图分类号：O643.36 文献标识码：A
DOI：10.13822/j.cnki.hxsj.2023.0243
Construction and Photocatalytic Hydrogen Production Performance Study of TiO2-NiO High Efficiency Catalyst Based on MOFs AN Yang*1, JIANG Wei-yi2, LU Xin-ling1, WANG Ling-ling1, PANG Huan1 (1a. School of Chemistry and Chemical Engineering, 1b. Institute for Innovative Materials and Energy, Yangzhou University, Yangzhou 225009, China; 2. State Key Lab of Crystal Materials, Shandong University, Jinan 250100, China)
Abstract： Design and preparation of green and efficient photocatalyst for hydrogen production from water decomposition is an urgent demand in current energy field. Metal organic framework material (MOFs) NH2-MIL-125 (Ti) was first synthesized by solvothermal method, and then Ni-NH2-MIL-125 (Ti) was prepared by the coordination of Ni2+ and -NH2. Finally, the prepared precursor was calcined at high temperature to obtain a highly efficient TiO2-NiO photocatalyst with small particles, high dispersion, and strong hydrophilicity. The catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (HR-TEM), infrared spectroscopy (FI-IR), specific surface area analysis, Ultraviolet-visible diffuse reflection spectroscopy (UV-Vis DRS) and photoluminescence spectroscopy (PL). Hydrogen production activity was tested through photocatalytic experiments. Experimental results showed that the best conditions for preparing TiO2-NiO photocatalyst were that ratio of nickel to titanium was 0.6:1, calcination temperature was 600 ℃ and the specific surface area of the synthesized TiO2-NiO photocatalyst was 51.064 m2/g, which was smaller and more dispersed than the photocatalyst synthesized by sol-gel method. Its hydrogen production rate could reach up to 1396 μmol·h-1·g-1, which was 11 times higher than that of traditional photocatalytic materials. The experiment demonstrates the superiority of MOFs as the precursor of TiO2-NiO synthesis reaction, which provides a new idea for the production of efficient photocatalysts.
Key words：photocatalyst; MOF; TiO2-NiO; hydrogen production; mechanism study
引用本文：安阳, 姜为易, 吕新玲, 等.基于金属有机框架的TiO2-NiO高效催化剂构建及光催化产氢性能研究[J]. 化学试剂, 2023, 45（8）：1-7..
非金属掺杂g-C3N4光催化的研究进展
王昊1，陈芳2，张国新*3
（1. 中国中煤能源集团有限公司 科技创新部，北京 100120；2. 中化化工科学技术研究总院有限公司 科技规划部，北京 100083；3. 山东科技大学 储能技术学院，山东 青岛 266590）
摘要：近年来，石墨相氮化碳（g-C3N4）材料作为光催化剂受到了科研工作者们的广泛关注。未改性的氮化碳具有一定的可见光吸收性能，热稳定性好、合成工艺简单，但导电性较差、光生载流子再复合速率高、比表面积小等亟待解决的问题。对其进行非金属掺杂是一种重要的材料改性策略，广泛应用于石墨相氮化碳材料的结构调控及催化性能提升。从非金属掺杂角度出发，以元素掺杂种类、数量作为分类标准，对近年来非金属掺杂石墨相氮化碳的研究成果进行了综述，总结了其在光催化方向应用的研究进展，并对其未来发展进行了展望。
关键词：石墨相氮化碳；非金属掺杂；导电性；光吸收；光催化
中图分类号：O6-1 文献标识码：A 文章编号：0258-3283(2023)—
DOI：10.13822 /j.cnki.hxsj.2023.0235
Progresses on the Photocatalysis Based on Non-metal Doped Graphitic Carbon Nitride WANG Hao1, CHEN Fang2, ZHANG Guo-xin*3 (1. Department of Science and Technology Innovation, China National Coal Group Corp., Beijing 100120, China; 2. Department of Science and Technology Innovation, Central Research Institute of China Chemical Science and Technology Co. Ltd, Beijing 100083, China; 3. College of Energy Storage Technology, Shandong University of Sciencd Technology, Qingdao 266590, China)
Abstract: In recent years, graphitic carbon nitride materials (g-C3N4) have attracted widespread attention from researchers as photocatalysts. Unmodified g-C3N4 has advantages such as visible light absorption capacity, good thermal stability, and easiness of preparation, yet there are still disadvantages such as poor conductivity, high recombination rate of photogenerated charge, and not high enough specific surface area. Non-metal doping as an important strategy to modify g-C3N4 materials has been widely applied in the structural regulation and catalytic performance improvement of g-C3N4. From the perspective of non-metal doping, this paper summarizes the research achievements of non-metal-doped g-C3N4 in recent years based on the classification criterion of doping element, and its research progresses in the direction of photocatalytic reaction are systematically discussed. Finally, a prospect of its future development was presented.
Key words: graphitic carbon nitride; none-metal doping; conductivity; photoadsorption; photocatalysis
引用本文：王昊，陈芳，张国新. 非金属掺杂g-C3N4光催化的研究进展[J]. 化学试剂, 2023, 45(8): 8-16.
马惠1,2，宋利2，于彦龙*1，李雷*2
(1. 东北石油大学 化学化工学院，黑龙江 大庆 163318；2. 嘉兴学院 生物与化学工程学院，浙江 嘉兴 314001)
摘要：以可再生电力为电源的电解水制氢是一种制备高纯氢气的可持续发展路径。其中，析氢反应（HER）电催化剂的性能仍需进一步提升。阴离子空位具有增加活性位点、提升电导率以及优化中间体物质的吸附能的作用，已被广泛应用于提高HER电催化剂性能。综述了近几年阴离子空位调控HER电催化剂的研究进展，以促进电解水制氢的进一步发展。重点分析了阴离子空位的制备与表征、阴离子空位对电解水析氢的影响与机制，并对阴离子空位工程提升电解水制氢催化剂性能研究的挑战进行分析与展望。
关键词：电解水；析氢反应；阴离子空位；氧空位；硫空位；硒空位；磷空位；双空位
中图分类号：O643.36 文献标识码：A 文章编号：0258-3283（2023）
DOI：10.13822/j.cnki.hxsj.2023.0123
Research Progress of Transition Metal-Based Catalyst for Hydrogen Production by Electrochemical Water Splitting Regulated by Anionic Vacancy MA Hui1,2, SONG Li2, YU Yan-long*1, LI Lei*2 (1. College of Chemistry and Chemical Engineering, Northeast Petroleum University, Daqing, Heilongjiang 163318, China; 2. College of Biological, Chemical Sciences and Engineering, Jiaxing University, Jiaxing, Zhejiang 314001, China)
Abstract：Hydrogen production by electrochemical water splitting with renewable electric power is a sustainable way to produce high-purity hydrogen. Among them, the performance of hydrogen evolution reaction (HER) electrocatalysts need to be further improved. Anion vacancy has the function of increasing the active site, improving the conductivity and optimizing the adsorption energy of intermediates, which has been widely used to improve the performance of HER electrocatalysts. We provide a brief overview on the research progress of anion vacancies regulating HER electrocatalysts to promote the development of hydrogen production by electrochemical water splitting in recent years. The preparation and characterization of anion vacancy, the influence and mechanism of anionic vacancy on HER by electrochemical water splitting were emphatically analyzed. In addition, the challenges of improving the performance of catalysts for hydrogen production from electrochemical water splitting by anionic vacancy engineering were analyzed and prospected.
Key words: electrochemical water splitting; hydrogen evolution reaction; anion vacancies; oxygen vacancies; sulfur vacancies; selenium vacancies; phosphorus vacancies; binary vacancies.
引用本文：马惠，宋利，于彦龙，等.阴离子空位调控电解水制氢过渡金属基催化剂的研究进展[J]. 化学试剂，2023，45(8)：17-24.
何川a，朱英明*b，薛雨a，吴可荆b，鲁厚芳a
（四川大学 a. 化学工程学院；b. 新能源与低碳技术研究院，四川 成都 610207）
摘要：纳米泡沫银（AgNFs）具有疏松多孔的内部结构，这种结构利于CO2气体的传递，非常适合应用于流动池电催化体系。首先通过化学还原法制备了乙酸银前驱体，然后进行电化学还原制得AgNFs催化剂。进一步研究了不同CO2流量、不同催化层厚度和不同pH电解质对AgNFs催化CO2还原性能的影响，结果表明AgNFs在CO2流量大于5 mL/min、催化层厚度为52.3 μm、电解质为0.5 mol/L KOH时具有更好的催化活性和CO选择性，在−20 ~ −80 mA/cm2范围内，CO的法拉第效率（FECO）始终大于99%。在70 h的稳定性测试中，FECO稳定在93%以上。AgNFs的多孔结构能促进更多反应活性位点的暴露，利于CO2的传质扩散，这是AgNFs在流动池中CO2电催化还原性能好的主要原因。
关键词：纳米泡沫银；电催化还原；流动池；多孔结构；法拉第效率
中图分类号：O611.2 文献标识码：A 文章编号：0258-3283（2023）
DOI：10.13822/j.cnki.hxsj.2023.0300
Electrocatalytic Reduction of CO2 by Nano Silver Foams in the Flow Cell HE Chuana, ZHU Ying-ming*b, XUE Yu a, WU Ke-jingb, LU Hou-fanga (a. School of Chemical Engineering, b. New Energy and Low-Carbon Technology, Sichuan University, Chengdu 610207, China)
Abstract: Nano silver foams (AgNFs) possess a loose and porous internal structure, making it conducive to the transfer of CO2 gas and highly suitable for application in the electrocatalytic systems of a flow cell. Herein, silver acetate precursor was prepared using the chemical reduction method, and then AgNFs catalyst was obtained through electrochemical reduction. Additionally, the effects of different CO2 flow rates, different catalytic layer thickness and pH electrolyte on the catalytic performance of AgNFs for CO2 reduction were investigated. The results indicated that AgNFs exhibited superior catalytic activity and CO selectivity when the CO2 flow rate was greater than 5 mL/min, the catalytic layer thickness was 52.3 μm and the electrolyte was 0.5 mol/L KOH. The Faraday efficiency of CO (FECO) remained greater than 99% in the range of −20 ~ −80 mA/cm2. During the 70 h stability test, the FECO was stable at more than 93%. The good electrocatalytic reduction performance of AgNFs in the flow cell is mainly attributed to the porous structure of AgNFs, which promotes the exposure of more reactive sites and facilitates the mass transfer and diffusion of CO2.
Key words: nano silver foams; electrocatalytic reduction; flow cell; porous structure; faraday efficiency
引用本文：何川, 朱英明, 薛雨, 等. 纳米泡沫银用于流动池电催化还原CO2[J]. 化学试剂，2023，45（8）：25-31.
胡俊，葛鑫峰，王明辉，舒婷，梁云霄*
(宁波大学 材料科学与化学工程学院，浙江 宁波 351211)
摘要：采用多模板法制备了一种毫米级尺寸的分等级孔钛硅材料（HPTS），通过在HPTS表面还原Cu2+制得Cu-CuO/HPTS复合光催化剂。用SEM、TEM、XRD、XPS、ICP、N2吸附-脱附和电化学测试等技术对所制备材料的微观结构和形貌、组成和性质进行表征。结果表明，Cu-CuO/HPTS具有两套完整的的三维连贯的大孔孔道，大孔孔壁由超薄的微-介孔纳米薄膜构成。HPTS兼具宏观材料和纳米材料的优点。HPTS在模拟太阳光下对罗丹明B(RhB)有着良好的光催化降解效果，负载Cu-CuO纳米颗粒以后，提高了材料的光生载流子分离效率，Cu-CuO/HPTS复合催化剂的光催化性能显著提升，表观速率常数k值达到0.52 h-1，是HPTS的2.4倍。整体型毫米级尺寸的Cu-CuO/HPTS光催化剂易于回收并且具有良好的稳定性，在经过5次循环使用后仍保留着良好的光催化活性。
关键词：多级孔；金属纳米颗粒；光催化；毫米级尺寸；RhB；复合材料
中图分类号：O64 文献标识码：A 文章编号：0258-3283（2023）--
DOI：10.13822 /j.cnki.hxsj.2023.0234
Preparation and Photocatalytic Properties of Porous Cu-CuO/HPTS Composites Hu Jun, Ge Xin-feng, Wang Ming-hui, Shu Ting, Liang Yun-xiao* (School of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, China)
Abstract：A millimeter sized hierarchical porous titanium silicon material (HPTS) was prepared using a multi template method. Cu CuO/HPTS composite photocatalyst was prepared by reducing Cu 2+on the surface of HPTS. The microstructure, morphology, composition, and properties of the prepared materials were characterized using techniques such as SEM, TEM, XRD, XPS, ICP, N2 adsorption desorption, and electrochemical testing. Results showd that Cu-CuO/HPTS has two complete sets of three-dimensional coherent macroporous channels, and the macroporous wall is composed of ultra-thin micro mesoporous nano films. HPTS has the advantages of both macro materials and nano materials. HPTS has a good photocatalytic degradation effect on Rhodamine B (RhB) under simulated sunlight. After loading Cu-CuO nanoparticles, the photocatalytic separation efficiency of the material was improved, and the photocatalytic performance of Cu-CuO/HPTS composite catalyst was significantly improved. The apparent rate at constant k reached 0.52 h-1, 2.4 times that of HPTS. The monolithic millimeter sized Cu-CuO/HPTS photocatalyst was easy to recover and had good stability, and retains good photocatalytic activity after five cycles of use.
Key words：multistage hole; metal nanoparticles; photocatalysis; millimeter size; RhB; compound material
引用本文：胡俊，葛鑫峰，王明辉，等. 多孔Cu-CuO/HPTS复合材料的制备及其光催化性能[J]. 化学试剂, 2023, 45( 8): 32-39.
高分散Cu/SiO2逆水煤气变换反应催化剂研究
刘宁a, b，曹忠a, b，崔莎a, b，刘辉c，王路辉*a, b, d
（浙江海洋大学 a. 浙江省石油化工环境污染控制重点实验室；b. 石油化工与环境学院；c. 食品与药学学院；d. 临港石油天然气储运技术国家地方联合工程研究中心，浙江 舟山 316022）
摘要：逆水煤气变换(RWGS)反应可以有效的将CO2转化为更具有价值的CO，被认为是最具有应用前景的反应之一。在本研究中，将Cu/SiO2催化剂用于RWGS反应，考察了在浸渍过程中添加尿素对催化剂结构和性能的影响。采用包括H2-TPR、XRD和TEM等对催化剂进行表征，并且在400 ~ 750 ℃的温度范围内进行RWGS性能测试。结果表明，与Cu/SiO2催化剂相比，尿素辅助法制备的Cu/SiO2-N催化剂在逆水煤气变换反应中具有较高的催化活性，并且对CO具有100%的选择性，尿素的引入可以有效地减小活性金属Cu的粒径，使其具有高分散性，Cu/SiO2-N催化剂金属分散度达到26.5%，催化剂的活性得到了显著提高。
关键词：逆水煤气变换反应；CO2；Cu/SiO2催化剂；尿素；高分散
中图分类号：X701 文献标识码：A 文章编号：0258-3283（2023）--
DOI：10.13822/j.cnki.hxsj.2023.0194
Highly Dispersed Cu/SiO2 Catalyst for Reverse Water-Gas Shift Reaction LIU Ninga, b, CAO Zhonga, b, CUI Shaa, b, LIU Huic, WANG Lu-hui*a, b, d (a. Zhejiang Provincial Key Laboratory of Petrochemical Pollution Control; b. School of Petrochemical Engineering and Environment; c. School of Food and Pharmaceutical; d. National & local Joint Engineering Research Center of Harbor Oil & Gas Storage and Transportation Technology, Zhejiang Ocean University, Zhoushan 316022, China)
Abstract: Reverse water gas shift (RWGS) reaction can effectively convert CO2 into more valuable CO, which is considered to be one of the most promising reactions. In this study, Cu/SiO2 catalyst was used in RWGS reaction, and the effect of adding urea on the structure and performance of the catalyst during impregnation was investigated. The catalysts were characterized by H2-TPR, XRD and TEM, and the RWGS performance was tested in the temperature range of 400 ~ 750 ℃. The results showed that compared with Cu/SiO2 catalyst, the Cu/SiO2-N catalyst prepared by urea-assisted method had higher catalytic activity and 100% CO selectivity in reverse water gas shift reaction. The introduction of urea could effectively reduce the particle size of active metal Cu and make it highly dispersed. The metal dispersion of Cu/SiO2-N catalyst reached 26.5%, and the activity of the catalyst was significantly improved.
Key words: reverse water gas shift reaction; CO2；Cu/SiO2 catalyst; urea; highly dispersed
引用本文：刘宁，曹忠，崔莎，等. 高分散Cu/SiO2逆水煤气变换反应催化剂研究[J]. 化学试剂，2023，45（8）：40-46.
【生化与药用试剂】
抗阿尔兹海默症灯盏乙素苷元衍生物设计、合成及活性研究
李慧a,b，何筑a,b，陈娇a,b，李勇军a,b，汤磊*, a,c，傅晓钟*,a,b
（贵州医科大学 a. 药学院，b. 贵州省药物制剂重点实验室，c. 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:基于阿尔兹海默症（AD）发病机制的复杂性，为了开发多功能的抗AD药物，根据多靶点导向配体（multi-target directed ligands，MTDLs）策略，以灯盏乙素苷元为骨架，通过不同的连接体，连接具有胆碱酯酶抑制作用的N,N-双取代氨基甲酸酯片段和具有单胺氧化酶抑制作用的炔丙胺、N-甲基炔丙胺片段，设计并合成9个双靶点抗AD化合物，结构经过1HNMR、13CNMR和ESI-MS鉴定。对目标化合物进行胆碱酯酶和单胺氧化酶的活性测试，其中2-(4-((二甲基氨基甲酰基)氧基)苯基)-5，6-二羟基-4-氧代-4H-色烯-7-基5-(甲基(丙-2-炔-1-基)氨基)-5-氧代戊酸酯对两种酶具有相对较好的抑制活性。酶动力学结果说明该化合物对乙酰胆碱酯酶是混合型抑制。上述化合物不仅对自身和Cu2+诱导的Aβ1-42聚集具有良好的抑制作用（87.57%和82.22%），而且还能诱导自身和Cu2+诱导的Aβ1-42原纤维的分解（75.01%和77.40%）。该化合物可以进行进一步结构优化和活性测试，为多靶点抗阿尔兹海默症提供候选化合物。
关键词：阿尔兹海默症；灯盏乙素苷元；胆碱酯酶；单胺氧化酶；多靶点定向配体
中图分类号:R914.5 文献标识码：A 文章编号：0258-3283（2023）
DOI：10.13822/j.cnki.hxsj.2023.0245
Design, Synthesis and Activity of Anti-Alzheimer's Scutellarein Derivatives LI Huia,b, HE Zhua,b, CHEN Jiaoa,b, LI Yong-juna,b, TANG Lei*a,c, FU Xiao-zhong*a,b ( a. College of Pharmacy, b. Guizhou Provincial Key Laboratory of Pharmaceutics, c. Guizhou Provincial Engineering Technology Research Center for Chemical Drug R&D, Guizhou Medical University, Guiyang 550004, China)
Abstract: In order to develop multifunctional anti-AD drugs, nine double-target anti-AD compounds were designed and synthesized by using the multi-target directed ligand (MTDLs) strategy. The structures were identified by 1HNMR, 13CNMR and ESI-MS. The target compounds were tested for their inhibition potency against cholinesterase and monoamine oxidase, respectively, where 2-(4-((dimethylcarbamoyl)oxy)phenyl)-5,6-dihydroxy-4-oxo-4H-chromen-7-yl-5-(methyl(prop-2-yn-1-yl)amino)-5-oxopentanoate had relatively good enzyme inhibitory activity. In addition, this compound displayed not only good inhibition of self-induced and Cu2+-induced Aβ1–42 aggregation (87.57% and 82.22% inhibition, respectively) but also induced disassembly of self-induced and Cu2+-induced Aβ1–42 fibrils (75.01% and 77.40% disaggregation, respectively). This compound was worthy of further structural optimization and activity testing to provide candidate compounds for multi-target anti-Alzheimer's disease.
Key words: Alzheimer's disease; scutellarein; cholinesterase; monoamine oxidase; multitarget-directed ligands
引用本文：李慧, 何筑, 陈娇, 等. 抗阿尔兹海默症灯盏乙素苷元衍生物设计、合成及活性研究[J]. 化学试剂, 2023, 45（8）：47-56.
黄嘌呤衍生物的设计、合成及抗血小板聚集与神经保护活性研究
崔恩静1，王宏伟1，李家明*1,2，金凡1
（1. 安徽中医药大学 药学院，安徽 合肥 230038；2. 安徽省中医药科学院 药物化学研究所，安徽 合肥 230012）
摘要：为发现具有抗血小板聚集与神经保护作用的缺血性脑卒中候选药物，以可可碱、茶碱为原料，经取代、醚化、水解以及酸化反应，得到14个新型黄嘌呤芳酸类衍生物，并通过1HNMR、13CNMR和ESI-MS对其进行结构确证。采用Bron比浊法测定目标化合物抗血小板聚集活性；进一步使用氧糖剥夺/复氧（Oxygen-glucose deprivation/reperfusion，OGD/R）诱导的大鼠大脑皮层神经元损伤模型对优选化合物进行神经保护活性测试。4-(3-(1,3-二甲基-2,6-二氧代-1,2,3,6-四氢-7H-嘌呤-7-基)丙氧基)3-甲氧基苯甲酸对花生四烯酸（Arachidonic acid，AA）和二磷酸腺苷（Adenosine diphosphate，ADP）诱导的血小板聚集均具有显著的抑制活性。4-(3-(1,3-二甲基-2,6-二氧代-1,2,3,6-四氢-7H-嘌呤-7-基)丙氧基)苯甲酸表现出与丁苯酞无显著性差异的神经保护活性。
关键词：黄嘌呤衍生物；缺血性脑卒中；抗血小板聚集；神经保护；合成
中图分类号：R914.5 文献标识码：A 文章编号：0258-3283（2023）
DOI：10.13822/j.cnki.hxsj.2023.0195
Design, Synthesis and Anti-platelet Aggregation and Neuroprotection Activities Study of Xanthine Derivatives CUI En-jing1, WANG Hong-wei1, LI Jia-ming*1,2, JIN Fan1 (1. College of Pharmacy, Anhui University of Chinese Medicine, Hefei 230038, China; 2. Department of Medicinal Chemistry, Anhui Academy of Chinese Medicine, Hefei 230012, China)
Abstract: To develop ischemic stroke candidates with antiplatelet aggregation and neuroprotection, 14 novel xanthine derivatives were obtained by substitution, etherification, hydrolysis and acidification reaction with theobromine and theophylline as starting materials, which were confirmed by 1H-NMR, 13C-NMR and ESI-MS. The antiplatelet aggregation activity of the target compounds were measured by Bron turbidimetry and further tested for neuroprotective activity against oxygen and glucose deprivation/reperfusion (OGD/R)-induced neurotoxicity in rat cortical neurons. Compound F-8 had significant inhibitory activity on platelet aggregation induced by arachidonic acid (AA) and adenosine diphoshate (ADP). Compound F-11 presented no significant difference in neuroprotective activity compared with n-butylphthalide (NBP).
Key words: Xanthine derivatives; ischemic stroke; anti-platelet aggregation; neuroprotective; synthesize
引用本文：崔恩静, 王宏伟, 李家明, 等. 黄嘌呤衍生物的设计、合成及抗血小板聚集与神经保护活性研究[J]. 化学试剂，2023，45（8）：57-64.
2,4-二取代-6-氯三氮唑类化合物的合成及其抗肺癌活性研究
曾宪霞，黄怀征，凌珍，张洁，谭凯丽，石欣武，何林洪*
（广西医科大学 药学院，广西 南宁 530021）
摘要：为寻找具有抗肺癌活性的先导化合物，以2,4,6-三氯-1,3,5-三嗪为起始原料通过2 ~ 4步反应合成一系列2,4-二取代-6-氯三氮唑衍生物，结构由NMR和MS鉴定。体外细胞抗肺癌活性研究表明，多个化合物（T3、T10、T14、T15和T16）对受测细胞株表现良好的抗增殖活性，尤其是对突变型细胞株PC9、HCC827和H1975。其中，N2-([1，1'-联苯]-4-基)-6-氯-N4-(3-硝基苯基)-1,3,5-三嗪-2,4-二胺的抗增殖活性最强，所有IC50值均小于10 µmol/L。尽管该化合物因为亲脂性过高难以进入后续研究，但其可作为先导化合物为该类结构衍生物的开发提供一定的指导意义。
关键词：2-氯-4,6-二取代三氮唑；肺癌；表皮生长因子受体；野生型；突变型
中图分类号：R914 文献标识码：A 文章编号：0258-3283（2023）--
DOI：10.13822/j.cnki.hxsj.2023.0096
Synthesis and Evaluation of Anti-Lung Cancer Activity for 2,4-Disubstituted 6-Chlorotriazole Compounds ZENG Xian-xia, HUANG Huai-zheng, LING Zhen, ZHANG Jie, TAN Kai-li, SHI Xin-wu, HE Lin-hong* (Pharmaceutical College,Guangxi Medical University, Nanning 530021, China)
Abstract: A series of 2,4-disubstituted 6-chlorotriazole derivatives were synthesized from the raw material of cyanuric chloride through two to four steps in order to find lead compounds owing anti-lung cancer activities. All the compound were identified by NMR and MS. Results of anti-lung cancer activities in vitro demonstrated that several compounds (T3, T10, T14, T15 and T16) displayed favourable anti-proliferative activities against all the cells lines in assay, especially for the cell lines with mutation including PC9, HCC817 and H1975. Among them, compound T10 revealed the best anti-proliferative activity, whose IC50 values were all less than 10 µmol/L. Although the lipophicity of this compound was so high that it could not been carried out further study, it could be used as the lead compound to provide guidance for the development of such structural derivatives.
Key words: 2,4-disubstituted 6-chlorotriazole; lung cancer; epidermal growth factor receptor; wild type; mutant type
引用本文：曾宪霞，黄怀征，凌珍，等. 2,4-二取代-6-氯三氮唑类化合物的合成及其抗肺癌活性研究[J]. 化学试剂, 2023, 45（8）：65-71.
还原响应性聚合物纳米胶束的制备及体外评价
李世玺，冯佳敏，刘雪，梁旭华，王学军*
（商洛学院 生物医药与食品工程学院，陕西 商洛 726000）
摘要：以还原响应性两亲性嵌段共聚物PLA-SS-PHEMA为载体，阿霉素（DOX）为模型药物，通过透析法制备载药聚合物胶束，并选择HeLa细胞进行体外抗肿瘤研究。所制备的类球形聚合物胶束具有适宜的粒径尺寸和较好的载药性能（载药量5.7%，包封率60.8%）。在模拟的还原性条件下纳米载体的双硫键发生断裂，实现药物的快速释放。体外细胞毒性结果显示聚合物胶束对HeLa细胞具有良好的杀伤作用。采用激光共聚焦显微镜（CLSM）和流式细胞仪（FCM）观察和测定HeLa细胞对胶束的摄取和细胞内的药物释放与分布情况，结果显示载药胶束能够有效地被肿瘤细胞摄取，在细胞质内快速释药并进入细胞核。因此，还原响应性聚合物PLA-SS-PHEMA在抗肿瘤药物的靶向递送及可控释放方面具有良好的应用前景。
关键词：还原响应性；聚合物；胶束；阿霉素；纳米载体
中图分类号：O631.5 文献标识码：A 文章编号：0258-3283（2023）--
DOI：10.13822/j.cnki.hxsj.2023.0240
Preparation and in Vitro Evaluation of Reduction-responsive Polymeric Nanomicelles LI Shi-xi, FENG Jia-min, LIU Xue, LIANG Xu-hua, WANG Xue-jun* (College of Biology Pharmacy and Food Engineering, Shangluo University, Shangluo 726000, China)
Abstract: Using the reduction-responsive amphiphilic block copolymer PLA-SS-PHEMA as the drug carrier, doxorubicin (DOX) as the model drug, the drug-loaded polymeric micelles were prepared by dialysis method. And HeLa cells were selected for the further investigating anti-tumor effect in vitro. The prepared spherical micelles with the suitable particle size had excellent drug loading capacity (LE: 5.7%, EE: 60.8%). The in vitro release results demonstrated the cleavage of the intervening disulfide bonds in carrier in the simulated reductive tumor microenvironment led to fast release of anti-cancer drug. The cytotoxicity results demonstrated that the drug loaded micelles could effectively inhibit tumor cell proliferation. Subsequently, the uptake of HeLa cells to corresponding micelles and their intracellular drug release and distribution were observed and determined by confocal laser scanning microscopy (CLSM) and flow cytometry (FCM). The CLSM results jibed with that of the flow cytometry, indicating the drug loaded micelles could be efficiently internalized into the HeLa cells, released drug in cytoplasm and entered the nuclei. Herein, the reduction-responsive polymer PLA-SS-PHEMA has potential application in the field of the targeted delivery and controlled release of anti-tumor drug.
Key words: reduction-responsive; polymer; micelle; doxorubicin; nanocarrier
引用本文：李世玺，冯佳敏，刘雪，等. 还原响应性聚合物纳米胶束的制备及体外评价[J]. 化学试剂, 2023, 45(8): 72-78.
【功能材料】
SBA-15负载咪唑盐离子液体催化剂用于CO2环加成反应的失活机理研究
邓涵，白诗扬*，孙继红
（北京工业大学 化学工程与技术系 绿色催化与分离北京市重点实验室，北京 100124）
摘要：采用后嫁接法将咪唑盐离子液体负载在SBA-15上制备了多相催化剂SBA-15-Imi并将其用于CO2环加成反应，研究了介孔氧化硅负载离子液体催化剂的失活机理。采用XRD、SEM、TEM、TG、FT-IR、EA等多种表征手段探究了潜在的失活原因；同时将基于分形理论、Porod理论的SAXS数据用于催化剂失活原因的分析，对催化剂的微观结构进行深入的研究。结果表明：催化剂循环使用5次后产率降低了74%，失活原因主要是离子液体流失及有机物杂质沉积的问题。
关键词：离子液体；多相催化剂；CO2环加成反应；失活机理
中图分类号：O69 文献标识码：A 文章编号：0258-3283（2023）
DOI：10.13822/j.cnki.hxsj.2023.0304
Deactivation Mechanism of SBA-15 Supported Imidazole Ionic Liquids Catalyst Used in CO2 Cycloaddition Reaction DENG Han, BAI Shi-yang*, SUN Ji-hong (Beijing Key Laboratory of Green Catalysis and Separation, Department of Chemical Engineering, Beijing University of Technology, Beijing 100124, China)
Abstract：Imidazolium ionic liquids were immobilized on SBA-15 (SBA-15-Imi) via post-grafting method to prepare heterogeneous catalyst for CO2 cycloaddition reaction to investigate the deactivation mechanism of mesoporous silica supported ionic liquids catalyst. Then, various characterization methods such as XRD, SEM, TEM, TG, FT-IR, EA, etc. were employed to explore the potential causes of deactivation. Besides, SAXS based on fractal theory and Porod theory was used to analyze both the fresh and recycled catalysts to demonstrate the microstructure changes after reaction.The results showed that the yield of SBA-15-Imi decreased by 74% after 5 cycles of use, the primary reason of deactivation was the loss of ionic liquids, and the organic deposition.
Key words：ionic liquids; heterogeneous catalyst; CO2 cycloaddition reaction; deactivation mechanism
引用本文：邓涵, 白诗扬, 孙继红. 负载型离子液体催化剂的稳定性研究[J]. 化学试剂, 2023, 45（8）：79-86.
Cu2O/CuO复合材料的高效合成及其在葡萄糖检测中的应用
阙永辉1a,1b，曹阳* 1,2，陈德伦1a,1b，高帆1c，赖彩颜1a，许永涛1a，袁润1a
(1.海南大学 a. 材料科学与工程学院；b. 南海海洋资源利用国家重点实验室；c. 化学工程与技术学院，海口 570208；2.琼台师范学院 儿童认知与行为发展重点实验室，海口 571127)
摘要：Cu2O由于其具有优异的机械、热、化学稳定性和较低的过电势受到人们的重视，但是Cu2O中由于Cu处于+1价态，属于亚稳态，在酸，碱性条件下都不稳定，因此需要对Cu2O的表面进行优化处理。采用液相还原法和低温煅烧法高效合成Cu2O/CuO复合纳米材料，利用X-射线衍射、扫描电子显微镜、透射电子显微镜、X-射线光电子能谱以及拉曼光谱对所制备的复合材料进行表征，并将其负载于玻碳电极（GCE）构建修饰电极用于检测葡萄糖浓度。结果表明，Cu2O/CuO复合纳米材料具有更优秀的电催化性能，同时修饰电极对葡萄糖显示出较低的检测限和较高的灵敏度。因此Cu2O/CuO纳米复合材料将在非酶葡萄糖传感领域具有良好的应用前景。
关键词：氧化亚铜；复合材料；异质结；电化学；葡萄糖生物传感器
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2023）--
DOI：10.13822/j.cnki.hxsj.2023.0178
Efficient Synthesis of Cu2O/CuO Composite and Its Application in Glucose Sensor QUE Yong-hui1a,1b, CAO Yang* 1,2, CHEN De-lun1a,1b, GAO fan1c, LAI Cai-yan1a, XU Yong-tao1a, YUAN Run1a (1a. School of Materials Science and Engineering, 1b. State Key Laboratory of Marine Resources Utilization In south China Sea, 1c. School of Chemical Engineering and Technology, Hainan University, Haikou 570208,China;2. Qiongtai Normal University Key Laboratory Of Child Cognition & Behavior Development Of Hainan Province, Haikou 571127, China)
Abstract: Cu2O has attracted people's attention on account of its excellent mechanical, thermal and chemical stability and low overpotential. However, The Cu in Cu2O is +1 valence, which is in metastable state，resulting in its instability under both acid and alkaline conditions. Therefore，it is necessary to optimize the surface of Cu2O. Cu2O/CuO composite nanomaterials were efficiently synthesized by liquid phase reduction and low-temperature calcination. Various techniques, including X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and Raman spectroscopy were applied to
evaluate the morphological characteristics of the obtained composite materials. The modified electrode was constructed by loading it on glassy carbon electrode (GCE) to detect glucose concentration. The results exhibited that the calcined surface of Cu2O/CuO nanocomposites obtain better electrocatalytic performance, and the modified electrode showed lower detection limits and higher sensitivity for glucose. Therefore, Cu2O/CuO nanocomposites will have widespread application prospects in non-enzymatic glucose sensing.
Key words: Cu2O; composite; heterojunction; electrochemistry; glucose biosensor
引用本文：阙永辉，曹阳，陈德伦，等.Cu2O/CuO复合材料的高效合成及其在葡萄糖检测中的应用[J].化学试剂，2023，45（8）：87-93.
张 霖1 ,李宏达*1,2
(1.中国刑事警察学院 刑事科学技术学院, 辽宁 沈阳 110035；2.文件检验鉴定公安部重点实验室, 辽宁 沈阳 110035)
摘要：碳量子点距今已被提出多年，由于碳量子点自身物理和化学性质十分突出，引起国内外的广泛研究。随着人们对其研究的深入，碳量子点的性质和原理也逐渐被人们了解，并逐渐开始掌握其制备与应用。综述了3种碳量子点制备方法的国内外研究进展, 分别是化学氧化法、微波辅助法和水热法，详细阐述了碳量子点的表面修饰以及碳量子点在爆炸物检测方面的应用，最后对碳量子点在爆炸物检测方面存在的问题进行分析和展望。
关键词：碳量子点；合成方法；表面修饰；爆炸物检测
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2023）
DOI：10.13822/j.cnki.hxsj.2023.0341
Synthesis of Carbon Quantum Dots and Its Application in Explosives Detection ZHANG Lin1, LI Hong-da*1, 2
(1. College of Criminal Science and Technology, China Criminal Police University, Shenyang 110035, China; 2. Key Laboratory of Document Inspection and Authentication, Ministry of Public Security, Shenyang 110035, China)
Abstract：Carbon quantum dots have been proposed for many years. Due to their outstanding physical and chemical properties, carbon quantum dots have been extensively studied at home and abroad. With the in-depth study of carbon quantum dots, the properties and principles of carbon quantum dots are gradually understood, and gradually began to master their preparation and application. In this paper, the research progress of three carbon quantum dots preparation methods at home and abroad is reviewed, which are chemical oxidation method, microwave assisted method and hydrothermal method. The surface modification of carbon quantum dots and the application of carbon quantum dots in the detection of explosives are described in detail. Finally, the existing problems of carbon quantum dots in the detection of explosives are analyzed and prospected.
Key words：carbon quantum dots; synthesis method; surface modification; explosive detection
引用本文：张 霖,李宏达.碳量子点的合成及在爆炸物检测中的应用[J].化学试剂，2023,45（8）：94-103.
静电纺丝法制备氧化铈纳米纤维及光催化性能
李百裕1，周杰*1，陈玲霞1，朱蓓蓓1，王璐1，黄艳芳1，李亚2
（1. 南通职业大学 药品与环境工程学院，江苏 南通 226007；2. 南通科技职业学院 环境与生物工程学院，江苏 南通 226007）
摘要：采用静电纺丝法合成了CeO2纳米纤维，利用X-射线衍射光谱（XRD）、扫描电镜（SEM）、透射电镜（TEM）、红外光谱（FT-IR）、X-射线光电子能谱（XPS）和紫外-可见漫反射（UV-vis DRS）对氧化铈纳米纤维进行表征。通过光催化还原Cr(VI)评估CeO2纳米纤维的光催化活性。结果表明，制备的CeO2纳米纤维纯度较高、分散均匀，具有较大的长径比；纳米材料中Ce元素主要以+4和+3价态存在，部分Ce3+的存在促进了氧缺陷的形成；CeO2纳米纤维的形成有效调节了CeO2的禁带宽度，增强了其可见光吸收性能；在酸性条件下，可在60 min内实现Cr(VI)的完全还原，其反应速率常数是P25的8.2倍，同时CeO2纳米纤维具有良好的稳定性，电子是该还原反应的主要活性物种。
关键词：静电纺丝法；CeO2；Cr(VI)还原；光催化
中图分类号：O643.36 文献标识码：A 文章编号：
DOI：10.13822/j.cnki.hxsj.2023.0221
Synthesis and Photocatalytic Properties of Cerium Oxide Nanofibers by Electrospinning LI Bai-yu1, ZHOU Jie*1, CHEN Ling-xia1, ZHU Bei-bei1, WANG Lu1, HUANG Yan-fang1, LI Ya2 (1. College of Pharmaceutical and Environmental Engineering, Nantong Vocational University, Nantong 226007, China; 2. College of Environment and Bioengineering, Nantong College of Science and Technology, Nantong 226007, China)
Abstract: CeO2 nanofibers were synthesized by electrospinning, and characterized by X-ray diffraction spectroscopy (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and ultraviolet visible diffuse reflectance (UV-vis DRS). The photocatalytic activity of CeO2 nanofibers was evaluated by photocatalytic reduction of Cr(VI). The results suggested that the prepared CeO2 nanofibers had high purity, uniform dispersion, and a large aspect ratio. In nanomaterials, Ce mainly exists in the +4 and +3 valence states, and the presence of some Ce3+ promotes the formation of oxygen defects. The formation of CeO2 nanofibers effectively adjusts the band gap width of CeO2 and enhances its visible light absorption performance. Under acidic conditions, the complete reduction of Cr(VI) could be achieved within 60 min, with a reaction rate constant of 8.2 times that of P25. Meanwhile, CeO2 nanofibers have good stability, and electrons are the main active species in this reduction reaction.
Key words: electrospinning; CeO2; Cr (VI) reduction; photocatalysis
引用本文：李百裕, 周杰, 陈玲霞, 等. 静电纺丝法制备氧化铈纳米纤维及光催化性能[J]. 化学试剂, 2023, 45（8）：104-110.
【化学品与环境】
移动式-气相色谱-质谱法-测定环境空气中的34种消耗臭氧层物质
荣瑞1，毛卫鸿1，吴淑萍2，詹光1，丁雁鑫1，马乔1*
（1.杭州谱育科技发展有限公司，杭州 310052；2.杭州多禧生物科技有限公司，杭州 310052）
摘要：建立了一种以移动式-气相色谱-质谱法分析测定环境空气中34种消耗臭氧层物质的方法。该方法以氦气作为流动相，样品无需冷阱聚焦，直接通过仪器的自带的微型采样泵进入到吸附管富集，高温解吸，经Gas-Pro色谱柱（60 m×0.32 mm×0 μm）分离后，进入质谱定量分析。结果表明，在相应的范围内，34种ODS混合标准气体的摩尔分数与其响应强度呈线性关系，检出限为0.18 ~0.62 nmol/mol（3.14s），回收率为88.6%~106.9%，相对标准偏差为3.02%~19.06%（n=6）。采用上述方法分析测试浙江衢州某化工园区环境空气样品，22种ODS被检出，检出量在0.20 ~10.00 nmol/mol，表明该方法具有一定的实用价值。
关键词：消耗臭氧层物质；气相色谱质谱联用法；环境空气；Gas-Pro柱；检出限
中图分类号：X831 文献标识码：A
DOI：10.13822/j.cnki.hxsj.2023.0184
Mobile-Gas Chromatography-mass Spectrometry Determination of 34 Ozone Depleting Substances in Ambient Air RONG Rui1, Mao Wei-Hong1，WU Shu-Ping2, ZHAN Guang1,DING Yan-xing1,Ma Qiao1*( 1.Hangzhou Puyu Technology Development Co., Ltd. Hangzhou 310052;2. Hangzhou Duoxi Biological Technology Co., Ltd. Hangzhou 310052 China)
Abstract: A method for the determination of 34 ozone depleting substances in ambient air by mobile-gas chromatography-mass spectrometry has been established; ambient air samples enter the adsorption tube through the sampling pump of the instrument for enrichment, without the need for cold trap focusing, and then desorbed under high temperature conditions, the desorbed gas samples are connected in series to the Gas-Pro column (60 m×0.32 mm×0 µm) for separation and analysis, in which helium is used as the mobile phase; enter the mass spectrometry for quantitative analysis.The carrier, thermal desorbent conditions and injection mode of sample separation and analysis are optimized.The experimental results show that the quantity fraction of the 34 ODS mixed standard gas substances has a linear relationship with the response intensity of their substances within the corresponding range, and the detection limit is (3.14s) 0.18nmol·mol-1~0.62 nmol·mol-1; the recovery rate is 88.6%~106.9%, and the relative standard deviationis 3.02%~19.06% (n=6).Then according to the above method, 22 kinds of ODS were detected in the ambient air samples of a chemical park in Quzhou, Zhejiang. The detection amount was 0.20 ~10.00 nmol/mol, indicating that this method is of great significance in practical applications.
Key words: ozone depleting substances; gas chromatography mass spectrometry; ambient air; gas-pro column; detection limit
引用本文：荣瑞，吴淑萍，詹光，等.移动式-气相色谱-质谱法-测定环境空气中的34种消耗臭氧层物质[J]. 化学试剂, 2023, 45（8）:111-115.
生物炭材料分散固相萃取环境水中有机氯农药
李睿1,2，曹月阳1,2，刘郁枫1,2，赵汗青*1,2，赵文婷*1,2
（1. 北京农学院 生物与资源环境学院，北京 102206；2. 农业农村部华北都市农业重点实验室，北京 102206）
摘要：以头发为原材料制备生物炭作为分散固相萃取方法的吸附剂，结合气相色谱，建立了一种新的样品前处理方法，用于检测环境水体中8种有机氯（OCPs）农药的残留量。头发生物炭通过低温裂解法，在300℃恒温条件下，经过3 h烧制而成。研磨成大小均匀的颗粒，可作为吸附剂。将其与包含目标分析物的水溶液超声混合。离心分离后，再用正己烷将生物炭中的目标分析物充分洗脱，洗脱溶剂过膜，进气相色谱检测分析。对超声时间、洗脱溶剂、加炭量、pH值以及盐含量等影响萃取效率的因素进行优化。选择最优参数，建立最优分散固相萃取方法。研究结果表明：该方法LODs为1.3～8.8 μg/L，LOQs为4.4～29.4 μg/L，相对标准偏差为4.2%～6.4%，在2～100 μg/L的添加浓度范围内呈现良好的线性，相关系数范围为0.9913～0.9951。该方法操作简单、萃取效率高、重现性好，且废弃物得到了重复利用，可应用于环境水体中的8种OCPs农药残留的检测。
关键词：生物炭；分散固相萃取；有机氯农药；气相色谱；环境水
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2023）--
DOI：10.13822/j.cnki.hxsj.2023.0057
Biochar Materials Dispersed Solid Phase Extraction Of Organochlorine Pesticides In Environmental Water LI Rui1,2, CAO Yue-yang1,2, LIU Yu-feng1,2, ZHAO Han-qing*1,2, ZHAO Wen-ting*1,2 (1. College of Bioscience and Resources Environment, Beijing University Of Agriculture, Beijing 102206; 2.Key laboratory of Urban Agriculture In North China, Ministry Of AgricultureRural Affairs, P.R.China, Beijing 102206)
Abstract: Using hair as raw material to prepare biochar as a sorbent for dispersive solid phase extraction method, a new sample pretreatment method was established to detect 8 organochlorine pesticide residues in environmental water bodies combined with gas chromatography. The hair biochar was through the low temperature pyrolysis method, under the condition of 300 ℃ temperature, kept 3 h, and ground to a uniform size, it could be used as a sorbent for dispersive solid-phase extraction. The biochar was mixed with sample solution by ultrasonic, which contained the target analyte. After centrifugal separation, n-hexane was used to elution target analyte in biochar adequately. N-hexane was recycled for filtration and analyzed in gas chromatography. Ultrasonic time, elution solvent, carbon content, pH value, salt content and other factors affecting extraction efficiency were optimized. The optimal dispersive solid phase extraction method was established by selecting the optimal parameters. The limits of detection were 1.3～8.8 μg/L, and the limits of quantitation were 4.4～29.4 μg/L. The relative standard deviations were 4.2%～6.4%, and the correlation coefficients ranged from 0.9913 to 0.9951 in the range of 2～100 μg/L. The method has the advantages of simple operation, high efficiency and good reproducibility, and wastes were reused. The method can be applied to detect 8 organochlorine pesticides residues in environmental water.
Key words: biochar; dispersed solid phase extraction; organochlorine pesticide; gas chromatography; ambient water
引用本文：李睿，曹月阳，刘郁枫，等. 生物炭材料分散固相萃取环境水中有机氯农药[J]. 化学试剂, 2023, 45(8): 116-121.
【分析与测试】
一种基于高分辨液质联用仪的13C标记葡萄糖同位素丰度检测方法
范若宁1,2，赵雅梦*1,2,3，王储尧1,2，廖望1,2，解龙1,2，赵诚1，罗勇1，雷雯*1,2
（1. 上海化工研究院有限公司，上海 200062；2 .上海市稳定同位素检测及应用研发专业技术服务平台，上海 200062;
3.上海交通大学医学院 仁济医院 核医学科，上海 200127）
摘要：[U-13C6]葡萄糖是一种重要的同位素试剂，在代谢组学等生物医药领域具有重要应用。开发了一种基于超高效液相色谱-高分辨质谱联用仪的[U-13C6]葡萄糖同位素丰度检测方法。在确定检测[U-13C6]葡萄糖同位素丰度的适用条件后，进行液质联用上机检测，根据不同同位素标记模式峰的强度值进行丰度计算；考察了样品浓度、质谱分析图数、流动相背景干扰对同位素丰度计算的影响，在最优条件取出峰时间窗口内所有质谱图并扣除流动相背景干扰下，重复7次进样测得浓度为10 μg/mL的[U-13C6]葡萄糖试剂13C丰度为99.05%（理论值99.2%）且RSD为0.15%。该方法无需复杂的前处理过程，具有较好的准确性和稳定性，是一种具有潜力的同位素试剂质量控制方法。
关键词：[U-13C6]葡萄糖；高分辨质谱；同位素丰度检测
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2023）
DOI：10.13822/j.cnki.hxsj.2023.0212
A High-resolution Liquid Mass Spectrometer-based Method for the Detection of 13C-labeled Glucose Isotope Abundance FAN Ruo-ning1,2, ZHAO Ya-meng*1,2,3, WANG Chu-yao1,2, Liao Wang1,2, XIE Long1,2, ZHAO Cheng1, LUO Yong1, LEI Wen*1,2（1.Shanghai Research Institution of Chemical Industry Co. Ltd., Shanghai 200062; 2. Shanghai Professional Technology Service Platform on Detection and Application Development for Stable Isotope，Shanghai 200062;3. Department of Nuclear Medicine, Renji Hospital, School of Medicine, Shanghai Jiaotong University, Shanghai 200127）
Abstract：[U-13C6]glucose is an important isotopic reagent with commonly used for tracking metabolic fluxes in living organisms or cell cultures. An ultra performance liquid chromatography-high resolution mass spectrometry-based method was developed to determine isotopic abundance of [U-13C6]glucose. After optimizing the applicable conditions the method was applied to calculate the abundance of [U-13C6]glucose based on the intensity values of the mass isotopomer peaks. Effects of sample concentration, number of mass spectrometry scans, and background interference from the mobile phase on the calculation of isotope abundance were also investigated. Under the optimal conditions, i.e., all the mass spectra within the peak time window were used for calculation and the mobile phase background interference was removed, the 13C abundance of [U-13C6] glucose reagent at a concentration of 10 μg/mL was 99.05% (theoretical value is 99.2%) with an RSD of 0.15% for 7 repeated measurements. The method described here features good accuracy and stability while requiring minimal sample preprocessing, making it an efficient and robust quality control protocol for stable isotope labeled reagents.
Key words：[U-13C6] glucose; high-resolution mass spectrometry; detection of isotopic abundance
引用本文：范若宁，赵雅梦，王储尧，等. 超高效液相色谱-高分辨质谱联用法检测13C标记葡萄糖的同位素丰度[J]. 化学试剂，2023，45（8）：122-126.
【标准物质与标准品】
电解质分析仪用系列混合溶液标准物质的研制
张鹏辉1，罗婷婷1，司升玲1，张蒙1，张惠1，刘季业1，杨嘉伟*2
（1. 四川中测标物科技有限公司，四川 成都 610052；2. 中国测试技术研究院，四川 成都 610021）
摘要：以国家一级纯度标准物质氯化钾、氯化钠和纯度经准确定值的高纯试剂无水醋酸钠、氯化锂、氯化钙为原料研制电解质分析仪用系列混合溶液标准物质。采用重量-容量法制备了该系列混合溶液标准物质，以配制值为标准值，钾、钠、氯、锂、钙5种离子的混合溶液为该系列混合溶液标准物质。采用电解质分析仪对研制的系列混合溶液标准物质进行了均匀性检验和稳定性考察，其结果表明该系列混合溶液标准物质具有良好的均匀性和稳定性，有效期为12个月，详细分析了该系列混合溶液标准物质的不确定度来源，其相对扩展不确定度为2%（k = 2）。该系列混合溶液标准物质可用于电解质分析仪的检定校准、分析方法确认与质量控制。
关键词：电解质分析仪；不确定度；检定；校准；标准物质
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2023）
DOI：10.13822/j.cnki.hxsj.2023.0076
Preparation of a Series of Mixed Solution Reference Materials for Electrolyte Analyzers ZHANG Peng-hui1, LUO Ting-ting1, SI Sheng-ling1, ZHANG Meng1, ZHANG Hui1, LIU Ji-ye1, YANG Jia-wei*2 (1. Sichuan Zhongce RM Co. ltd., Chengdu 610052, China; 2. National Institute of Measurement and Testing Technology, Chengdu 610021, China)
Abstract: The solution reference materials for electrolyte ananlyzers were prepared with the national primary standard materials potassium chloride, sodium chloride and high-purity reagents anhydrous sodium acetate, lithium chloride and calcium chloride which purity were certified. The series of solution reference materials for the verification of electrolyte ananlyzers were prepared by the weight-volume method with the formulating concentration as certified value, and the standard substance of the solution were mixed solution of potassium sodium, chloride, lithium and calcium ions. The homogeneity and stability of series standard solution were tested by electrolyte analyzers, the results were considered to be good. The uncertainty of solution reference material used in the verification of the series of electrolyte ananlyzers were evaluated, and the relative expanded uncertainty was 2% (k = 2) in 12 months. This series of reference materials can be used for verification and calibration of electrolyte ananlyzers, the confirmation of analytical methods and quality control.
Key words: electrolyte ananlyzer; uncertainty; verification; calibration; reference material
引用本文：张鹏辉, 罗婷婷, 司升玲, 等. 电解质分析仪用系列混合溶液标准物质的研制[J]. 化学试剂, 2023, 45（8）：127-135.
【合成与工艺技术】
可见光促进的镍催化苄位C-H胺化反应研究
周少方，凌芳*，丁海全
(上海沃凯生物技术有限公司，上海 201506)
摘要：苄胺类化合物是一类重要的有机结构单元，广泛存在于生物活性分子分子和天然产物中。苄胺基团的引入可以有效的增加分子的生物活性，加快生物活性分子的发现过程，并可以进一步促进对天然产物衍生候选药物的探索。通过光和过渡金属双催化可以高效地实现苄位C-H键的直接胺化，从而合成一系列苄基磺酰胺类化合物。该方法具有较好的位点及化学选择性、适用范围广、普适性好，为苄胺类化合物的合成提供了一种绿色高效的方法。
关键词：苄胺类化合物；光催化；过渡金属催化；苄位C-H键胺化；叠氮类化合物
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2023）--
DOI：10.13822/j.cnki.hxsj.2023.0290
Nickel/Photoredox Dual Catalytic Benzyl C-H bond Amination ZHOU Shao-fang, LING Fang*, DING Hai-quan (Shanghai Our ChemBio-Technology Co., LTD., Shanghai, 201506, Shanghai, China)
Abstract: Benzylamine compounds are an important organic structural unit, which widely existed in bioactive molecules and natural products. The introduction of benzylamine groups can effectively increase the biological activity of molecules, accelerate the discovery process of bioactive molecules, and further promote the exploration of candidate drugs derived from natural products. A series of benzyl sulfonamides can be synthesized by nickel/photoredox dual catalytic benzyl C-H bond amination. The method has the advantages of good site and chemical selectivity, wide application range, good universality. Meanwhile it provides a green and efficient method for the synthesis of benzylamine compounds.
Key words: Benzylamine compounds; photocatalysis; transition metal catalysis; Benzyl C-H bond amination; azides
引用本文：周少方，凌芳，丁海全. 可见光促进的镍催化苄位C-H键胺化反应研究[J]. 化学试剂, 2023, 45(8):136-144.
吡咯并吡咯衍生物的合成及光化学性质研究
刘玉坤，王磊，张安，张清清，王乃晴，马瑛，贺彩莲，刘炳炀，陈瑜*
(天津理工大学 化学化工学院 ，天津 300384)
摘要：近年来，并吡咯化合物的性质研究越来越受到关注，最初人们的关注点仅仅是此类化合物与吲哚的相似性以及它们可能具有的药理活性，但这一类化合物目前已发展成为光子学和有机电子学领域的研究热点。研究表明，吡咯[3,2-b]吡咯类化合物在成膜、光化学、有机发光二极管器件等方面有着良好的应用，通过合理地改变电子供体（D）、电子受体（A）或共轭π桥，可以容易地调节其光学和电子性质。在之前的研究中发现，通过合理的结构设计，并吡咯化合物具有光引发活性，能够引发丙烯酸酯聚合。主要讨论了含不同取代基的四芳基吡咯并吡咯化合物的合成及光化学性质研究，以芳胺、芳醛及2,3-丁二酮为原料，在催化剂和溶剂反应条件下生成目标产物。之后测定并分析其光谱性能，比较和筛选它们的光引发活性，从而有利于并吡咯化合物作为光引发剂应用于光聚合领域。
关键词：吡咯[3,2-b]吡咯；光化学；光引发剂；光聚合
中图分类号：O69 文献标识码：A 文章编号：0258-3283（2023）
DOI：10.13822/j.cnki.hxsj.2022.0896
Synthesis and Photochemical Property Studies of Pyrrolo[3,2-b]pyrrole Derivatives LIU Yu-kun, WANG Lei，ZHANG An，ZHANG Qing-qing，WANG Nai-qing，MA Ying，HE Cai-lian, LIU Bing-yang，CHEN Yu*( School of Chemistry and Chemical Engineering, Tianjin University of Technology, Tianjin 300384, China)
Abstract：In recent years, more and more attention has been paid to the properties of fused pyrrole compounds. At first, people only focused on their similarity to 1H-indole and their possible pharmacological activities; however, these compounds have become the focus of research in the field of photonics and organic electronics. The results show that pyrrolo[3,2-b]pyrrole compounds have good applications in film-forming, photochemistry, organic light-emitting diode devices and so on, and the optical and electronic properties can be easily adjusted by reasonably changing the electron donor (D) , electron acceptor (A) or conjugated π bridge. In our previous studies, we found that pyrrolo[3,2-b]pyrrole compounds have photo-initiating activity through a reasonable structural design, and they can photoinitiate acrylate to polymerize. In this paper, the synthesis and photochemical properties of tetraarylpyrrolo[3,2-b]pyrrole compounds with different substituents were discussed, and the target products were produced under the condition of catalyst and solvent used in the reaction. Their photopolymerization activities are compared and screened, which is beneficial to the application of fused pyrrole compounds as photoinitiators in the field of photopolymerization.
Key words：pyrrolo[3,2-b]pyrrole;photochemistry; photoinitiator; photopolymerization
引用本文：刘玉坤，王磊，张安，等. 吡咯并吡咯衍生物的合成及光化学性质研究[J]. 化学试剂，2023，45（8）：145-151.
稳定同位素标记氯霉素-D5的合成及表征
(上海安谱实验科技股份有限公司，上海 201600)
摘要：稳定同位素标记的氯霉素-D5是以氘代甲苯为标记前体，经硝化、溴化、氧化得到氘标记的对硝基苯甲醛-D5，对硝基苯甲醛-D5再与手性中间体(R,R)-伪二苯羟甲胺甘氨酸酰胺经醛酮缩合、还原、酰化等一系列反应制得。以甲苯-D8物质的量计算氯霉素-D5收率为19.3%。目标产物结构经核磁共振、质谱、高效液相色谱进行表征。氯霉素-D5的化学纯度为99.89%，氘同位素丰度为99.68 atom% D，均优于外购标准品，具有更优的纯度及更高的氘同位素丰度，可作同位素内标用于食品中氯霉素类药物的残留检测。
关键词：氯霉素-D5；稳定同位素标记；合成；同位素内标
中图分类号：O628.1 文献标识码：A 文章编号：0258-3283（2023）
DOI：10.13822/j.cnki.hxsj.2023.0210
Synthesis and Characterization of Chloramphenicol-D5 WANG Rong, GUO Hui, CHEN Wu-lian* (Anpel Laboratory Technologies ( Shanghai) Inc., Shanghai 201600, China)
Abstract：The stable isotope labeled chloramphenicol-D5 was prepared by deuterated toluene as the labeling precursor, deuterated p-nitrobenzaldehyde-D5 was obtained through nitration, bromination, oxidation, and then combined with the chiral intermediate (R,R)-pseudoephenamine glycinamide through a series of reactions such as aldehyde-ketone condensation, reduction, and acylation. According to the amount of toluene-D8, the yield of chloramphenicol-D5 was 19.3%. The structure of the target product was characterized by NMR, mass spectrometry and high performance liquid chromatography. The chemical purity of chloramphenicol-D5 was 99.89%, and the abundance of deuterium isotope was 99.68 atom% D, which were better than the purchased standard, with better purity and higher deuterium isotope abundance. It can be used as the isotope internal standard for the determination of chloramphenicol residues in food.
Key words：chloramphenicol-D5; stable isotope labeling; synthesis; isotope internal standard
引用本文：汪榕，郭会，陈武炼，等. 稳定同位素标记氯霉素-D5的合成及表征[J].化学试剂，2023，45（8）：152-157.
