二茂铁基咪唑并[1,2-a]喹啉化合物的合成及抗氧化性能研究
席高磊1，赵志伟1，王鹏飞1，蔡莉莉1，刘强1，刘宛凌2，许克静1，陈芝飞*1
(1. 河南中烟工业有限责任公司 技术中心，河南 郑州 450000；2. 河南中烟工业有限责任公司 许昌卷烟厂，河南 许昌 461000)
摘要：以LaCl3催化2-氨基喹啉、二茂铁甲醛和异氰类化合物之间的Groebke-Blackburn-Bienaymé三组分反应（GBB-3CR），合成5种二茂铁基咪唑并[1,2-a]喹啉化合物；通过抑制HO·和还原型谷胱甘肽自由基（GS·）引发的DNA氧化反应体系对化合物的抗氧化活性进行了检测；采用捕获二苯苦味酰肼自由基（DPPH·）和2,2¢-偶氮-双-(3-乙基苯并噻唑啉-6-磺酸)二铵盐自由基（ABTS+·）体系检测了化合物还原自由基的能力，进而探究了取代基对二茂铁基咪唑并[1,2-a]喹啉化合物抗氧化性能的影响。其中，在抑制HO·引发的DNA氧化反应体系中，5种化合物相对空白硫代巴比妥酸活性物质（TBARS）吸光度百分数（TBARS百分数）可达57.5% ～ 88.9%；在抑制GS·引发的DNA氧化反应体系中，5种化合物TBARS百分数可达21.5% ～ 56.3%；5种二茂铁基咪唑并[1,2-a]喹啉化合物均能够捕获DPPH·和ABTS+·；双二茂铁基化合物捕获自由基能力和抑制自由基引发的DNA氧化反应活性优于单二茂铁基化合物。结果表明：5种目标化合物不仅能够捕获自由基，还能够抑制自由基引发的DNA氧化反应，具有较强的还原能力和自由基清除能力，是一类潜在的抗氧化剂。
关键词：Groebke-Blackburn-Bienaymé反应；二茂铁基咪唑并[1,2-a]喹啉；抗氧化；自由基；DNA
中图分类号：R914.5 文献标识码：A 文章编号：0258-3283（2020）
Synthesis and Antioxidant Properties of Ferrocenyl Imid-azo[1,2-a]quinline Compounds XI Gao-lei1, ZHAO Zhi-wei1, WANG Peng-fei1, CAI Li-li1, LIU Qiang1, LIU Wan-ling2, XU Ke-jing1, CHEN Zhi-fei*1 (1.Technology Center, China Tobacco Henan Industrial Co.Ltd., Zhengzhou 450000, China; 2. Xuchang Cigarette Factory, China Tobacco Henan Industrial Co.Ltd., Xuchang 461000, China), Huaxue Shiji, 2020, 42(4)
Abstract：Five ferrocenyl imidazo[1,2-a]quinline compounds were synthesized by Groebke- Blackburn-Bienaymè three-component-reaction (GBB-3CR) among 2-aminoquinline, ferrocenecarboxaldehyde, and isocyanide compounds with LaCl3 being catalyst. Antioxidant abilities were evaluated by inhibiting HO·- and Cu2+/glutathione (GSH)-induced oxidation of DNA. The radical-scavenging properties of the obtained compounds were estimated by quenching2,2¢-diphenyl-1-picrylhydrazyl (DPPH·) and 2,2¢-azinobis(3-ethylbenzothiazoline-6-sulfo- nate) cationic radical (ABTS+·), and then the effects of substituents on the antioxidant properties of ferrocenyl imidazo[1,2-a]quinline compounds could be explored. The thiobar- bituric acid reactive substances (TBARS) percentages of five compounds were 57.5%~88.9% in inhibiting HO·- induced oxidation of DNA. The TBARS percentages of five compounds were 21.5%~56.3% in inhibiting GS·- induced oxidation of DNA. All five ferrocenyl imidazo[1,2-a]quinline compounds could scavenge DPPH·and ABTS+·. N-Ferrocenylmethyl-2-ferrocenylH-imidazo[1,2-a]quinline-1-amine containing two ferrocenyls exhibits higher activity than other compounds in quenching radicals and inhibiting radicals induced oxidation of DNA. The five target compounds can effectively inhibit radicals induced oxidation of DNA and quench radicals, which indicated that they had strong radical scavenging properties and reduction ability and can be a potential antioxidant.
引用本文：席高磊，赵志伟，王鹏飞，等. 二茂铁基咪唑并[1,2-a]喹啉化合物的合成及抗氧化性能研究[J]. 化学试剂，2020, 42（4）：341-347.
多孔PMoAl胶体球的原位制备及加氢性能研究
谢凯宏，方岩雄*，蔡晓兰，孙大雷
（广东工业大学 轻工化工学院，广东 广州 510009）
摘要：采用原位合成方法，制备了一系列具有核壳结构的PMoAl多孔胶体球。通过X-射线衍射（XRD）、透射电镜（TEM）、H2-程序升温还原(H2-TPR)和N2吸附脱附对所制备的材料进行表征。选用二苯并噻吩（DBT）和萘作为模型化合物，研究催化剂结构与活性的关系。结果表明，采用原位制备方法，可以使得Mo物种较为均匀地分散在多孔胶体球上。通过调节反应体系中磷钼酸的添加量，能够有效地调控胶体球的孔结构参数。通过对催化活性研究发现，催化剂的孔隙结构对催化活性具有较大的影响。以NiPMoAl(SP)-0.20作为催化剂，反应温度为340 ℃，二苯并噻吩的转化率可达99.87%，萘的转化率可达81.28%。
关键词：多孔胶体球；原位合成；加氢反应；二苯并噻吩；萘
中图分类号：TQ426 文献标识码：A 文章编号：0258-3283（2020）
In situ Preparation of Porous PMoAl Colloidal Spheres and Their Catalytic Performance of Hydrogenation XIE Kai-hong, FANG Yan-xiong*, CAI Xiao-lan, SUN Da-lei (Faculty of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510009, China), Huaxue Shiji, 2020, 42(4)
Abstract： A series of PMoAl porous colloidal spheres with core-shell structure were successful in-situ synthesized and characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), H2-programmed temperature reduction (H2-TPR), and N2 adsorption and desorption. The catalysts were evaluated in the reaction of simultaneously hydrodesulfurization (HDS) of dibenzothiophene (DBT) and hydrogenation of naphthalene. As a result, the NiPMoAl(SP)-0.20 catalyst displayed promising catalytic activities for the reaction of HDS with both DBT conversion of 99.87% and naphthalene conversion of 81.28% at 340 oC. The obtained results show that the Mo species were uniformly dispersed on the porous colloidal spheres. Meanwhile, the pore structure of the colloidal spheres can be effectively adjusted by controlling the addition of phosphomolybdic acid. In addition, the pore structure of the catalyst was also crucial to the performance of catalyst in the reaction of simultaneously hydrodesulfurization (HDS) of dibenzothiophene (DBT) and hydrogenation of naphthalene.
Key words: porous colloidal spheres; in situ synthesis; hydrogenation reaction; dibenzothiophene; naphthalene
引用本文：谢凯宏，方岩雄，蔡晓兰，等. 多孔PMoAl胶体球的原位制备及加氢性能研究[J]. 化学试剂， 2020， 42（4）:348-353.
基于MIL-53(Fe)的微生物传感器在抗生素检测中的应用
陈立志，韩笑，何迪，贺敬婷，于佳雪，马烨，刘畅*
(锦州医科大学 药学院，辽宁 锦州 121000)
摘要：通过将大肠杆菌（E. coli）、海藻酸钠(SA)和MIL-53(Fe)掺杂到聚乙烯醇(PVA)胶体中形成纳米复合材料，并与硼酸交联得到MIL-53(Fe)/E. coli/SA/PVA颗粒。以E. coli作为受试体，K3[Fe(CN)6]为媒介体负责转运固定化微生物呼吸作用产生的电子至电极表面，通过监测还原产物([Fe(CN)6]4-)的量的变化，从而得到微生物活性变化的信息，进而衡量药物的有效性。通过筛选MIL-53(Fe)/E. coli/SA/PVA颗粒的最佳形成条件制备了灵敏的生物探针，搭建了基于固定化微生物的传感体系，并应用于不同抗生素类药物的检测。
关键词：抗生素有效性检测；电化学检测；固定化大肠杆菌；媒介体传感器；铁基金属有机骨架材料；复合材料
中图分类号：O657.1 文献标识码：A 文章编号：0258-3283（2020）
Applications of Microbial Sensor Based on MIL-53(Fe) for Antibiotic Measurements
CHEN Li-zhi, HAN Xiao, HE Di, HE Jing-ting, YU Jia-xue, MA Ye, LIU Chang*(College of Pharmacy, Jinzhou Medical University, Jinzhou 121000, China), Huaxue Shiji, 2020, 42(4)
Abstract: Escherichia coli (E. coli), sodium alginate (SA) and MIL-53(Fe) were doped into polyvinyl alcohol (PVA) to form a nanocomposite. As used herein, boric acid was used as a crosslinking agent to prepare MIL-53(Fe)/E. coli/SA/PVA pellets. The quality control strain of E. coli and K3[Fe(CN)6] were taken as tested strain and mediator, respectively. Then K3[Fe(CN)6] was responsible for transporting electrons generated by immobilized microorganism respiration to the electrode surface. In order to measure the efficiencies of the drugs, the changes of microbial activity had to be measured by monitoring the quantity changes of reduced product ([Fe(CN)6]4-). The optimal conditions of MIL-53(Fe)/E. coli/SA/PVA were screened to prepare a sensitive biological probe, which was used to building a sensing system based on immobilized microorganisms, for applying in the detection of different antibiotics.
Key words: Antibiotic efficacy testing; electrochemical determination; immobilized E. coli; mediator sensor; Fe-MOFs metal organic framework material; composite material
引用本文：陈立志, 韩笑, 何迪, 等. 基于MIL-53(Fe)的微生物传感器在抗生素检测中的应用[J]. 化学试剂, 2020, 42(4): 354-358.
介孔Co-Cu-Ox吸附剂的制备及其吸附有机污染物的性能研究
郭一飞，魏坤领，毛艳丽，扶咏梅，刘盼，宋忠贤,刘雪平*
（河南城建学院 市政与环境工程学院 河南省水体污染防治与修复重点实验室，河南 平顶山 467000）
摘要：以金属Co为基础，通过加入不同的金属进行合成双金属氧化物Co-M-Ox（M：Fe、Cu、Ni），用于水溶液中2,4-二氯苯酚（2,4-DCP）的吸附去除。结果表明：Co、Cu金属质量比为50%∶50%，以NaOH为沉淀剂调节至pH 9，300 ℃焙烧条件下制得的双金属氧化物对水溶液中2,4-DCP具有很好的吸附性；在25 ℃吸附条件下，吸附剂的最佳用量为0.2 g；并通过离子干扰实验、动力学以及等温吸附方程拟合得知金属离子的存在基本不影响吸附剂的吸附性能，吸附过程更符合准一级动力学方程及Freundlich等温吸附模型。
关键词：双金属氧化物；吸附；2,4-二氯苯酚；动力学；热力学
中图分类号：O647.32 文献标识码：A 文章编号：0258-3283（2020）
Preparation and Adsorption Performance of Mesoporous Co-Cu-Ox for Organic Pollutants GUO Yi-fei, WEI Kun-ling,TIAN Li, FU Yong-mei , LIU Pan, FU Zi-zhen, SONG Zhong-xian, LIU Xue-ping*（Henan Province Key Laboratory of Water Pollution Control and Rehabilitation Technology, , Henan University of Urban Construction, Pingdingshan 467000, China）, Huaxue Shiji, 2020, 42(4)
Abstract：Based on serious pollution of organic matters in water, the removal of organic compounds in water has become a hot topic for environmental protection. On the basis of metal Co, the bimetallic oxide Co-M-Ox (M: Fe, Cu, Ni) was synthesized by adding different metals, and then the best metal with Co was selected as Cu. The optimum pH is 9, the precipitant is NaOH, the calcination temperature is 300, and the Co:Cu metal ratio is 50%:50% and other adsorbents. The optimum adsorption temperature was 25℃, and the adsorbent mass was 0.2g. Finally, the main adsorption process is chemical adsorption.
Key words：bimetallic oxide; adsorption; 2,4-DCP; kinetics; thermodynamics
引用本文：郭一飞，魏坤领，毛艳丽，等. 介孔Co-Cu-Ox吸附剂的制备及其吸附有机污染物的性能研究[J]. 化学试剂, 2020, 42(4): 359-363.
系列尾式卟啉化合物的合成及光电性质研究
白晓燕，常玉，乔小霞，郭佳琦，翟慧洁，金秋，孙二军*
(长春师范大学 化学学院，吉林 长春 130032)
摘要：卟啉化合物是一类具有共面的18p电子共轭大环体系化合物，其卟啉环上可引入各类取代基，并能与多种金属配位。设计合成了3种带有不同取代基的甲基丙烯酰氧基修饰的尾式卟啉配体，并以有机金属盐法、苯甲腈法合成了与其对应的金属锌、铂配合物。通过红外光谱、核磁共振氢谱和UV-Vis光谱等对卟啉化合物的结构进行表征，证实了所合成的化合物为目标产物，并系统研究了卟啉化合物在二氯甲烷溶剂中的荧光性质与电化学性质。实验结果表明，通过改变卟啉苯环上取代基的种类及中心金属配位，可以对卟啉化合物的光学性质和电化学性质产生明显的影响。
关键词：尾式卟啉；取代基；配合物；光电性质；共轭大环；红外光谱
中图分类号：O621. 3 文献标志码：A 文章编号：0258-3283（2020）
Synthesis and Optoelectronic Properties of Tailed Porphyrins BAI Xiao-yan, CHANG Yu, QIAO Xiao-xia, GUO Jia-qi, ZHAI Hui-jie, JIN Qiu, SUN Er-jun* (College of Chemistry, Changchun Normal University, Changchun 130032, China), Huaxue Shiji, 2020, 42(4)
Abstract: Porphyrins are a kind of coplanar 18 p electron conjugated macrocyclic compounds. Various substituents could be introduced into the porphyrin ring and various metal ions could coordinate with porphyrin ligand. In this work, three tailed porphyrin ligands with different substituents were synthesized. The corresponding Zinc and Platinum complexes were synthesized by organometallic salt method and benzonitrile method. The structures of porphyrin compounds were confirmed by IR, 1HNMR and UV-Vis spectra, and the fluorescence and electrochemical properties of the compounds dissolved in dichloromethane were investigated. The optical and electrochemical properties of porphyrin compounds can be significantly affected by changing the kinds of substituents and the central metal coordination.
Key words: tailed porphyrin; substituent group; complex; optoelectronic properties; conjugated macrocyclic; IR
引用本文：白晓燕, 常玉, 乔小霞, 等. 系列尾式卟啉化合物的合成及光电性质研究[J]. 化学试剂, 2020,42(4): 364-369.
磁改性甘蔗渣对铜离子的吸附研究
牛静*，孙婉琪，王利瑶，黄会彬，张宁
（黄淮学院 化学与制药工程学院，河南 驻马店 463000）
摘要：以三氯化铁、氯化镍和甘蔗渣为原料制备磁改性生物质吸附材料，并以吸附率作为评价指标考察其对二价铜离子的吸附性能。实验研究了吸附剂用量、铜离子初始浓度、pH、温度以及时间对改性材料吸附效果的影响。结果表明，在Cu2+初始浓度为10 mg/mL，pH 7吸附，300 µL（5mg/mL）吸附剂，常温下吸附150 min，材料对铜离子的吸附率达到72%。此外，吸附材料在吸附后可通过磁性分离，有利于二次利用。廉价、高效、可回收的生物质吸附剂在环境废水处理方面展现了良好的应用前景。
关键词：改性；甘蔗渣；铜离子；吸附率；磁分离
中图分类号：X522 文献标识码：A 文章编码：0258-3283（2020）--
Magnetic Modified Bagasse and Adsorption of Copper Ion NIU Jing*, SUN Wan-qi, WANG Li-yao, HUANG Hui-bin, ZHANG Ning (College of Chemistry and Pharmaceutical Engineering, HuangHuai University, Zhumadian 463000, China), Huaxue Shiji, 2020, 42(4), ～
Abstract: Magnetical modified biomass adsorption materials was prepared using ferric chloride, nickel chloride and bagasse as precursor, and its adsorption performance on copper ions was investigated simultaneously by taking adsorption rate as the evaluation index. Some key factors on the adsorbent performance such as dosage, initial concentration of copper ions, pH, temperature and time were explored. The adsorption rate of copper ions was 72% when the initial concentration of Cu2+ was 10 mg/mL, adsorption pH was 7 and the amount of adsorbent was 300 μL (5 mg/mL) In addition, the adsorbent material can be magnetically separated after adsorption, which is advantageous for secondary use. The cheap, efficient and recyclable biomass adsorbent exhibits a promising prospect in wastewater treatment.
Key words: modification; bagasse; copper ion; adsorption rate; magnetic separation
引用本文：牛静, 孙婉琪, 王利瑶, 等. 磁改性甘蔗渣对铜离子的吸附研究[J]. 化学试剂, 2020, 42(4): 370-374.
自组装纳/微分级结构CoNi前驱体多孔微球对氢醌的选择性检测
孙晓红1，刘梅1，杨池2，程旺兴*1
（1.安徽中医药大学 药学院，安徽 合肥 230031；2.南京信息工程大学 应用气象学院气候与环境变化国际合作联合实验室大气环境中心，江苏 南京 210044）
摘要:开发了一种基于玻碳电极表面修饰钴镍前驱体多孔微球 (CoNiP/GCE) 的电化学传感器，用于选择性测定氢醌。通过SEM、XRD和BET等多种手段对CoNi前驱体进行了表征。运用循环伏安法和示差脉冲伏安法研究氢醌在CoNiP/GCE表面的电化学性能。结果表明：CoNiP/GCE对氢醌有良好的电催化氧化性能。DPV峰电流对0.5～5.0 mmol/L检测范围内的氢醌有较好的线性关系，R2=0.9968，检测限为3.5 μmol/L。此外，该修饰电极能够在强干扰物质多巴胺的存在下实现对氢醌的特异性检测，检测范围是0.2～1.8 mmol/L，检测限为2.29 μmol/L，R2=0.9928。该CoNiP/GCE具有良好的选择性和抗干扰能力，适合进一步开发用于生物样品中氢醌检测的传感器。
关键词:钴/镍复合物；氢醌；分级结构；多孔微球；电化学分析
中图分类号：O 657.12 文献标识码：A 文章编号：0258-3283（2020）
Self-assembly of Hierarchical Porous CoNiP Nano/micro Micspherical Superstructures for Detection of Hydroquinone Selectively SUN Xiao-hong1，LIU Mei1，YANG Chi 2，CHENG Wang-xing*1 (1. College of Pharmacy, Anhui University of Traditional Chinese Medicine, Hefei 230031, China; 2. Yale-NUIST Center on Atmospheric Environment, International Joint Laboratory on Climate and Environment Change (ILCEC), Nanjing University of Information Science and Technology, Nanjing 210044, China), Huaxue Shiji, 2020, 42(4)
Abstract: An electrochemical sensor based on CoNi precursor porous microspheres (CoNiP) for selective determination of hydroquinone was developed. The morphology and structure of CoNiP were characterized by scanning electron microscopy and X-ray diffraction. Specific surface area and pore-size distribution of the material were measured by BET method. The electrochemical behaviors of hydroquinone on CoNiP modified glassy carbon electrodes (CoNiP/GCE) were investigated by cyclic voltammetry and differential pulse voltammetry. CoNiP/GCE exhibited excellent electrocatalytic activity to hydroquinone. The DPV peak current has a good linear relationship between oxidation current and concentration of hydroquinone in the range of 0.5 ～ 5.0 mmol/L, R2=0.9968, and the detection limit is 3.5 μmol/L. In addition, under the influence of dopamine, the detection limit of hydroquinone from 0.2 mmol/L to 1.8 mmol/L is 2.29 μmol/L and R2 = 0.9928. The modified electrode CoNiP/GCE has good selectivity and anti-interference ability, and is suitable for further development of a sensor for hydroquinone in biological samples.
Key words: Cobalt/Nickel precursor; hydroquinone; nano/micro hierarchical superstructures; porous microsphere superstructure; electrochemical analysis
引用本文：孙晓红，刘梅，杨池，等. 自组装纳/微分级结构CoNi前驱体多孔微球对氢醌的选择性检测[J]. 化学试剂, 2020, 42(4): 375-379。
烟草中西松烷型二萜类化学成分研究进展
杨鹏飞，华涛，黄申，杨靖，魏涛，毛多斌*
（郑州轻工业大学 食品与生物工程学院，河南 郑州 450002）
摘要：为了保证烟草行业的可持续、高质量发展，发现并充分挖掘烟草中的高附加值产品是重要途径之一。烟草中西松烷型二萜是一类由4个异戊二烯组成的结构新颖、特殊且具有重要生物活性的天然产物，本文综述了至今从烟草中发现的105个包含异丙基、开环及其他3大类结构的西松烷型二萜，及其在抗菌、杀虫、抗肿瘤和神经保护等方面的生物活性，并推测设计其可能生物合成途径，最后对此类化合物的研究和应用进行了展望，为烟草行业可持续高质量发展提供依据。
关键词：烟草；西松烷型二萜；化学结构；生物活性；生物合成
中图分类号：S572 文献标识码：A 文章编号：0258-3283（2020）
Progress on Cembranoid Diterpenes in Nicotiana tabacum L. YANG Peng-fei, HUA Tao, YANG Jing, HUANG Shen, WEI Tao, MAO Duo-bin* (College of Food and Biological Engineering, Zhengzhou University of Light Industry, Zhengzhou 450002, China), Huaxue Shiji, 2020, 42(4)
Abstract: For the sustainable and high-quality development of tobacco industry, discovering and exploring the real high value-added products in tobacco is an important way. Cembranoid diterpenes, composed of four isoprene units, are important natural products with novel structures and remarkable bioactivities in Nicotiana tabacum L. Our work reviews chemical structures of the 105 occurring tobacco cembranoid diterpenes reported to date, including isopropyl cembranoids, secocembranoids and other cembranoids, and their antimicrobial, insecticidal, antitumor and neuroprotective activities, and their possible biosynthetic pathway. Lastly, an outlook to the development and application of this kind of compounds was provided.
Key words: tobacco; cembranoid diterpenes; structure; bioactivity；biosynthesis
引用本文：杨鹏飞, 华涛, 黄申, 等. 烟草中西松烷型二萜类化学成分研究进展[J]. 化学试剂, 2020, 42(4): 380-388.
浅谈试剂联盟建设协同创新模式进展
顾小焱，刘征宙*
（国药集团化学试剂有限公司, 上海 200002）
摘要：协同创新有一定的实现模式。产业技术创新战略联盟是联盟式协同创新体，通过参加试剂联盟项目建设与开展的承担技术合作、共建的公共技术服务平台以及试剂联盟所实施的技术转移、联合培养人才，不仅感受到企业作为创新主体带来优势，而且试剂联盟也是可持续的发展。试剂联盟模式可实现政府推进的产学研用合作、产业技术创新战略联盟构建。试剂联盟创新模式建设后，证实协同创新弥补发展短板，体现出多方面的优势。
关键词：试剂联盟；联盟建设；协同创新；创新模式；进展
中图分类号：O6-1 文献标识码：A 文章编号：0258-3283(2020)
Progress of Cooperative Innovation Model in Reagent Alliance Construction GU Xiao-yan, LIU Zheng-zhou*（Sinopharm Chemical Reagents Co., Ltd., Shanghai 200002, China）, Huaxue Shiji, 2020, 42(4)
Absrtact: Collaborative innovation has a certain realization mode. The strategic alliance of industrial technological innovation is an alliance-type collaborative innovation body. Through participating in the construction and development of practical reagent alliance projects, undertaking technical cooperation, co-building of public technology service platform, technology transfer and joint training of talents implemented by reagent alliance, we can not only feel the advantages brought by enterprises as innovators, but also the sustainable development of reagent alliance. The model of reagent alliance can realize the strategic alliance of industry-university-research cooperation and industrial technology innovation promoted by the government. After the construction of the innovation model of reagent alliance, it is confirmed that collaborative innovation can make up for the shortcomings of development, which reflects many advantages.
Key words: reagent alliance; alliance construction; collaborative innovation; innovation model; progress
引用本文：顾小焱，刘征宙. 浅谈试剂联盟建设协同创新模式进展[J]. 化学试剂， 2020， 42（4）：389-395.
脉冲电沉积氧化石墨烯纳米带修饰电极测定盐酸四环素
兰天宇a，董泽刚a，陈孟娇a，陈慧平b，杜海军*a
（贵州民族大学 a.化学工程学院，b.预科教育学院，贵州 贵阳 550025）
摘要：以多壁碳纳米管为原料制备氧化石墨烯纳米带（GONRs），通过红外光谱、紫外-可见吸收光谱和拉曼光谱对其进行表征。将制备好的GONRs脉冲电沉积到玻碳电极表面制备修饰电极（GONRs/GCE），研究了盐酸四环素（TC）在GONRs/GCE上的电化学行为及伏安法测定。结果表明，与裸玻碳电极相比，GONRs/GCE对TC有更高的电催化活性。TC在GONRs/GCE上发生受吸附控制的不可逆氧化反应，且在pH 3.0的柠檬酸-柠檬酸钠缓冲溶液中氧化峰电流最高。优化条件下，TC的氧化峰电流与浓度线性相关，线性范围为4.0×10-7～1.0×10-4 mol/L，最低检测限为2.0×10-7 mol/L（S/N = 3）。将该电极用于河水样品中TC的检测，加标回收率为97.2%～104.1%。
关键词：盐酸四环素；氧化石墨烯；纳米带；脉冲电沉积；电化学传感
中图分类号：O657.1；X832 文献标识码：A 文章编号：0258-3283（2020）
Determination of Tetracycline Hydrochloride by Graphene Oxide Nanoribbons Modified Electrode via Pulse Electrodeposition LAN Tian-yua, DONG Ze-ganga, CHEN Meng-jiaoa, CHEN Hui-pingb, DU Hai-jun*a (a.School of Chemical Engineering, b.College of Prep-education, Guizhou Minzu University, Guiyang 550025, China), Huaxue Shiji, 2020, 42(4)
Abstract: Graphene oxide nanoribbons (GONRs) were prepared by using multi-walled carbon nanotubes as raw materials, and characterized by infrared spectroscopy, ultraviolet-visible absorption spectroscopy and Raman spectroscopy. The prepared GONRs were electrodeposited onto the surface of glassy carbon electrode to obtain modified electrode (GONRs/GCE). The electrochemical behavior and voltammetric determination of tetracycline hydrochloride (TC) on GONRs/GCE were investigated. The results showed that GONRs/GCE had higher electrocatalytic activity for TC comparing with bare glassy carbon electrode. TC undergone adsorption-controlled irreversible oxidation reaction on GONRs/GCE, and the oxidation peak current was highest in the pH 3.0 citric acid-sodium citrate buffer solution. Under optimized conditions, the oxidation peak current of TC showed a good linear relationship with the concentration. The linear range was 4.0×10-7 ~ 1.0×10-4 mol/L, and the detection limit was 2.0 × 10-7 mol/L (S/N = 3). The modified electrode was applied to the detection of TC in river samples, and the recovery rate was 97.2%～104.1%..
Key words: tetracycline hydrochloride; graphene oxide; nanoribbons; pulse electrodeposition; electrochemical sensor
引用本文：兰天宇, 董泽刚, 陈孟娇, 等. 脉冲电沉积氧化石墨烯纳米带修饰电极测定盐酸四环素[J]. 化学试剂, 2020, 42(4): 396-400.
气相色谱-三重四极杆质谱法测定大肠杆菌中有机酸的含量
高慧敏1, 2，侯捷2，盛立彦2，张鹏帅2，雷雯*2，李丹1
（1. 上海应用技术大学 化学与环境工程学院，上海 201418；2. 上海化工研究院，上海 200062）
摘要：建立了气相色谱-三重四极杆质谱联用法（GC-MS/MS）同时测定大肠杆菌三羧酸（TCA）循环中6种有机酸的方法。样品经细胞破壁处理、固相萃取（SPE）富集净化，由硅烷化试剂N-(特丁基二甲基硅烷)-N-甲基三氟乙酰胺（MTBSTFA）衍生化后，利用GC-MS/MS多反应监测模式测定，外标法定量。6种有机酸在20～10000 μg/L范围内线性良好，相关系数均大于0.99，加标回收率为82.3%～100.4%，相对标准偏差为2.3%～4.5%，方法检出限为2.0～18μg/L。方法受基质影响小，重现性好，适合于复杂生物基质样本中有机酸含量的测定。
关键词：GC-MS/MS；衍生化；TCA循环；有机酸；固相萃取
中图分类号：O657.63 文献标识码：A 文章编号：0258-3283（2020）--
Determination of Organic Acids in E. coli by Gas Chromatography-Tandem Mass Spectrometry GAO Hui-min1, HOU Jie2, SHENG Li-yan2, ZHANG Peng-shuai, LEI Wen*2, LI Dan (1. School of Chemical and Environmental Engineering, Shanghai Institute of Technology, Shanghai 201418, China; 2. Shanghai Research Institute of Chemical Industry, Shanghai 200062, China), Huaxue Shiji, 2020, 42(4), ～
Abstract： A method has been developed to determine the six organic acids in E. coli tricarboxylic acid cycle (TCA cycle) by gas chromatography-tandem mass spectrometry (GC-MS/MS).The sample was purified by cell disruption and solid-phase extraction(SPE), derivatized with the silylation reagent N-(tert-butyldimethylsilyl)-N-methyltrifluoroacetamide (MTBSTFA), and then analyzed by GC-MS/MS ( MRM) mode, extraterritorial method for quantification. The linear correlation coefficients(R2) of the six organic acids is greater than 0.99 in the linear range of 20 ~1×104 μg/L，the recovery was 82.3%~100.4% ,the relative standard deviation(RSD) is 2.3%~4.5%,and the detection limit ( LOD) of the method was 2.0 ~18μg/L. The method is less affected by the matrix and has good reproducibility, and is suitable for determining the content of organic acids in complex biological matrix samples.
Key words：GC-MS/MS; derivatization reaction; TCA cycle; organic acids; solid-phase extraction
引用本文：高慧敏, 侯捷, 盛立彦, 等. 气相色谱-三重四极杆质谱法测定大肠杆菌中有机酸的含量[J]. 化学试剂, 2020, 42(4): 401-405。
QuEChERS-SPE结合超高效液相色谱-四级杆飞行时间质谱法筛查牛奶样品中15类37种药物残留
李永利*，陈黎明，李杰，李春华，陈鹰
（上海市计量测试技术研究院，上海 201203）
摘要：应用QuEChERS-SPE结合超高效液相色谱-飞行时间质谱（UPLC-Q-TOF-MS）技术开发了快速测定牛奶中15类37种药物的方法。牛奶样品采用0.2%甲酸乙腈溶液和Na2EDTA-Mcllvaine 缓冲溶液提取，有机相和水相分别经C18吸附剂和HLB固相萃取柱净化后合并测定。目标化合物采用BEH C18柱分离，以甲醇和0.1%甲酸水溶液为洗脱剂进行程序洗脱，正离子扫描模式检测。结果表明，牛奶样品中种化合物的定量限为0.4 ～ 8.0 μg/kg，3个浓度加标浓度的平均回收率范围为70.2 %～105.3%。方法具有快速、简便、高通量等特点，可以用于牛奶样品15类37种药物残留的快速测定。
关键词：液相色谱-四级杆飞行时间质谱；QuEChERS；药物残留；筛查；牛奶
中图分类号：O657.6 文献标识码：A 文章编号：0258-3283（2020）--
Simultaneous Determination for 15 Kinds of 37 Drugs in Milk by Ultra Performance Liquid Chromatography Coupled with Quadrupole-time of Flight Mass Spectrometry LI Yong-li*, CHEN Li-ming, LI Jie, LI Chun-hua, CHEN Ying (Shanghai Institute of Measurement and Testing Technology, Shanghai 201203, China), Huaxue Shiji, 2020, 42(4), ～
Abstract：A method was developed for rapid identification of 37 drugs in milk based on QuEChERS-SPE by ultra performance liquid chromatography coupled with quadrupole-time of flight mass spectrometry (UPLC-Q-TOF-MS). The target analysts in milk were extracted with acetonitrile containing 0.2% formic acid. The organic phase was purified with dispersive solid phase extraction with C18 sorbent, while the aqueous phase was cleaned with solid phase extraction. The target compounds were separated on a BEH C18 column with the gradient elution using the mobile phases of methanol and water containing 0.1% formic acid. The accurate relative molecular masses were obtained under positive ion mode. As a result, the limits of quantification (LOQ, S/N = 10) of the compounds were from 4 to 50 μg /kg in milk. Based on blank sample, the average recoveries of the 37 compounds set at three concentration levels were ranged from 70.2% to 105.3%. This method can be applied to the determination of the 37 drugs in milk by virtue of its fastness, simplicity, and high-throughput.
Key words: liquid chromatography coupled with quadrupole-time of flight mass spectrometry ( UPLC-Q-TOF-MS ) ; QuEChERS; drug residues; screening; milk
氮中甲醛气体标准物质分析方法研究
袁娇阳*，蒋昌怀，王宇，赵杨兰，李志昂
（四川中测标物科技有限公司，四川 成都 610021)
摘要：采用气相色谱-质谱法和傅里叶红外光谱法对称量法制备的氮中甲醛气体标准物质进行定量分析，对两种分析方法的重复性、一致性、线性及检出限进行研究。结果发现，对于1.00～10.00 μmol/mol氮中甲醛气体标准物质，气相色谱-质谱法的RSD优于0.5%，傅里叶红外光谱法的RSD优于1.2%，均满足准确分析定量的要求。两种分析方法的测量值与称量法标称值的一致性比对结果在1%以内。两种分析方法的响应值与甲醛含量呈良好的线性关系，R2＞0.999。将研制的1.00 μmol/mol氮中甲醛气体标准物质送至上海市计量测试技术研究院进行了测试比对，采用En值评定比对结果，结果判定为满意。
关键词：气体标准物质；甲醛；气相色谱-质谱；红外光谱
中图分类号：0657.71 文献标识码：A 文章编号：0258-3283（2020）--
Analysis Method of Formaldehyde in Nitrogen Gas Reference Material YUAN Jiao-yang*, JIANG Chang-huai, WANG Yu, ZHAO Yang-lan, LI Zhi-ang (Sichuan Zhongce Reference Material Technology Limited Company, Chengdu 610021, China), Huaxue Shiji, 2020, 42(4), ～
Abstract: The formaldehyde in nitrogen gas reference material prepared by gravimetric method was determined by gas chromatography-mass spectrometry and Fourier infrared spectroscopy. The repeatability, linearity, consistency and detection limit of the method was also investigated. The analysis result of formaldehyde in nitrogen at 1μmol·mol-1 level indicated that the RSD of gas chromatography-mass spectrometry was less than 0.5%，the RSD of Fourier infrared spectroscopy was less than 1.2%，satisfying the requirement of accurate analysis quantitatively．The values of the reference material prepared by gravimetric method have been compared to analysis data and the result of consistency test is less than 1%.The linear range of formaldehyde was 1~10μmol·mol-1，the correlation coefficients (R2) was greater than 0.999.The validation result from Shanghai institute of metrology showed a satisfied consistency and a reliable accuracy of calculated concentration value，as En values were applied to evaluate the comparison result.
Key words: gas reference material; formaldehyde; gas chromatography-mass spectrometry; infrared spectroscopy
引用本文：袁娇阳, 蒋昌怀, 王宇, 等. 氮中甲醛气体标准物质分析方法研究[J]. 化学试剂, 2020, 42(4): 411-415。
几种典型银杏保健茶活性物质定量分析
武文君，张丝柳，雷家珩*，杜小弟，胡婧
（武汉理工大学 化学化工与生命科学学院，湖北 武汉 430070）
摘要：采用高效液相色谱（HPLC）法对几种不同工艺制作的银杏茶及其茶汤中各保健物质和风味物质含量进行了定量分析。其中绿茶工艺制作的银杏叶茶，其保健物质黄酮（苷）、萜内酯含量分别为：13.48、1.36 mg/g；风味物质儿茶素（+C）、单宁、氨基酸、没食子酸含量分别为：0.80、12.58、51.47、0.59 mg/g；首泡茶汤其溶出的保健物质和风味物质含量分别为：185.21、25.24和10.65、96.77、429.75、9.01 mg/L。3种茶叶的茶汤中，有毒物质银杏酸含量均不超过3 mg/L，远低于中国药典银杏叶提取物中银杏酸10 mg/L限量。
关键词：银杏茶；银杏叶茶；黄酮；萜内酯；风味物质
中图分类号：TS207.3 文献标识码：A 文章编号：0258-3283(2020)
Quantitative Analysis of Active Substances in Several Typical Ginkgo Health Teas WU Wen-jun, ZHANG Si-liu, LEI Jia-heng*, DU Xiao-di, HU Jing (School of Chemistry, Chemical Engineering and Life Sciences, Wuhan University of Technology, Wuhan 430070, China), Huaxue Shiji, 2020, 42(4)
Abstract： Health care substances and flavor substances in ginkgo leaf teas and tea infusions made in several different processes were quantitatively analyzed by HPLC. The contents of flavonoid glycosides and terpene lactones (mg/g) in ginkgo leaf tea made by processing technology for green tea were 13.48 and 1.36, and the content of catechin, tannins, amino acids and gallic acid (mg/g) were 0.80, 12.58, 51.47, 0.59, respectively. The contents of health care substances and flavor substances (mg/L) in the first infusion were 185.21, 25.24, 10.65, 96.77, 429.75, 9.01, respectively. The content of ginkgolic acid in three different kinds of tea infusions was no more than 3 mg·L-1, which was much lower than the limit requirement of the Chinese pharmacopoeia for ginkgo leaves extract.
Key words： Ginkgo tea; Ginkgo leaf tea; flavonoid; terpene lactones; flavor substance
引用本文：武文君, 张丝柳, 雷家珩, 等. 几种典型银杏保健茶活性物质定量分析 [J]. 化学试剂, 2020, 42(4): 416-419.
一种新型汽车排气标准物质的研制
王德发*，韩桥，张体强，刘智勇
（中国计量科学研究院，北京 100029）
摘要：介绍了一种新型汽车排气标准物质的研制方法。该标准物质是将一氧化碳、二氧化碳、1,3-丁二烯和氮气充装到气瓶中制备而成，采用称量法定值。对原料气体中的杂质进行了测量，对分析检测方法进行了比较研究，对标准物质的稳定性进行了考查。结果显示：该气体标准物质在12个月内的稳定性良好，浓度的相对扩展不确定度为0.5％（k=2）。该标准物质中，一氧化碳的浓度范围为2.000% ～ 8.000% mol/mol，二氧化碳的浓度范围为9.400% ～ 13.60% mol/mol，1,3-丁二烯的浓度范围为40.00×10- 6 ～ 160.0×10-6 mol/mol，氮气为平衡气。
关键词：汽车排气；标准物质；称量法；不确定度；一氧化碳；二氧化碳；1,3-丁二烯
中图分类号：0657.71 文献标识码：A 文章编号：0258-3283（2020）
Preparation of a New Type of Certified Reference Materials for Automotive Exhaust Gas WANG De-fa, HAN Qiao, ZHANG Ti-qiang, LIU Zhi-yong(National Institute of Metrology, Beijing 100029, China), Huaxue Shiji, 2020, 42(4)
Abstract: Preparation of a new type of certified reference materials for automotive exhaust gas was reported. The gas mixture was prepared by filling pure carbon monoxide, carbon dioxide, 1,3-dibutene and nitrogen into cylinder. The certified value was from gravimetric method. The impurities in parent gas were determined. The measurement methods of gas mixtures were investigated. The long-term stability of this reference material was evaluated by classical stability study. Results showed it had good stability in twelve month. The relative expanded uncertainty is 0.5% (k=2) for the mole fraction of carbon monoxide 2.000% ～ 8.000% mol/mol, carbon dioxide 9.400% ～ 13.60% mol/mol and 1,3-dibutene 9.400% ～ 13.60% mol/mol.
Key words: automotive exhaust gas；gas reference material；gravimetric method；uncertainty；carbon monoxide；carbon dioxide；1,3-dibutene
引用本文：王德发，韩桥，张体强，等. 一种新型汽车排气标准物质的研制[J].化学试剂，2020,42（4）：420-424.
氢定量核磁共振法测定金丝桃苷标准物质纯度
王萌玉1，全灿2，孙永跃*1，李蔚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）
摘要：基于核磁谱峰的积分信号与产生此信号的原子核数成正比的原理，建立准确的氢定量核磁共振法（1H-qNMR）测定金丝桃苷标准物质纯度，并评估不确定度。实验以二甲基亚砜（DMSO-d6）为氘代溶剂，尼泊金乙酯GBW(E)100064为内标物，谱宽为16 ppm，激发偏置为5.23 ppm，弛豫延迟时间为 12 s，扫描次数为32 次，采用金丝桃苷化学位移（δ 6.21）为定量峰，尼泊金乙酯化学位移（δ 4.24）为内标峰，定量金丝桃苷纯度。1H-qNMR测得金丝桃苷纯度为91.78%，精密度RSD为0.085%，重复性RSD为0.53%，质量浓度在9.85～32.02 g/L范围内的线性关系为：y＝6.3355x-0.1556（R2＝0.9988，y、x分别代表金丝桃苷与尼泊金乙酯的质量比和积分信号比），评估不确定度为0.55%。1H-qNMR测定结果与质量平衡法一致，表明氢定量核磁共振法适用于金丝桃苷的定量分析。
关键词：金丝桃苷；氢定量核磁共振法(1H-qNMR)；定量分析；质量平衡法
中图分类号：0657.61 文献标识码：A 文章编号：0258-3283（2020）--
Purity Assignment of Hyperoside CRMs by 1H-QNMR WANG Meng-yu1, QUAN Can2, SUN Yong-yue*1, LI Wei1 (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), Huaxue Shiji, 2020, 42(4), ～
Abstract：Based on the principle that the integrated signal of NMR peak is proportional to the number of nucleus producing this signal, an accurate hydrogen quantitative nuclear magnetic resonance (1H-QNMR) method is established to determine the purity assignment of hyperoside CRMs and evaluate the uncertainty. The experiment used dimethyl sulfoxide (DMSO-d6) as the deuteration reagent, and ethylparaben was used as the internal standard. The spectral width (SW) was 16 ppm, and the excitation bias (OIP) was 5.23 ppm, relaxation delay time (DI) is 12 s, number of scans (NS) is 32,The chemical shift (δ 6.21) of hyperoside was used as the quantitative peak, and the chemical shift (δ 4.24) of ethylparaben was used as the internal standard peak to quantify the purity of hyperoside. The purity of hyperoside was 91.78% as determined by 1H-QNMR., the precision RSD was 0.085%, the repetitive RSD was 0.53%, The linear regression equation with mass concentration in the range of 9.85 g/L to 32.02 g/L is: Y = 6.3355X-0.1556 (correlation coefficient R2 = 0.9988, Y and X represent the mass ratio and integral area ratio of hyperoside and ethyl p-hydrobenzoate respectively), and the uncertainty of the QNMR measurement result was 0.55%. The purity of the hyperoside measured by 1H-QNMR was consistent with the results of the mass balance method, indicating that the hydrogen quantitative nuclear magnetic resonance method is suitable for the quantitative analysis of hyperoside.
Key words: hyperoside; hydrogen quantitative nuclear magnetic resonance ( 1H-QNMR) ; quantitative analysis; mass balance method
引用本文：王萌玉, 全灿, 孙永跃, 等. 氢定量核磁共振法测定金丝桃苷标准物质纯度[J]. 化学试剂, 2020, 42(4): 425-429.
季膦盐离子液体对AOT/环己烷反相微乳液增溶水性质的影响
王璐，刘金彦*，王勇力，郑天宇
（内蒙古科技大学 化学与化工学院，内蒙古 包头 014010）
摘要：季膦盐离子液体由于其独特的物理化学性质而被广泛应用，由于其结构的多样化，目前还没有对其基本性质进行系统地研究。采用傅立叶变换红外光谱法（FT-IR）研究了AOT/环己烷中分别加入两种季膦盐离子液体P[4444]FeCl4和P[44414]FeCl4水溶液后所形成W/O型微乳液的性质，并与加入普通咪唑型离子液体[Bmim]Cl作对比。采用peakfit解峰技术，将增溶水分为结合水、本体水和束缚水，并且用电位粒度仪测试了微乳液粒度的大小。经过对加入不同浓度的离子液体，微乳液水状态的变化进行比较，发现3种离子液体在微乳液中增溶的位置不同，按照[Bmim]Cl、P[4444]FeCl4、P[44414]FeCl4的顺序由微乳液的油水界面向栅栏层移动。由微乳液的粒径随浓度的变化关系，印证了离子液体在微乳液中增溶位置的正确性。通过研究两种季膦盐离子液体对于微乳液性质的影响，总结其作用规律，为新型离子液体的应用奠定基础。
关键词：W/O微乳液；季膦盐离子液体；增溶水；FT-IR；粒径分析
中图分类号：O648.23 文献标识码：A 文章编号：0258-3283（2020）
Effect of Quaternary Phosphine Ionic Liquid on Water Soluble Properties of AOT/cyclohexane Reverse Microemulsion WANG Lu, LIU Jin-yan*, WANG Yong-li, ZHENG Tian-yu (School of Chemistry and Chemical Engineering, Inner Mongolia University of Science and Technology, Baotou 014010, China), Huaxue Shiji, 2020, 42(4)
Abstract: Quaternary phosphine ionic liquids are widely used due to the unique physical and chemical properties. Based on the diversity of the structures, the basic properties have not been systematically studied. In this work, when added two kinds of quaternary phosphine ionic liquids P[4444]FeCl4 and P[44414]FeCl4 aqueous solutions to the microemulsion, the properties of W/O microemulsions formed by AOT/cyclohexane have been investigated by Fourier transform infrared spectroscopy(FT-IR). The results were compared with the addition of common imidazolium ionic liquid [Bmim]Cl solution. There existed three states of water in the microemulsions, which were bound water, bulk-like water and trapped water, were obtained by a deconvolution technique. The particle size of microemulsion was measured by potentiometric particle size analyzer. By comparing the changes of water state of microemulsion with different concentrations of ionic liquids, it was found that the solublesites of three ionic liquids in microemulsion were different. In the order of [Bmim]Cl, P[4444]FeCl4, P[44414]FeCl4, the solublesites of them moved from the oil-water boundary to the palisade layer of the microemulsion. Based on the relationship between the particle size of the microemulsion and the concentration, it was confirmed that the solublesites of the ionic liquid molecule in the microemulsion was correct. Based on the effects of two kinds of quaternary phosphine ionic liquids on the properties of microemulsions and summarizing the function rules, there are beneficial for the application of new ionic liquids.
Key words: W/O microemulsion; quaternary phosphine ionic liquid; water soluble; FT-IR; particle size analysis
引用本文：王璐，刘金彦，王勇力，等. 季膦盐离子液体对AOT/环己烷反相微乳液增溶水性质的影响[J]. 化学试剂，2020,42（4）：430-434.
溶胶-凝胶法制备粒径可控的纳米钛酸铅
乔仙蓉1，薛永强*1, 2，王姝婷2，郝赳赳1
（1.山西工程职业学院 冶金与环境工程系，山西 太原 030009；2.太原理工大学 应用化学系，山西 太原 030024 )
摘要：纳米钛酸铅是一种应用广泛的压电材料。采用溶胶-凝胶法研究了纳米钛酸铅的制备，考察了凝胶的煅烧温度、反应物的浓度及溶胶的反应温度对纳米颗粒粒径的影响和变化规律。研究表明，控制钛酸丁酯-醇溶液浓度为0.100～1.000 mol/L、醋酸铅-醋酸浓度为0.500～1.500 mol/L、溶胶反应温度70～90 ℃、凝胶煅烧温度为400～800 ℃，可制备出平均直径在20～50 nm范围的近似球形的四方相纳米钛酸铅。制备条件对纳米钛酸铅的粒径有显著影响：随溶胶反应温度和凝胶煅烧温度的升高，所制备纳米钛酸铅平均粒径增大，而随着反应物浓度的升高，所制备纳米钛酸铅粒径先增大后减小。制备粒径可控的纳米钛酸铅对其性能及应用具有重要的实用价值。
关键词：溶胶-凝胶法；钛酸铅；纳米微粒；制备条件；粒径可控
中图分类号: TQ134.1+1 文献标识码: A 文章编号: 0258-3283（2020）
Preparation of Nano-PbTiO3 with Controllable Sizes by Sol-gel Method QIAO Xian-rong1, XUE Yong-qiang *1, 2, WANG Shu-ting2, HAO Jiu-jiu1 (1. Department of Metallurgical and Environmental Engineering, Shanxi Engineering Vocational College, Taiyuan 030009, China; 2. Department of Applied Chemistry, Taiyuan University of Technology, Taiyuan 030024, China), Huaxue Shiji, 2020, 42(4)
Abstract: Nano-PbTiO3 is a widely used piezoelectric material. Preparation of nano-PbTiO3 was investigated by sol-gel method. The effects of calcination temperature, concentrations of reactants and reaction temperature on the particle size were investigated. The results show that the nearly spherical tetragonal nano-PbTiO3 with average diameters in the range of 20~50nm can be prepared by controlling the concentration of butyl titanate alcohol solution 0.100~1.000mol/L, the concentration of lead acetate acetic acid 0.500~1.5000 mol/L, the reaction temperature of 70~90 ℃ and the calcination temperature of 400~800 ℃. The preparation conditions have a significant effect on the sizes of nano-PbTiO3. With the increase of sol reaction temperature and gel calcination temperature, the average size of nano-PbTiO3 increases. With the increase of reactants concentration, the particle size of nano-PbTiO3 first increases and then decreases. The preparation of nano-PbTiO3 with controllable particle size has important practical value for its performances and applications.
Key words: sol-gel method; PbTiO3; nanoparticle; preparation condition; controllable particle size
引用本文：乔仙蓉, 薛永强, 王姝婷, 等. 溶胶-凝胶法制备粒径可控的纳米钛酸铅[J]. 化学试剂, 2020, 42(4): 435-438.
Pd催化3-氧吲哚酮类底物参与的Conia-ene反应研究
唐永琴1， 费兴海1， 杨芬芬1，安建雄1，段东柱2，赵永龙*1
（1. 贵州医科大学 药学院，贵州 贵阳 550004；2. 宝鸡文理学院 化学化工学院 陕西省植物化学重点实验室, 陕西 宝鸡 721013）
摘要：开发3-氧吲哚酮类底物参与的Conia-ene反应，为吡咯并[1,2-a]吲哚结构单元的合成提供一种高效、便捷的方法。首先通过三步反应合成N1位烷炔基取代3-氧吲哚酮类底物，然后通过对反应溶剂、碱、催化剂等条件的筛选，以N1位烷炔基取代3-氧吲哚酮类底物为原料，10 mol% PdCl2为催化剂，K2CO3为碱在丙酮中于室温下反应，实现了3-氧吲哚衍生物的分子内Conia-ene环化反应。以26%～82%的产率合成了3个吡咯并[1,2-a]吲哚类衍生物，产物经1H NMR、13C NMR、HRMS分析确证。以N1位烷炔基取代3-氧吲哚酮为底物，发展了一个Pd催化的分子内Conia-ene反应，以温和的反应条件实现了吡咯并[1,2-a]吲哚结构的构建。
关键词：Pd 催化；3-氧吲哚酮；Conia-ene反应；合成；吡咯并[1,2-a]吲哚
中图分类号：R914 文献标识码：A 文章编号：0258-3283（2020）--
Palladium-catalyzed Conia-ene Reaction of Indolin-3-ones TANG Yong-qin1, FEI Xing-hai 1, YANG Fen-fen 1, AN Jian-xiong 1, DUAN Dong-zhu 2, ZHAO Yong-long*1 (1. School of Pharmacy, Guizhou Medical University, Guiyang 550004, China; 2. Shanxi Key Laboratory of Phytochemistry, College of Chemistry & Chemical Engineering, Baoji University of Arts and Sciences, Baoji 721013, China), Huaxue Shiji, 2020, 42(4), ～
Abstract: To develop the Conia ene reaction of indolin-3-one substrates, so as to provide an efficient and convenient method for the synthesis of pyrrolo[1,2-a]indole units. Firstly, three-step reactions were used to synthesize the N1 alkynyl substituted indolin-3-one substrates. Then, by screening reaction conditions such as solvents, bases, catalysts and so on, the Conia-ene reaction of 1-alkynylindolin-3-ones have been realized via using 10 mol% PdCl2 as catalyst and K2CO3 as base in acetone at room temperature. Three examples of pyrrolo[1,2-a]indoles derivatives were readily obtained with 26%～82% yields utilizing this strategy. The structures were confirmed by 1HNMR, 13CNMR, and HRMS. Under mild reaction conditions, the Pd-catalyzed intramolecular Conia ene reaction has been developed to construction of pyrrolo [1,2-a] indole structure via using N1 alkynyl substituted indolin-3-one as the substrates.
Key words: palladium-catalyzed；1-alkynylindolin-3-ones；conia-ene reaction；synthesis；pyrrolo[1,2-a]indole
引用本文：唐永琴，费兴海，杨芬芬，等.Pd催化3-氧吲哚酮类底物参与的Conia-ene反应研究[J].化学试剂，2020，42（4）:439-444.
离子液体促进的萘并[1,2,3-de]苯并吡喃-2,7-二酮的合成
郑纪芳，谭伟强*，吕丽莉，杨启鹏
（青岛理工大学 环境与市政工程学院 生物环保与绿色化工研究中心 山东 青岛 266033）
摘要：以1-乙酰氧基-4-甲氧基-9,10-蒽醌和b-酮酸酯（丙二酸二乙酯、乙酰乙酸乙酯和苯甲酰乙酸乙酯）为主要原料，碳酸钾为碱，经离子液体促进的Knoevenagel缩环反应合成了萘并[1,2,3-de]苯并吡喃-2,7-二酮类化合物。合成条件为n（1-乙酰氧基-4-甲氧基-9,10-蒽醌）：n（b-酮酸酯）：n（碳酸钾）＝1：1.5：5，反应温度40 °C，离子液体为[Mmim][DMP]，所得产物收率分别为85.5%、50.0%、65.0%。产物及中间体经1HNMR、13CNMR、LC-MS和HRMS方法进行确证。比较了离子液体相对于有机溶剂对反应的影响，考察了离子液体类型、反应温度、碱及用量对反应收率的影响。实验结果表明，离子液体中反应收率优于常规有机溶剂，对反应有促进作用，离子液体[Mmim][DMP]中产物收率最高，反应温度适中，较高会导致原料分解，无机碱更适合b-酮酸酯为底物的反应。
关键词：蒽醌类化合物；离子液体；Knoevenagel缩环反应
中图分类号：O626.2 文献标识码：A 文章编号：0258-3283（2020）--
Synthesis of Naphtho[1,2,3-de]benzopyran-2,7-dione Promoted by Ionic Liquids ZHENG Ji-Fang, TAN Wei-Qiang*, LV Li-Li, YANG Qi-Peng (School of Environmental and Municipal Engineering, Research Center of Environmental Biology and Green Chemistry, Qingdao University of Technology, Qingdao 266033, China), Huaxue Shiji, 2020, 42(4), ～
Abstract：Naphtho[1,2,3-de]benzopyran-2,7-dione compounds were synthesized via Knoevenagel condensation reaction promoted by ionic liquids from 1-acetoxy-4-methoxy-9,10-anthraquinone and b-keto esters (diethyl malonate, ethyl acetoacetate and ethyl benzoyl acetate) as the main raw materials, potassium carbonate as base. The synthesis conditions were n(4-methoxy-9,10-dioxo-9,10-dihydroanthracen-1-yl acetate): n(b-keto esters): n(K2CO3) = 1: 1.5: 5, reaction temperature 40 °C, ionic liquid [Mmim][DMP]. The product yields achieved 85.5%, 50.0%, 65.0%, respectively. The structure of products and intermediate were confirmed by 1HNMR, 13CNMR, LC-MS and HRMS. The effects of ionic liquids on the reaction were compared with those of organic solvents. The effects of ionic liquids type, reaction temperature, base and its amount on the yield were investigated. The experimental results show that the ionic liquids as solvent can promote the reaction, which is better than organic solvent. Ionic liquids [Mmim] [DMP] as solvent achieved the highest yield. The reaction temperature is moderate, and higher will lead to the decomposition of raw materials. Inorganic bases are more suitable for the reaction of b-keto esters as substrates.
Key words：anthraquinones; ionic liquids; Knoevenagel condensation reaction
引用本文：郑纪芳, 谭伟强, 吕丽莉, 等. 离子液体促进的萘并[1,2,3-de]苯并吡喃-2,7-二酮的合成[J]. 化学试剂, 2020, 42(4): 445-449。
细菌纤维素膜基图灵斑图聚合物膜的制备
楚占营1，张凌怡1,3，朱曼曼1，张文鸿2，张维冰*1,陈本顺3,徐春涛3
(1. 华东理工大学 上海市功能材料化学重点实验室，上海 200237；2.上海奈雅生物科技有限公司，上海 200120；3.江苏阿尔法药业有限公司，江苏 宿迁 223800）
摘要：细菌纤维素膜具有超精细的纳米网络框架结构以及优良的力学特性，因而基于细菌纤维素膜的复合材料应用十分广泛。基于“反应-扩散”模型，采用界面聚合反应，在细菌纤维素膜的网状结构上自组装构建出具有微米尺度图灵结构的聚合物薄膜，并采用扫描电子显微镜（SEM）对图灵结构聚合物表面形貌进行表征。探讨了不同反应条件对所得聚合物形貌的影响，结果表明：所用细菌纤维素膜的厚度及其与均苯三甲酰氯溶液的接触面积会影响氨基化合物的浓度衰减速率，从而影响其聚合形成特定斑图形貌的时间。这一结果将为图灵结构聚合物膜复合材料的合成提供指导。
关键词：细菌纤维素；图灵斑图；界面聚合反应；“反应-扩散”模型；有机聚合物；复合薄膜
中图分类号： O633.5 文献标识码：A 文章编号：0258-3283（2020）
Preparation of Turing Pattern Polymer Membrane Based on Bacterial Cellulose Membrane CHU Zhan-ying1, ZHANG Ling-yi1,3, ZHU Man-man1, ZHANG Wen-hong2, ZHANG Wei-bing*1, CHEN Ben-shun3, XU Chun-tao3 (1. Key Laboratory of Functional Materials Chemistry, East China University of Science and Technology, Shanghai 200237, China; 2. Shanghai Naya Bio-tech Co., LTD, Shanghai 200120,China; 3. Suqian 223800,China), Huaxue Shiji, 2020, 42(4)
Abstract：Bacterial cellulose membrane (BCM) has hyperfine nano-network structure and excellent mechanical properties so that the composite materials based on BCM have been widely used. In this work, the polymer films with micron-scale Turing structure were self-assembled on BCM to form a novel composite membrane material by interfacial polymerization based on the "reaction-diffusion" theory. The surface morphology of Turing polymers was characterized by scanning electron microscope (SEM). The influences of experimental conditions on the surface morphology were investigated. The thickness of BCM used and the contact area with the solution of trimesoyl chloride would affect the concentration attenuation rate of activator and further affect the time for forming a certain pattern. The results will provide guidance for the synthesis of Turing polymer membrane composites.
Key words：bacterial cellulose; Turing pattern; interfacial polymerization; "reaction-diffusion" theory; organic polymer; composite film
引用本文：楚占营，张凌怡，朱曼曼，等. 细菌纤维素膜基图灵斑图聚合物膜的制备[J].化学试剂, 2020, 42(4): 450-454.
3,4-二-O-乙酰基-D-鼠李糖的合成
王浩，洪伟*
（北方民族大学 化学与化学工程学院，宁夏 银川 750021）
摘要：标题化合物作为一种重要的有机合成中间体，在有机合成活性较高的天然产物中具有重要意义。以三-O-乙酰基-D-己烯糖作为起始原料，经脱乙酰基反应、磺酰化反应、乙酰化反应、亲核取代反应和还原反应合成目标产物。其中间体及目标产物的结构均经IR、1HNMR和MS进行表征。对提高目标产物收率进行深入探索，结果表明，适当的反应时间、温度及投料的物质的量比分别能够有效提高乙酰化反应、亲核取代反应和还原反应的产品收率，总收率为63%。
关键词: 3,4-二-O-乙酰基-D-鼠李糖；合成；酰化反应；亲核取代反应；还原反应
中图分类号： 文献标识码：A 文章编号：0258-3283（2020）
Synthesis of 3,4-Di-O-acetyl-D-rhamnal WAHG Hao, HONG Wei*(School of Chemistry and Chemical Engineering, North Minzu University, Yinchuan 750021, China), Huaxue Shiji, 2020, 42(4)
Abstract: :3,4-Di-O-acetyl-D-rhamnal is an important organic synthetic intermediate in synthesizing highly active natural products. In this work, using tri-O-acetyl-D-glucal as starting material, the target product 3,4-di-O-acetyl-D-rhamnal was synthesized by deacetylation, sulfonylation, acylation, nucleophilic substitution and reduction reaction. The structures of the intermediates and product were confirmed by IR, 1HNMR and MS. In order to improve the yield of the target product, the results show that the appropriate reaction time, temperature, and ratio of material mass can effectively increase the acetylation reaction, product yield of nucleophilic substitution reaction and reduction reaction, and total yield, it is 63%.
Key words: 3,4-di-O-acetyl-D-rhamnal; synthes; acylation reaction; nucleophilic substitution reaction; reduction reaction
引用本文：王浩，洪伟. 3,4-二-O-乙酰基-D-鼠李糖的合成[J]. 化学试剂，2020，42（4）：455-458.
2,2-二羟甲基丁酸的合成
罗莎，蒋琳*，金文斐，刀家普，袁明龙
（云南民族大学 化学与环境学院 生物基材料绿色制备技术国家地方联合工程研究中心，云南 昆明 650500）
摘要：标题化合物是一种具有多官能团的新型功能性单体，可以广泛地应用于水性聚氨酯、聚酯、环氧树脂、涂饰剂工业等方面。为了优化其合成路线，以丙二酸二乙酯为原料，先在碱的催化下与溴乙烷发生烷基化反应；该单取代中间体再与甲醛进行羟甲基化反应，最后再经过单酯水解以及酯基还原共四步反应合成，总收率为66%。产物结构经1HNMR、13CNMR、MS确证。与已有的文献方法相比，报道的合成路线具有化学选择性好、操作简便、生产安全性好的特点。
关键词：丙二酸二乙酯；烷基化反应；2,2-二羟甲基丁酸；还原反应；合成
中图分类号：O621.3 文献标识码：A 文章编号：0258-3283（2020）
Synthesis of 2,2-Bis(hydroxymethyl)butyric Acid LUO Sha, JIANG Lin*, JIN Wen-fei, DAO Jia-pu, YUAN Ming-long(National and Local Joint Engineering Research Center for Green Preparation Technology of Biobased Materials, School of Chemistry & Environment, Yunnan Minzu University, Kunming 650500, China), Huaxue Shiji, 2020, 42(4)
Abstract: 2,2-Bis(hydroxymethyl)butyric acid is a novel functional monomer with polyfunctional groups, which can be widely used in water polyurethane, polyester, epoxide resin, water-based finish, etc. In order to optimize the synthesis route, diethylmalonate is used as a raw material, and an alkylation reaction with bromoethane is carried out under the catalysis of sodium ethoxide. Then, the mono-substituted intermediate was hydroxymethylated with formaldehyde. Finally, hydrolysis followed by reduction was carried out successively to generate 2,2-bis(hydroxymethyl)butyric acid. Thus, the target product was synthesized in 66% total yield in four steps. The structure was confiemed by 1HNMR, 13CNMR and MS. Compared with the reported synthetic routes, this protocol takes the advantage of high chemoselectivity, convenient operation and good safety.
Key words: diethyl malonate; alkylation; 2,2-bis(hydroxymethyl)butyric acid; reduction reaction; synthesis
引用本文：罗莎，蒋琳，金文斐, 等. 2,2-二羟甲基丁酸的合成[J]. 化学试剂, 2020, 42(4):459-462.
用双螺杆挤出机制备聚琥珀酰亚胺的绿色合成工艺研究
胡小明＊1, 2，颜英杰2，李青彬1，贾苗苗1，腊明1，彭勤龙1，齐建华2
（1. 平顶山学院 化学与环境工程学院，河南 平顶山 467000；
（2. 中国平煤神马集团能源化工研究院，河南 平顶山 467000）
摘要：以顺丁烯二酸酐和碳酸铵作为聚合原料，采用双螺杆挤出机作为聚合反应器制备了聚琥珀酰亚胺产品，研究了催化剂、反应温度、物料配比和螺杆转速对反应的影响。用FTIR对其进行了结构表征，并用极限粘度法测定了聚琥珀酰亚胺的聚合度。结果表明，最佳合成条件为n（顺酐）：n（碳酸铵）：n（催化剂） ＝ 1：1.5：0.07，聚合温度为180、195、210 ℃，螺杆转速为60 r/min。该条件下的聚琥珀酰亚胺的聚合度可以达到276，单体转化率为91.6 %。方法原料易得、操作简单、条件温和、无污染，为聚琥珀酰亚胺提供了一条绿色的合成方法。
关键词：双螺杆挤出机；顺丁烯二酸酐；碳酸铵；聚琥珀酰亚胺；聚合反应
中图分类号：TQ335 文献标识码：A 文章编号： 0258-3283（2020）--
Green Synthesis of Polysuccinimide by Twin Screw Extrude Hu Xiao-ming*1, 2, YAN Ying-jie2, LI Qing-bin1, JIA Miao-miao1, LA-Ming1, PENG Qin-long1, QI Jian-hua2 (1. College of Chemistry and Environmental Engineering, Pingdingshan University, Pingdingshan 467000, China; 2. China Pingmei Shenma Group Energy and Chemical Research Academy, Pingdingshan 467000, China), Huaxue Shiji, 2020, 42(4), ～
Abstract：The polysuccinimide was produced by polymerization of maleic anhydride and ammonium carbonate in the twin screw extruder reactor. The effects of the catalyst, reaction temperature, material ratio and screw speed on the reaction were investigated. The structures were confirmed by FTIR, and the polymerization degree of polysuccinimide was determined by limiting viscosity method. The excellent synthesis conditions for polysuccinimide were determined as follows: the molar ratio of maleic anhydride, ammonium carbonate and catalyst for 1:1.5:0.07, polymerization temperature was 180,195,210 ℃, screw rotation speed was 60 r/min. Under these conditions, the polymerization degree of the polysuccinimide can reach 276, its monomer conversion is 91.6%. This method has advantages such as available raw materials, simplicity of operates, mild reaction conditions, and pollution-free, which provides a new green strategy for the synthesis of polysuccinimide.
Key words：twin-screw extruder；maleic anhydride；ammonium carbonate；polysuccinimide；polymerization reaction
引用本文：胡小明, 李青彬, 贾苗苗, 等. 用双螺杆挤出机制备聚琥珀酰亚胺的绿色合成工艺研究[J]. 化学试剂, 2020, 42(4): 463-467.
2-（4-溴-2-（氯磺酰基）苯氧基）乙酸乙酯的合成研究
张茂风*1,2，王昌铭1，郭秋玉1，吴锡山1
(1. 泰州职业技术学院 药学院，江苏 泰州 225300；
2. 江苏省固体制剂工程技术研究开发中心，江苏 泰州 225300)
摘要：标题化合物是一种含有多官能团的磺酰氯衍生物，在构建新型活性先导化合物方面具有重要作用。该化合物及其合成方法目前尚无文献报道。以对溴苯酚为原料，经取代、氯磺化首次实现了目标化合物的合成。此外，提供了氯磺化步骤中可能的反应机理，为一锅法的建立提供理论依据。通过对投料比、反应物浓度、反应时间和反应温度等因素进行考察，确定较佳的工艺条件为n（2-（4-溴苯氧基）乙酸乙酯）∶n（氯磺酸）∶n（氯化亚砜）＝1∶6∶13、反应时间为4.5 h、反应温度为室温。目标产物经1HNMR、13CNMR、MS和IR确证。该路线步骤短、操作简单，总收率达82%，适合工业化生产。
关键词：2-（4-溴-2-（氯磺酰基）苯氧基）乙酸乙酯；对溴苯酚；磺酰氯；氯磺化反应；一锅法；合成
中图分类号：O625.75 文献标识码：A 文章编号：0258-3283（2020）
Synthesis of Ethyl 2-(4-Bromo-2-(Chlorosulfonyl)Phenoxy)Acetate ZHANG Mao-feng*1,2, WANG Chang-ming1, GUO Qiu-yu1, WU Xi-shan1(1. College of Pharmacy, Taizhou Polytechnic College, Taizhou 225300, China;2. Jiangsu Solid Preparation Engineering Technology Research and Development Center, Taizhou 225300, China), Huaxue Shiji, 2020, 42（4）
Abstract: Ethyl 2-(4-bromo-2-(chlorosulfonyl)phenoxy)acetate is a sulfonyl chloride derivative with multifunctional groups which is conducive to the construction of novel active lead compounds. At present, the compound and its synthetic methods have not been reported in the literature. In this work, the target compound was synthesized by substitution and chlorosulfonation of the raw material of p-bromophenol. In addition, this workpresents a presumed reaction mechanism of the chlorosulfonation step, which provides a theoretical basis for the establishment of one-plot synthetic method. The effects of feeding ratio, concentration of reactants, reaction timeand reaction temperaturewere investigated. The preferred conditions are obtained as follows: the molar ratio of n (ethyl 2-(4-bromophenoxy)acetate))∶n (chlorosulfonic acid)∶n (thionyl chloride)was 1∶6∶13, under the reaction time of 4.5 h, and the reaction temperature of room temperature. The structure was confirmed by 1HNMR, 13CNMR, mass spectrum and IR. The route has the advantages of short steps, simple procedure for operation and an overall yield of 82%, which is suitable for industrial production.
Key words: ethyl 2-(4-bromo-2-(chlorosulfonyl)phenoxy)acetate; p-bromophenol; sulfonyl chloride; chlorosulfonation reaction; one-plot method; synthesis
引用本文：张茂风，王昌铭，郭秋玉，等. 2-（4-溴-2-（氯磺酰基）苯氧基）乙酸乙酯的合成研究[J]. 化学试剂，2020, 42（4）：468-471.
（编辑：MCM）
