二氧化锰基纳米复合材料电极在超级电容器应用中的研究进展
周健，金浩天，常思思，陈慧玲，余高敏，秦宇，王峰*，蒋少华*
（南京林业大学 材料科学与工程学院，江苏 南京 210037）
摘要：超级电容器是一种具有高的功率密度、良好的循环稳定性和快的充放电速率的储能器件。与传统的电容器相比，由于较高的成本和较低能量密度的限制，超级电容器目前仍很难替代传统能源。在此前提条件下，寻求一种电化学储能能力更强、成本更低的电极材料是目前超级电容器电极材料的研究重点。二氧化锰由于其价格低廉、来源广泛和能量密度高的优点成为当前研究最为广泛的电极材料之一。该文以二氧化锰基的纳米复合材料为研究对象，从二氧化锰的制备与改性方法的角度出发，总结了当前二氧化锰基的纳米复合材料在超级电容器方面的应用研究进展，并对未来的发展趋势提出了展望。
关键词：二氧化锰；电极材料；超级电容器；能量密度；电化学储能
中图分类号：911.1 文献标识码：A 文章编号：0258-3283（2021）
Research Progress Inmanganese Dioxide-based Nanocomposite Electrodes and Their Application in Supercapacitors ZHOU Jian, JIN Hao-tian, CHANG Si-si, CHEN Hui-ling, YU Gao-min, QIN Yu, WANG Feng, JIANG Shao-hua (College of Materials Science and Engineering, Nanjing Forestry University, Nanjing 210037, China), Huaxue Shiji, 2021, 43(9)
Abstract: Supercapacitor is a kind of energy storage device with high power density, good cycle stability and fast charge and discharge rate. Compared with traditional capacitors, supercapacitors are still difficult to replace traditional energy due to their higher cost and low energy density. In this context, it is focused on developing low-cost and excellent electrochemical performance electrode for supercapacitor. Manganese dioxide (MnO2) has become one of the most widely studied electrode materials because of abounding source and high energy density. In this paper, we have summarized the preparation and modification methods of MnO2-based nanocomposite materials for supercapacitor. Finally, we have also proposed the research trend of MnO2-based nanocomposite materials for supercapacitor in the future.
Key words: manganese dioxide; electrode material; supercapacitor; energy density; electrochemical energy storage
引用本文：周健，金浩天，常思思，等. 二氧化锰基纳米复合材料电极在超级电容器应用中的研究进展[J]. 化学试剂，2021, 43（9）：1161-1170.
黑磷纳米复合材料的制备及其在传感中的研究进展
张春媚*，莫明虾，钱相豪
（苏州科技大学 材料科学与工程学院 材料科学与器件研究院，江苏 苏州 215009）
摘要：黑磷是一种新型的二维材料，具有独特的蜂窝褶皱结构、良好的生物相容性、较高的载流子迁移率以及可调的带隙，在传感中展现了巨大的潜力。但单独的黑磷在空气中易被氧化，这限制了其应用。黑磷纳米复合材料的构建不仅有利于提升黑磷稳定性，而且有利于增强材料传感性能。该文综述了黑磷复合材料的制备及其在传感中的研究进展。首先介绍几类黑磷复合材料的制备方法，包括黑磷/金属氧化物、黑磷/金属硫化物、黑磷/单层材料、黑磷/金属纳米粒子和黑磷/碳等复合材料。然后，介绍黑磷复合材料在电化学传感和气敏传感的研究进展。最后,对黑磷复合材料在传感领域的发展与面临的挑战进行了展望。
关键词：黑磷；纳米复合材料；制备；电化学传感；气敏传感
中图分类号：O657.1 文献标识码：A 文章编号：0258-3283（2021）
Recent Progress in Preparation and Sensing Application of Black Phosphorus-based Nanomaterials ZHANG Chun-mei*, MO Ming-xia, QIAN Xiang-hao (Institute of Materials Science and Devices, College of Materials Science and Engineering, Suzhou University of Science and Technology, Suzhou 215009, China), Huaxue Shiji, 2021, 43(9)
Abstract: As a new two-dimensional material, black phosphorus (BP) has been the focus of research in sensing because of its good biocompatibility, high carrier mobility and adjustable band gap. However, black phosphorus is easily oxidized in the air, which limits its application. BP based nanomaterials can not only improve the stability of BP, but also enhance the sensing properties of materials. In this paper, the preparation of BP based materials and their recent progress in sensing are reviewed. Firstly, the preparation of BP based nanomaterials, including BP/metal oxide, BP/metal sulfide, BP/monolayer materials, BP/metal nanoparticles and BP/carbon composites, is discussed. Then, the research progress of BP based nanomaterials in electrochemical sensing and gas sensing are reviewed. Finally, the development and challenges of BP based nanomaterials in the sensing field are prospected.
Key words: black phosphorus; nanomaterial; electrochemical sensing; gas sensing
引用本文：张春媚，莫明虾，钱相豪. 黑磷纳米复合材料的制备及其在传感中的研究进展[J]. 化学试剂, 2021, 43(9): 1171-1179.
五氧化二铌/碳纳米管水系锌离子混合电容器负极材料的制备及其电化学性能
张思佳，范宪楷，陈晗，周伟*
（湖南工业大学 冶金与材料工程学院，湖南 株洲 412007）
摘要：水系锌离子混合电容器具有高能量密度和高功率密度等优点，从而到了广泛的关注。开发高性能锌离子电容器的关键在于寻找电池型电极材料，以匹配其与电容型电极材料之间的功率不平衡。本文通过水热法制备出了碳纳米管与五氧化二铌的复合物（Nb2O5@CNTs），在0.2 A/g的电流密度下放电比容量为257 F/g，显示出其作为锌离子混合电容器的电极材料的巨大潜力。将Nb2O5@CNTs作为负极，高比表面积的活性炭（AC）作为正极组装成Nb2O5@CNTs//AC锌离子混合电容器，该电容器的电压区间为0～1.9 V，在0.2 A/g的电流密度下其放电比容量高达95 F/g，经过3000次循环后容量保持率为72%，具有良好的倍率性能和循环稳定性，能量密度最高达48 W·h/kg，功率密度最高达1831 W/kg，Nb2O5@CNTs//AC锌离子混合电容器有望作为下一代高性能锌离子混合电容器。
关键词：水热法；Nb2O5；碳纳米管；复合材料；锌离子混合电容器
中国分类号：TQ13 文献标识码：A 文章编号：0258-3283（2021）
Preparation and Electrochemical Properties of Nb2O5@CNTs Anode Material for Aqueous Zinc-ion Hybrid Capacitor ZHANG Si-jia, FAN Xian-kai, CHEN Han, ZHOU Wei* (School of Metallurgy and Materials Engineering, Hunan University of Technology, Zhuzhou 412007, China), Huaxue Shiji, 2021, 43(9)
Abstract: Aqueous zinc-ion hybrid capacitors have been widely paid attention because of their high energy density and power density. The key to developing the high-performance zinc-ion capacitors is to find battery-type electrode materials which can match the power imbalance between them and capacitive electrode materials. In this paper, the carbon nanotubes/niobium pentoxide (Nb2O5@CNTs) composites with the specific capacity of 257 F/g at the current density of 0.2A/g, were prepared via hydrothermal method, which showed their great potential as electrode materials for zinc-ion hybrid capacitors. The activated carbon (AC) with high specific surface area as the positive electrode and Nb2O5@CNTs as the negative electrode were assembled into a Nb2O5@CNTs//AC zinc-ion hybrid capacitor. The discharge specific capacity of the capacitor with voltage range of 0～1.9 V was up to 95 F/g at the current density of 0.2 A/g and the capacity retention rate was 72% after 3000 cycles, showing good rate performance and cycle stability. Meanwhile, the maximum energy density was 48 Wh/kg and the power density was up to 1831 W/kg. The Nb2O5@CNTs//AC zinc-ion hybrid capacitor can be expected to be used as the next generation of high-performance zinc ion hybrid capacitors.
Key words: hydrothermal method; Nb2O5; carbon nanotubes; composite materials; zinc-ion hybrid capacitor
引用本文：张思佳，范宪楷，陈晗，等. 五氧化二铌/碳纳米管水系锌离子混合电容器负极材料的制备及其电化学性能[J]. 化学试剂，2021，43（9）：1180-1187。
生物质模板法制备Bi掺杂ZnO及其太阳光催化性能
杨为森1,3,4，李路平1，孙守严1，段改改2，简绍菊*1,3,4
（1. 武夷学院 生态与资源工程学院 福建 武夷山 354300；2. 南京林业大学 材料科学与工程学院，江苏 南京 210037；3. 闽北竹产业公共技术创新服务平台 福建 武夷山 354300；4. 福建省生态产业绿色技术重点实验室(武夷学院)，福建 武夷山 354300）
摘要：采用生物模板法，以脱脂棉为模板、Zn(OAC)2·2H2O为锌源、Bi(NO3)3·5H2O为铋源、乙醇-水为溶剂，在不同的浸泡时间、焙烧温度、焙烧时间和掺杂摩尔分数下通过浸渍-热转化制备了一系列Bi2O3/ZnO催化剂。使用扫描电子显微镜、热重分析、X射线衍射等技术表征了产物形貌和结构。以亚甲基蓝作为模板反应，太阳光为光源，考察了Bi2O3/ZnO系列材料的光催化活性。结果表明：浸泡2 h、焙烧温度为600 ℃、焙烧时间为2 h的条件下制得的Bi掺杂摩尔分数1.0%的Bi2O3/ZnO催化剂，在太阳光照射390 min时对亚甲基蓝的降解效果最佳，降解率高达95.21%。与纯氧化锌ZnO相比，降解率提高了16.77%。Bi2O3/ZnO具有良好的稳定性和可循环使用性，在光降解偶氮染料方面具有潜在的应用价值。
关键词：Bi2O3；ZnO；光催化活性；亚甲基蓝
中图分类号：O643; TB383 文献标识码：A 文章编号：0258-3283（2021）
Biotemplate Synthesis of Bismuth-Doped ZnO Sunlight Catalyst and Its Photocatalytic Property under Sunlight YANG Wei-sen1,3,4, LI Lu-ping1, SUN Shou-yan1, DUAN Gai-gai2, JIAN Shao-ju*1,3,4
(1. School of Ecology and Resources Engineering, Wuyi University, Wuyishan 354300, China; 2. College of Materials Science and Engineering, Nanjing Forestry University, Nanjing 210037, China; 3. Science and Technology Innovation Public Service Center of Minbei Bamboo Industry, Wuyishan 354300, China; 4. Fujian Key Laboratory of Eco-Industrial Green Technology(Wuyi University), Wuyishan 354300, China), Huaxue Shiji, 2021, 43(9)
Abstract: Using biological template, a series of Bi2O3/ZnO composites with different Bi doping amount were prepared by using Zn(OAC)2·2H2O and Bi(NO3)3·5H2O as raw materials, cotton fiber as template, ethanol-water as solvent via impregnation-thermal conversion under different immersion time, calcination temperature, calcination time and Bi contents in mole percent. The samples were characterized by scanning electron microscopy (SEM), thermal gravimetric analyzer (TGA), X-ray diffraction (XRD), and its photocatalytic degradation of methylene blue was investigated under sunlight. The results showed that 1.0% Bi2O3/ZnO could be produced under the optimum fabrication condition of immersion time 2 h, calcination temperature 600 ℃, and calcination time 2 h, and its best degradation rate of methylene blue could be as high as 95.21% under sunlight irradiation of 390 min. Compared with pure ZnO, the degradation rate is increased by 16.77%. Bi2O3/ZnO catalyst has good stability and recyclability, and has potential application value in photo degradation of azo dyes.
Key words: Bi; ZnO; photo-catalytic activity; methylene blue
引用本文：杨为森，李路平，孙守严，等. 生物质模板法制备Bi掺杂ZnO及其太阳光催化性能[J]. 化学试剂, 2021, 43(9): 1188-1193。
双信号放大的电化学发光体系的构建及高灵敏检测FLT3基因
孙莹莹*，张佳佳，张越时，王奡
（辽宁中医药大学 医学检验学院，辽宁 沈阳 110847）
摘要：生物标志物的快速、精准检测对控制和预防疾病具有重要意义。首先合成了具有多个枝状手臂的金纳米星 (AuNSs)，并将其作为一种理想的基底，修饰在玻碳电极上；随后利用无酶的目标催化发夹反应 (CHA) 构筑高灵敏的电化学发光DNA传感器，用于急性髓系白血病FLT3基因的高灵敏检测。AuNSs不仅具有良好的导电性和生物相容性，其多个纳米级的手臂结构可以提供更多的活性位点并加载更多的发夹DNA，显著增加了传感器的响应信号。无酶CHA的引入，使得单个FLT3基因可以反复利用，实现了信号的指数放大。采用电化学交流阻抗法对组装过程进行了跟踪，证实了该传感器组装的可行性；采用电化学发光法，研究了传感器对底液中不同浓度的FLT3响应。结果表明，该传感器实现了对FLT3的灵敏检测，其线性范围为0.7～50 pmol/L，检测限为0.3 pmol/L。此外，该传感器结构简单、选择性好、重现性高，为构建其他类型的电化学发光传感器提供了可能。
关键词：金纳米星；目标催化发夹反应；电化学发光；FLT3
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2021）
Sensitive Electrochemiluminescence Determination of the FLT3 Gene Based on a Dual Signal Amplified Strategy: Gold Nanostars and a Target-catalyzed Hairpin Assembly SUN Ying-ying*, ZHANG Jia-jia, ZHANG Yue-shi, WANG Ao (Department of Medical Laboratory Science, Liaoning University of Traditional Chinese Medicine, Shenyang 110847, China), Huaxue Shiji, 2021, 43(9)
Abstract: The accurate and rapid quantitative detection of biomarkers has a significant influence on controlling and preventing disease. In this study, we introduced gold nanostars (AuNSs) as a desirable substrate for sensitive electrochemiluminescence (ECL) detection of FLT3 genes. Then, the hairpin DNA probe 1 (H1), with a thiol group at the 3’ end was immobilized on the AuNSs modified electrodes through Au-S bonding. When the FLT3 appeared, it hybridized with and opened the hairpin structure of H1. Subsequently, the hairpin DNA probe 2 (H2) bound to H1, freeing the FLT3 to trigger another reaction cycle. Each FLT3 had the ability to hybridize with many H1, leading to a considerably higher signal gain. In addition, the AuNSs acted as a substrate material with desirable electrical conductivity, excellent biocompatibility, and a large specific surface area for loading abundant H1, which gave an amplified signal compared with the traditional biosensors. The proposed ECL sensor possessed good analytical performance with a wide linear range from 0.7～50 pmol/L, and it had a detection limit of 0.3 pmol/L (S/N=3). The proposed strategy exhibited the advantages of excellent stability and selectivity for determination of the FLT3, which provide a sensitive and novel ECL analysis platform for the trace detection of other biomarkers.
Key words: gold nanostars; target-catalyzed hairpin assembly; electrochemiluminescence; FLT3
引用本文：孙莹莹，张佳佳，张越时，等. 双信号放大的电化学发光体系的构建及高灵敏检测FLT3基因[J]. 化学试剂，2021，43（9）：1194-1199.
新型5-脂氧合酶激活蛋白抑制剂的设计、合成及活性评价
贺依依1，姜祎1，徐虹1，邓翀1，张化为1，许洪波1，宋小妹1，刘海静*2
（1. 陕西中医药大学 药学院，陕西 咸阳 712046；2. 陕西省食品药品监督检验研究院，陕西 西安 710065）
摘要：设计、合成5-脂氧合酶激活蛋白（FLAP）抑制剂，并评价其活性。基于靶向FLAP蛋白结构采用计算机辅助药物设计，筛选并合成了一系列FLAP抑制剂，利用1H NMR、13C NMR和HR-ESI-MS表征结构。通过酶联免疫双抗夹心法测定了其对FLAP的抑制活性，并计算半数有效抑制浓度（IC50）。设计了558个不同芳基、不同碳链长度的2, 2-二甲基-5-烷基-5-取代氨基-1, 3-二氧六环衍生物，通过氧化反应、格氏反应、Appel反应、胺代反应合成11个化合物，经1H NMR、13C NMR和HR-ESI-MS确认结构。酶抑制实验表明N-（3-甲氧基苄基）-2, 2-二甲基-5-十八烷基-1, 3-二噁烷-5-胺对FLAP的抑制活性强于阳性药MK-591(IC50=13.78 nmol/L)，其IC50达到10.52 nmol/L，具有发展成为FLAP抑制剂的潜力。合成的新型FLAP抑制剂表现出对FLAP较强的抑制作用，在炎症相关疾病的治疗中有潜在应用价值。
关键词：5-脂氧合酶激活蛋白抑制剂；鞘氨醇类似物；炎症反应；白三烯
中图分类号：R914 文献标识码：A 文章编号：0258-3283（2021）
Design, Synthesis, and Biological Evaluation of Novel 5-Lipoxygenase-activating Protein Inhibitors HE Yi-yi1, JIANG Yi1, XU Hong1, DENG Chong1, ZHANG Hua-wei1, XU Hong-bo1, SONG Xiao-mei1, LIU Hai-jing*2 (1. School of Pharmacy, Shaanxi University of Chinese Medicine, Xianyang 712046, China; 2. Shaanxi Food and Drug Administration, Xi’an 712046, China), Huaxue Shiji, 2021, 43(9),
Abstract: Design, synthesize the inhibitors of 5-lipoxygenase activating protein (FLAP) and evaluate their inhibitory activity. In this study, a series of FLAP inhibitors were screened and synthesized by computer-aided drug design based on the targeting FLAP. The structure was characterized by 1H NMR, 13C NMR and HR-ESI-MS. The enzyme linked immunosorbent assay test was performed to evaluate the inhibitory activity of the compounds. Furthermore, the IC50 was calculated. 558 2, 2-Dimethyl-5-alkyl-5-amino-1, 3-dioxane derivatives with different aryl groups and carbon chains were designed, 11 compounds were selected by computer virtual screening and synthesized via four steps including oxidation reaction, Grignard reaction, Appel reaction, amination reaction. The structure was confirmed by 1H NMR, 13C NMR and HR-ESI-MS. Bioactive evaluation test showed that the inhibitory activity of N-(3-methoxybenzyl)-2,2-dimethyl-5-octadecyl-1,3-dioxan-5-amine (IC50=10.52 nmol/L) is better than positive drug MK-591(IC50=13.78 nmol/L). Therefore, it has potential to develop into FLAP inhibitor. In this study, the novel FLAP inhibitors exhibit strong inhibitory effect on FLAP and have potential to treat inflammatory diseases.
Key words: 5-lipoxygenase-activating protein inhibitors；sphingosine analogs；inflammatory reaction；leukotrienes
引用本文：贺依依，姜祎，徐虹，等. 新型5-脂氧合酶激活蛋白抑制剂的设计、合成及活性评价[J]. 化学试剂, 2021, 43(9)：1200-1209。
七元瓜环与阿德福韦衍生物的自组装体系研究
韩宜霖a,b,c，吴帝容a,b,c，罗可可a,b,c，李慧a,b,c，陈启清a,b,c，李勇军a,c，傅晓钟*b,d
（贵州医科大学 a. 贵州省药物制剂重点实验室, b. 药学院, c. 国家苗药工程技术研究中心,
d. 民族药与中药开发应用教育部工程研究中心，贵州 贵阳 550004）
摘要：利用1HNMR、红外光谱、紫外吸收光谱、质谱及等温量热滴定(ITC)等方法分析了七元瓜环(Q[7)]与阿德福韦单熊去氧胆酸-3-丙基酯，单L-异亮氨酸-3-丙基酯(X3I3)草酸盐的包合作用；并进行了自组装包结物的体外累积释放度研究和吸湿稳定性考察。结果表明，随着Q[7]比例的增大，体系内的主客体多种作用模式并存，甚至存在1个客体分子“挂满”4个Q[7]的包合物，波谱及ITC结果显示1:1包合模式为稳定作用模式。在人工胃液中，Q[7]对X3I3草酸盐起到控释作用；在人工肠液中，Q[7]对X3I3草酸盐释放起到促进作用。X3I3与Q[7]形成的固体包结物的吸湿稳定性明显提高，常温、常湿条件下放置90 d仍然为白色固体。
关键词：阿德福韦；七元瓜环；熊去氧胆酸；L-氨基酸；主客体包合
中图分类号：O625.6 文献标识码：A 文章编号：0258-3283（2021）
Study on the Self-assembly System of Cucurbit[7]uril with Adefovir Derivative HAN Yi-lina,b,c, WU Di-ronga,b,c, LUO Ke-kea,b,c, LI Huia,b,c, CHEN Qi-qinga,b,c, LI Yong-juna,c, FU Xiao-zhong*a,d (a. Guizhou Provincial Key Laboratory of Pharmaceutics, b. School of Pharmacy, c. National Engineering Research Center of Miao's Medicines, d. Engineering Research Center for the Development and Application of Ethnic Medicine and TCM ( Ministry of Education), Guizhou Medical University, Guiyang 550004, China), Huaxue Shiji, 2021, 43(9)
Abstracts: The interaction properties and mechanism of host-guest of cucurbit[7]uril with adefovir mono L-isoleucine-3-propyl ester, mono ursodeoxycholic acid-3-propyl ester derivative were investigated by 1H NMR technique, IR spectroscopy, UV absorption spectrum, high resolution mass spectrometry and isothermal calorimetry(ITC). Moreover, cumulative release in vitro and hygroscopic stability were evaluated. The experimental results revealed that cucurbit[7]uril can form host-guest complex with adefovir prodrug, and the inclusion ratio of Q[7] and X3I3 oxalate was related to the concentration of Q[7]. When the molar ratio of Q[7] to X3I3 oxalate was 3:1, multiple action modes of host and guest coexisted in the system, and even existed an guest molecule "loaded" with four Q[7] clathrates, but only the 1:1 mode was the most stable one. Studies on cumulative release in vitro showed that Q[7] play a controlling role in the release of X3I3 oxalate in artificial gastric juice, and it promoted the release of X3I3 oxalate in artificial intestinal fluid. The hygroscopic stability of the solid inclusion formed by X3I3 and Q[7] was significantly improved, and it remained white solid for 90 d under normal temperature and constant humidity.
Key words: adefovir; Cucurbit[7]uril; ursodeoxycholic acid; L-amino acid; host-guest complex
引用本文：韩宜霖，吴帝容，罗可可，等. 七元瓜环与阿德福韦衍生物的自组装体系研究[J].化学试剂，2021，43（9）：1210-1217.
碳糊电极无酶催化双氧水和葡萄糖的研究
李妍，孟祥乐，李舒，乔欣欣，刘畅*
(锦州医科大学 药学院，辽宁 锦州 121000)
摘要：利用普鲁士蓝（PB）与壳聚糖（CS）滴涂在碳糊电极（CPE）表面制成电化学传感电极(PB/CS/CPE)，并以循环伏安法(CV)、差分脉冲伏安法(DPV)及交流阻抗法(EIS)分别考察修饰电极的性能及H2O2在该电极上的电化学行为。结果证明，经PB/CS配比、温度、pH和扫描速度等条件优化的修饰电极对H2O2的检测范围为10×10-6～10×10-4 mol/L，检出限为2.81×10-7 mol/L，且同浓度典型干扰活性物质抗坏血酸(AA)、柠檬酸(CA)和尿素(UA)对H2O2样品的检测无明显干扰。同时，优化的PB/CS/CPE被应用于葡萄糖（Glu）样品测试，检测范围为5×10-5～10×10-3 mol/L，检出限为2.27×10-7 mol/L（S/N = 3），AA、UA的干扰可忽略不计。
关键词：壳聚糖；普鲁士蓝；碳糊电极；H2O2；葡萄糖
中图分类号：O657.1 文献标识码：A 文章编号：0258-3283（2021）--
Study on Enzyme-Free Catalysis of Hydrogen Peroxide and Glucose by Carbon Paste Electrode LI Yan, MENG Xiang-le, LI Shu, QIAO Xin-xin, LIU Chang* (College of Pharmacy, Jinzhou Medical University, Jinzhou 121000, China), Huaxue Shiji, 2021, 43(9), ～
Abstract: Prussian blue (PB) and chitosan (CS) were coated on the surface of carbon paste electrode (CPE) to prepare an electrochemical sensing electrode (Pb/CS/CPE). The performance of modified electrode and the electrochemical behavior of H2O2 on the modified electrode were investigated by cyclic voltammetry (CV), differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy(EIS), respectively. The detection range of modified electrode optimized by PB/CS ratio, temperature, pH and scanning speed is 10×10-6~10×10-4 mol/L, and the detection limit is 2.81×10-7 mol/L. Moreover, the same concentration of typical interfering active substances, such as ascorbic acid (AA), citric acid (CA) and urea (UA), do not significantly interfere the detection of H2O2 samples. The optimized PB/CS/CPE was also applied to detect the glucose (Glu) samples. The detection range of Glu on the modified electrode is 5×10-5~10×10-3 mol/L, and the corresponding detection limit is 2.27×10-7 mol/L (S/N = 3). The interferences of AA and UA are negligible.
Key words: chitosan; prussian blue; carbon paste electrode; H2O2; glucose
引用本文：李妍, 孟祥乐, 刘畅. 碳糊电极无酶催化双氧水和葡萄糖的研究[J]. 化学试剂, 2021, 43(9): 1218-1223.
Maillard反应香料的制备工艺优化及加香应用研究
李瑞丽1，陈康1，徐达2，赵琪3，苏加坤2，张峻松1，蔡继宝*2
(1. 郑州轻工业大学 烟草科学与工程学院，河南 郑州 450001；2. 江西中烟工业有限责任公司技术中心，江西 南昌 330096；3. 浙江中烟工业有限责任公司宁波卷烟厂，浙江 宁波 315040)
摘要：以高粱酒基和丙二醇为反应底液，以葡萄糖和天冬氨酸为原料通过Maillard反应制备烟用香料，利用正交设计优化Maillard反应工艺，剖析Maillard反应产物香味成分，考察其在卷烟加香中的应用效果。结果表明，Maillard反应最优工艺条件为葡萄糖与天冬氨酸的物质的量比2:1、反应体系pH 10.5、反应温度95 ℃、反应时间6 h，糖氨物质的量比对Maillard反应产物的影响最大，反应体系pH、反应时间次之，反应温度对Maillard反应产物的影响相对较小。Maillard反应香料中检出的香味成分主要有12种吡嗪、3种呋喃类化合物及呋喃酮、吡嗪酮类化合物各4种。葡萄糖和天冬氨酸制备的Maillard反应产物以烟丝质量0.10%的比例添加到卷烟中，可改善卷烟的香气质、香气量，增补甜感，抑杂降刺，提升卷烟吸食品质。
关键词：葡萄糖；天冬氨酸；Maillard反应；正交优化；加香作用
中图分类号：TS411 文献标识码：A 文章编号：0258-3283（2021）--
Preparation Technology Optimization and Application of Maillard Reaction Products LI Rui-li1, CHENG Kang1, XU Da2, ZHAO Qi3, SU Jia-kun2, ZHANG Jun-song1, CAI Ji-bao*2 (1. School of Tobacco Science and Engineering, Zhengzhou University of Light Industry, Zhengzhou 450001, China; 2. Technology Center, Tobacco Jiangxi Industrial Co., Ltd., Nanchang 330096, China; 3. Ningbo Cigarette Factory, Tobacco Zhejiang Industrial Co., Ltd., Ningbo 315040, China), Huaxue shiji, 2021, 43(9), ～
Abstract: Tobacco spice was prepared by Maillard reaction with glucose and aspartic acid, based on sorghum wine base and propylene glycol. The Maillard reaction process was optimized by orthogonal design, the flavor components of Maillard reaction products were analyzed, and the application effect in cigarette was investigated. The results showed that: ①The optimal reaction conditions of Maillard reaction were as follows: the molar ratio of glucose to aspartic acid was 2:1, the reaction system pH was 10.5, the reaction temperature was 95 ℃, and the reaction time was 6 h. The Influence of sugar ammonia molar ratio on Maillard reaction products was the greatest, followed by the reaction system pH and reaction time, and the influence of reaction temperature on Maillard reaction products was relatively small. ②There were 12 pyrazines, 3 furans, 4 furanone and 4 pyrazinone in Maillard reaction spices. ③The Maillard reaction product prepared by glucose and aspartic acid was added to cigarette at the ratio of 0.10% of cut tobacco weight, the aroma quality and quantity of cigarette could be improved, the sweet after taste could be added, impurities and thorns could be suppressed, and the smoking quality of cigarette could be improved in general.
Key words: glucose; aspartic acid; Maillard reaction; orthogonal optimization; cigarette flavoring
引用本文：李瑞丽，陈康，徐达，等. Maillard反应香料的制备工艺优化及加香应用研究[J].化学试剂, 2021, 43(9)：1224-1228.
萘酞菁衍生物在光动力疗法中的研究进展
何贤会，付阳洋，田雪莹，杨舜禹，杨敏*
（贵州大学 药学院，贵州 贵阳 550025）
摘要：光动力治疗作为一种非侵入性治疗方式，具有微创、毒副作用小、可重复治疗等优点。光敏剂是光动力治疗的关键因素之一，萘酞菁作为第二代光敏剂，扩展的π-共轭体系使其最大吸收波长位于近红外区（740～780 nm），该近红外光有较深的组织穿透性，且能量足够激发光敏剂，也能避免可见光区吸收带来的皮肤光毒性。但萘酞菁具有较强的聚集倾向，影响其光化学性质及光动力疗效。综述了通过合成萘酞菁衍生物和纳米载体包封来改善其光学性质或增强光动力疗效的进展。
关键词：光动力治疗；萘酞菁衍生物；纳米载体；光动力学特征
中图分类号：O62 文献标识码：A 文章编号：0258-3283(2021)
Research Progress of Naphthalocyanine Derivatives in Photodynamic Therapy HE Xian-hui, FU Yang-yang, TIAN Xue-ying, YANG Shun-yu, YANG min* (College of Pharmacy, Guizhou University, Guiyang 550025, China), Huaxue Shiji, 2021, 43(9)
Abstract: As a non-invasive treatment, photodynamic therapy has the advantages of minimally invasive, less toxic and side effect, and repeatable treatment. Photosensitizer is one of the key factors of photodynamic therapy. Naphthalocyanine is the second generation photosensitizer, the expanded π-conjugated system makes its maximum absorption wavelength in the near infrared region (740～780 nm) which has deep tissue penetration, and the energy is enough to stimulate the photosensitizer, photosensitizer in near infrared region can also avoid the skin phototoxicity caused by absorbing the visible region. However, naphthalocyanine has a strong aggregation tendency, which affects its photochemical properties and photodynamic efficacy. This paper reviews the progress in the synthesis of naphthalocyanine derivatives and nano-carrier encapsulation to improve their optical properties or enhance photodynamic efficacy.
Key words: photodynamic therapy; naphthalocyanine derivatives; nanocarriers; photodynamic characteristics
引用本文：何贤会，付阳洋，田雪莹，等. 萘酞菁衍生物在光动力疗法中的研究进展[J]. 化学试剂，43（9）：1229-1236.
多金属氧酸盐抗RNA病毒的研究进展
高瑞，宋雪，卜静，肖宇，王蕴鹏*
（哈尔滨医科大学 药学院，黑龙江 哈尔滨 150081）
摘要：RNA病毒是病毒家族的重要成员，由于其变异快、疫苗较难开发，世界各地每年都会有几种RNA病毒爆发，严重威胁人类的生命健康。多金属氧酸盐由于可以在分子水平上设计空间结构，且对正常细胞无毒，所以在医学上具有很好的应用前景。综述了近20年多金属氧酸盐对粘病毒(流感病毒、呼吸道合胞病毒)、黄病毒(丙型肝炎病毒、寨卡病毒)和慢病毒(人类免疫缺陷病毒1型)等RNA病毒作用的研究进展，发现多金属氧酸盐具有广谱抗病毒活性，为开发高效的抗病毒新药提供参考。
关键词：多金属氧酸盐；RNA病毒；广谱抗病毒活性；研究进展
中图分类号：R511;O611.4 文献标识码：A 文章编号：0258-3283（2021）
Research Progress of Polyoxometalates Against RNA Viruses GAO Rui, SONG Xue, BU Jing, XIAO Yu, WANG Yun-peng* (School of Pharmacy, Harbin Medical University, Harbin 150081, China), Huaxue Shiji, 2021, 43(9)
Abstract: RNA viruses are important members of the virus family. Several RNA viruses break out all over the world every year and the rapid mutations make the development of vaccines to be difficult, so they threaten human life and health seriously. Since polyoxometalates’ spatial structures can be designed at the molecular level and are non-toxic to normal cells, they have very promising potential in medicine field. This article reviews the effects of polyoxometalates on RNA viruses such as myxoviruses (influenza virus, respiratory syncytial virus), flavivirus (hepatitis C virus, Zika virus) and lentivirus (human immunodeficiency virus type 1) in the past 20 years. The research progress indicated that polyoxometalates had broad-spectrum antiviral activity, and would provide a reference for the development of highly effective new antiviral drugs.
Key words: polyoxometalate; RNA virus; broad-spectrum antiviral activity; research progress
引用本文：高瑞，宋雪，卜静，等. 多金属氧酸盐抗RNA病毒的研究进展[J]. 化学试剂，2021,43（9）：1237-1242.
杨迪，刁学文，赵小丽，蔡小华*
（贵州民族大学 化学工程学院，贵州 贵阳 550025）
摘要：甲酰胺是合成药物、染料和香料的有机中间体和重要的工业合成原料，同时在作为工业溶剂和路易斯碱催化剂方面也发挥着重要作用,发展简单、绿色和经济的甲酰胺合成策略引起合成化学和工业领域的广泛关注。近年来，以生物质来源的甲酸及甲酸铵为原料的N-甲酰化反应研究得到了快速发展，许多新颖的合成方法和具有工业应用价值的研究成果不断涌现。从胺的直接甲酰化及硝基或含氮杂环化合物的还原甲酰化方面着手，综述了N-甲酰化反应研究的新进展。
关键词：甲酰胺；甲酸；合成中间体；N-甲酰化；还原甲酰化
中图分类号：O621 文献标识码：A 文章编号：0258-3283（2021）
Recent Progress in the N-Formylation Reactions Using Formic Acid and Its AmmoniumSalt as Substrates YANG Di, DIAO Xue-wen, ZHAO Xiao-li, CAI Xiao-hua* (School of Chemical Engineering, Guizhou Minzu University, Guiyang 550025, China), Huaxue Shiji, 2021, 43(9)
Abstract: Formamides as organic intermediates in the synthesis of pharmaceuticals, dye and flavor are one of valuable substrates in industrial synthesis. Formamides have also played significant roles as industrial solvents and Lewis base catalysts, and the development of simple, green and economic strategy to synthesize formamides has always attracted extensive attention in synthetic chemistry and industry. The rapid developments in the N-formylations have been obtained and many novel methods and attractive achievements using formic acid and formamide as substrates from biomass have been made in recent years. This paper reviews recent advances on the direct N-formylations of amines and reduction and N-formylations of nitro-compounds or heterocycles including nitrogen atom.
Key words: formamide; formic acid; synthetic intermediate; N-formylation; reduction and formylation
引用本文：杨迪，刁学文，赵小丽，等. 以甲酸及其铵盐为原料的N-甲酰化反应新进展[J]. 化学试剂，2021,43（9）：1243-1251.
HPLC-MS/MS法测定化妆品中黄曲霉毒素G2、G1、B2、B1
牛水蛟1，倪亚萍2，李启艳1，胡文岳1，胡德福1，于海英*1
（1. 山东省食品药品检验研究院 化妆品原料质量控制重点实验室，山东 济南 250101；2. 山东大学 药学院，山东 济南 250012）
摘要：建立高效液相色谱-串联质谱法（HPLC-MS/MS）测定化妆品中黄曲霉毒素G2、G1、B2、B1的方法。化妆品经70%甲醇提取并经免疫亲和柱净化，采用C18柱（2.1 mm×100 mm, 1.7 μm），流动相体系为2.0 mmol/L乙酸铵甲醇溶液（含0.1%甲酸）和2.0 mmol/L乙酸铵水溶液（含0.1%甲酸），流速为0.3 mL/min进行梯度洗脱，扫描方式为正离子多反应监测模式（MRM）。黄曲霉毒素G2、G1、B2、B1线性关系均良好，相关系数不低于0.998。检出限范围为0.028～0.078 ng/g。精密度及稳定性均良好，回收率85.0%～96.2%。该方法准确、高效，为化妆品中黄曲霉毒素的测定提供了技术支持。
关键词：HPLC-MS/MS法；黄曲霉毒素G2、G1、B2、B1；免疫亲和；化妆品
Determination of Aflatoxin G2, G1, B2 and B1 in Cosmetics by HPLC-MS/MS NIU Shui-jiao1, NI Ya-ping2, LI Qi-yan1, HU Wen-yue1, HU De-fu1; YU Hai-ying*1 (1. NMPA Key Laboratory for Quality Control of Cosmetics Raw Material, Shandong Institute for Food and Drug Control, Ji’nan 250101, China; 2. School of Pharmaceutical Sciences, Shandong University, Ji’nan 250012, China), Huaxue Shiji, 2021, 43(9)
Abstract: A method for determining aflatoxin G2, G1, B2 and B1 in cosmetics by high performance liquid chromatography was established. Samples were extracted by 70% methanol and purified with immune affinity column. A C18 (2.1 mm×100 mm, 1.7 μm) column was employed for separation, with 2.0 mmol/L ammonium acetate methanol containing 0.1% formic acid and 2.0 mmol/L ammonium acetate solution containing 0.1% formic acid as mobile phase for gradient elution at a flow rate of 0.3 mL/min. Positive ion multiple reaction monitoring mode (MRM) was used for scanning. Good linearity were obtained with nice correlation coefficients no less than 0.998. Aflatoxins G2、G1、B2、B1 had good precision and stability, with spiked recoveries ranging from 85.1% to 96.2%, and the LODs were between from 0.028 to 0.078 ng/g. This accurate and efficient method will provide technical support for the determination of aflatoxins in cosmetics.
Key words: liquid chromatography-tandem mass spectrometry (LC-MS/MS); aflatoxin G2、G1、B2、B1; immunoaffinity; cosmetic
引用本文：牛水蛟，倪亚萍，李启艳，等. HPLC-MS/MS法测定化妆品中黄曲霉毒素G2、G1、B2、B1[J]. 化学试剂, 2021, 43(9): 1252-1256。
QuEChERS-分散固相萃取-液质联用法测定婴幼儿奶粉中9种禁用安眠药
许晓辉1，王小乔*1，石晓峰2，张虹艳1，潘秀丽1，李晨曦1，李赟1
（1. 兰州市食品药品检验检测研究院，甘肃 兰州 730050;
2. 甘肃省医学科学研究院，甘肃 兰州 730050）
摘要：违法添加安眠药是影响婴幼儿奶粉质量安全的主要风险因子之一，建立了QuEChERS-分散固相萃取-液质联用法快速测定婴幼儿奶粉中9种禁用安眠药的方法。样品采用QuEChERS提取，然后采用增强型脂质去除分散式固相萃取管 (EMR-Lipid dSPE) 进行净化，多反应监测采集模式（MRM）进行定性和定量检测，外标法定量。结果表明，9种禁用安眠药在各自线性范围呈良好的线性关系，相关系数（R2）均大于0.9921，检出限在0.050 ～ 0.72 ng/g之间，定量限在0.16 ～ 2.9 ng/g之间，3个添加水平的回收率在64.1% ～ 107.4%之间，精密度在1.5%～9.4%之间。方法具有前处理操作简单、结果准确、检出限低、灵敏度高等优点，适用于婴幼儿奶粉中9种禁用安眠药的快速筛查。
关键词：QuEChERS；分散固相萃取；液质联用法；婴幼儿奶粉；安眠药；筛查
中图分类号：R917 文献标识码：A 文章编号：0258-3283（2021）--
QuEChERS-dispersed Solid Phase Extraction-ultra Performance Liquid Chromatography- tandem Mass Spectrometry for Determination of 9 Kinds of Soporifics in Infant Milk Powder XU Xiao-hui1, WANG Xiao-qiao*1, SHI Xiao-feng2, ZHANG Hong-yan1, PAN Xiu-li1, LI Chen-xi1, LI Yun1 (1. Lanzhou Institute for Food and Drug Control, Lanzhou 730050, China; 2. Gansu Provincial Academic Institute for Medical Research, Lanzhou 730050, China), Huaxue Shiji, 2021, 43(9)
Abstract: Illegal addition of sleeping pills that affecting the quality and safety of infant milk powder is one of the major risk factors. The QuEChERS-dispersed solid phase extraction-ultra performance liquid chromatography- tandem mass spectrometry (QuEChERS-dSPE-UPLC-MS/MS) was established for the rapid determination of 9 kinds of banned soporifics in infant milk powder. The sample was extracted with Quick、Easy、Cheap、Effective、Rugged and Safe (QuEChERS), then purified with enhanced matrix removal lipid-dispersed solid phase extraction (EMR-Lipid-dSPE). The multiple reaction monitor (MRM) acquisition mode was used for qualitative and quantitative detection, and external standard method was used for quantitative detection. The analytes showed good linearities in corresponding concentration ranges with their correlation coefficients (R2) greater than 0.9921. The limit of detection was 0.050 ~ 0.72 ng/g, the limit of quantitative was 0.16 ~ 2.9 ng/g, the spiked recoveries for analytes at three spiked levels were in the range of 64.1% ~ 107.4%, and the precisions were 1.5% ~ 9.4%. The matrix removal effect of this method is sufficient, the pretreatment method is simple, reproducible and sensitive, and suitable for the rapid screening of 9 kinds of banned soporifics in infant milk powder.
Key words: QuEChERS; dSPE; UPLC-MS/MS; infant milk powder; soporifics; screening
引用本文：许晓辉，王小乔，石晓峰，等. QuEChERS-分散固相萃取-液质联用法测定婴幼儿奶粉中9种禁用安眠药[J]. 化学试剂, 2021, 43(9): 1257-1261.
薜荔果总黄酮提取工艺及抗氧化性研究
黄秋萍，黄秋婵，郑燕菲，曾振芳，黄丽彬，韦友欢*
（广西民族师范学院 a. 化学与生物工程学院，b. 广西高校桂西南特色植物资源化学重点实验室培育基地，广西 崇左 532200）
摘要：以薜荔果为研究对象，采用超声波辅助法提取薜荔果总黄酮，通过单因素实验和正交试验设计确定最佳提取工艺条件，并从对·OH、DPPH·及·NO的清除效果研究薜荔果总黄酮的抗氧化活性。结果表明：薜荔果总黄酮的最佳提取工艺条件为：60%乙醇、1∶25（g/mL）料液比、提取温度60 ℃及提取时间120 min，在此条件下薜荔果总黄酮得率为8.87%。薜荔果总黄酮对·OH、DPPH·及·NO的清除效果与浓度间存在量效关系，其中对DPPH·的清除效果较好，IC50值为0.0033 mg/mL，表明薜荔果中的总黄酮具有一定的抗氧化活性。
关键词：薜荔果；总黄酮；超声辅助；提取工艺；抗氧化活性
中图分类号：TS255.1 文献标识码：A 文章编号：0258-3283（2021）
Extraction and Antioxidant Activities of Total Flavonoids from Ficus Pumila Fruit HUANG Qiu-ping, HUANG Qiu-chan, ZHEN Yan-fei, ZENG Zhen-fang, HUANG Li-bin, WEI You-huan* (a. College of Chemical and Biological Engineering, b. Guangxi College and Universities Key Laboratory Breeding Base of Chemistry of Guangxi Southwest Plant Resources, Guangxi Normal University for Nationalities, Chongzuo 532200, China), Huaxue Shiji, 2021, 43(9),
Abstract: The fruits of Ficus pumila were taken as the research object, the total flavonoids were extracted from Ficus pumila fruit by ultrasonic-assisted extraction. The optimum extraction conditions were investigated based on orthogonal design. The antioxidant activity of Ficus pumila fruit total flavonoids was evaluated from scavenging effects on ·OH, DPPH· and ·NO. Results showed that the optimum extraction conditions were 60% ethanol, 1:25 (g/mL) ratio of material to liquid, extraction temperature of 60 ℃ and 120 min of extraction time, respectively. Under this condition, the extraction rate of total flavonoids from Ficus pumila fruit was 8.87%. The scavenging effects of Ficus pumila fruit total flavonoids on ·OH, DPPH· and ·NO showed dose-effect relationship with the total flavonoids concentration. And the scavenging effect of DPPH· was better, the corresponding IC50 value was 0.0033 mg/mL. The results showed that the total flavonoids in Ficus pumila fruit had certain antioxidant activity.
Key words: Ficus pumila fruit; total flavonoids; uultrasonic-assisted; extraction technology; antioxidant activity
引用本文：黄秋萍，黄秋婵，郑燕菲，等. 薛荔果总黄酮提取工艺及抗氧化性研究[J]. 化学试剂, 2021, 43(9): 1262-1267。
Box-Behnken模型优化榕树须多酚提取工艺及抗氧化活性
高林晓*1,2，邓晓霞1，石慧丽3，郭纯1，杨再波1,2
（1．黔南民族师范学院 化学化工学院，贵州 都匀 558000；2．贵州省普通高校民族药用植物资源开发工程研究中心，贵州 都匀 558000；3．中国食品发酵工业研究院有限公司，北京 100015）
摘要：为综合开发榕树须的利用价值，本实验以榕树须为原材料，通过单因素试验进一步设计Box-Behnken模型，优选出提取榕树须多酚的最佳工艺，并以铁离子还原/抗氧化能力（Ferric ion reducing antioxidant power，FRAP）法和1,1-二苯基-2-三硝基苯肼（1,1-diphenyl-2-picrylhydrazyl radical，DPPH）自由基法评价了抗氧化活性。根据Box-Behnken模型实验数据的结果显示，当实际操作乙醇浓度、液料比、超声时间、超声温度分别调整为70%、50:1 mL/g、40 min、60 ℃时，3次平行验证试验得到多酚提取率平均值为4.39%（RSD为1.33%），与Box-Behnken模型的预测值相近。此条件下提取液总抗氧化能力为0.218 mmol/L（FeSO4当量值），而0.3 mg/mL提取物的DPPH自由基清除率可达到89.4%，这表明榕树须提取液中可展现出好的抗氧化活性，可为榕树须药用价值的进一步开发提供参考。
关键词：榕树须；多酚；Box-Behnken模型；优化；抗氧化活性
中图分类号：R284.2 文献标识码：A 文章编号：0258-3283(2021)--
Optimization of Extraction Technology and Antioxidant Activity of Polyphenols from Radix Aerio Ficus Microcarpa by Box-Behnken Model GAO Lin-xiao*1,2, DENG Xiao-xia1, SHI Hui-li3, GUO Chun1, YANG Zai-bo1,2 (1. School of Chemistry and Chemical Engineering, Qiannan Normal College for Nationalities, Duyun 558000, China; 2. Guizhou Province College Research Center of Ethnical Medicinal Plant Resources Exploitation Engineering, Duyun 558000, China; 3. China National Research Institute of Food & Fermentation Industries Corporation Limited, Beijing 100015, China), Huaxue Shiji, 2021, 43(9), ～
Abstract: In order to develop the utilization value of radix aerio Ficus microcarpa comprehensively, Box-Behnken model was designed further by single factor experiment with radix aerio Ficus microcarpa as raw material, and then the optimum process conditions of polyphenols were optimized. Therefore, the antioxidant activity was evaluated by FRAP method and DPPH free radical method. According to the experimental results of Box-Behnken model, when the actual ethanol concentration, liquid-solid ratio, ultrasonic time and ultrasonic temperature were adjusted separately to 70%, 50:1 mL/g, 40 min and 60 ℃, three parallel verification tests showed that the average extraction rate of polyphenols was 4.39% and RSD was 1.33%, which were close to the predicted value of Box-Behnken model. Under these conditions, the total antioxidant capacity was equivalent to 0.218 mmol/L (FeSO4 equivalent value), and the DPPH free radical scavenging rate of the 0.3 mg/mL extract could reach 89.4%, which indicated that the extract of radix aerio Ficus microcarpa could exhibit good antioxidant activity, and which could provide reference for further development of medicinal value of radix aerio Ficus microcarpa.
Key words: radix aerio Ficus microcarpa; polyphenol; Box-Behnken model; optimization; antioxidant activity
引用本文：高林晓，邓晓霞，石慧丽，等. Box-Behnken模型优化榕树须多酚提取工艺及抗氧化活性[J]. 化学试剂, 2021, 43(9): 1268-1274.
凌霄花多酚微波提取工艺优化及其抗氧化研究
郑茜a，杨俊a，张富贵a，郝新才a, b, c，赵永恒*a, b, c
（湖北医药学院 a. 药学院，b. 武当特色中药研究湖北省重点实验室，
c. 湖北省药用植物综合利用工程技术研究中心，湖北 十堰 442000）
摘要：以凌霄花为原料，在单因素考察的基础上，考察乙醇浓度、微波功率、提取时间和液料比等因素，通过响应面法优化微波辅助提取凌霄花多酚的工艺，并研究其抗氧化活性。结果表明，微波提取凌霄花多酚的最优工艺为：乙醇浓度40%、微波功率281 W、提取时间37 s、液料比32∶1（mL/g），在此条件下凌霄花多酚的平均提取率为8.07%，与预测值间相对标准偏差（2.58%）较为接近。优化的提取工艺科学可行，重现性良好，适用于凌霄花多酚的提取，可为凌霄花的开发利用提供参考。抗氧化研究表明，凌霄花具有较强的抗氧化作用，为凌霄花多酚天然抗氧剂的研发提供了基础。
关键词：凌霄花；多酚；微波提取；Box-Behnken响应面法
中图分类号：284.2 文献标识码：A 文章编号：0258-3283(2021)
Study on Microwavewe Extraction Process of Polyphenols from Campsis radicans (L.) and Its Antioxidant Activity ZHENG Xia, YANG Juna, ZHANG Fu-guia, HAO Xin-caia, b, c, ZHAO Yong-henga, b, c*（a. School of Pharmaceutical Sciences, b. Hubei Key Laboratory of Wudang Local Chinese Medicine Research, c. Hubei Provincial Technology and Research Center for Comprehensive Development of Medicinal Herbs, Hubei University of Medicine, Shiyan 442000, China）, Huaxue Shiji, 2021, 43(9)
Abstract：Using Campsis radicans (L.) as raw material, the influence of ethanol concentration, microwave power, extraction time and liquid to solid ratio on the yield of polyphenols in Campsis radicans (L.), are evaluated by single factor test and Box-Behnken response surface method. And antioxidant activity of polyphenols from Campsis radicans (L.) was studied. The results showed that the optimal process was as below: ethanol content 40%, microwave power 281 W, extraction time 37 s, liquid-solid ratio 32∶1 (mL/g). Under these extraction process parameters, the average extraction yield of polyphenols was 8.07%, and the relative standard deviation between the predicted values was 2.58%, which was close to the predicted value. The optimized extraction technique is stable and feasible，which can provide a reference for the development and utilization of Campsis radicans (L.). And antioxidant studies have shown that Campsis radicans (L.) has a good antioxidant effect, which provides a basis for the research and development of natural antioxidants of Campsis radicans (L.) polyphenol.
Key words：Campsis radicans (L.); polyphenols; Box-Behnken response surface method; microwave extraction process
引用本文：郑茜，杨俊，张富贵，等. 凌霄花多酚微波提取工艺优化及其抗氧化研究[J]. 化学试剂，2021,43（9）：1275-1280.
稳定同位素标记特布他林-D9的合成研究
徐仲杰1,2，罗勇2，胡祖明*1
(1. 东华大学 材料科学与工程学院 化纤与高分子材料改性国家重点实验室，上海 201620；2. 上海化工研究院有限公司，上海 200062)
摘要：稳定同位素标记的特布他林-D9是以叔丁胺-D9为标记前体，以3,5-二羟基苯乙酮为起始原料进行合成。3,5-二羟基苯乙酮经过苄基保护、溴化、胺化、还原、脱苄基等5步反应制备得到特布他林-D9。通过对反应条件的优化，得到稳定的较优合成工艺路线。以投入的叔丁胺-D9的物质的量计算，特布他林-D9产率为 23.3%。目标产物结构经核磁共振波谱、高效液相色谱和高分辨质谱等表征确认。特布他林-D9的化学纯度98.5%，同位素丰度98.4atom%D，可作为同位素内标用于肉类食品中特布他林残留检测。
关键词：稳定同位素标记；特布他林-D9；β-受体激动剂；叔丁胺-D9；合成
中图分类号：TQ421.6 文献标识码：A 文章编号：0258-3283(2021)--
Synthesis of Stable Isotope Labeled Terbutaline-D9 XU Zhong-jie1,2, LUO Yong2, HU Zu-ming*1 (1. State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Donghua University, Shanghai 201620, China; 2. Shanghai Research Institute of Chemical Industry Co., Ltd., Shanghai 200062, China), Huaxue Shiji, 2021, 43(9), ～
Abstract: The stable isotope labeled terbutaline-D9 was synthesized with 3,5-dihydroxyacetophenone as starting material and using t-butylamine-D9 as a stable isotope starting labeling raw material. It was prepared by benzyl protection, bromination, amination, reduction and debenzyreaction from 3,5-dihydroxyacetophenone. By the optimization of the reaction conditions, a stable and better synthetic process route was obtained. The yield of terbutaline-D9 was 23.3% based on the consumed t-butylamine-D9. The targeted product was characterized by NMR, HPLC and HRMS. Its chemical purity was 98.5%, and isotopic abundance was 98.4atom%D. The prepared terbutaline-D9 can be used as an internal standard reagent for the determination of residual terbutaline of meat.
Key words: stable isotope labeling; terbutaline-D9; beta receptor agonist; t-butylamine-D9; synthesis
引用本文：徐仲杰, 罗勇, 胡祖明. 稳定同位素标记特布他林-D9的合成研究[J]. 化学试剂, 2021, 43(9): 1281-1285.
2-(4-氨基-4-甲基戊基)丙二酸二甲酯的合成与表征
仝红娟*，刘斌，赵梅梅
(陕西省中药绿色制造技术协同创新中心，陕西国际商贸学院医药学院，陕西 咸阳 712046）
摘要：报道一种新结构的7,7-二甲基吖庚环-2-酮中间体标题化合物的合成方法及表征。以丙烯酸甲酯和2-硝基丙烷为原料，经过Michael加成反应、酯水解反应、缩合反应、羰基还原反应、酯交换反应以及硝基还原反应，合成得到目标化合物。6步反应总产率达到40%。产物及中间体结构经1HNMR、13CNMR、FT-IR、元素分析及ESI-MS表征。其中，Michael加成4-甲基-4-硝基戊酸的结构进一步通过X-单晶衍射确定。并对每一步反应条件进行了简单讨论。该研究为吖庚环-2-酮类化合物的合成提供了一种新颖的中间体结构。
关键词：吖庚环衍生物；吖庚环-2-酮；X-单晶衍射；合成；表征
中图分类号：TQ463 文献标识码：A 文章编号：0258-3283（2021）--
Synthesis and Characterization of Dimethyl 2-(4-Amino-4-methylpentyl)malonate TONG Hong-juan*1, LIU Bin1, ZHAO Mei-mei1 (Collaborative Innovation Center of Green Manufacturing Technology for Traditional Chinese Medicine in Shaanxi Province, School of Pharmacy, Shaanxi Institute of International Trade & Commerce, Xianyang 712046, China), Huaxue Shiji, 2021, 43(9), ～
Abstract: The synthesis and characterization of a novel 7,7-dimethyl-2-heptyl-2-one intermediate compound 2-(4-amino-4-methylpentyl)malonate was reported. The target compound was synthesized from methyl acrylate and 2-nitropropane through a six-step reaction in a total yield of 40%, involving Michael addition reaction, hydrolyzation of ester, condensation reaction, carbonyl reduction, transesterification and nitro reduction. The structure of intermediates and the product were characterized by 1H NMR, 13C NMR, FT-IR, elemental analysis and ESI-MS. The structure of Michael addition product 4 was further determined by X-ray diffraction analysis. Also, the reaction conditions of each step were discussed briefly. This study provides a novel intermediate structure for the synthesis of azepan-2-one derivatives.
Key words: azepanederivatives; azepan-2-one; X-ray single crystal diffraction; synthesis; characterization
引用本文：仝红娟，刘斌，赵梅梅. 2-(4-氨基-4-甲基戊基)丙二酸二甲酯的合成与表征[J]. 化学试剂, 2021, 43(9): 1286-1290.
（-）-5-氮杂螺[2,4]庚烷-7-醇的合成
吕列超*1，邵翀1，朱小华1，张文超1，刘巧云2，秦东2，刘咏琪2
(1. 常州佳德医药科技有限公司，江苏 常州 213164；2. 常州工程职业技术学院，江苏 常州 213164)
摘要：AL8326是一种新型多靶点小分子酪氨酸激酶抑制剂，目前正处于临床研究中，手性化合物（-）AL8326能发挥更好的治疗效果。以10-（苯基甲基-5,8-二氧杂-10-氮杂[2.0.4.3]十一烷为起始原料，采用(-)-α-苯乙胺作为化学拆分剂制备了手性化合物（-）AL8326的重要关键中间体（-）-5-氮杂螺[2,4]庚烷-7-醇，GC纯度大于99%，总产率达16.8%，其化学结构经 MS、1HNMR 和 13CNMR 确证。探讨了还原反应中硼氢化钠的用量对中间体5-苄基-5-氮杂螺[2.4]庚烷-7-醇产率的影响，当n(硼氢化钠): n(5-苄基-5-氮杂螺[2.4]庚烷-7-酮)= 0.75:1时，还原反应产率最高，达到90.9%。考察了脱苄反应中甲酸铵及钯碳的用量对目标化合物产率的影响，当n(甲酸铵): n((-)-5-苄基-5-氮杂螺[2.4]庚烷-7-醇)= 2.0:1、钯碳用量为（-）-5-苄基-5-氮杂螺[2.4]庚烷-7-醇的0.4倍时，脱苄反应产率最佳，可达到85.0%。实验结果表明此方法操作简单、反应条件温和、适用工业生产。
关键词：AL8326；中间体；激酶抑制剂；合成；手性化合物；化学拆分
中图分类号：TQ224.6 文献标识码：A 文章编号：0258-3283（2021）--
Synthesis of (-)-5-Azaspiro [2,4]heptane-7-ol LV Lie-chao*1, SHAO Chong1, ZHU Xiao-hua1, ZHANG Wen-chao1, LIU Qiao-yun2, QIN Dong2, LIU Yong-qi2 (1. Changzhou Jiade Pharmaceutical Technology Co., Ltd., Changzhou 213164, China；2. Changzhou Institute of Engineering Technology, Changzhou 213164, China), Huaxue Shiji, 2021, 43(9), ～
Abstract: AL-8326 is a novel, high efficient multi-target small molecule tyrosine kinase inhibitor in clinical research at present, and the chiral compound (-) AL-8326 can give better therapeutic effect. By using 10- ( phenylmethyl-5,8-dioxa-10-aza [2.0.4.3] undecane as starting material, (-)-5-azaspiro[2,4]heptane-7-ol, an important key intermediate of (-) AL-8326 was synthesized by using (-)-α-phenethylamine as the resolution agent, The GC purity was more than 99%, and the total yield was 16.8%. The structure was confirmed by MS, 1HNMR, 13CNMR. The effect of the amount of NaHB4 on the yield of intermediate 5-benzyl-5-azaspiro [2.4] heptane-7-ol was discussed, when n (sodium borohydride): n (5-benzyl-5-azaspiro [2.4] heptane-7-one) = 0.75:1. The yield of 5-benzyl-5-azaspiro [2.4] heptane-7-ol by reduction reaction was up to 90.9%. The amount of ammonium formate and palladium carbon in debenzylation was discussed, when n (ammonium formate): n ((-) - 5-benzyl-5-azaspiro [2.4] heptane-7-ol) = 2.0:1 and the amount of palladium carbon was 0.4 times that of (-) - 5-benzyl-5-azaspiro [2.4] heptane-7-ol. The yield of target compound 1 by the final debenzylation could reached 85.0%. The experimental results showed that the method was simple, mild and suitable for industrial production.
Key words: AL8326; intermediate; tyrosine kinase inhibitor; synthesis; chiral compound; chemical resolution
引用本文：吕列超, 邵翀, 朱小华, 等. （-）-5-氮杂螺[2,4]庚烷-7-醇的合成[J]. 化学试剂, 2021, 43(9): 1291-1295.
催化剂载体γAl2O3涂层的制备工艺研究
张亮*，刘锦洪，李佳，陈勇，曾诚，康武，杨盼星
（中国核动力研究院 核燃料元件与材料研究所，四川 成都 610041）
摘要：由于核电站较苛刻的服役环境，对催化剂载体的稳定性提出了较高的要求，有必要深入研究提高其稳定性的技术方法。采用溶胶凝胶法制备催化剂载体涂层，并研究讨论了不同工艺过程对涂层牢固性及比表面积的影响。研究表明制备的催化剂涂层为面心立方构型的γAl2O3；不同预处理金属基体表面的粗糙度明显不同，随着基体表面粗糙度的增大，其涂层抗热冲击能力得到增强，其中以砂纸打磨后经1000 ℃空气气氛中氧化10 h样品的涂层牢固性最强。涂层前后的比表面积分析表明，涂层能增大催化剂载体的比表面积近40倍。
关键词：非能动氢复合器；催化剂载体；涂层；Al2O3；表面预处理
中图分类号：O643 文献标识码：A 文章编号：0258-3283(2021)--
Research on Preparation Process of γAl2O3 Coating for Plate Catalyst Carrier ZHANG Liang*, LIU Jin-hong, LI Jia, CHEN Yong, ZENG Cheng, KANG Wu, YANG Pan-xing (Nuclear Fuel Element and Material Sub-institute, Nuclear Power Institute of China, Chengdu 610041, China), Huaxue Shiji, 2021, 43(9), ～
Abstract: Owing to the harsh condition in nuclear power plant, higher stability of catalyst carrier is required and it is necessary to research the techniques to improve its stability. In this paper, sol-gel method was used to prepare the catalytic coatings, and the effects of different technological processes on the firmness and specific surface area of the coatings were discussed. The results showed that the surface roughness of the metal substrate in different pretreatment stages was obviously different. With the increase of the surface roughness of the substrate, the thermal shock resistance of the coating is enhanced, and the coating firmness of the sample treated by sandpaper and oxidation for 10 h in air at 1000 ℃ is the strongest. The analysis of the specific surface area before and after the coating showed that the specific surface area of catalyst supporter could be increased nearly 40 times by the coating.
Key words: passive H2 recombiner; catalyst substrate; coating; Al2O3; surface pretreatment
引用本文：张亮, 刘锦洪, 李佳, 等. 催化剂载体γAl2O3涂层的制备工艺研究[J]. 化学试剂, 2021, 43(9):1296-1300.
蓝光诱导N-苯基甲基丙烯酰胺的烷基化环化合成吲哚酮衍生物的研究
宋小文1，倪珊梅2，李萍1，刘懿锋1，李兆栋*1
(1. 华南农业大学 材料与能源学院，广东 广州 510642；2. 揭阳职业技术学院， 广东 揭阳 522000)
摘要：室温条件下，以蓝色LED为光源诱导四（三苯基膦）钯〔Pd(PPh3)4〕催化激活烷基卤代烃生成烷基自由基，与N-苯基甲基丙烯酰胺发生烷基化环化反应来简单高效的合成21个3,3-二取代吲哚酮衍生物。在室温下即可反应，具有较好的底物适用性与官能团包容性，与含有多元环、烯烃、长链烷烃、大位阻的溴代物反应均能以较高的产率得到目标产物，产率为70%～87%，很大程度上提升反应的效率，且可避免底物预官能团化、转化率低、副产物多等问题，是探索制备吲哚酮类化合物和开发新试剂的一种更加绿色高效的方法。通过1HNMR、13CNMR和HR-MS确证产物的结构，2,2,6,6-四甲基哌啶-1-氧（TEMPO）来验证该反应可能经过自由基反应过程。
关键词：N-苯基甲基丙烯酰胺；烷基卤代烃；吲哚酮衍生物；蓝光诱导；自由基反应
中图分类号：O626.13 文献标识码：A 文章编号：0258-3283（2021）
Blue-light Induced Alkylation and Cyclization of N-phenylmethacrylamide to Indolone Derivatives SONG Xiao-wen1, NI Shan-mei2, LI Ping1, LIU Yi-feng1, LI Zhao-dong*1 (1. College of Materials and Energy, South China Agricultural University, Guangzhou 510642, China; 2. Jieyang Institute of Technology, Jieyang 522000, China), Huaxue Shiji, 2021, 43(9)
Abstract: Study on using blue LED as light source to induce alkyl halide to be catalyzed and activated by tetrakis (triphenylphosphine) palladium〔Pd(PPh3)4〕to generate the alkyl free radical, which undergo alkylation and cyclization reaction with N-phenylmethacrylamide for concise and efficient synthesis twenty-one 3,3-disubstituted indolinone derivatives at room temperature. This experiment can be reacted at room temperature, with good substrate applicability and functional group inclusiveness. The target product can be obtained in high yield by reacting with brominated compounds containing polycyclic rings, olefins, long-chain alkanes and large steric hindrance, and the yield of the reaction is in the range from 70% to 87%, which can greatly improve the reaction efficiency. It is a more green and efficient method to prepare indolinone and to develop new reagents, which avoids the problems of pre-functional group of substrates, low conversion rate and many by-products. Confirm the structure of the product by 1HNMR, 13HNMR, and HR-MS. Alkyl free radicals were captured by using 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) to verify that the reaction process may have gone through a free radical reaction process.
Key words: N-phenylmethacrylamide; alkyl halide; indolone derivatives; blue light induced; free radical reaction
引用本文：宋小文，倪珊梅，李萍，等. 蓝光诱导N-苯基甲基丙烯酰胺的烷基化环化合成吲哚酮衍生物的研究[J]. 化学试剂，2021,43（9）：1301-1308.
一种新型苯并呋喃并咔唑化合物的合成与表征
梁现丽，温洁*，陈婷，王德志，向陆军，段陆萌，杭德余*
（北京燕化集联光电技术有限公司，北京 102502）
摘要：苯并呋喃并咔唑类化合物具有卓越的给电子能力、荧光特性和结构易于修饰等优点，常被用作制备有机电致发光材料的重要中间体。使用廉价的二苯并呋喃和硼酸三异丙酯为反应物，经Suzuki-Miyaura偶联、Suzuki偶联以及Cadogan关环反应合成一种新型苯并呋喃并咔唑化合物3-溴-5H-苯并呋喃[3,2-c]咔唑，并优化合成工艺，其最佳合成工艺为：催化剂为四（三苯基膦）钯、碳酸钾提供碱性环境、邻二氯苯为Cadogan关环反应的溶剂、二氯甲烷为重结晶的溶剂。通过HPLC、1HNMR和13CNMR对3-溴-5H-苯并呋喃[3,2-c]咔唑的纯度和结构进行表征，并且通过DSC研究其热学性质。
关键词：有机电致发光材料：OLED；苯并呋喃并咔唑；咔唑；偶联
中图分类号：O626.13 文献标识码：A 文章编号：0258-3283
Synthesis and Characterization of a Novel Benzofurocarbazole Compound LIANG Xian-li, WEN Jie*, CHEN Ting, WANG De-zhi, XIANG Lu-jun, DUAN Lu-meng, HANG De-yu* (Beijing Yanhua Jilian Optoelectronic Technology Co., Ltd., Beijing 102502, China), Huaxue Shiji, 2021, 43(9)
Abstract: Benzofurocarbazole compound is used as a class of important intermediates for the preparation of organic electroluminescent materials because it owns excellent electron donating ability, fluorescence characteristic and the easy-modified structure. A simple and facile synthesis of a novel benzofurocarbazole compound 3-bromo-5H-benzofuran[3,2-c]carbazole has been achieved using low-cost dibenzofuran and triisopropyl borateas substrate by sequence of Suzuki-Miyaura coupling reaction, Suzuki coupling and Cadogan ring closure reactions. Furthermore, the synthesis process was optimized, the best process was as follows: the catalyst was tetrakis(triphenylphosphine)palladium, potassium carbonate was chosen as an alkaline, o-dichlorobenzene was the solvent for Cadogan ring closure reaction, and dichloromethane was a solvent for recrystallization. The purity and structure of 3-bromo-5H-benzofuran[3,2-c]carbazole were characterized by HPLC, 1HNMR and 13CNMR. Besides, its thermal property was studied by DSC.
Key words: organic electroluminescent materials; OLED; dibenzofuran carbazole; carbazole; coupling
引用本文：梁现丽，温洁，陈婷，等. 一种新型苯并呋喃并咔唑化合物的合成与表征[J]. 化学试剂，2021，43（9）：1309-1312.
